JP2003531955A - Ion-sensitive water-dispersible polymer, method for producing the same, and articles using the same - Google Patents

Abstract

The present invention relates to ion-sensitive, water-dispersible polymers. The present invention also relates to a method for preparing an ion-sensitive water-dispersible polymer and its applicability as a binder formulation. Furthermore, the invention relates to fiber-containing fabrics and webs comprising an ion-sensitive water-dispersible binder formulation and their applicability in water-dispersible personal care products.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to ion-sensitive, water-dispersible polymer formulations. The invention also relates to a method of making an ion-sensitive, water-dispersible polymer formulation and its use as a binder composition for disposable articles. Further, the present invention relates to disposable articles, such as wet wipes, containing an ion-sensitive, water-dispersible binder composition.

BACKGROUND OF THE INVENTION Disposability issues have long been a source of worries in the industry of producing disposable items such as diapers, wet wipes, incontinence garments and feminine care products.
The approach to this problem has been greatly advanced, but one of the weaknesses is that it dissolves or decomposes easily in water but still fails to produce an economical coherent fibrous web with sufficient strength during use. Met. For example, British Patent Publication No. 2,241,373.
See U.S. Pat. No. 4,186,233. Without such a product, the user would have to flush the product down the toilet for disposal, if not impossible.
It will be extremely difficult. In addition, the majority of product components are often biodegradable or photodegradable, but they are either wrapped in plastics or are bonded to one another by plastics, which, if decomposed, take a long time. Therefore, the ability of the product to decompose in a landfill is very limited. Thus, if the plastic decomposes in the presence of water, the internal components can decompose by breaking the plastic wrap or bond.

Disposable products such as diapers, feminine care products and adult incontinence care products are
It can be made to be disposed of by flushing it to the toilet. Typically, such products include a bodyside liner that must allow a fluid, such as urine or menstruation, to quickly pass through and be absorbed by the absorbent core of the product. Typically, the body side liner
A coherent fibrous web, which desirably has many properties such as softness and flexibility. The body side liner fibrous web material is typically
It can be formed by wet or dry (air) laying a plurality of generally random fibers, bonding them together and forming a coherent web with a binder composition.
This function is often achieved in the binder compositions to date. However,
Fibrous webs containing such compositions are non-dispersive and have been a problem in typical household hygiene systems.

In recent years, binder compositions have been developed that are more dispersible and ecologically suitable than previous binder compositions. One type of binder composition includes polymeric materials that have reverse solubility in water. Such a binder composition is insoluble in hot water, but soluble in cold water such as in toilets. It is known that many polymers exhibit cloud points or reverse dissolution properties in aqueous media. Such a polymer is (1) an evaporation retardant (Japanese Patent No. 6207162), and (2) a temperature-sensitive composition useful as a temperature indicator (Japan) because its color change is sensitive to the corresponding temperature change. (Patent No. 6192527), (3) Thermosensitive material that is opaque at a specific temperature and becomes transparent when cooled below a specific temperature (Japanese Patent No. 51003248 and Japanese Patent No. 81035703), (4) Absorption characteristics Good and easy to remove wound dressing (JP 6233809) and (5) Toilet flushable personal care product material (Richard S. Ye on April 23, 1996).
US Patent No. 5 assigned to Kimberly Clark Corporation
, 509,913).

Other current binders of interest include those types of binders that are ion sensitive. Several US and European patents assigned to Lion Corporation of Tokyo, Japan, disclose ion sensitive polymers containing acrylic acid and alkyl or aryl acrylates. US Pat. Nos. 5,312,883, 5,317,06
See 3 and 5,384,189. These disclosures are incorporated herein by reference along with European Patent Publication No. 608460A1.
U.S. Pat. No. 5,312,883 discloses terpolymers as a binder suitable for nonwoven webs that can be flushed into the toilet. The disclosed acrylic acid-based terpolymers include partially neutralized acrylic acid, butyl acrylate and 2-ethylhexyl acrylate, and in certain parts of the world non-woven webs that can be flushed to the toilet. Is a binder suitable for use in. However, due to the small amount of sodium acrylate present in the partially neutralized terpolymer,
Such binders cannot disperse in water containing more than about 15 ppm Ca ²⁺ and / or Mg ²⁺ . When placed in water containing greater than about 15 ppm of Ca ²⁺ and / or Mg ²⁺ ions, the nonwoven web with the above-described binder has a viscosity of 30
It maintains tensile strength in excess of g / inch, which has a detrimental effect on the "dispersion" of the web. As a mechanism for causing such a failure, it has been proposed that each calcium ion binds to two carboxylic acid groups either intramolecularly or intermolecularly. The intramolecular association causes the polymer chains to spiral, which ultimately precipitates the polymer. Intermolecular association causes cross-linking. Regardless of whether intramolecular or intermolecular association occurs, the terpolymer has a C content above about 15 ppm.
It is insoluble in water containing a ²⁺ and / or Mg ²⁺ . Due to the strong interaction between the calcium ions and the carboxylic acid groups of the terpolymer, this association is irreversible and the probability of dissociation of the complex is extremely low. Therefore, the above polymer once placed in a solution with a high Ca ²⁺ and / or Mg ²⁺ concentration will not disperse in water even if the calcium concentration is reduced. This limits the use of this polymer as a toilet flushable binder material as it is hard water containing more than 15 ppm of Ca ²⁺ and / or Mg ²⁺ in most parts of the United States. .

A pending application assigned to Kimberly Clark, namely December 31, 1998.
U.S. patent application Ser. No. 09 / 223,999, filed dated, discloses the patented acrylic acid terpolymer modifications granted to Lion Corporation, cited above. This disclosure is incorporated herein by reference. In particular, U.S. patent application Ser. No. 09 / 223,999 discloses a dispersion in relatively hard water, for example up to 200 ppm Ca ²⁺ and / or Mg ²⁺ when compared to unmodified Lion polymer. Sulfonate anion modified acrylic acid terpolymers with improved properties are disclosed. However, the above-cited patent Lion Corporation ion-sensitive polymer and the pending application sulfonate anion-modified acrylic acid terpolymer, when used as a binder for personal care products such as wet wipes, In general, the wettability of the sheet is reduced, the sheet becomes harder and thicker, the binder is difficult to spray, and the product cost is relatively high.

Another approach to disposable personal care products is disclosed in US Pat. No. 5,281,306 issued to Kao Corporation, Tokyo, Japan. This patent discloses a water decomposable wiping sheet or wet wipe comprising water dispersible fibers treated with a water soluble binder having a carboxyl group. The cleaning sheet has been treated with a cleaning agent containing an organic solvent compatible with 5% to 95% water and 95% to 5% water. The preferred organic solvent is propylene glycol. The cleaning sheet maintains wet strength and does not disperse in organic solvent based cleaning agents, but disperses in water.

A number of patents disclose various ionic and temperature sensitive compositions for water dispersible or toilet flushable materials, but are soft, flexible, steric, and Elastic, wicking and structurally in the presence of body fluids (including faeces) at body temperature, with true fiber dispersability after being flushed into the toilet, roots of trees or bends in sewers What is needed is a dispersible product that is entangled in. Also,
Known ion-sensitive polymers, such as those of Lion Corp. and Kimberly Clark's pending applications, have relatively high viscosities at high shear rates,
This makes spray application impossible or impractical. There is also a need in the art for a product that can be flushed into a water dispersible toilet in any part of the world, including soft and hard water. Further, there is a need for a water dispersible binder that does not reduce the wettability of products using it, yet can be easily and uniformly applied or penetrated into the product using a spray. Finally, dispersion in water moistened with a wetting composition that is stable during storage and maintains a desirable level of wet strength during use, and is relatively free or substantially free of organic solvents. There is a need for a wet wipe that is capable and flushes down the toilet. Such products need to be relatively inexpensive without compromising product safety and environmental considerations, something that could not have been possible with previous products.

DISCLOSURE OF THE INVENTION The present invention is an ion sensitive polymer formulation developed to address the aforementioned problems associated with currently available ion sensitive polymers and other polymers described in the literature. Regarding The ion-sensitive polymer formulation of the present invention has “trigger properties”
This “triggering property” means that the polymer is insoluble in a wet composition containing certain types and concentrations of ions, such as a solution of a monovalent salt with a concentration of about 0.3% to 10%. However, it has properties such that it can be made soluble when diluted with water containing a divalent salt solution such as hard water containing up to 200 ppm (parts per million) of calcium and magnesium ions. Unlike some ion-sensitive polymer formulations that lose their dispersibility in hard water due to ionic cross-linking with calcium ions,
The polymer formulations of the present invention are relatively insensitive to calcium and / or magnesium ions. As a result, toiletable products containing the polymer formulations of the present invention maintain dispersibility in hard water. Further, the ion-sensitive polymer formulation of the present invention can be seen to have improved properties such as ease of spraying, that is, reduction of high shear viscosity, improvement of product wettability, and reduction of product hardness or tackiness.

The polymer formulations of the present invention are binders for air-laid and wet-laid nonwovens used in applications such as bodyside liners, fluid distribution materials, fluid uptake materials (surges) or cover stocks in various personal care products. And is useful as a component. INDUSTRIAL APPLICABILITY The polymer preparation of the present invention is suitable for personal care products that can be flushed in the toilet, particularly for cleaning or treating the skin including wipes including a cleaning agent, a disinfectant, cosmetics removal, manicure removal, medical care. In addition to wet wipes for personal use, it is particularly useful as a binder material for wipes used for cleaning hard surfaces and car care. Toiletable products maintain integrity or wet strength during storage and use and decompose or disperse when the concentration of salt drops below critical levels after disposal in the toilet. Substrates suitable for processing include tissue such as textured or non-textured tissue, coform products, hydraulically entangled webs, air-laid mats, fluff pulp, nonwoven webs, and composites thereof. The method for producing the non-textured tissue and shaped three-dimensional tissue web utilized in the present invention is 1
F.R. -J. U.S. patent application Ser. No. 08 / 912,906, assigned to the same applicant, entitled "Wet Elastic Web and Disposable Articles Made Thereof," filed by Chen et al., Chiu et al. U.S. Pat. No. 5,429,686 to Mar. 21, 1995; J. Suda
ll and S. A. US Pat. No. 5,399,412, 19 to Engel.
US Pat. No. 5,672,248 issued to Wendt et al. On September 30, 1997, and US Pat. No. 5 issued to Farrington et al. On March 4, 1997.
, 607,551. All of these are incorporated herein by reference in their entirety. The molded tissue structure of the above patent is particularly useful for imparting good wipeability to wet wipes. Good wiping properties can also be improved by texturing the other substrate to some extent and subjecting the textured fabric to embossing, molding, wetting, and air drying.

The air-laid material is metered in a substantially dry state onto a screen, typically made of horizontally moving wires, containing a stream of air containing fibers and other optional materials. Can be formed. A suitable system and apparatus for air-depositing a mixture of fibers and thermoplastics is disclosed, for example, on June 12, 1979 and reissued on Dec. 25, 1984 as reissued US Pat. No. 31,775. U.S. Pat. No. 4,157,724 (Persson) issued, U.S. Pat. No. 4,278,113 (Persson) issued July 14, 1981,
U.S. Pat. No. 4,264,289 (Day) issued Apr. 28, 1981.
, U.S. Pat. No. 4,352,649 issued October 5, 1982 (Jac
Obsen et al.), U.S. Pat. No. 4,353, issued Oct. 12, 1982.
No. 687 (Hosler et al.), US Pat. No. 4, issued January 22, 1985.
, 494,278 (Kroyer et al.), U.S. Pat. No. 4,627,806 (Johnson) issued Dec. 9, 1986, U.S. Pat. No. 4,650, Mar. 17, 1987. 409 (Nistri et al.) And US Pat. No. 4,724,980 (Farley) issued February 16, 1988, and US Pat. No. 4,640,810 issued February 3, 1987. Issue (Laur
Sen et al.).

The present invention also discloses a method of making a water dispersible nonwoven comprising a cover stock (liner), an uptake (surge) material and a wet wipe, the nonwoven binding the unique polymer formulation described above. By being used as an agent composition, it is stable in a fluid having a first ionic composition, such as a specific concentration of monovalent ions, substantially greater than that found in typical hard water. The resulting non-woven fabric is ionic sensitive so that it can be triggered regardless of the hardness of the water found in toilets in the United States and around the world so that it can be flushed and dispersible in water. is there.
The dispersible products according to the invention can also have improved softness and flexibility properties. Also, such products have reduced stickiness. In some embodiments, polymer formulations for treating such articles may have improved sprayability characteristics, which may improve polymer distribution on the product and penetration into the product. In addition to ease of application, it also leads to cost reduction.

Further, the present invention discloses an improved wetting composition for wet wipes. Wet wipes using the polymeric formulations of the present invention are stable during storage and maintain a desirable level of wet strength during use and are relatively free of organic solvents.
Moistened with a substantially free wetting composition or wipe. Such features and advantages of the invention will be apparent upon consideration of the following detailed description of the disclosed embodiments and the accompanying drawings and claims.

BEST MODE FOR CARRYING OUT THE INVENTION In order to be an effective ion-sensitive formulation suitable for use in a toilet or water dispersible personal care product, the formulation must be , (1) functional, that is, it maintains wet strength under controlled conditions and quickly dissolves or disperses in soft or hard water such as found in toilets and sinks worldwide, and (2) is safe Yes (no toxicity), (3) It is desirable to be relatively economical. In addition to the factors mentioned above, the ion-sensitive formulation may be (4) processed on a commercial basis when used as a binder composition for non-woven substrates such as wet wipes, ie by spraying or the like. In order to be able to be applied relatively quickly on a large scale basis, the binder composition must have a relatively low viscosity for high shear, (5)
It is desirable to provide an acceptable level of sheet or substrate wettability to (6) improve the flexibility of the product and reduce tackiness to improve the feel of the product. The moisturizing compositions for treating wet wipes of the present invention provide some of the aforementioned benefits, in addition to (7) improved skin care, such as reduced skin irritation or other benefits. ) One or more of improved hand feel and (9) improved wipeability by balancing the friction and lubricity (skin slip) of the skin during use. Ion-sensitive polymer formulations of the present invention and articles made therefrom, particularly wet wipes comprising the particular wetting composition described below, can meet many or all of the above criteria. Of course, to fall within the scope of the present invention,
Not all the advantages of the preferred embodiments of the present invention need to be met.

The polymer formulations of the present invention can be formed of a single triggerable polymer such as an ion sensitive polymer, or two or more different polymers such as a triggerable polymer and a cobinder. At least one polymer formulation of the present invention
The two polymers are preferably ion-sensitive polymers. Ion-sensitive polymers are known in the art and include any polymer whose water solubility is altered by the type and amount of ions present in the water. Ion-sensitive polymers useful in the present invention are not limited to the Lion polymers discussed above, such as Lion's acrylic acid terpolymers, but are pending in pending application 09/223, assigned to Kimberly-Clark Worldwide Incorporated. No. 999, sulfonate anion-modified acrylic acid terpolymer, filed on May 4, 2000, entitled "Ion-Sensitive Polymers Dispersible in Hard Water and Their Applications", also by Kimberly-Clark Worldwide. Co-pending U.S. Patent Application No. (identified as KC No. 15851, J & A No. 11302-0481, Express Label No. EL498682165US) assigned to Incorporated, as well as Murnick on March 28, 2000. And the key Included are other polymers that are ion and chemical sensitive, including the polymer of US Pat. No. 6,043,317 assigned to Nbury Clark Worldwide Incorporated. Incidentally, these disclosures are incorporated herein by reference in their entirety.

Other known triggerable polymers include temperature and heat sensitive polymers as well as 1
Dispersing aid to toilet bowls or other water sources as discussed in US Pat. No. 5,948,710 granted to Pomplun et al. On Sep. 7, 999 and assigned to Kimberly Clark Worldwide Inc. Included are polymers that become dispersible upon addition of the agent. Pomplun et al. Note that another means of making polymers degradable in water is by utilizing temperature changes. Certain polymers exhibit a cloud point temperature. As a result, such polymers will precipitate out of solution at a certain temperature, which is the cloud point. Such polymers can be used to form fibers that are insoluble in water above a certain temperature but are soluble in cold water and therefore degradable. As a result, it does not decompose in body fluids such as urine at body temperature (37 ° C) or near body temperature, but is lower than body temperature, for example room temperature (23
It is possible to select or blend polymers that will decompose when placed in water (° C.). An example of such a polymer is polyvinyl methyl ether, which has a cloud point of 34 ° C. Exposure of the polymer to body fluids such as urine at 37 ° C. does not result in decomposition as the temperature is above the cloud point (34 ° C.). However, when the polymer is placed in room temperature (23 ° C.) water, it will come back into solution over time as it is now exposed to water below the cloud point. As a result, the polymer will begin to decompose. Blends of polyvinyl methyl ether and copolymers can be considered as well. Other cold water soluble polymers include poly (vinyl alcohol) graft copolymers supplied by Nippon Synthetic Chemical Co., Ltd. of Osaka, Japan, which are commercially available from Economy AX2.
000, AX10000 and AX300G.

Ion-Sensitive Polymers The ion-sensitive Lion polymers and the above-referenced Kimberley-Clark Worldwide Incorporated pending application and US patent ion-sensitive polymers are useful in the present invention. The sulfonate anion modified acrylic acid terpolymer of co-pending patent application No. 09 / 223,999 assigned to Kimberly-Clark Worldwide Inc. is different from the polymers of Lion Corporation and other polymers cited in the technical literature. , Less than about 10 ppm Ca ²⁺ and / or
Or for the Mg ²⁺ is soluble in water with Ca ²⁺ and / or Mg ²⁺ up to about 200 ppm, the terpolymer is desired. The polymers of the pending application are formulated to minimize the strong interactions that may occur between polymer anions and cations in water. This strong interaction is due to R. G. Pearson, "American Society of Chemistry," Vol. 85, page 3533 (1963), or N.
． S. Isaacs, Longman Scientific, New York
and Technical with John Wiley & Sons,
Inc. It can be explained by the hard acid-base theory and the soft acid-base theory proposed in the textbook "Physical Organic Chemistry" (1987) published by. Hard anions and hard cations interact strongly with each other. Also, soft anions and soft cations interact strongly with each other. However, soft anions and hard cations, and vice versa, interact weakly with each other. In Lion's polymer, the sodium acrylate carboxylate anion is a hard anion and interacts strongly with medium hard water and the 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, anion triggerable polymer anions,
The interaction between moderately hard water and the hard cations Ca ²⁺ and / or Mg ²⁺ present in hard water is reduced.

As used herein, the term “soft water” has a divalent ion content of about 10 p.
Water that is less than pm. As used herein, the term "moderately hard water" refers to water having a content of divalent ions of about 10 to about 50 ppm. As used herein, the term "hard water" has a divalent ion content of greater than about 50 ppm and about 2
Says water that is up to 00 ppm. Hydrophobic / hydrophilic balance and polymer composition,
By controlling the combination of polymers forming the formulation, an ion-sensitive polymer formulation is produced that has desirable bond strength during use and is dispersible in water in water. The ion sensitive polymer can be a copolymer such as a terpolymer.

The ion-sensitive acrylic acid copolymers of the present invention comprise any combination of acrylic acid monomers and acrylic acid ester (alkyl acrylate) monomers that can be free radical polymerized into copolymers, in particular terpolymers. be able to. Suitable acrylic acid monomers include, but are not limited to, acrylic acid and methacrylic acid. Suitable acrylic acid monomers include acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, the alkyl group having 1 to 12 carbon atoms. Alternatively, acrylic acid esters and / or methacrylic acid esters having a cycloalkyl group having 3 to 12 carbon atoms are preferably used alone or in combination, but are not limited thereto. Other suitable monomers include acrylamide,
Acrylamide and methacrylamide based monomers such as N, N-dimethylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, and hydroxymethylacrylamide; N-vinylpyrrolidinone; N-vinylformamide; and hydroxyethyl methacrylate and acrylic Included, but not limited to, hydroxyalkyl acrylates and hydroxyalkyl methacrylates such as hydroxyethyl acidate. Other suitable acrylic acid and acrylate monomers are disclosed in US Pat. No. 5,317,063 assigned to Lion Corporation of Tokyo, Japan. The disclosure of this patent is
The entire specification is incorporated herein by reference. A particularly preferred acrylic acid terpolymer is LION SSB-3b available from Lion Corporation. (In another embodiment, the ion-sensitive polymer is formed from monomers other than acrylic acid or its derivatives and is relatively free of acrylic acid, methacrylic acid, and salts thereof.)

The relative amounts of monomers in the acrylic acid copolymer of the present invention can be varied depending on the desired properties of the resulting polymer. The mole percent of acrylic acid monomer in the copolymer is up to about 70 mole percent. Specifically, the mole percent of acrylic acid monomer in the copolymer is from about 15 to about 50 mole percent. Most specifically, the mole percent of acrylic acid monomer in the copolymer is from about 25 to about 40 mole percent.

More specifically, examples of acrylic acid copolymers useful in the present invention include 10 weight percent to 90 weight percent, desirably 20 weight percent to 70 weight percent acrylic acid and / or methacrylic acid, and carbon atoms. Copolymers with 90% to 10% by weight, preferably 80% to 30% by weight, of acrylic and / or methacrylic acid esters having alkyl groups of 1 to 18 or cycloalkyl groups of 3 to 18 carbon atoms. so,
1 to 60 mole percent, preferably 5 to 50 mole percent of acrylic acid and / or methacrylic acid neutralized to form a salt, or 30 to 75 weight percent, preferably 40 to 65 weight percent Percent acrylic acid, 5 to 30 weight percent, preferably 10 to 25 weight percent acrylic and / or methacrylic acid having an alkyl group having 8 to 12 carbon atoms, and 2 carbon atoms.
Copolymers with 20 to 40 weight percent, preferably 25 to 35 weight percent acrylic and / or methacrylic acid esters having from 4 to 4 alkyl groups, 1 to 50 mole percent, preferably 2 to 40 Mention may be made of a salt formed by neutralizing mole percent of acrylic acid.

The acrylic acid copolymers of the present invention have an average molecular weight, which depends on the ultimate end use of the polymer. The weight average molecular weight of the acrylic acid copolymer of the present invention is about 1
It ranges from 50,000 to about 5,000,000. Specifically, the acrylic acid copolymers of the present invention have a weight average molecular weight of from about 25,000 to about 2,000,0.
00, more particularly in the range of about 200,000 to about 1,000,000.

The acrylic acid copolymer of the present invention can be prepared by various polymerization methods, preferably solution polymerization methods. Suitable solvents for the polymerization process include lower alcohols such as methanol and ethanol and propanol, mixed solvents of water with one or more of the above lower alcohols, and water with one or more of acetone or methyl ethyl ketone. Examples of mixed solvents with lower ketones include, but are not limited to:

Any polymerization initiator can be used in the polymerization method of the present invention. The particular initiator is selected by a number of factors including, but not limited to, polymerization temperature, solvent, and monomers used. Suitable polymerization initiators for use in the present invention include 2,
2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2-
Azobis (2-amidinopropane) dihydrochloride, 2,2-azobis (N,
N'-dimethylene isobutylamidine, potassium persulfate, ammonium persulfate,
And hydrogen peroxide water, but are not limited thereto. The amount of polymerization initiator can desirably range from about 0.01 to 5 weight percent based on the total amount of monomers present. The polymerization temperature can vary depending on the polymerization solvent, the monomer, and the initiator used, but is generally in the range of about 20 ° C to about 90 ° C. The polymerization time is
Generally, it will range from about 2 to about 8 hours.

The sulfonate anion modified acrylic acid copolymer according to the present invention comprises a hydrophilic monomer such as acrylic acid or methacrylic acid incorporated into the acrylic acid copolymer of the present invention together with one or more sulfonate containing monomers. included. The sulfonate anion of such a monomer has a negative charge of sulfonate of 3
While delocalized over one oxygen atom and a large sulfur atom, the carboxylate anion is softer than the carboxylate anion because it has only two oxygen atoms and a small carbon atom. Such a monomer containing a soft sulfonate anion has little interaction with polyvalent ions existing in hard water, particularly Ca ²⁺ and Mg ²⁺ ions. Suitable sulfonate containing monomers include 2-acrylamido-
2-Methyl-1-propanesulfonic acid (AMPS) and 2-acrylamido-2
-Organic or inorganic salts of methyl-1-propanesulfonic acid, such as the alkaline earth metal salts and organic amine salts of 2-acrylamido-2-methyl-1-propanesulfonic acid, especially 2-acrylamido-2-methyl-1 -Including but not limited to the sodium salt of propanesulfonic acid (NaAMPS). Other suitable sulfonate-containing monomers include 2-methyl-2-propene sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-sulfopropyl methacrylate and acrylic acid 3
-Sulfopropyl, and its organic or inorganic salts, such as, but not limited to, organic amine salts such as alkaline earth metal salts and alkyl ammonium hydroxides (where the alkyl group is C ₁ -C ₁₈ ). 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 copolymer of the present invention comprises the following monomers: acrylic acid, methacrylic acid, or combinations thereof; 2-acrylamido-methyl-1-propanesulfonic acid (AMPS) and It can be formed from monomers including its organic or inorganic salts, such as its sodium salt (NaAMPS); butyl acrylate; and 2-ethylhexyl acrylate. The ion-sensitive sulfonate anion-modified acrylic acid copolymer of the present invention comprises acrylic acid; AM
PS, NaAMPS or a combination thereof; butyl acrylate; and acrylic acid 2
It is preferably produced from ethylhexyl. Each of the monomers was added to the sulfonate anion-modified acrylic acid copolymer with the following mole percents: acrylic acid up to about 35 to less than 80 mole percent, AMPS or NaAMPS above 0 to about 20 mole percent, and butyl acrylate. Desirably, greater than 0 to about 65 mole percent and 2-ethylhexyl acrylate are present at greater than 0 and up to about 45 mole percent. Specifically, each monomer is incorporated into the sulfonate anion-modified acrylic acid copolymer in the following mole percents: from about 50 to about 67 mole percent acrylic acid, and from greater than 0 to about 10 mole percent AMPS or NaAMPS. Butyl acrylate is present in about 15 to about 28 mole percent and 2-ethylhexyl acrylate is present in about 7 to about 15 mole percent. Most specifically, each monomer is incorporated into the sulfonic acid anion modified acrylic acid copolymer in the following mole percentages: from about 57 to about 66 mole percent acrylic acid, AM.
About 1 to about 6 mole percent PS or NaAMPS, about 15 to about 28 mole percent butyl acrylate, about 7 to about 13 mole percent 2-ethylhexyl acrylate, and especially about 60 mole percent acrylic acid. , AM
PS or NaAMPS is present at about 5 mole percent, butyl acrylate at about 24.5 mole percent, and 2-ethylhexyl acrylate at about 10.5 mole percent.

If AMPS is used as one of the monomers, it is desirable to at least partially neutralize the acidic component. Any inorganic or organic base can be used as a neutralizing agent to neutralize the acidic components. Examples of neutralizing agents are inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium carbonate, and monoethanolamine, diethanolamine, diethylaminoethanol, ammonia, trimethylamine, triethylamine, tripropylamine, morpholine. And amines such as, but not limited to. Preferred neutralizing agents include sodium hydroxide, potassium hydroxide, or combinations thereof.

Salt sensitive sulfonate modified copolymers can also be produced by sulfonation of existing polymers such as copolymers of terpolymers derived from acrylic acid. Methods of sulfonation of polymers are known in the art. A method for producing a sulfonated or sulfated polymer is described in Sch.
U.S. Pat. No. 3,624,069 issued to Welger, U.S. Pat. No. 4,419,403 issued to Varona on Dec. 6, 1983, U.S. granted to Shet on Jun. 4, 1996. No. 5,522,967, US Pat. No. 4,220,739, 199, issued to Walles on September 2, 1980.
In addition to U.S. Pat. No. 5,783,200 issued to Motley et al. On Jul. 21, 8th, the following patents were given: U.S. Pat.
6, No. 2,786,780, No. 2,832,696, and No. 3,740,
No. 258. All of these patents are incorporated herein by reference. The principles of sulfation and sulfonation (eg, sulfamic acid treatment, reaction with thionyl chloride or chlorosulfonic acid, or exposure to sulfur trioxide) are based on Samu.
el Shore and D.L. R. Berger, "Sulfate Alcohols and Sulfate Alcohol Ethers"("AnionicSurfactants" Part 1, Warner M. Linf
ield, New York Marcel Dekker, Inc. 1976 1
35-149), and Ben E. "The Mechanism of Sulfonation and Sulfation" by Edwards ("Anionic Surfactants" Part 1, Warner M. et al.
Edited by Linfield, New York Marcel Dekker, Inc. 19
1976, pages 111-134). The two documents are incorporated herein by reference.

In another embodiment of the present invention, the ion-sensitive polymer formulation described above is used as a binder material for toilet flushable and / or non-toilet flushable products. To be effective as a binder material in toilet flushable products in the United States, the ion-sensitive polymer formulations of the present invention remain stable in the dry state or at relatively low concentrations of monovalent ions. It maintains its integrity, but about 2
It becomes soluble in water containing up to 00 ppm of divalent ions, especially calcium and magnesium ions. Desirably, the ion-sensitive polymer formulations of the present invention, including acrylic acid copolymers, are in a salt solution containing at least about 0.3 weight percent of one or more inorganic and / or organic salts containing monovalent ions. Is insoluble in. More desirably, the ion-sensitive polymer formulations of the present invention, including acrylic acid copolymers, contain from about 0.3 weight percent to about 5.0 weight percent of one or more inorganic and / or monovalent ion containing and / or monovalent ions. Alternatively, it is insoluble in a salt solution containing an organic salt. More desirably, the ion sensitive polymer formulations of the present invention, including acrylic acid copolymers, comprise from about 1 weight percent to about 3.0 weight percent of one or more inorganic and / or organic containing monovalent ions. It is insoluble in salt solutions containing salts. Suitable monovalent ions include Na ⁺
But not limited to, ions, K ⁺ ions, Li ⁺ ions, NH ₄ ⁺ ions, low molecular weight quaternary ammonium compounds (eg, all side chains having less than 5 carbon atoms), and combinations thereof.

In another embodiment, the ion-sensitive polymer formulations of the present invention, including sulfonate anion-modified acrylic acid copolymers, contain at least about 1 monovalent ion.
It is insoluble in salt solutions containing weight percent of one or more inorganic and / or organic salts. Desirably, the ion-sensitive polymer formulations of the present invention, including sulfonate anion modified acrylic acid terpolymers, contain from about 1 weight percent to about 5.0 weight percent of one or more monovalent ions. Inorganic and /
Alternatively, it is insoluble in a salt solution containing an organic salt. More desirably, the ion-sensitive polymer formulations of the present invention, including sulfonate anion-modified acrylic acid terpolymers, comprise from about 1 weight percent to about 3.0 weight percent of one or more monovalent ions. It is insoluble in a salt solution containing the inorganic and / or organic salt of. Suitable monovalent ions include Na ⁺ ions, K ⁺ ions, Li ⁺ ions, NH ₄ ⁺
Examples thereof include, but are not limited to, ions, low molecular weight quaternary ammonium compounds (eg, those in which all the side chains have less than 5 carbon atoms), and combinations thereof.

Based on a recent study conducted by the American Society of Chemistry, the hardness of water in the United States varies significantly, with CaCO ₃ concentrations ranging from almost zero in soft water to approximately 500 pp in highly hard water.
m CaCO ₃ (ca. 200 ppm Ca ²⁺ ions). To ensure that the polymer formulation is dispersible domestically (and all over the world), the ion-sensitive polymer formulation of the present invention is soluble in water containing up to about 50 ppm Ca ²⁺ and / or Mg ²⁺ ions. Is desirable. More desirably, the ion-sensitive polymer formulations of the present invention are solubilized in water containing up to about 100 ppm Ca ²⁺ and / or Mg ²⁺ ions. More desirably, the ion-sensitive polymer formulations of the present invention are solubilized in water containing up to about 150 ppm Ca ²⁺ and / or Mg ²⁺ ions. More desirably, the ion-sensitive polymer formulation of the present invention comprises about 2
It is solubilized in water containing up to 00 ppm Ca ²⁺ and / or Mg ²⁺ ions. Ion-Sensitive Lion Polymers and Co-pending Patent Application No. 09 with Various Polymer / Surfactant Systems and Without the Need for Sulfone or Carboxyl Group Components
It can have the same functionality as the ion-sensitive sulfonate anion-modified acrylic acid terpolymer of / 223,999. Other systems will be described below.

Phosphorylated polymers containing phosphonic acid groups, thiophosphonic acid groups, or other organophosphorus groups as “soft” anions that can be incompatible with Ca ⁺⁺ are used as the ion-sensitive polymers of the present invention. be able to. This may include modified cellulose or cellulose derivatives and related gums which are rendered insoluble by the presence of monovalent salts or other electrolytes. In one embodiment, soluble cellulose derivatives, such as CMC, are phosphorylated to render them insoluble and useful as ion-sensitive polymer formulations in solutions of high ionic strength or pH. Yes, but dispersible in tap water. In other embodiments, aminophosphinic acid groups, which can be anionic or amphoteric, are added to the polymer. The aminophosphinic acid group can be added by condensing the hypophosphite with a primary amine. Also, Guenther W. "Phosphorus-containing Anionic Surfactant" by Wasow ("Anionic Surfactant" Organic Chemistry, Helmut W. St.
Ache, New York Marcel Dekker, 1996, 589-
The reaction of chloromethylphosphinic acid with amines can also yield useful anionic groups, as described in (page 590). 551-629 of the book
The entire page-filling chapter by Wasow features another technique, equivalent to producing polymers containing useful phosphorus groups, which is incorporated herein by reference.

Alternative methods of preparing phosphorylated cellulose fibers are known. Such a method can be adapted to the CMC so that this CM
C can act as a binder. A typical method is disclosed in US Pat. No. 3,739,782 issued to Bernardin on June 19, 1973. Cellulose and synthetic or natural polymers modified to have other "soft" anionic groups can also be useful as the ion-sensitive polymers of the present invention. Natural polymers that already have useful anionic groups can also be useful in the present invention. Such polymers include agar and carrageenan, which have multiple sulfate ester groups. These can be further modified, if desired, to additionally have an anionic group (eg sulphonation,
Phosphorylation etc.).

In polymers having two or more different soft anion groups, such as both sulphonic acid groups and phosphonic acid groups, different anions will optimize the strength, ion sensitivity and dispersibility of the polymer. The relative amount of the can be adjusted and these are also useful in the present invention. It also includes zwitterionic and amphoteric compounds. In particular, amphoteric polyelectrolytes are readily soluble above or below their isoelectric point, but are insoluble at their isoelectric point and may serve as a trigger mechanism based on electrolyte and pH. Examples of amphoteric polyelectrolytes include copolymers of methacrylic acid and allylamine, copolymers of methacrylic acid and 2-vinylpyridine, polysiloxane ionomers with pendant amphoteric groups, and ion pairs (IPC) of the comonomers of Salamone et al.
Such polymers include, but are not limited to, polymers formed directly from zwitterionic monomer salts such as All of these are referred to by Irja Pirma as "polymeric surfactants" (New York Marcel Dekker, Inc. 1992 251).
~ 254), which is incorporated herein by reference. Proteins that can be salted out, optionally modified to have additional soft ionic groups, can be useful as the ion-sensitive polymers of the present invention.

High concentrations of calcium ions (much higher than levels of 250 ppm or less visible in hard water) render the binder insoluble, but hard water also binds if the calcium ions are sufficiently diluted. Systems such as those containing algin derivatives or natural sulfonated polymers that make the agent dispersible are useful in the present invention. Thus, although it is desirable that the ion-sensitive binders of the present invention be insoluble in solutions containing monovalent metal ions in excess of the critical concentration, in some of the embodiments,
Useful ion-sensitive binders are insoluble in solutions containing divalent metal ions above the critical concentration but have divalent metal ion concentrations of about 200 ppm, specifically about 100 p.
The fiber base layer containing the ion-sensitive polymer as a binder has a good wet strength in a solution having a high concentration of divalent metal ions, and becomes soluble in hard water or medium hard water by decreasing to pm. To be dispersible in water. As described above, the trigger function that allows the wet strength of the pre-moistened wipe to be lost and allows flushing even in hard water to the toilet is a monovalent or divalent metal ion, particularly an alkali metal ion having a monovalent ion, for example, It can be preferably done by diluting with sodium. Natural polymers and rubbers can be adapted for use as ion-sensitive binders, these are described by R.M. L. Whistler and J
． N. "Industrial Rubber" by BeMiller (New York Academic
Press, Inc. 1973) and incorporated herein by reference. Natural polymers that harden or form gels in the presence of calcium ions are described below.

Algin (reported behavior when used as a binder in medicated tablets (Whist)
According to Ler and Be Miller, page 62), it may be necessary to be in the form of sodium alginate and calcium alginate in order to have good dispersibility. ) Is insoluble as alginic acid, calcium alginate, or generally as salts of most polyvalent metals, but soluble as sodium alginate or as salts with low molecular weight amines or quaternary ammonium compounds (page 67). Therefore, it can be useful in the present invention. This material can be used especially when zinc is the insolubilizing metal ion. Other useful polymers include carrageenan and iridophane.
ycan), all of which are seaweed derivatives containing a sulfate ester. Both natural and synthetic polymers, including cellulose, are capable of cross-linking to other molecules in the presence of the appropriate type and concentration of ions, such as sulfonic acid groups, phosphonic acid groups, and carboxyl groups. Ionic groups can be provided. When the ionic concentration changes substantially, such as by placing the wipes of the present invention in a toilet bowl, the articles lose strength and can decompose.

The ion sensitive polymer is dispersible in an aqueous environment under certain conditions,
Includes those that are not dispersible in all aqueous environments. Examples include materials that are alkaline, dispersible or insoluble in saline. For example, E
astman AQ copolymer (Eastman Chemical Company, Kingsport, TN) is dispersible in deionized water but may be insoluble in saline. Such copolymers have been proposed for use in articles such as diapers intended to absorb body fluids. Other information regarding such polymers can be found in S. et al., Published May 14, 1997. U. A
Obtained from hmed European Patent Application 773,315-A1 "Nonwoven webs containing water-soluble polyamides and articles made therefrom". Useful amphoteric polyelectrolytes include polyacrylamide-based copolymers that are highly sensitive to sodium chloride concentration.

US Pat. No. 3,93, the disclosure of which is incorporated herein by reference
No. 9,836, which imparts good dry tensile strength to fabrics when such fabrics are contacted with a solution of a salt, which is typically a body fluid such as blood, menstrual fluid, or urine, Alkaline salts of sulphated cellulose ester resins are described which ensure that the strength is maintained to a considerable extent and are easily dispersible in water. The degree of sulfuric acid substitution of this resin is from 0.10 to 0.45. U.S. Pat. No. 4,419,403, the disclosure of which is incorporated herein by reference, uses a colloidal sulfate of cellulose as an effective water dispersible binder. The agent has a much higher degree of sulfuric acid substitution than the '836 patent. The binder of the '403 patent forms a gel in the presence of potassium ions. Other patents related to disposable polymers and wet wipes include US Pat. No. 4,117,
187, No. 5,417,977, No. 4,309,469, No. 5,317,
No. 063, No. 5,312,883, No. 5,384,189, No. 5,543.
No. 488, No. 5,571,876, No. 5,709,940, No. 5,718,
790 is mentioned. These disclosures are incorporated herein by reference.

Cobinder Polymer As mentioned above, the polymer formulations of the present invention are formed of a single ion-sensitive polymer, or two or more different polymers, at least one of which is an ion-sensitive polymer. . The second polymer can be a cobinder polymer. When the co-binder polymer is combined with the ion-sensitive polymer, preferably the majority of the co-binder polymer is dispersed within the ion-sensitive polymer, that is, the ion-sensitive polymer is preferably in the continuous phase and the co-binder The polymer is preferably of a type that provides a discontinuous phase and is in such an amount. It is also desirable that the cobinder polymer be able to meet some additional criteria. For example, the co-binder polymer can have a glass transition temperature, or Tg, that is below the glass transition temperature of the ion-sensitive polymer. Additionally or alternatively, the cobinder polymer can be water insoluble or can reduce the shear viscosity of the ion sensitive polymer. The cobinder is about 45% or less, more specifically about 30% or less, more specifically about 20% or less, more specifically about 10%, relative to the solid mass of the triggerable polymer. Or lower levels, with typical ranges of about 1% to about 45% or about 25% to about 35%, as well as about 1% to about 20% or about 5%. To about 25%. The amount of co-binder present should be sufficiently low for water-insoluble bonds or co-binders that may form films that the cross-linking, i.e. cross-linking, in order to weaken the dispersibility of the treated substrate. It is necessary to ensure that it remains in the discontinuous phase, which is incapable of producing insoluble bonds. In one embodiment, the ion-sensitive polymer formulation of the present invention comprises about 75 weight percent acrylic acid terpolymer and about 25 weight percent poly (ethylene-
A vinyl acetate) co-binder may be included.

The co-binder polymer, when combined with the ion-sensitive polymer, will reduce the shear viscosity of the ion-sensitive polymer to the extent that the combination of ion-sensitive polymer and co-binder polymer is sprayable. Is preferred but not necessarily so. Sprayable means that the polymer can be applied to the non-woven fibrous base layer by spraying, the distribution of the polymer throughout the base layer and the penetration of the polymer into the base layer such that the polymer formulation is evenly applied to the base layer. Means The cobinder polymer can be in the form of an emulsion latex.
The surfactant system used in such latex emulsions should be such that they do not substantially interfere with the dispersibility of the ion-sensitive polymer.

In some of the embodiments, the combination of the ion-sensitive polymer and the cobinder polymer reduces the stiffness of the article when applied to the article as compared to an article coated with the ion-sensitive polymer alone. When an ion-sensitive polymer, such as a sulfonate anion-modified acrylic acid terpolymer, is applied to a non-woven substrate such as an air-laid layer of wood pulp for the purpose of forming a wet wipe, the non-woven sheet becomes fragile to the dry substrate. It may have an undesirably high degree of stiffness, which can compromise conformability, which may have a detrimental effect on the feel of the dried product or the treatment of the dried web during processing. Has been issued. The combination of ion-sensitive polymers and cobinder polymers can reduce the stiffness of such articles. The average molecular weight of the cobinder polymers of the present invention can be varied depending on the ultimate use of the polymer. Desirably, the weight average molecular weight of the cobinder polymer ranges from about 500,000 to about 200,000,000. More desirably, the weight average molecular weight of the cobinder polymer ranges from about 500,000 to about 100,000,000.

Cobinder polymers that can meet many or all of the above criteria include:
Poly (ethylene-vinyl acetate), poly (styrene-butadiene), poly (styrene-acrylic), vinyl acrylic terpolymer, neoprene, polyester latex, acrylic emulsion latex, polyvinyl chloride, ethylene-vinyl chloride copolymer, carboxylated vinyl acetate Latex and the like, all of which are non-crosslinked (eg, free of N-methylolacrylamide or other crosslinkers),
It can be, but is not limited to, being crosslinked, or capable of being crosslinked (ie prepared in the presence of a crosslinker) but not substantially crosslinked in the final product. A particularly preferred uncrosslinked poly (ethylene-vinyl acetate) is National Starch and Chemi, Bridgewater, NJ.
cal Co. Dur-O-Set® RB available from A particularly preferred uncrosslinked poly (styrene-butadiene) is Ro available from Mallad Creek Polymers of Charlotte, NC.
vene (registered trademark) 4817. A particularly preferred uncrosslinked poly (styrene-acrylic) is Rohm and Ha, Philadelphia, PA.
Rhoplex® NM1715K available from as.

When using a latex co-binder or any potentially crosslinkable co-binder, the latex does not form a substantially water-insoluble bond that binds the fibrous base layers together and interferes with the dispersibility of the article. Needs to be done. Thus, the latex may be free of crosslinkers such as NMA or catalysts for crosslinkers or both. Alternatively, crosslinking agents or inhibitors that interfere with the catalyst can be added to prevent the article from cross-linking well when heated to normal crosslinking temperatures. Such inhibitors may include free radical scavengers, methylhydroquinone, t-butylcatechol, pH adjusters such as potassium hydroxide, and the like. For example, pH
N-methylol-acrylamide (NM with an increased pH of 8 or more)
Some latex cross-linking agents such as A) have normal cross-linking temperatures (eg about 13).
Crosslinking at 0 ° C or higher) can be prevented. Alternatively, the article containing the latex co-binder may be maintained at a temperature below the temperature range at which cross-linking will occur and will not cross-link in the presence of a cross-linking agent so that the dispersibility of the article is not compromised or the degree of cross-linking is sufficient. It can also be lowered. Alternatively, the amount of crosslinkable latex can be maintained below a threshold level so that the article remains dispersible in the presence of the crosslinker. For example, a small amount of crosslinkable latex dispersed as individual particles in an ion-sensitive binder may not interfere with dispersibility when fully crosslinked. In the latter embodiment, the amount of latex may be less than about 20 weight percent, specifically less than about 15 weight percent, based on the ion-sensitive binder.

The latex compound, whether crosslinkable or not, need not be a cobinder. SEM micrographs of successful ion-sensitive binder films with useful non-crosslinked latex emulsions dispersed therein allow latex co-binder particles to maintain their individual presence in the ion-sensitive binder. It has been shown that, to some extent, it can act as a filler material. It is believed that other materials, including mineral or particulate fillers dispersed in an ion-sensitive binder with optionally added surfactant / dispersant, can play a similar role. For example, in one of the envisioned embodiments, Presperse, Inc. (
Free-flowing Ganzpe (Piscataway, NJ)
Arl PS-8F particles, about 0.4 micron particles of styrene / divinylbenzene copolymer, were dispersed in the ion-sensitive binder at a level of about 2 to 10 weight percent to obtain the mechanical and tactile properties of the ion-sensitive binder. , And visual characteristics can be modified. Other filler-like solutions include metal, glass, carbon, minerals, quartz, and / or microparticles, microspheres, or beads of plastic such as acrylic or phenol, and an inert gas inside. It may include sealed hollow particles. Examples include EXPANCEL phenolic microspheres that expand substantially when heated from Expancel of Sweden, or acrylic microspheres known as PM6545 available from PQ Corporation of Pennsylvania. In addition, blowing agents such as CO ₂ dissolved in an ion-sensitive binder also generate discontinuities that serve as bubbles in the matrix of the ion-sensitive binder and are dispersed in the ion-sensitive binder. The phase can act as a co-binder. Generally, any coexisting material that is immiscible with the binder, especially one that is adhesive or cohesive by itself, must be in a state that results in a substantial covalent bond that joins the fibers so as to hinder the water dispersibility of the product. For example, it can be used as a co-binder. However, materials that also provide additional benefits such as reduced spray viscosity may be particularly preferred. Adhesive co-binders such as latexes with no cross-linker or small amounts of cross-linker have been found to be particularly useful in achieving good results over a wide range of processing conditions including drying at elevated temperatures. .

As described above, the Tg of the cobinder polymer is the Tg of the ion-sensitive polymer.
It is believed that lower temperatures can be used, which improves the flexibility of the treated substrate, especially in the dry state. A comparison of the glass transition temperatures of some of the preferred polymers useful in the present invention is shown in Table 1 below.

[0046]

[Table 1] Table 1 Glass transition temperatures of selected polymers

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

As mentioned above, useful co-binder polymers include Rovene®.
Series (Mallard Creek, Charlotte, NC)
Styrene Butadiene Latex available from Polymers), Rhon
A variety of commercially available latex emulsions can be included, including those selected from Rhoplex® latex from and Haas Company, and Elite® from National Starch. Polymer emulsions or dispersions generally contain small polymer particles, such as crosslinkable ethylene vinyl acetate copolymers, which are typically spherical and dispersed in water, of low molecular weight emulsifiers or high molecular weight protective colloids. Stabilized with such surfactant raw materials. Such liquid binders may be prepared by any method known in the art of binder treatment of nonwoven webs, including spraying or foaming coating, liquid nip impregnation, curtain coating, etc., followed by drying. It can be applied to other base layers. 76RES7800, commonly obtained from Union Oil Chemistry, and National Starch and Che.
Resyn (R) 2 available from medical Corporation
5-1103, vinyl acetate copolymer latex such as Resyn® 25-1109, Resyn® 25-1119, and Resyn® 25-1189, Air Products and Chemical.
als Inc. Airflex® ethylene-vinyl acetate copolymer emulsions, such as Airflex® ethylene-vinyl acetate, available from Rohm and
Rhoplex® AR-, available from Hass Company
74, Reichhold Chemicals Inc. Obtained from Sy
nthemul (registered trademark) 97-726, Natural Starch a
Resyn (available from nd Chemical Corporation
Registered trademarks) 25-1140, 25-1141, 25-1142, and Resyn
Acrylic-vinyl acetate copolymer emulsion such as -6820, Union
76-RES3103, obtained from Oil Chemistry, and Nationala
A vinyl acrylic terpolymer latex such as Resyn® 251110, available from Starch and Chemical Corporation, Rhoplex® B-15J, Rhoplex® P-37, available from Rhom and Hass Company.
6, Rhoplex (registered trademark) TR-407, Rhoplex (registered trademark) E
-940, Rhoplex (R) TR934, Rhoplex (R) TR-520, Rhoplex (R) HA-24, and Rhoplex.
(Registered trademark) NW1825, and B.I. F. Goodrich Chemical
Hycar® 2600X322, Hyc, available from Group
Acrylic emulsion latex, such as ar® 2671, Hycar® 2679, Hycar® 26120, and Hycar® 2600X347, available from Union Oil Chemistry Division 7
6RES4100 and 76RES8100, Reichhold Chemical
al Inc. Tylac® resin emulsion 68-available from
412, Tylac (registered trademark) resin emulsion 68-067, 68-319.
, 68-413, 68-500, 68-501, and Dow Chemical
DL6672A, DL6663A, DL663 available from Company
8A, DL6626A, DL6620A, DL615A, DL617A, DL6
20A, DL640A, styrene-butadiene latices such as DL650A, and rubber latices such as neoprene available from Serva Biochemicals, Eas available from Eastman Chemical Company.
a polyester latex such as tmanAQ29D, B.I. F. Goodric
h Geon® 352 from h Chemical Group
Chloride Latex, Air Products and Chem
Airflex® ethylene-vinyl chloride copolymer emulsion, such as Airflex® ethylene-vinyl chloride, Air Products
Vinyl Acetate Homopolymer Emulsion, such as Vinac®, available from S. and Chemicals, Reichhold Chemi.
cals Inc. Synthemul® Synthetic Resin Emulsions 40-502, 40-503, and 97-664, available from Rohma.
Polyco® 21 available from nd Haas Company
Various latex compounds including carboxylated vinyl acetate emulsion resins such as 49, 2150, and 2171 and other resins or emulsions can be considered. Silicone emulsions and binders are also conceivable.

The co-binder polymer can include activating compounds that improve the wetting of the base layer after application of the binder mixture. The hydrophobic portion of the ion-sensitive polymer formulation may selectively orient toward the gas phase during drying to produce a hydrophobic surface, which, when subsequently applied with the wetting composition,
In some embodiments, the wettability of a dry substrate treated with an ion-sensitive polymer formulation may be difficult because wetting may be difficult if no surfactant has been added to the wetting composition. It can be a problem. Surfactants, or other surface-active ingredients, in the co-binder polymer can be treated with the ion-sensitive polymer formulation to improve the wettability of the dried base layer. Surfactants in the cobinder polymer do not significantly interfere with the ion sensitive polymer formulation. Thus, the binder will maintain good integrity and tactile properties with the wipe pre-moistened in the presence of the surfactant. In one embodiment, the effective co-binder polymer replaces a portion of the ion-sensitive polymer formulation, allowing the pre-wetted wipe to achieve any strength level, while at the same time the wipe is , Less stiff, less touchy than the same pre-moistened wipe but without the co-binder polymer but containing a sufficient level of ion-sensitive polymer formulation to achieve a given tensile strength. It excels in at least one of goodness (eg, smooth feel or smoothness), or cheap cost.

Other Cobinder Polymers WACKER POLYMER, such as VINNEK® based binders
Dry emulsion powder (DEP) from Systems (Burghausen, Germany)
) Can be applied to some of the embodiments of the present invention. These are redispersible free flowing binder powders made from liquid emulsions. The small polymer particles of the dispersion are contained within a protective matrix of water-soluble protective colloid in the form of powder particles. The surface of the powder particles is protected from solidification by the mineral crystal platelets. As a result, polymer particles that were originally liquid dispersions are now available in the form of free-flowing dry powders that either redisperse in water or become swollen sticky particles when water is added. can do. Such particles are
By depositing with the fibers during the air deposition process, the nonwoven can be made bulky and then 10% to 30% water can be added to swell the particles and attach them to the fibers. This is sometimes referred to as the "chewing gum effect" and means that the dry, non-sticky fibers in the web, once wet, become sticky, like chewing gum. Good adhesion to polar and other surfaces is obtained. Such binders are available as free-flowing particles made by treating a latex emulsion with a drug and drying it so that it does not become cohesive in the dry state.
They can also be entrained with the air and deposited with the fibers during the air deposition process and applied to the substrate by electrostatic means, direct contact, gravity feed, and other means. They can be applied separately from the binder, either before or after the binder is dried. Upon contact with either liquid or vapor moisture, the latex particles rehydrate and swell and adhere to the fibers. Upon drying and increasing temperature (eg above 160 ° C.), the binder particles crosslink and become water resistant, but when dried at low temperatures (eg below 110 ° C.) a film is formed and pre-wet Some fibrous bonding can be formed without significantly reducing the water dispersibility of the wipe. Thus, commercial products do not reduce the amount of crosslinker, for example by limiting the time and temperature of drying and controlling the cure of the cobinder polymer by causing some bonding with less crosslinking. It is believed that it can be used for.

Dr. "New Air Deposition Binder" by Klaus Kohlhammer (
"Nonwovens Report International" 1999
September 342, pp. 20-22, 28-31), dry emulsion binder powders form a web as opposed to applying the material to an existing base layer. It has the advantage of being easily incorporated into a non-woven or air-laid web in between and providing improved control over the placement of the cobinder polymer. Thus, the non-woven or air-laid web is prepared so that it already has a dry emulsion binder therein, which is subsequently wetted with the ion-sensitive polymer formulation solution when the dry emulsion powder is present. However, it becomes viscous and can help bond the substrates. Alternatively, the dry emulsion powder can be incorporated into the base layer by a filtration mechanism after the base layer has been treated with an ion-sensitive binder and dried, after which the dry emulsion powder becomes viscous when the wetting composition is added. become. In other embodiments, the dry emulsion powder is dispersed by applying the powder as the ion sensitive polymer formulation solution is sprayed onto the web or by adding the dry emulsion powder particles to the ion sensitive polymer formulation solution and then dispersing. ,spray,
The mixture is dispersed in the ion-sensitive polymer formulation solution by applying the mixture to the web using a foam coating method or other techniques known in the art.

Binder Formulation and Fabric Containing It 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 base layer. This binder is particularly suitable for use in water dispersible products. Suitable fibrous base layers include, but are not limited to, non-woven fabrics and woven fabrics. In many of the embodiments, especially personal care products, the preferred substrate is a non-woven fabric. As used herein, the term "nonwoven" refers to a fabric (including paper) having a composition of individual fibers or filaments randomly arranged in a mat. Nonwoven fabrics can be made by a variety of processes including, but not limited to, air deposition processes, wet deposition processes, hydraulic entanglement processes, staple fiber carding and bonding, and solution spinning.

The binder composition can be applied to the fibrous base layer by any known application method. Suitable processes for applying the binder material include, but are not limited to, printing, spraying, electrostatic spraying, coating, liquid nip, metering press rolls, impregnation, or any other technique. The amount of binder composition can be metered and distributed homogeneously within the fibrous base layer or non-homogeneously distributed within the fibrous base layer. The binder composition can be distributed throughout the fibrous base layer or within a number of small contiguous zones. In most embodiments, it is desirable that the binder composition be homogeneously distributed.

To facilitate application to the fibrous base layer, the binder can be dissolved in water or a non-aqueous solvent such as methanol, ethanol, acetone and the like, water being the preferred solvent. The amount of binder that dissolves in the solvent can vary depending on the polymer used and the application of the fabric. Desirably, the binder solution comprises up to about 25 percent by weight binder composition solids. More desirably, the binder solution comprises from about 10 to 20 percent by weight binder composition solids, especially about 12 percent by weight binder composition solids. If desired, plasticizers, fragrances, colorants, defoamers, bactericides, preservatives, surfactants, thickeners, fillers, opacifiers, tackifiers, detackifiers in binder solution. , And similar additives can be incorporated.

When the binder composition is applied to the base layer, the base layer is dried by any conventional means.
When dried, the tensile strength of the tacky fibrous base layer is improved as compared to the tensile strength of untreated wet-laid or dry-laid base layers, yet in soft water or hard water containing relatively high concentrations of polyvalent ions. It has the ability to quickly "break apart" or decompose when stirred. For example, the dry tensile strength of the fibrous base layer can be increased by at least 25 percent compared to the dry tensile strength of the untreated base layer without binder. In particular, the dry tensile strength of the fibrous base layer can be increased by at least 100 percent compared to the dry tensile strength of the untreated base layer without binder. More specifically, the dry tensile strength of the fibrous base layer can be increased by at least 500 percent compared to the dry tensile strength of the untreated base layer without binder.

A desirable feature of the present invention is that the improvement in tensile strength is achieved when the amount of binder composition present in the resulting fibrous base layer, ie, the "load", is only a portion of the total base layer by weight. To be achieved. The amount of "additional amount" can be varied depending on the specific application, but when the "additional amount" is the optimum amount, it has integrity during use, and quickly when stirred in water. It becomes the dispersed fiber base layer. For example, the binder component is typically about 5 to about 65 percent by weight of the total weight of the base layer.
In particular, the binder component can be from about 10 to about 35 percent by weight of the total weight of the base layer. More specifically, the binder component can be from about 17 to about 22 percent by weight of the total weight of the base layer.

The nonwoven fabric of the present invention has not only good strength during use but also ion triggerability. Desirably, the non-woven fabrics of the present invention are abrasion resistant, in aqueous solutions containing greater than about 0.3 weight percent NaCl, or a mixture of monovalent ions, for formulations using acrylic acid terpolymers. Thus, for formulations using sulfonate anion modified acrylic acid terpolymers, high tensile strength is maintained in aqueous solutions containing greater than about 1 weight percent NaCl, or a mixture of monovalent ions. Moreover, the nonwoven fabric is dispersible in water from highly soft water to moderately hard water. Due to this latter property, the non-woven fabrics of the invention are suitable for sanitary napkins, diapers, adult incontinence-like products and dry and pre-moistened wipes (wet wet) that can be flushed to flush toilets after use in all parts of the world. Very suitable for disposable products such as wipes).

The fibers forming the above fabric can be made of a variety of materials including natural fibers, synthetic fibers, and combinations thereof. The fiber is selected, for example, depending on the intended end use of the finished fabric and the cost of the fiber. For example, a suitable fibrous base layer is cotton,
Mention may be made, without limitation, of natural fibers such as flax, jute, hemp, wool, wood pulp and the like. Similarly, regenerated cellulose fibers such as viscose rayon and cupra rayon, modified cellulose fibers such as cellulose acetate,
Alternatively, synthetic fibers such as derivatives of polypropylene, polyethylene, polyolefins, polyesters, polyamides, polyacrylics, etc. can be used alone or in combination with each other. Also, blends of one or more of the above fibers can be used if desired. Among the wood pulp fibers, any known papermaking fibers including softwood and hardwood fibers can be used. For example, the fibers can be chemically or mechanically pulped, bleached or unbleached, virgin or regenerated, high yield or low yield, and the like. Also, mercerized fibers, chemically cured fibers or crosslinked fibers can be used.

Synthetic cellulosic fiber types include all types of rayon and other viscose-derived fibers or chemically modified cellulose, including regenerated cellulose and solvent-spun cellulose such as Lyocel. Chemically treated natural cellulosic fibers such as mercerized pulp, chemically hardened or crosslinked fibers, or sulfonated fibers can also be used. Recycled fibers are used as well as virgin fibers. Cellulose produced by microorganisms and other cellulosic derivatives can also be used. As used herein, the term "cellulosic" includes all materials having cellulose as a major component, and in particular including at least about 50 percent by weight cellulose or cellulose derivatives. Thus, the term refers to cotton, typical wood pulp, non-wood cellulosic fibers, cellulose acetate, cellulose triacetate,
Contains rayon, thermomechanical wood pulp, chemical wood pulp, debonded chemical wood pulp, milkweed, or microbial cellulose. Fiber length is important in producing the fabrics of the present invention. In some of the embodiments, such as toilet flushable products, fiber length is even more important. The minimum fiber length depends on the method chosen to form the fiber substrate. For example, if the fibrous base layer is formed by carding, the fiber length should typically be at least about 42 mm to ensure homogeneity. If the fibrous base layer is formed by an air-laid or wet-laid process, the fiber length can desirably be about 0.2 to 6 mm. Fibers having a length of greater than 50 mm are included within the scope of the present invention, but have a length of about 1
When a large amount of fiber (> 5 mm) is placed in a toilet washable cloth, it tends to form a “rope” of fiber due to its length, even if the fibers disperse and fall apart in the water. Yes, this "rope" has been determined to be undesirable when flushed into a domestic toilet. Therefore, in such a product, the fiber length is about 15 mm.
Or less, so that the fibers do not tend to become "ropes" when flushed down the toilet. Fibers of various lengths are available for the present invention,
The fibers are less than about 15 mm long and it is desirable for the fibers to readily disperse with each other when in contact with water. Fibers, especially synthetic fibers, can also be crimped.

The fabric of the present invention can be formed of a single layer or multiple layers. In the case of multiple layers, each layer is generally positioned in a side-by-side or face-to-face relationship such that all or a portion of the layers can be bonded to adjacent layers. The nonwoven web of the present invention may also be formed of a plurality of separate nonwoven webs, the separate nonwoven webs may be formed of a single layer or multiple layers. In the example where the non-woven web comprises multiple layers, the binder can also be applied over the entire thickness of the non-woven web, with each individual layer being separately applied with the binder and then combined with other layers in a side-by-side relationship. The nonwoven web can also be completed.

In one embodiment, the fabric substrate of the present invention is used in sanitary napkins, diapers, adult incontinence products, surgical dressings, wipes and fluid-absorbing products such as tissues, wet wipes and the like. Can be incorporated. Such products can include an absorbent core that includes one or more layers of absorbent fiber material. The core can also include one or more layers of fluid permeable elements such as fiber tissue, gauze, plastic netting, and the like. They are generally useful as wrapping materials for materials that hold the core components together. Also, the core passes through the core,
Fluid impermeable elements or barrier means may also be included to prevent the passage of fluids on the outer surface of the product. It is also desirable that the barrier means be water dispersible. Films of polymers having substantially the same composition as the water dispersible binders described above are particularly suitable for this purpose. In accordance with the present invention, the polymeric composition is useful for forming the layers of the absorbent core, the fluid permeable elements, the wrapping material, and the components of the above-described products, including the fluid impermeable elements or barrier means. is there.

The binder formulation of the present invention is particularly useful for binding fibers of air-laid nonwoven fabrics. Such air-laid materials are useful in bodyside liners for various water dispersible personal care products, fluid distribution materials, fluid uptake materials such as surge materials, absorbent wrap sheets and cover stocks. Air-deposited material is pre-wetted wipe (
It is particularly useful as a wet wipe. The basis weight of the air-laid nonwoven fabric is
From about 20 to about 200 grams per square meter ("gsm"), the denier of the staple fibers can be from about 0.5 to 10 and the length can be from about 6 to 15 millimeters. The surge, or entrapped material, must be elastic and bulky, so staple fibers of about 6 denier or higher are used to make such products. The desired final density of surge, or entrapped material, is about 0.025 grams / cubic centimeter ("
g / cc ") to about 0.10 g / cc. The fluid distribution material can be denser than this and the preferred range is from about 0.1 to about 0.20 g / cc with small denier fibers, most preferably less than about 1.5 denier fibers.
Is. Wipe fiber densities generally range from about 0.025 g / cc to about 0.2 g / cc.
cc, and the basis weight can be from about 20 gsm to about 150 gsm, specifically from about 30 to about 90 gsm, and most specifically from about 60 gsm to about 65 gsm.

The nonwoven fabric of the present invention can also be incorporated into body fluid absorbent products such as sanitary napkins, diapers, surgical dressings, tissues and the like. In one embodiment, the binder is a body fluid because the concentration of monovalent ions in the body fluid exceeds the level required for dissolution, ie, 0.3% by weight and / or more than 1% by weight. It does not dissolve when contacted with. The non-woven fabric maintains its structure and softness, and exhibits sufficient toughness for practical use. However, upon contact with water up to a concentration of about 200 ppm of polyvalent ions such as Ca ²⁺ and Mg ²⁺ ions, binders such as those containing sulfonate anion modified acrylic acid terpolymers disperse. Similarly, upon contact with water in which the concentration of polyvalent ions such as Ca ²⁺ and Mg ²⁺ ions is less than about 10 ppm, the binder containing acrylic acid terpolymer disperses. The nonwoven structure then breaks and disperses easily in water.

In one embodiment of the present invention, the tensile strength of the non-woven fabric in use forms a non-woven fabric with a binder material comprising the ion-sensitive polymer formulation of the present invention, followed by one or more of the non-woven fabrics. It can be enhanced by applying more monovalent and / or polyvalent salts. The salt can be applied to the non-woven fabric by any method known to those of skill in the art, including, but not limited to, applying a solid powder to a cloth and spraying the cloth with a solution of the salt. . The amount of salt can vary depending on the particular application. However, the amount of salt applied to the fabric is typically based on the total weight of the fabric,
From about 0.1 weight percent to about 10 weight percent salt solids. 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 dressings, and diapers.

It will be appreciated that the binder formulations and fibrous base layers of the present invention can be advantageously used to produce a variety of products including, but not limited to, absorbent personal care products designed to contact body fluids. I think that it will be easily understood by the trader. Such products may include only a single layer of fibrous base layer or may include a combination of elements as described above. Although the binder formulation and fibrous base layer of the present invention are particularly suitable for personal care products, the binder formulation and fibrous base layer can also be advantageously used in various consumer products. The improved product of the present invention by combining an acrylic acid terpolymer or a sulfonate anion modified acrylic acid terpolymer with an uncrosslinked poly (ethylene-vinyl acetate) gives superior results than using the terpolymer alone. .. For example, when the ion-sensitive polymer formulation of the present invention is used in a binder composition for wet wipes, the wettability of the wet wipes when first wet is improved without compromising dispersibility, which results in the wipes being wetted. The basesheet can be easily wetted with a wet wipe solution at industrial production rates. The ion-sensitive polymer formulation of the present invention also reduces the rigidity of the dry base sheet, improves the adaptability of dry and other conditions of fragile sheets during further processing of the product, and reduces wipe stickiness. And / or improve the sprayability of the ion-sensitive binder, thereby improving the distribution and penetration of the binder into the base sheet.

Unlike other binder systems known in the art, the ion-sensitive polymer formulations of the present invention can be activated as a binder without increasing temperature. Drying or removal of water helps to better distribute the binder within the fibrous web,
This binder crosslinks with a large activation energy to act as a binder,
The high temperature itself is not essential, as it does not require any other chemical reaction to take place. Rather, interaction with a soluble activating compound, typically a salt, is sufficient to activate (insolubilize) or "salt out" the binder. Thus, the drying step can be omitted or replaced with a cold water removal operation such as room temperature drying or freeze drying if desired. The elevated temperature generally aids in drying, but it can also be dried at room temperature below that normally required for the crosslinking reaction to occur. Therefore, the maximum temperature to which the substrate is exposed or reached is the following temperatures: 180 ° C, 160 ° C,
140 ° C, 120 ° C, 110 ° C, 105 ° C, 100 ° C, 90 ° C, 75 ° C, and 6
It can be lower than any of 0 ° C. and typical ranges of maximum web temperatures are from about 50 ° C. to about 110 ° C., or from about 70 ° C. to about 140 ° C. Of course,
Higher temperatures can be used, but are not required in most embodiments. Also, cobinder systems, such as commercially available latex emulsions, may contain crosslinkers suitable for reaction at temperatures of 160 ° C. or higher, and maintaining the maximum temperature at low temperatures results in excessive strength in the cobinder polymer. It can be advantageous to avoid. Excessive strength in the cobinder polymer can interfere with the water dispersibility of the pre-wetted wipe.

Wet Wipes Wetting Composition and Wet Wipes Containing It One of the particularly interesting embodiments of the present invention is to provide a pre-moistened wipe, ie a wet wipe, from an ion-sensitive binder composition as described above and a fibrous material. Is to generate. For wipes, the fibrous material can be in the form of woven or non-woven fabric, although non-woven fabric is preferred. The non-woven fabric is preferably formed of relatively short fibers such as wood pulp fibers. The minimum fiber length depends on the method selected to form the nonwoven. If the non-woven fabric is formed by a wet or dry process, the fiber length is preferably about 0.1 millimeters to 15 millimeters. The nonwoven of the present invention desirably has a relatively low wet tack strength when not bonded to each other with an adhesive or binder material. Such non-woven fabrics lose their bond strength in tap water and in sewer water when they are bound together with a binder composition, and the cloth is agitated by flushing it into the toilet or moving through it. Will break more easily.

The finished wipes are individually packaged in a moisture resistant bag with the moistening composition applied to the wipes, preferably in the folded state, or held in a watertight package to hold the desired number of sheets. Can be packaged in a container. The finished wipe can also be packaged as a roll of separable sheets in a moisture resistant container that holds the desired number of sheets on the roll, with the wetting composition applied to the wipe. The roll can be either hollow or solid without a core. Has a hollow center,
That is, coreless rolls, including rolls without a solid center, are SRP Industr
y, Inc. (San Jose, Calif.), Winding machine from Shimizu Corporation (Japan),
And U.S. Pat. No. 4,667 issued to Gietman on May 26, 1987.
, 890 can be produced on known coreless roll winders including the apparatus disclosed in US Pat. Solid wound coreless rolls can contain many products for any volume and can be adapted to various dispensers.

Wipes preferably comprise from about 10 percent to about 400 percent wetting formulation, more preferably from about 100 percent to about 300 percent wetting formulation, and even more preferably about 180 percent by weight of the dry fabric. To about 240 percent by weight of the moisturizing formulation. Wipes are stored in the warehouse, transported,
Maintain desirable properties over the time period associated with retail display and storage by consumers. Therefore, the shelf life can range from 2 months to 2 years. Various forms of impermeable bags and storage means for containing wet packaged materials such as wipes and wet napkins and the like are known in the art. Any of these can be used to package the pre-moistened wipes of the present invention.

Desirably, the pre-moistened wipes of the present invention are wetted with an aqueous moisturizing composition, and (1) coexisting with the above-described ion-sensitive binder composition of the present invention, (2) allowing the pre-moistened wipe to maintain wet strength during processing, storage and use (including removal from the dispenser), and dispersibility in the toilet bowl; (3) No irritation to the skin, (4) Decrease the adhesiveness of the wipe, and create unique tactile properties such as skin slip and "lotion-like feel" (5) "Humidifying and wiping" and others Acting as a medium to bring about skin health benefits.

The wetting composition should not act as a solvent for the binder and may have a small amount (<1%) of polysorbate 20 depending on the concentration of perfume and salt in the wetting composition.
Although such a fragrance | flavor dissolution aid may exist, generally, it does not contain a solvent other than water, and does not contain an organic solvent especially. Desirably, the wetting composition comprises less than about 10 weight percent of an organic solvent such as propylene glycol or other glycols, polyhydroxy alcohols, etc., based on the total weight of the wetting composition. More desirably, the wetting composition comprises less than about 4 weight percent organic solvent. More desirably, the wetting composition comprises less than about 1 weight percent organic solvent. The wetting composition may be substantially free of organic solvents.

In one aspect of the invention, the wetting composition comprises an activator compound that maintains the strength of the water-dispersible binder until the activator compound is diluted with water. When diluted, the strength of the water dispersible binder begins to decline. The water dispersible binder can be any of the ion sensitive binder compositions of the present invention, or any other ion sensitive binder composition. The activating compound in the wetting composition can be a salt such as sodium chloride, or some other compound, which is
It imparts strength to the water dispersible binder composition during use and storage, and when diluted with water to trigger the binder polymer into a brittle state, can disperse the base layer. Desirably, the wetting composition comprises less than about 10 weight percent of the activating compound, based on the total weight of the wetting composition. Specifically, the wetting composition comprises
About 0.3 weight percent to about 5 weight percent activating compound can be included. More specifically, the wetting composition can include from about 2 weight percent to about 4 weight percent 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 dispersibility of the wipe are not compromised. . Suitable additives in the moisturizing composition include the following additives: skin care additives; odor control agents; detackifiers to reduce stickiness of binders; microparticles; antibacterial agents; preservatives; detergents. , Surfactants, and some silicone wetting and wiping agents;
Emollients; surface texture modifiers for improving the feel (eg, lubricity) of the skin; fragrances; fragrance dissolution aids; opacifiers; fluorescent brighteners; UV absorbers; drugs; and malic acid or hydroxylation. Includes, but is not limited to, pH adjusters such as potassium.

Skin Care Additives As used herein, a "skin care additive" means one or it, such as reducing the likelihood of diaper rash and / or other skin damage caused by fecal enzymes. It represents an additive that brings the above advantages to the user. Such enzymes, especially trypsin, chymotrypsin and elastase, are proteolytic enzymes produced in the digestive tract to digest food. For example, in infants, faeces are watery and contain other substances as well, but tend to contain bacteria and some undiminished digestive enzymes. Such enzymes have been found to cause irritation if they have been in contact with the skin for a significant period of time, which, although uncomfortable on its own, causes bacterial infection of the skin. May make it easier. As a countermeasure, skin care additives include, but are not limited to, the enzyme inhibitors and sequestrants described below. The moisturizing composition can include less than about 5 weight percent skin care additives, based on the total weight of the moisturizing composition. Specifically, the moisturizing composition can include from about 0.01 weight percent to about 2 weight percent skin care additives. More specifically, the moisturizing composition can include from about 0.01 weight percent to about 0.05 weight percent skin care additive.

Various skin care additives can be added to or included in the moisturizing compositions and pre-moistened wipes of the present invention. In one of the embodiments of the invention, skin care additives in the form of particles are added to act as fecal enzyme inhibitors, providing the potential benefit of reducing diaper rash and skin damage caused by fecal enzymes. U.S. Patent No. 6, granted to Schulz et al. On April 18, 2000.
No. 051,749 discloses organophilic clays in woven or non-woven webs,
It is said to be useful in inhibiting fecal enzymes. All disclosures are incorporated herein by reference. Such materials can also be used in the present invention, which include long chain organic quaternary ammonium compounds and one or more of the following clays: montmorillonite, bentonite, beidellite, hectorite, saponite, and Includes reaction products with stevensite.

Other known enzyme inhibitors and sequestrants can also be used as skin care additives in the moisturizing compositions of the present invention, which inhibit trypsin and other digestive or fecal enzymes. And urease inhibitors. For example, enzyme inhibitors and antibacterial agents can be used to prevent odors from developing in body fluids. For example, urease inhibitors are said to play a role in odor absorption as well.
Issued on May 25th It is disclosed in International Patent Application No. 98/26808, "Absorptive Articles Having an Odor Control System," by Trinh. All disclosures are incorporated herein by reference. Such inhibitors can be incorporated into the wetting compositions and pre-wetted wipes of the present invention, which include transition metal ions such as silver, copper, zinc, ferric and aluminum salts. And soluble salts thereof. Further, anions such as borate and phytate can also serve as urease inhibitors. Compounds of potential value include silver chlorate, silver nitrate, mercury acetate, mercury nitrate, copper metaborate, copper bromate, copper bromide, copper chloride, copper dichromate, copper nitrate, copper salicylate, sulfuric acid. Copper, zinc acetate, zinc borate, zinc phytate, zinc bromate, zinc bromide, zinc chlorate, zinc chloride, zinc sulfate, cadmium acetate,
Includes, but is not limited to, cadmium borate, cadmium bromide, cadmium chlorate, cadmium chloride, cadmium formate, cadmium iodate, cadmium iodide, cadmium permanganate, cadmium nitrate, cadmium sulfate, and gold chloride.

Other salts disclosed as having urease inhibiting properties include ferric and aluminum salts, especially nitrates, and bismuth salts. Other urease inhibitors have also been disclosed by Trinh, hydroxamic acid and its derivatives; thiourea; hydroxylamine; salts of phytic acid; various tannins, such as various plant extracts containing carobtannin, and chlorogens. Derivatives thereof such as acid derivatives; naturally derived acids such as ascorbic acid, citric acid, and salts thereof; phenylphosphorodiamidate / diaminophosphoric acid phenyl ester; metal aryl phosphoramidate complexes containing substituted phosphorodiamidate compounds. Phosphoramidates having no nitrogen substituents; in particular borax, and / or boric acid and / or salts thereof containing organoboron compounds; compounds disclosed in European Patent Application No. 498,199; sodium dithiocarbamate. , Copper, manganese, and / or zinc; quinone; pheno ; Thiuram; substituted rhodanine acetic acid; alkylated benzoquinones; disulfide formamidine; 1,3-diketones maleic anhydride; succinamic; anhydride;
Pehenic acid; / N, N-dihalo-2-imidazolidinone; N-halo2-oxazolidinone; thio- and / or acyl-phosphorylamide and / or
Or a substituted derivative thereof, thiopyridine-N-oxide, thiopyridine, and thiopyrimidine; sulfur oxide derivative of diaminophosphinyl compound; cyclotriphosphazatriene derivative; ortho-diaminophosphinyl derivative of oxime; bromo-nitro compound; S -Aryl and / or alkyldiamide phosphorothiolates; diaminophosphinyl derivatives; mono- and / or polyphosphorodiamide; 5-
Substituted-benzooxathiol-2-ones; N (diaminophosphinyl) aryl carboxamides; alkoxy-1,2-benzothiazine compounds and the like.

Many other skin care additives may also be incorporated into the moisturizing compositions and pre-moistened wipes of the present invention, including sunscreen and UV absorbers, acne treatments, drugs, and Baking soda (including capsules), vitamins such as vitamin A or E and its derivatives, plant extracts such as hazel and aloe vera, allantoin, emollients, disinfectants, for wrinkle control or anti-aging effects Hydroxy acids, sunscreens, sunscreens, whitening agents, deodorants and antiperspirants, ceramides for the skin and for other purposes, astringents, moisturizers, depigmenting agents, insect repellents, anti Oxidant,
Preservatives, anti-inflammatory agents and the like are included, but are not limited thereto. However, these additives can coexist with the ion-sensitive binder composition accompanying them, particularly the ion-sensitive binder composition of the present invention (i.e., they are diluted in water while maintaining dispersibility in water). Of the pre-wetted wipe prior to application) does not substantially impair the wet strength of the wipe. Materials useful for skin care and other benefits include "McCutche," published by MC Publishing Company, Glen Rock, NJ.
on's 1999 "Volume 2, Functional Materials. Many plants useful for skin care are Active Organi, Lewisville, Texas.
Supplied from cs.

Odor Control Additives Odor control additives suitable for use in the moisturizing compositions and pre-moistened wipes of the present invention include zinc salts; talc powder; encapsulated flavors (microcapsules, macrocapsules, and liposomes; Containing fragrances encapsulated in vesicles or microemulsions; chelating agents such as ethylenediaminetetraacetic acid; zeolites; activated silica,
Activated carbon granules or fibers; Activated silica microparticles; Polycarboxylic acids such as citric acid; Cyclodextrin and cyclodextrin derivatives; Chitosan or chitin and its derivatives; Oxidizing agents; Silver-loaded zeolites (eg trade name HEALTHSHIEEL
BF Tech in Beverley, Massachusetts sold for D ™
(including those of Nologies); triclosan; diatomaceous earth; and mixtures thereof. In addition to controlling odors from the body or body exudates, odor control strategies can also be utilized to mask or control any odor in the treated substrate. Desirably, the wetting composition comprises less than about 5 weight percent odor control additives, based on the total weight of the wetting composition. More desirably, the moisturizing composition comprises from about 0.01 weight percent to about 2 weight percent odor control additive. More desirably, the wetting composition comprises from about 0.03 weight percent to about 1 weight percent odor control additive.

In one embodiment of the invention, the wetting composition and / or the pre-moistened wipe comprises in solution a derivatized cyclodextrin, such as hydroxypropyl β-cyclodextrin, which is wiped off. It remains on the skin later and becomes an odor absorbing layer. In other embodiments, the odor source is removed or neutralized by applying an odor control additive. This typically illustrates the action of chelating agents that attach metal groups required for the function of many normally odor producing proteases and other enzymes. Chelating a metal group interferes with the action of the enzyme and reduces the risk of odors in the product. The principle of applying chitosan or chitin derivatives to non-woven webs and cellulosic fibers is described in S. Lee et al., "Antibacterial and Blood-Repellent Finish for Cotton and Nonwovens Based on Chitosan and Fluoropolymers" (Textile Re, February 1999).
search Journal 69 (2) 104-112).

Higher concentrations of detackifying agent salts may reduce the tackiness of the ion-sensitive polymer, but other means of reducing tackiness are often desirable. Thus, if a detackifying agent is used in the wetting composition and the ion-sensitive binder is tacky, the tackiness can be reduced. Suitable detackifiers include any substance known in the art for reducing the tack between two adjacent fibrous sheets treated with an adhesive-like polymer or an adhesive-like polymer on skin. Includes substances that can reduce the stickiness of. Detackifiers are solid particles in dry form and can be applied as a suspension or slurry of particles. Deposition can be by spraying, coating, electrostatic deposition, impregnation, filtration (ie, a gas phase containing particles is passed through the gas phase by a pressure difference and the particles are deposited by a filtration mechanism), etc. It can be applied homogeneously to one or more surfaces, or it can be applied to the surface of the base layer or a part of each surface in a pattern (eg a repeating or random pattern). The detackifying agent can be present throughout the thickness of the base layer, but can also be concentrated on one or both of the surfaces, or substantially only on one or both of the base layers.

Specific detackifying agents include powders such as talc powder, calcium carbonate, mica; starches such as cornstarch; schizoushi powder; mineral fillers such as titanium dioxide; silica powder; alumina; common metals. Oxides; baking powders; diatomaceous earth and the like are included, but are not limited thereto. Polymers with low surface energy and other additives can also be used, including various fluorinated polymers, silicone additives, polyolefins and thermoplastics, waxes, alkyl side chains with 16 or more carbon atoms. Release agents known in the paper manufacturing industry, including compounds having Also, like the dry lubricants and fluorinated release agents, compounds used as mold and release agents for the production of candles can be considered.

In one of the embodiments, the detackifying agent is Miller-St as a spray-type product.
PTFE telomer (KRYTOX) used in PTFE release agent dry lubricant MS-122DF, commercially available from Ephenson (Dunbury, Conn.).
(Registered trademark) DF) compounds such as polytetrafluoroethylene (PTFE). For example, the PTFE particles can be applied by spraying to one side of the base layer prior to winding the pre-wetted wipe. In one embodiment, the detackifying agent is applied to only one side of the base layer before being wound into a roll. The wetting composition desirably comprises less than about 25 weight percent detackifying agent, based on the total weight of the wetting composition. More desirably, the wetting composition comprises from about 0.01 weight percent to about 10 weight percent detackifying agent, specifically about 5% or less. More desirably, the wetting composition comprises from about 0.05 weight percent to about 2 weight percent detackifying agent.

In addition to acting as a detackifying agent, starch compounds can also improve the strength properties of pre-wetted wipes. For example, non-gelling starch particles such as hydrophilic tapioca starch are present in the pre-wetted wipes free of starch when present at a level of about 1% or more by weight, based on the weight of the wetting composition. It has been found that the same strength can be maintained at lower salt concentrations than sometimes expected. Thus, for example, a given strength can be achieved by including 2% salt in the wetting composition in the presence of salt as compared to the level of 4% salt required in the absence of starch. The starch can be applied by adding the starch to the Laponite suspension to improve the dispersion of the starch in the wetting composition.

Microparticulates The wetting composition of the present invention can be further modified by the addition of solid microparticles or microparticulates. Suitable particulates include, but are not limited to, mica, silica, alumina, calcium carbonate, kaolin, talc, and zeolites. The particles, if desired, can be treated with stearic acid or other additives to make them easier to attract or crosslink to the binder system. It is also possible to use a two-component microparticulate system which is often used as a retention aid in the paper industry. Such two-component microparticulate systems generally include a colloidal particle phase, such as silica particles, and a water soluble cationic polymer for crosslinking the particles to the fibers of the forming web. The presence of particulates in the wetting composition (1) increases the opacity of the pre-wetted wipe, (2) modifies the rheology or reduces the tack of the pre-wetted wipe, and (3) the wipe. Can serve one or more useful functions of improving the tactile properties of, or (4) delivering the desired drug to the skin via a porous carrier or a particulate carrier such as microcapsules. . Desirably, the wetting composition comprises less than about 25 weight percent particulates, based on the total weight of the wetting composition. Specifically, the wetting composition can include from about 0.05 weight percent to about 10 weight percent microparticulates. More specifically, the wetting composition can include from about 0.1 weight percent to about 5 weight percent microparticulates.

Microcapsules and Other Delivery Vehicles Also using microcapsules and other delivery vehicles in the moisturizing compositions of the present invention, skin care agents; pharmaceuticals; comfort promoters such as eucalyptus; perfumes; skin care. Agent;
Odor control additives; vitamins; powders; and other additives can be applied to the skin of the wearer. Specifically, the wetting composition comprises about 25 weight percent based on the total weight of the wetting composition.
Up to weight percent microcapsules or other delivery media can be included. More specifically, the wetting composition can include from about 0.05 weight percent to about 10 weight percent microcapsules or other delivery media. More specifically, the wetting composition can include from about 0.2 weight percent to about 5.0 weight percent microcapsules or other delivery media.

Microcapsules and other delivery media are known in the art. For example, POLY-PORE® E200 (Chemical Corp., Arlington Heights, Illinois) is a delivery agent containing soft hollow spheres that can contain more than 10 times the additive weight of delivery media. POLY
Known additives that have been reported for use with PORE® E200 include benzoyl peroxide, salicylic acid, retinol, retinol palmitate, octyl methoxycinnamate, tocopherols, silicon compounds (DC435) and mineral oils. However, the present invention is not limited to this. Another useful delivery medium is POLY-P.
A sponge-like material marketed as ORE® L200, which has been reported for use with silicone (DC435) and mineral oil. Other known delivery systems include cyclodextrin and its derivatives, liposomes, polymer sponges, and spray dried starch. The additives contained in the microcapsules are isolated from the surrounding and other agents in the moisturizing composition until the wipe is applied to the skin, and when the wipe is applied to the skin, the microcapsules break and the contents are Delivered to skin or other surfaces.

Preservatives and Antibacterial Agents The moisturizing composition of the present invention may also include preservatives and / or antibacterial agents. Macstaty H66 (McIntyre Gr in Chicago, IL)
It has been found that some preservatives and / or antibacterial agents (such as those available from Oup) give excellent results in preventing the growth of bacteria and mold. Other suitable preservatives and antibacterial agents include DMDM hydantoin (eg, Glydant Plus ™ from Lonza, Inc. of Fairlawn, NJ).
), Iodopropynyl butyl carbamate, Kathon (Rohm and Hass, Philadelphia, PA), methylparaben, propylparaben, 2-bromo-2-nitropropane-1,3-diol, benzoic acid and the like, but are not limited thereto. Not done. Desirably, the wetting composition comprises less than about 2 weight percent preservatives and / or antimicrobial agents on an active basis, based on the total weight of the wetting composition. More desirably, the wetting composition is from about 0.01 weight percent to about 1 weight percent.
Includes up to weight percent preservatives and / or antimicrobial agents. More desirably, the wetting composition comprises from about 0.01 weight percent to about 0.5 weight percent preservatives and / or antimicrobial agents.

Wetting Agents and Wiping Agents Various wetting agents and / or wiping agents can be used in the wetting compositions of the present invention. Suitable wetting and / or wiping agents include, but are not limited to, detergents and nonionic, amphoteric, and anionic surfactants, especially amino acid-based surfactants. Amino acid-based surfactant systems are derived, for example, from the amino acid L-glutamic acid and other natural fatty acids, are compatible with the pH of human skin and have good wiping power while at the same time providing other anionic interfaces. It is relatively safe compared to active agents and has excellent tactile and moisturizing properties. One of the functions of the surfactant is to improve the dry base layer so that it becomes more wettable by the wetting composition. Another function of the surfactant may be to disperse the soil when the pre-wetted wipe contacts the soiled portion of the toilet and to make it more readily absorbed by the substrate. Surfactants can also aid in makeup removal, general personal wiping, hard surface wiping, odor control, and the like.

One commercially available example of an amino acid based surfactant is acyl glutamate, which is commercially available from Ajinomoto Co., Inc., Tokyo, Japan under the name Amisoft. Desirably, the wetting composition comprises less than about 3 weight percent wetting and / or wiping agents, based on the total weight of the wetting composition. More desirably, the wetting composition is
Includes from about 0.01 weight percent to about 2 weight percent wetting and / or wiping agents. More desirably, the wetting composition is from about 0.1 weight percent to about 0.
． Includes up to 5 weight percent wetting and / or wiping agents.

Amino acid-based surfactants are particularly useful in the wetting compositions of the present invention, although various surfactants can be used in the present invention. Suitable nonionic surfactants include, but are not limited to, condensation products of ethylene oxide with a hydrophobic (lipophilic) polyoxyalkylene base formed by condensation of propylene oxide and propylene glycol. The molecular weight of the hydrophobic portion of such a compound is sufficiently large, and it is desirable that the compound be water-insoluble. Adding a polyoxyethylene component to this hydrophobic moiety increases the water solubility of the molecule as a whole and maintains the liquid properties of the product up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product. It Examples of compounds of this type include the commercially available Pluronic L
-62 surfactants (BASF Wyandotte Corp.), especially those having a polyoxypropylene ether molecular weight of about 1500-3000 and a polyoxyethylene content of about 35-55% by weight of the molecule.

Other useful nonionic surfactants include, but are not limited to, condensation products of C _{8 to} C ₂₂ alkyl alcohols with 2 to 50 moles of ethylene oxide per mole of alcohol. Examples of this type of compounds include the condensation products of C ₁₁ -C ₁₅ secondary alkyl alcohols with an alcohol per mole 3-90 moles of ethylene oxide, which, Poly-Te from Olin Chemicals
TE as the rgent SLF series or from Union Carbide
RGITOL (registered trademark) series, i.e., commercially available about 7 moles of ethylene oxide as TERGITOL (R) 25-L-7 which is formed by the alkanol and the condensation of C ₁₂ -C _15. Other nonionic surfactants that can be used in the wetting composition of the present invention include:
It includes C ₆ -C ₁₂ ethylene oxide esters of alkyl phenols such as (nonylphenoxy) polyoxyethylene ether. Particularly useful are about 8 to
An ester prepared by condensing 12 moles of ethylene oxide with nonylphenol, ie IGEPAL® CO series (GAF Corp.).

Other non-ionic surfactants include alkyl polyglycosides (derived as condensation products of dextrose (D-glucose) and straight or branched chain alcohols (
APG), but is not limited thereto. The glycoside portion of the surfactant creates a hydrophilic portion with a high density of hydroxyl groups, which improves water solubility. In addition, the inherent stability of the glycoside bond with acetal makes it chemically stable in alkaline systems. Furthermore, unlike some non-ionic surfactants, alkyl polyglycosides have no cloud point, so they can be formulated without hydrotropic agents, are extremely gentle and are readily biodegradable. Nonionic surfactant. Surfactants of this type are commercially available from Horizon Chemical under the trade names APG-300, APG-350, APG-500, and APG-500.
It is available at.

Silicone is another type of wetting agent available in pure form or as a microemulsion, macroemulsion and the like. One of the typical group of nonionic surfactants is the silicone-glycol copolymer. Such surfactants are prepared by adding poly (lower) alkylenoxy chains to the free hydroxyl groups of dimethylpolysiloxanol, from Dow Corning Corp.
Available as Corning 190 and 193 surfactants (CTFA name: dimethicone copolyol). Such surfactants, regardless of whether volatile silicon is used as a solvent, control foaming produced by other surfactants and also provide gloss to metal, ceramic, and glass surfaces. Function. An anionic surfactant can also be used in the moistening composition of the present invention. Anionic surfactants are useful because they have high detergency, and are water-soluble higher fatty acid alkali metal soaps, for example, anionic detergents having an alkyl substituent having 8 to 22 carbon atoms, such as sodium myristate and sodium palmitate. Includes salt. A preferred class of anionic surfactants includes hydrophobic higher alkaline moieties such as higher alkyl mono- or polynuclear aryl sulfonates having from about 1 to 16 carbon atoms in the alkyl group (typically about 8 to 22). Water-soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal detergent salts, including Bio-Soft series, namely Bio-Soft D-40 (St.
pan Chemical Co. ) Is available as.

Another useful class of anionic surfactants are the alkali metal salts of alkylnaphthalene sulfonic acids (sodium methylnaphthalene sulfonate, Petrp 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 from about 10 to 18 carbon atoms (For example, sodium lauryl sulfate and sodium stearyl sulfate); Bio-Terge series (Step
an Chemical Co. C ₁₄ -C ₁₆ -α-sodium olefin sulfonate; such as alkali metal salts of sulfated ethyleneoxy fatty alcohols (sodium or ammonium of the condensation product of about 3 moles of ethylene oxide with a C ₁₂ -C ₁₅ n-alkanol). Sulfate, ie Neodol ethoxysulfate, She
ll Chemical Co. ); Alkali metal salts of higher fatty acid esters of low molecular weight alkylolsulfonic acid, such as fatty acid esters of sodium salt of isothionic acid, fatty ethanolamide sulfates; fatty acid amides of aminoalkyl sulfates, such as lauric acid amides of taurine, Numerous other anionic organic surfactants such as, but not limited to, sodium xylene sulfonate, sodium naphthalene sulfonate, sodium toluene sulphate and mixtures thereof. Another useful class of anionic surfactants include 8- (4-n-alkyl-2-cyclohexenyl) -octanoic acid in which the cyclohexenyl ring is replaced with additional carboxylic acid groups. Such a compound or its potassium salt is
o Commercially available as Diacid 1500 or H-240 from Corporation. Generally, such anionic surfactants can be used in the form of alkali metal salts, ammonium or alkaline earth metal salts.

The macroemulsion and microemulsion wetting composition of silicon particles can further comprise an aqueous microemulsion of silicon particles. For example, US Pat. No. 6,037, issued Mar. 14, 2000,
No. 407, "Method for Preparing Aqueous Emulsion of Silicone Oil and / or Rubber and / or Resin" discloses organopolysiloxanes in aqueous microemulsions. Desirably, the wetting composition comprises less than about 5 weight percent of a microemulsion of silicon particles based on the total weight of the wetting composition. More preferably,
The wetting composition comprises from about 0.02 weight percent to about 3 weight percent of a microemulsion of silicon particles. More desirably, the wetting composition comprises from about 0.02 weight percent to about 0.5 weight percent of a microemulsion of silicon particles.

In general, the silicone emulsion can be applied to the pre-moistened wipe by any known coating method. For example, a pre-moistened wipe can be moistened with an aqueous composition that includes a water-dispersible or water-miscible silicone-based component that is compatible with the activating compound in the moisturizing composition. In addition, the wipe is
It can include a nonwoven web of fibers with a water-dispersible binder, which web is moistened with a lotion containing a silicone-based sulfosuccinic acid. Silicone-based sulfosuccinate provides gentle and effective wiping without high levels of surfactants. Also, the silicon-based sulfosuccinate provides a lytic function, which prevents the deposition of oil-soluble components such as perfume ingredients, vitamin extracts, plant extracts, and essential oils.

In one of the embodiments of the present invention, the wetting composition comprises a silicon sulfosuccinate copolyol such as dimethicone sulfosuccinate copolyol 2Na and dimethicone copolyol diammonium sulfosuccinate. Desirably, the wetting composition comprises less than about 2 percent by weight silicon-based sulfosuccinate, and more desirably, from about 0.05 percent to about 0.30 percent by weight silicon-based sulfosuccinic acid. Another example of a product containing silicone emulsion is Dow Corni.
ng 9506 powder can also be present in the wetting composition. Dow Co
Ringing 9506 powder is believed to contain dimethicone / vinyl dimethicone crosspolymer and is a spherical powder that is said to be useful in controlling oil content of the skin ("new chemistry perspective" ( See "Soap and Cosmetics," Vol. 76, No. 3, March 12, 2000). Accordingly, water dispersible wipes that deliver powders that are effective in controlling skin oils are also within the scope of the present invention. The principle for preparing silicone emulsions is disclosed in WO 97/10100 issued Mar. 20, 1997.

Emollients The moisturizing compositions of the present invention can also include one or more emollients. Suitable emollients, PEG 75 lanolin, methyl gluceth benzoic acid 20, C ₁₂ -C ₁₅ alkyl benzoate, other ethoxylated cetylstearyl alcohol, Lambent wax WS-L, Lambent WD-F, Ce
thiol HE (Henkel Corp.), Glucan P20 (Ame
rchol), Polyox WSR N-10 (Union Carbide)
), Polyox WSR N-3000 (Union Carbide), L
ubiquat (BASF), Finsolv SLB 101 (Finete
x Corp. ), Mink oil, allantoin, stearyl alcohol, Es
tol 1517 (Unichema) and Finsolv SLB 201 (
Finetex Corp. ), But not limited thereto. The emollient may also be applied to the surface of the article before or after wetting with the wetting composition. Such emollients may be insoluble in the moisturizing composition and may not migrate except when under pressure. For example, petrolatum-based emollients can be applied in a pattern on one side and then moisturize the other side to saturate the wipe. Such products can have a wiping surface and an opposite skin treatment surface.

Emollient compositions of such products and other products of the present invention may comprise one or more liquid hydrocarbons (eg petrolatum), mineral oils, vegetable and animal fats (
Lanolin, phospholipids and their derivatives) and / or O on 6 April 1999.
Plastic or fluid emollients such as silicone materials such as one or more alkyl-substituted polysiloxane polymers containing the polysiloxane emollients disclosed in US Pat. No. 5,891,126 to Sborn III et al. Agents can be included. Optionally, a hydrophilic surfactant can be combined with the plastic skin moisturizer to improve the wettability of the coated surface. In some of the embodiments of the present invention, the liquid hydrocarbon emollient and / or alkyl-substituted polysiloxane polymer can be blended or combined with one or more fatty acid ester emollients derived from fatty acids or fatty alcohols. Is intended.

In an embodiment of the invention, the emollient material is in the form of a blend of emollients. Desirably, the emollient blend contains one or more liquid hydrocarbons (eg, petrolatum), mineral oils, etc., and one or more vegetable and animal fats (eg, lanolin, phospholipids and derivatives thereof). In combination with silicone materials such as the alkyl-substituted polysiloxane polymers of. More specifically, emollient blends include liquid hydrocarbons (eg, petrolatum) in combination with dimethicone, or dimethicone and other alkyl-substituted polysiloxane polymers.
In some of the embodiments of the present invention, the liquid hydrocarbon emollient and / or alkyl-substituted polysiloxane polymer is intended to be blended with one or more fatty acid ester emollients derived from fatty acids or fatty alcohols. ing. Also,
Standarddam HE (Henkel, Hoboken, NJ
Corp. ), PEG-7 coconut fatty acid glyceryl, also available as

Water-soluble self-emulsifying emollient oils are useful in the present moisturizing compositions, which include US Pat. No. 4,690,8 issued September 1, 1987 to Smith et al.
Included are polyoxyalkoxylated lanolin and polyoxyalkoxylated fatty alcohols as disclosed in No. 21. Desirably, the polyoxyalkoxy chain will comprise a mixture of propylenoxy and ethylenoxy units. Lanolin derivatives will typically will include such alkoxy units of about 20 to 70, C ₁₂ -C ₂₀ fatty alcohols will be derivatized with lower alkyl units of from about 8 to 15 .. One such useful lanolin derivative is L
annexol AWS (Croda, Inc., New York, NY
． PRC-12-PEG-50). Useful poly (15~20) C ₂ ~C ₃ alkoxyl embodying are PRG-5-ceteth -20, Procethyl
It is known as AWS (Croda, Inc.). According to one embodiment of the present invention, the emollient material reduces the undesired tactile attributes of the moisturizing composition, if any. For example, emollient materials containing dimethicone reduce the level of viscosity that can be caused by ion-sensitive binders or other ingredients in the moisturizing composition and can act as detackifiers.

Desirably, the moisturizing composition comprises less than about 25 weight percent emollient, based on the total weight of the moisturizing composition. More specifically, the moisturizing composition can include less than about 5 weight percent emollients, and most particularly less than about 2% emollients. More desirably, the moisturizing composition can include from about 0.01 weight percent to about 8 weight percent emollient. More desirably, the moisturizing composition can include from about 0.2 weight percent to about 2 weight percent emollient. In one embodiment, the moisturizing composition and / or pre-moistened wipes of the present invention are described in US Pat. No. 4,559 to Smith et al., Dec. 17, 1985.
, 157, at least one dispersed in an oil phase containing at least one emollient oil and an aqueous phase containing at least one polyhydric alcohol emollient and at least one organic water-soluble detergent. Oil-in-water emulsion with one emollient wax stabilizer.

Surface Texture Modifiers Surface texture modifiers can be used to improve the feel (eg, lubricity) of the skin during use of the product. Suitable surface feel modifiers include commercially available release agents; emollients such as those used in tissue manufacturing including quaternary ammonium compounds having fatty acid side groups, silicones, waxes, etc. Not limited. A typical quaternary ammonium compound useful as a softening agent is H 2 on January 12, 1971.
U.S. Pat. No. 3,554,862 issued to ervey et al., March 1, 1979.
U.S. Pat. No. 4,144,122 issued to Emanuelsson et al. On March 3, U.S. Pat. No. 5,5 issued to Ampulski et al. On Nov. 12, 1996.
73,637 and U.S. Pat. No. 4,476,323 issued to Hellsten et al. On Oct. 9, 1984. All disclosures are incorporated herein by reference. Desirably, the wetting composition comprises less than about 2 weight percent surface feel modifier, based on the total weight of the wetting composition. More desirably, the wetting composition comprises from about 0.01 weight percent to about 1 weight percent surface feel modifier. More desirably, the wetting composition comprises from about 0.01 weight percent to about 0.05 weight percent surface feel modifier.

Fragrances A variety of fragrances can be used in the moisturizing composition of the present invention. Desirably,
The wetting composition comprises less than about 2 weight percent perfume, based on the total weight of the wetting composition. More desirably, the wetting composition is from about 0.01 weight percent to about 1 weight percent.
Contains up to weight percent fragrance. More desirably, the wetting composition is about 0.0
Includes from 1 weight percent to about 0.05 weight percent fragrance.

Fragrance Dissolution Aids Furthermore, various flavor dissolution aids can be used in the wetting composition of the present invention. Suitable perfume solubilizers include polysorbate 20, propylene glycol,
Ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, Amerox
ol-2 (Amerchol Corp.), Brij 78 and Bri.
j 98 (ICI Surfactants), Arlasolve 200 (
ICI Surfactants), Calfax 16L-35 (Pilot)
Chemical Co. ), Capmul POE-S (Abitec C)
orp. ), Finsolv SUBSTANTIAL (Finetex), and the like, but are not limited thereto. Desirably, the wetting composition comprises less than about 2 weight percent perfume solubilizing agent, based on the total weight of the wetting composition. More desirably, the wetting composition comprises from about 0.01 weight percent to about 1 weight percent perfume dissolution aid. More desirably, the wetting composition comprises from about 0.01 weight percent to about 0.05 weight percent perfume dissolution aid.

[0107] opacifiers Suitable opacifiers include titanium or other mineral or pigment dioxide, and REACTOP
AQUE® Particles (Sequa, Chester, SC)
Chemicals, Inc. Synthetic opacifiers (such as those available from The Company). Desirably, the wetting composition comprises less than about 2 weight percent opacifying agent, based on the total weight of the wetting composition. More desirably, the wetting composition comprises from about 0.01 weight percent to about 1 weight percent opacifying agent. More desirably, the moisturizing composition comprises from about 0.01 weight percent to about 0.05 weight percent opacifying agent.

PH Adjusting Agents Suitable pH adjusting agents for use in the wetting compositions of the present invention include malic acid, citric acid, hydrochloric acid, acetic acid, sodium hydroxide, potassium hydroxide and the like. Not limited. In the proper pH range, the amount of skin irritation caused by moisturizing compositions on the skin is minimal. Desirably, the pH range of the wetting composition is about 3.5.
To about 6.5. More desirably, the pH range of the wetting composition is about 4
To about 6 Desirably, the wetting composition comprises less than about 2 weight percent of a pH adjusting agent, based on the total weight of the wetting composition. More desirably, the wetting composition comprises from about 0.01 weight percent to about 1 weight percent pH adjusting agent. More desirably, the wetting composition is from about 0.01 weight percent to about 0.0.
Includes up to 5 weight percent pH adjuster.

Various moisturizing compositions formed from one or more of the above-described components can be used in the wet wipes of the present invention, and in one embodiment, the moisturizing composition comprises: It contains the following ingredients shown in 2, which are shown as weight percentages of the wetting composition.

[0110]

Table 2 Table 2 Wetting composition components

In another embodiment of the present invention, the wetting composition comprises the following ingredients shown in Table 3 below, which are given as weight percentages of the wetting composition.

[0112]

Table 3 Wetting composition components

In another embodiment of the present invention, the wetting composition comprises the following ingredients shown in Table 4 below, which is given as a weight percentage of the wetting composition.

[0114]

Table 4 Typical wetting composition

It should be noted that the inventive moistening composition described above can be used with any of the inventive ion-sensitive binder compositions described above. In addition, the wetting compositions of the present invention described above can be used with any other binder composition, including conventional binder compositions, to disperse any fibers or It can also be used with an absorbent base layer.

Strength Properties Unless otherwise specified, the tensile test is conducted according to the following agreement. Dried product was tested according to ASTM-1117-8 under Tappi conditions (50% relative humidity, 73 ° F).
0 Follow the same procedure as in Chapter 7. Tensile tests are performed on a constant crosshead speed tensile tester, such as the Thwing Albert 1256-100 tensile tester equipped with an RSA-2 10 kg load cell. The sample piece is cut into 3 inch width and 6 inch length and mounted between the jaws with 4 inch gauge length. The crosshead speed is
12 inches / minute. Maximum load (tensile strength) and elongation at maximum load (stretch) are measured. In the cross machine direction (CD) tensile test, the sample is cut in the cross direction. Machine direction (
In the MD) tensile test, the sample is cut transversely. A dry tensile test is recorded on the web taken prior to applying the wetting composition. The machine direction dry tensile strength is "MDDT" and the transverse direction dry tensile strength is "
"CDDT". Results can also be recorded in kg / 3 inches and converted to g / inch or g / 2.54 cm units.

Excess amount of wetting solution (4% by weight, based on the dry weight of the appropriately sized sample pieces)
Saline solution. Unless otherwise stated, the solution addition amount is 25
Apply until it reaches 0-400%. The wet sample is then immediately placed in Atlas.
Experimental wringer (Atlas Electric Devi, Chicago, Illinois)
ce Company, No. 10404 LW-1, unloaded), the solution is homogeneously distributed over the sample, and excess solution is gently removed to achieve a final solution addition of 200%. Depending on the sample, it may be necessary to repeat or pass through several times to reach the additional goal. The completed pre-wetted sample is then placed in a plastic bag and allowed to dry until tested. Machine cross direction wet tensile test (CDWT) or machine direction wet tensile strength (MDWT)
Is performed as above using the pre-moistened sample as is after it has been equilibrated by placing it in a sealed plastic bag overnight.

In a test relating to the loss of strength of a pre-wet web that occurs after exposure to fresh solution, a selection of 700 ml was chosen for a container with dimensions of 200 mm × 120 mm and a depth sufficient to hold 1000 ml. Fill the soaked solution. Depending on the size of the sample piece, a sample of 108 square inches or less is immersed in 700 ml of the immersion solution.
The pre-wetted sample pieces that had been equilibrated overnight were dipped in the dipping solution, followed by undisturbed immersion for a specific time (typically 1 hour). At the end of the soak time, the sample is carefully removed from the soak solution and drained, then immediately tested as described above (ie, the sample is immediately mounted in the tensile tester and without passing through the wringer). test)
. In the case of highly dispersible materials, the sample often cannot be removed from the immersion solution without disintegrating. The dip tension value for such a sample is recorded as zero for the corresponding solution.

In the deionized dip transverse wet tensile test, S-CDWT, the samples are tested after being soaked in deionized water for 1 hour. Hard water immersion lateral wet tensile test, S-CDWT-M (
M represents a divalent metal ion), the sample is immersed in water containing 200 ppm of Ca ⁺⁺ / Mg ⁺⁺ in a 2: 1 ratio prepared from calcium chloride and magnesium chloride and immersed for 1 hour before testing. . Medium hard water immersion lateral wet tensile test, MS-CDWT-
For M, the samples are tested by immersing them in water containing 50 ppm of a 2: 1 ratio of Ca ⁺⁺ / Mg ⁺⁺ for 1 dwell. Tests conducted with other time increments or immersion solutions are S-CDW
It must be so indicated to avoid confusion with the T or S-CDWT-M tests.

In one of the embodiments of the present invention, a wet wipe comprises the wetting composition of Table 3 above, with about 80 weight percent bleached kraft fiber and 20 weight percent of the above ion-sensitive bond of the present invention. And an air-laid fibrous material containing any of the agent compositions, where the weight percentages are based on the total weight of the dry nonwoven. In another embodiment of the present invention, a wet wipe comprises the inventive moistening composition described above and 90 weight percent of softwood fibers and an acrylic acid terpolymer or copolymer substantially free of acrylic acid monomer. And an air-laid fibrous material comprising a weight percentage of an ion-sensitive binder composition, wherein the weight percentage is based on the total weight of the dry nonwoven fabric. The amount of wetting composition added to the nonwoven is desirably about 180 percent to about 240 percent by weight, based on the weight of the dried nonwoven of such embodiments.

Desirably, the wet wipes of the present invention have a wet tensile strength (CDWT) in use of at least 100 g / inch and a concentration of Ca ²⁺ and / or Mg ²⁺ ions of about 50 ppm in water. The tensile strength after soaking for 1 hour is less than about 30 g / inch (MS-CDWT-M). More desirably, the wet wipes have a wet tensile strength in use of at least 300 g / inch (CDWT), Ca ²⁺ and / or
Alternatively, the tensile strength after immersion in water having a Mg ²⁺ ion concentration of about 50 ppm for about 1 hour is less than about 30 g / inch (MS-CDWT-M). In another embodiment, the wet wipe desirably has a wet tensile strength in use of at least 200 g.
/ Inch (CDWT), Ca ²⁺ and / or Mg ²⁺ ion concentration is about 200p
Tensile strength after soaking in pm water for about 1 hour is about 20 g / inch (SC
It is less than DWT-M). More desirably, the wet wipes have a wet tensile strength in use of at least 300 g / inch and a tensile strength after immersion in water having a Ca ²⁺ and / or Mg ²⁺ ion concentration of about 200 ppm for about 1 hour. Approximately 20 g /
It is less than inches (S-CDWT-M).

Desirably, a wet wipe treated with a binder material of the present invention comprising an acrylic acid terpolymer has a monovalent ionic (NaCl) concentration of 10% to 400% by weight greater than 0.3%. Wet tensile strength in-machine direction is at least 100 g / inch for 1 inch wide samples when soaked with wet wipes solution, and tensile strength after immersion in deionized water for about 1 hour. Is less than about 30 g / inch. More desirably, the wet wipes treated with the binder material of the present invention comprising an acrylic acid terpolymer have a monovalent ion (NaCl) concentration of greater than 0.3% by weight and a wet wipe of 10% to 400%. When soaked in the solution, the wet tensile strength in use in the cross machine direction for a 1 inch wide sample is at least 200 g / inch and the tensile strength after immersion in deionized water for about 1 hour is: It is less than about 30 g / inch.

In another embodiment, a wet wipe treated with a binder material of the present invention comprising a sulfonate anion modified acrylic acid terpolymer desirably has a monovalent ion (N).
aCl) concentration is greater than 1% by weight and when immersed in a wet wipe solution of 10% to 400% by weight, it has a tensile strength in use in the cross machine direction of at least 200 g / inch for 1 inch wide samples. , Ca ²⁺ and / or Mg ²⁺ ions have a tensile strength of less than about 30 g / inch after being immersed in water having a concentration of about 50 ppm for about 1 hour. More desirably, the wet wipes treated with the binder material of the present invention comprising a sulfonate anion modified acrylic acid terpolymer are monovalent ionic (NaCl).
) When immersed in a wet wipe solution of 10% to 400% by weight in a concentration of more than 1% by weight, the tensile strength in use in the cross machine direction is at least 200 g / inch for a 1 inch wide sample, Ca ²⁺ and / or Mg ²⁺ ion concentration is about 200
Tensile strength is less than about 30 g / inch after soaking in water which is ppm for about 1 hour

Products having a higher basis weight or wet strength than wet wipes that can be flushed into the toilet can have relatively high wet tensile strength. For example, products such as pre-wetted towels or hard surface wipes have a basis weight of greater than 70 gsm, for example about 80.
It can be from gsm to 150 gsm. Such products have a CDWT value of 500 g / inch or higher and an S-CDWT value of 150 g / inch or lower, in particular about 100 g / inch or lower, most particularly about 50.
g / inch or less, and a similar range may be possible for the S-CDWT-M.

Dispersible Conventional attempts to measure the dispersibility of webs, whether dry or pre-wetted, generally measure the time to break the web while being agitated by a mechanical mixer. , A system that undergoes shear when the web is underwater. It is impractical and overly optimistic for products designed to be flushed down the toilet to have a condition of sustained shearing, as the level of shearing is low and extremely short when flushed down the toilet. It will be a test. Once the product has passed the toilet neck and entered the septic tank, the shear rate is negligible. Furthermore, the product may not be completely wet with the water in the toilet when flushed into the toilet, to be precise, when the momentary shearing during flushing is applied, the moisturizing composition of the product. There may not be an adequate time to replace the toilet water. Therefore, conventional measurements of dispersibility may suggest that the product is dispersible in practice, even though it is hardly suitable for septic tank systems.

A realistic assessment of dispersibility is to make a relatively static measurement and successfully simulate the low degree of shear that the actual product will experience after being completely wet with toilet water. Are considered necessary. Thus, a test method for dispersibility has been developed that is shear independent and has improved means for assessing the suitability of a product for septic system. In this method, the tensile strength of the product is determined in its original wet form (CDWT measurement described above) and after being immersed in the second solution for 1 hour (S-CSWT or S
-CDWT-M)). The second solution is deionized water for measuring the "deionized water dispersibility" value or hard water for measuring the "hard water dispersibility" value (
S-CDWT-M test). In any case, the dispersibility is defined as (1—transverse wet tensile strength in second solution / original transverse wet tensile strength) * 100%. Therefore, a pre-moistened wipe will
If the CD wet tensile strength is lost by 75% after immersion in hard water for 1 hour, the hard water dispersibility will be (
1-0.25) * 100% = 75%. The deionized water dispersibility of the articles of the present invention can be 80% or more, particularly 90% or more, and more particularly 95% or more, and about 100% deionized water. It can also be dispersible. The hard water dispersibility of the articles of the present invention can be 70% or more, particularly 80% or more, and more specifically 90% or more, with about 100% hard water dispersibility. You can also do it.

Methods of Making Wet Wipes The pre- wetted wipes of the present invention can be made in several ways. In one embodiment, the ion-sensitive polymer composition is applied to the fiber substrate as part of an aqueous solution or suspension, where water is removed and subsequent drying to promote fiber binding. is necessary. Specifically, during drying, the binder migrates to the intersections of the fibers and is activated there as a binder in that area, giving the substrate an acceptable strength. For example, the following steps can be performed. (1) Making a highly unbonded absorbent substrate (eg, unbonded air deposits, tissue webs, carded webs, fluff pulp, etc.). (2) Applying the ion-sensitive polymer composition to the base layer, typically in the form of a liquid, suspension, or foam. (3) Applying the cobinder polymer to the base layer. (4) Drying the base layer to promote bonding of the base layers. The base layer has a maximum base layer temperature of 160 ° C., or 140 ° C., or 120 ° C., or 110
It can be dried so as not to exceed 0 ° C or 100 ° C. In one of the embodiments, the temperature of the base layer does not exceed 80 ° C or 60 ° C. (5) Applying the wetting composition to the base layer. (6) Placing the moistened base layer in roll or stack form and packaging the product.

The application of the cobinder polymer and the binder composition can be carried out simultaneously by previously mixing the two, or the cobinder polymer can be added before or after the binder. The other steps are preferably performed in the order shown above. Application of the ion-sensitive polymer composition to the base layer can be accomplished by spraying, foaming, bath immersion, curtain coating, coating and metering with a wound rod, passing through the liquid nip of the base layer, previously coated with a binding solution. Contact with a metered wet roll, transfer to the base layer by crimping the base layer to a deformable carrier comprising an ion-sensitive polymer composition such as a sponge or felt, printing such as gravure, inkjet or flexographic printing, And by other means known in the art.

When foam is used to apply the binder or co-binder polymer, the mixture is typically foamed with a foaming agent to spread evenly over the substrate, and then vacuum is applied to draw the bubble through the substrate. . Any known foam, including the method of U.S. Pat. No. 4,018,647, "Method for Impregnating a Wet Fibrous Web with a Thermally Enhanced Foam Latex Binder," issued to Wietsma on Apr. 19, 1977. A coating method can be used. All disclosures are incorporated herein by reference. Wiet
sma discloses a method of increasing the thermal sensitivity of a foamed latex by adding thermal sensitizers such as functional siloxane compounds including siloxane oxyalkylene block copolymers and organopolysiloxanes. Specific examples of thermal sensitizers and their uses that can be used to increase the thermal sensitivity of latex are described in US Pat. No. 3,255.
, 140, 3,255,141, 3,483,240 and 3,48.
4,394. Note that all of these patents are incorporated herein by reference. The use of thermal sensitizers is said to result in a product that is extremely soft and has a woven-like feel compared to conventional methods of applying foamed latex binders.

The amount of thermal sensitizer added depends, inter alia, on the type of latex used, the desired coagulation temperature, the machine speed and the temperature in the drying zone of the machine and, when calculated as the dry weight dry matter amount of the latex, is generally: It will range from about 0.05 to about 3% by weight, although higher or lower amounts can be used. The thermal sensitizer can be added in such an amount that the latex will coagulate at temperatures well below the boiling point of water, for example in the range 35 ° C to 95 ° C, or about 35 ° C to 65 ° C. . Without wishing to be bound by theory, a drying step after application of the binder solution and prior to application of the wetting composition may result in the binder being driven to the fiber crossovers as the water is drained. It is believed that the bonding of the fibrous base layers is promoted, which results in more efficient use of the binder. However, other methods omit the drying step described above and apply the ion-sensitive polymer composition to the base layer followed by applying the wetting composition with little drying in between. In one version of this method, the ion-sensitive polymer composition selectively adheres to the fibers and, at an optional crimping step, can remove excess water from the substrate without significant loss of binder. Other types do not remove much water prior to applying the wetting composition. In yet another method, the ion-sensitive polymer composition and the wetting composition are applied simultaneously, optionally followed by the addition of salts or other activating compounds to activate or enhance the binding agent. . The present invention is further illustrated by the following examples, which are in no way to be construed as limiting the scope of the invention. Rather, upon reading the description herein, various other embodiments, modifications and variations thereof that can occur to those skilled in the art without departing from the spirit of the invention and / or the scope of the appended claims I think that it is clearly understood that equivalent measures can be taken.

As used herein, the "thickness" of the web is the Mitutoyo Digim
It is connected to the spindle of an attic Indicator (Mitutoyo Corporation of Shiba 5-chome 31-19 Shiba, Minato-ku, Tokyo 108, Japan), and is measured by a 3-inch acrylic plastic disk that gives a net load of 0.05 psi to the sample to be measured. . Mitutoyo Digimatic Indicato
r is zeroed when the disc is in the plane. If a sample of at least the same size as the acrylic disc is placed under the disc, the thickness can be read from the digital value of the indicator. The thickness of the water dispersible base layer of the present invention can be any suitable thickness, such as about 0.1 mm to 5 mm. With wet wipes, the thickness is
It can range from 0.2 mm to about 1 mm, in particular about 0.3 mm to about 0.7 mm. The thickness can be determined, for example, by applying a consolidating roll during or after web formation, or by applying a binder or wetting composition and then compressing, or winding tension when forming the roll product. Can be controlled by controlling. When the thickness is measured using the platen method, a macroscopic level of average thickness is obtained. The local thickness may be different, especially if the product is embossed or otherwise textured.

Example 1 Preparation of Sulfonic Acid Anion Modified Acrylic Acid Terpolymer Acrylic acid (43.3 g, 0.60 mol), AMPS (10.7 g, 0.05
2 mol), butyl acrylate (35.2 g, 0.27 mol), and acrylic acid 2
-Ethylhexyl (20 g, 0.11 mol) was added to 55 g of acetone / water (70/3
0) Dissolved in the mixture. The initiator, 2,2-azobisisobutyronitrile (A
IBN) (0.51 g, 3.1 × 10 ⁻³ mol) was dissolved in 20 ml of acetone. The monomer solution was deoxygenated by bubbling N ₂ through the solution for 20 minutes. To two 1000 ml three neck round bottom flasks equipped with a condenser, two addition funnels and a magnetic stirrer was added 120 g of acetone / water (70/30) mixture. The solvent was heated under nitrogen to a gentle reflux. Monomer and initiator were added simultaneously from the addition funnel over 2 hours. Polymerization was allowed to proceed for another 2 hours, at which point the addition funnel and condenser were replaced with a distillation head and mechanical stir bar to remove the acetone. The N ₂ continued to flow stably during the distillation and the temperature was gradually increased from about 65 ° C to about 90 ° C. Once the distillation was complete, 400 g of deionized water was added to reduce the viscosity of the polymer solution. A cloudy, but homogeneous solution was obtained.

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

[0134]

Table 5 Sulfonate anion modified acrylic acid terpolymer

Example 2 Preparation of Acrylic Acid Terpolymer Using the polymerization method outlined in Example 2 of US Pat. No. 5,312,883,
An acrylic acid terpolymer was produced. The following monomers were used. That is, acrylic acid (50 g, 0.69 mol), butyl acrylate (25 g, 0.20 mol), and 2-ethylhexyl acrylate (25 g, 0.14 mol). The polymer is
Neutralized with 0.1 molar sodium hydroxide.

Example 3 Preparation of Ion Sensitive Polymer Formulation Sample 9 in Table 5 and the polymer prepared in Example 2 above were Dur-O-Set RB
In combination with, an ion-sensitive polymer formulation of the present invention was made. Polymer formulations were prepared as shown in Table 6 below.

[0137]

Table 6 Ion-sensitive polymer formulations

Example 4 Solubility of Ion Sensitive Polymer Formulation The sensitivity of the polymer formulation of Example 3 to divalent cations present in hard water was determined. Samples 1-10 of Example 3 are placed in a number of CaCl ₂ solutions with Ca ²⁺ concentrations ranging from <10 to 200 ppm. Subsequently, it is immersed for 1 hour and the solubility of each polymer is recorded. The solubility results are shown in Table 7 below.

[0139]

[Table 7] Table 7 Results of solubility

In any case, the films formed from the blends containing NaAMPS are more soluble than the films containing acrylic acid terpolymers, especially with increasing calcium ion concentration.

Example 5 Bond Strength Testing of Polymer Formulations With and Without Crosslinking For testing on a pilot scale, a pulp base (CF405 or NB416 pulp from Weyerhaeuser) bonded to each other with 2-5% bicomponent fibers. An air-laid base sheet was used. The bicomponent fiber is Type 255 (KoSa Fiber, Salisbury, NC) having an active polyethylene sheath and a polyester core.
er's), or D with a polyethylene sheath and a polypropylene core
anaklon fiber (obtained from Fiber Visions, Valde, Denmark). Both types of bicomponent fibers are 2-3 denier,
It was cut to a length of 6 mm. The binder formulation was applied by spraying 12-15 weight percent solution on both sides of the base sheet. The strength of the base sheet under various conditions is recorded minus the base strength of the web with bicomponent fibers. Table 8 shows the strength of the base sheets of different formulations in 0.4 weight percent NaCl (CDWT) as well as after immersion in deionized water for 1 hour (S-CDWT).

[0142]

[Table 8] Table 8 Tensile strength BW: basis weight CDWT: cross machine direction wet tensile strength S-CDWT: CDWT after soaking in deionized water for 1 hour All codes above are compared to 100% acrylic acid terpolymer containing binder formulation, When it gets wet, it will get wet well. Also, binder formulations containing EVA are much more sprayable than 100% acrylic acid terpolymers, resulting in significantly improved distribution and penetration of the binder into the base layer. It is worth noting that the S-CDWT of the non-crosslinkable formulations, Samples 5, 11, and 12, were less than 30 g / inch.

Example 6 A binder formulation having the composition shown in Table 9 below is prepared. The binder formulation with 12 weight percent solids is sprayed on both sides of the airlaid web. The air-laid web is based on pulp (CF405 from Weyerchaeuser). Table 9 shows that in a 0.9% NaCl solution (CDWT) and after immersion in deionized water for 1 hour (
(S-CDWT) shows the strength of the base sheet. It also shows the effect on strength after being placed in salt solution for up to 16 weeks. A preservative such as Mackstat H66 is added to the sample to prevent mold growth on the base sheet when placed in salt solution.

[0144]

[Table 9] Table 9 Tensile strength of base sheet The results in Table 9 show that when Dur-O-Set RB is used as EVA, the web does not lose its original properties after prolonged exposure in the salt solution in use. The presence of the crosslinkable agent in EVA will result in diminished dispersibility after a few weeks of sample placement.

FIG. 1 shows the strength properties of the terpolymer modified with NaAMPS,
It is also dispersible in hard water (up to 200 ppm Ca ⁺⁺ / Mg ⁺⁺ solution). 75% by weight NaAMPS modified acrylic acid terpolymer (SS
B) and 25 weight percent EVA (Dur-O-Set® RB)
Base sheets based on show very good strength during use (1.5% or 4.0% NaCl solution) and disperse in high hardness water. SSB-4 dispersed in hard water after 10 minutes. SSB-5 was dispersed in hard water after 3 hours. NaAMPS-SSB is
Higher viscosity compared to Lion's -SSB. Tensile strength results for Examples 5 through 7 are Testworks ™ 3.10.
MTS500 / S, an MTS tensile tester, using Windows version software
Units (MTS Systems, Research Park, NC). Instead of the usual 3 inch strips for testing, 1 inch wide strips cut into 6 inch lengths were used. The gauge length between the jaws of the rubber coating of the test rig was 3 inches. Tested at 12 inches / at specific crosshead speed
Went in minutes. MTS devices with a modified test procedure generally yield comparable results to the tensile test procedure described above using a 3-inch wide sample and the Thwing-Albert tester.

Example 8 Addition of a cobinder polymer to an 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 shows the effect of adding various co-binder polymers to the acrylic acid terpolymer (SSB-2) according to the invention.

[0147]

Table 10 Effect of adding various cobinder polymers to SSB-2 Table 10 shows SSB when Rhoplex® NW 1715K, Rovene® 4817 and Dur-O-Set® RB are added.
-2 shows that the shear viscosity of acrylic acid terpolymer alone is significantly reduced. The addition of sodium polyacrylate significantly increases the shear viscosity of SSB-2, so the decrease in viscosity is not due to mere dilution of SSB-2.

Example 9 Rhoplex® NW 1715K, Rovene® 4
A dry solid bar was prepared from 817 and Dur-O-Set® RB.
The bar was conditioned by injecting an amount of polymer into a rectangular silicon mold, which was a 1 cm wide, 4 cm long, 3 mm deep open rectangular silicon mold.
The polymer in the mold was then heated at 60 ° C overnight. Next, the dried polymer in the mold was placed in a container containing 30 ml of deionized water at about 23 ° C. and left for 1 hour. None of the bars dispersed in deionized water. Next, sulfonate anion-modified acrylic acid terpolymer (NaAMPS + SS
Bar samples were prepared with B) separately blended with Rhoplex® NW 1715K, Rovene® 4817 and Dur-O-Set® RB. The polymer blend was made with 75% by weight sulfonate anion modified acrylic acid terpolymer and 25% by weight cobinder polymer. Bar samples were prepared as described above. The bar sample was then added to deionized water. The following polymer blend: NaAMPS + SSB / Rh
oplex NW 1715K, NaAMPS + SSB / Rovene 481
Each bar sample made of 7 and NaAMPS + SSB / Dur-O-Set RB dispersed in deionized water within 1 hour.

Example 10 A substrate in the form of an air-laid web was prepared on a commercial air-laid machine with a width of 66.5 inches. A Dan Web air deposition former with two forming heads was used to generate a base layer having a basis weight of about 60 gsm. Weyerh in the form of a pulp sheet
Aeuuser CF405 bleached softwood kraft fiber was used to break into fibers in a hammer mill before air-laid webs on moving wire at speeds of 200 to 300 feet / minute. The freshly formed web was densified on a heat compacting roll and conveyed to a second wire where it was wetted with a spray of water and immediately after giving an estimated 5% moisture loading level. A second heated consolidation roll further densified the web. The web is then conveyed to an oven wire and the exposed surface of the upper web is sprayed with the ion-sensitive polymer formulation mixture at 10 to dry fiber mass of the web.
% Ion-sensitive polymer formulation was applied. The ion-sensitive polymer formulation mixture contained water as a carrier with 12% binder solids and the binder was 75% SSB- as the ion-sensitive polymer formulation.
4 and 25% Rhoplex® NW- as cobinder polymer
1715K Latex Emulsion (Rohm and Haas Corp.
) Was included.

The spray was from Spraying Systems Co. Nozzle 730077, a series of Quick Veejet® nozzles manufactured by (Wheaton, IL), was run operating at 95 psi. The spray boom above the web is equipped with 13 such nozzles, a tip to wire distance of 8 inches and a center-to-center distance of 5.5 inches. In this arrangement, the spray cones for the ion-sensitive polymer formulation solution of this test have 100% overlap. After spraying, the web was conveyed to a ventilated oven at about 225 ° C to dry the binder solution. The web is then carried under another oven wire, where it is passed over another spray boom, and more ion sensitive polymer formulation is applied to the bottom side of the web, relative to the dry fiber mass of the web. And an additional 10 weight percent solids was added. The web was then passed through two consecutive drying units and dried completely by flash drying at 225 ° C. The pressure difference across the web was approximately 10 inches of water. The lengths of the three dry zones from the first to the third are approximately 9, 10 and 6 respectively.
It was a foot.

The thickness of the web after drying is 1.14 mm (this number can vary depending on the fiber, basis weight, etc., as well as other physical properties recorded herein). Met. The dry machine direction tensile strength (MDDT) of the web was measured to be 4.59 kg / 3 inches. The transverse dry tensile strength (CDDT) of the web is 3.82 kg.
/ 3 inch, CD stretch 8.98%. The dried and treated web was then cut into 60 inch wide and wound onto reels and then slit into 4 inch wide rolls which were then treated with the wetting composition and pre-wetted. A coreless roll suitable for use as a bath wipe. The moistening formulation was uniformly sprayed onto one side of a 4-inch wide web and then the web was wound into a roll of suitable size. The wetting composition was dissolved in deionized water 4
It was weight percent NaCl. The transverse wet tensile strength (CDWT) with 4 weight percent saline was 0.7.
Measured 6 kg / 3 inches. The soaked CDWT strength was virtually zero, as was the soaked CD stretch, indicating that the sheet was completely dispersible.

Example 11 The sheet formed had 75% softwood kraft and 25% fibers in the airlaid web.
Same as Example 10 except% PET fiber. The web thickness after drying was 1.35 mm. The machine direction dry tensile strength (MDDT) of the web is 3
． It was measured to be 87 kg / 3 inches. Transverse Dry Tensile Strength of Web (CDDT)
Was measured at 2.84 kg / 3 inches and the CD stretch was 11.31%. The transverse wet tensile strength (CDWT) in 4% saline was measured to be 0.82 kg / inch. The soaked CDWT strength was virtually zero, as was the soaked CD stretch.

Example 12 An additional example similar to Example 10 was performed except that the Rovene latex emulsion was used as the cobinder polymer and the basis weight and fiber composition varied as shown in Table 11. The immersion CDWT results were all 0, indicating complete loss of tensile strength. Other results are shown in Table 11, where pulp / PET is the ratio of softwood to synthetic fibers in the base layer, BW is the basis weight in gsm, and TH is m.
It represents the thickness in m units, and S-CDWT-M contains 200 ppm of Ca ⁺⁺ / Mg ⁺⁺ of 2
1-hour immersion CD wet tensile test for samples soaked in water containing 1: 1 ratio.

[0154]

Table 11 Table 11 Measured values for Examples 3A to 3F If the S-CDWT-M value (immersion wet tensile strength in hard water) is not zero, 2
Two tests with 5% PET fiber suggest that high amounts of synthetic fiber result in poor water dispersibility.

Example 13 A pre-moistened wipe was prepared as in Example 10 except that the cobinder polymer was a modified Elite® latex emulsion substantially free of crosslinker supplied by National Starch. It was Web basis weight is 61.35, thickness is 1.21 mm, MDDT is 5.09 kg / 3 inches, MD
Expansion is 7.89%, CDDT is 3.90 kg / 3 inches, CD expansion is 9.50%
The CDWT in 4% saline is 0.78 kg / 3 inches and the CDWT extension is 32.
The strength remaining after 96 hours of immersion in both deionized water (S-CDWT) and hard water (S-CDWT-M) for 1 hour was 0 kg / 3 inch.

Example 14 Particle Addition A pre-moistened wipe containing the base sheet of Example 10 was prepared with a wetting composition containing a slurry of particles. Particles were prepared according to the following Presperse, Inc. (Piscataway, NJ) selected from commercially available products.

[0157]

Table 12 Presperse selected for use in pre-moistened wipes,
Inc. Particles of

For each type of particles in Table 12, five batches of 1000 grams of a batch of wetting composition were made to a particle concentration of 0.5%, 1%, 2%, 5%, and 10% by weight. Prepared. Each batch was prepared by adding the appropriate amount of deionized filtered water to a 1.15 liter beaker (for 5 batches, the amount of water was 926.
3 g, 921.3 g, 911 g, 881 g, and 831 g). T in the bottle
It was placed on a hermolyne Cimarec 2 stirrer and the contents of the bottle were stirred with a 2.5 inch magnetic stir bar with the stirring speed set to maximum, creating a strong central vortex in each of the 5 bottles. Each batch contained 4 weight percent sodium chloride added to water as 40 g salt; 1 weight percent (10 g) Amisoft E.
CS22-P acylglutamate surfactant (Ajinomot, Tokyo, Japan)
o); 0.5 weight percent (5 g) of DC silicone emulsion (Dow Corning) added to saline and surfactant; 1 weight percent (10 g) of M.
ackstat H 66 preservative (McIntyre Gr, Chicago, IL)
); and initially 0.25 weight percent (2.5 g) of polysorbate 2
0, and then 0.05 weight percent (0.
5 g) perfume; and respective amounts of powder (0.5 to 10 weight percent, ie 5 to 100 g). The powder was added to the solution with stirring, and the powder was added and wetted and suspended for about 30 minutes. Some of the powders required additional hand agitation to proceed with the mixing. Once the powder is dispersed in the liquid,
The pH was adjusted to 5.0 by adding malic acid dissolved in water and adjusted to a strength of 50 weight percent. The pH was Cole Parmer Model 59002-00 pH / mV / ° C equipped with a Model 59002-72KK8 electrode.
It was measured with a meter.

Each of the particle suspensions was then added to a dry air-laid base sheet treated with NaAMPS binder and cobinder polymer according to Example 13. The additional level is
200%, spray applied to one side of the web. The wet web was then sealed in vinyl and left overnight. By testing a pre-wetted wipe treated with a particulate suspension as a wetting composition, the particles generally remain in the wet wipe without the need for additional thickeners or polymeric retention aids. Became clear. For example, squeezing a pre-wetted wipe will result in an almost clear fluid that is apparently substantially free of particulates, in contrast to the milky suspension used to wet the wipe. In general, it does not appear to be visible after using a wipe. In addition, fine particles generally improve opacity and slightly improve tactile properties (decrease tack, improve rheological feel).

Example 15 It was investigated that the role of non-gelling starch particles in the wetting composition of the present invention is a means of reducing the tack and improving the surface feel of pre-wetted wipes. Five moisturizing compositions containing tapioca starch were prepared according to the formulations in Table 13. The softwood airlaid web according to Example 10 wetted at a 300% add-on level of the wetting composition. (QS means "sufficient amount" to achieve the desired pH.)

[0161]

Table 13 Five moisturizing compositions containing starch Pre-wetted wipes with starch were less tacky to the touch than similar pre-wetted wipes without starch. Also, the wipes containing starch have a smoother feel.

Example 16 Additional pre-moistened wipes were prepared using the moisturizing composition shown in Table 14, one containing starch as an additive and the other containing the plant extract. The wetting composition was added to an air-laid fiber substrate containing an ion-sensitive binder. The wetting composition was added at addition levels of 300 and 200 percent, respectively.

[0163]

Table 14 Table 14 Formulation of Two Wetting Compositions

Example 17 Binder Specification Various ion sensitive polymers were prepared including acrylic acid (AA), butacrylic acid (BA), 2-ethylhexyl acrylate, and AMPS. The mole percentages and molecular weights are shown in Table 15.

[0165]

Table 15 Ion-sensitive binders containing AMPS These binders were prepared according to the method of Example 1, but scaled up to a batch operation capable of producing hundreds of gallons / batch.

Example 18 Typical Wetting Solution A wetting composition was prepared by combining the following ingredients according to the specified weight percentages. That is, 92.88 weight percent deionized water, 4 weight percent NaCl, 1 weight percent Macstat H-66 preservative (McIntyre Group, Chicago, IL), 1 weight percent CS22 acylglutamate anionic surfactant ( Amisoft Corp. of Tokyo, Japan.
), 0.5 weight percent DC1785 silicone emulsion (Dow Co
), 0.25 weight percent Solution L-575 (Un
PEG available from Amerchol, a division of Ion Carbide
-75 lanolin), 0.05 weight percent Dragoco fragrance 0/7087
68 (Dragoco of Cuautitlan Izcalli, Mexico City, Mexico)
SA), 0.25 weight percent polysorbate 20, and a solution of 50% malic acid at a weight of about 0.07 weight percent to bring the pH to 5.0.

Example 19 Treated Substrate An air-laid substrate was prepared with the equipment described in Example 10. The basis weight was 65 gsm and the fiber was 100% Weyerhaeuser CF405 bleached softwood kraft pulp. The binder solution had 12.8 weight percent binder solids, 75 weight percent of which was SSB Code H in Table 15 and 25 weight percent was Du.
r-O-Set RB Latex Cobinder (National Starc
h). The binder solution has a dry air temperature of 215 for all three oven sections.
Sprayed onto the web as described in Example 1 at 0 ° C.

Example 20 Treated Substrate An air-laid substrate was made according to Example 10 except the basis weight was gsm and the oven temperature was 227 ° C. The winding speed was 197 fpm. The dry web thickness was 1.30 mm. MDDT is 5.55 kg / 3 inches, S-CDWT and S-CDWT-
In M (1 hour immersion test), it was 0 kg / 3 inch. Some of the dry webs were cut lengthwise to 4.25 inches wide and treated with a 225% loading of wetting composition containing 4% NaCl in deionized water without surfactant. The wet web was perforated with a piercing knife operating at a depth of 0.070 inch to punch every 4.5 inch. The perforated web is rolled into a coreless roll with 100 perforated sheets / rolls (approximately 37.5 feet / roll) and then made of plastic for use in a pre-moistened wipe dispenser. I put it in a cartridge. Example 21 A portion of the dried treated web of Example 20 was wetted with the wetting composition of Example 18 and formed into perforated rolls for use as pre-wetted wipes, one by one, removed from a bathroom dispenser.

Comparative Example 22 The method described in Example 10 was used to produce a conventional adhesive bonded airlaid substrate having a basis weight of 60.1 gsm. Dur-O-Set E-646 (National
l Starch) was used with wood pulp (CF405). Base layer is 4% N
Wet with aCl solution and tested using the method described. The binder was a fully self-crosslinking Dur-O-Set E-646 compound, no salt sensitive binder was applied. The amount of binder solids was 17% of the base layer mass. The web has a dry thickness of 1.4 mm and a CDWT value of 1.3 kg / 3 inches, while the S-CDWT
Is 1.2 kg and S-CDWT-M is 1.15 kg, indicating that the web maintained almost all strength after soaking, with the crosslinked latex providing most of the tensile strength of the web. It is suggested that the latex bond did not substantially weaken in water.

Example 23 As shown below, the ion-sensitive binders of Table 15 and non-self-crosslinkable Tables 1
Various binder / cobinder combinations were prepared using the cobinders shown in 6.

[0171]

Table 16 Latex co-binder not self-crosslinkable An air-laid substrate was made of bleached kraft fibers using the method described in Example 10. The base layer was wet with a 4% NaCl solution and tested using the method described. All base layers included 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% cobinder selected from Table 16. The binder / cobinder column shows the binder and cobinder listed in Tables 15 and 16, respectively. For example, "A / 1" indicates SSB code A in Table 15 and cobinder 1 in Table 16.

[0172]

Table 17 Tensile strength data for various binder systems

As can be seen in Table 17, almost all of the substrate lost its tensile strength by more than 80% after immersion in deionized water for 1 hour (S-CDWT). The base layer is 200
After immersion in a solution of ppm divalent cation (Ca ⁺⁺ / Mg ⁺⁺ 2: 1) for 1 hour, it loses more than 60% of its strength (S-CDWT-M). In particular, in the test shown in Table 17, the sample completely lost its strength when immersed in a 200 ppm solution for 1 hour when the molecular weight of the salt sensitive binder was less than 1,200,000. Two
After soaking in 00 ppm divalent cation solution for 3 hours, the higher molecular weight SSB generally loses much of its strength, but the tensile strength may still not reach zero. In comparison, Comparative Example 22 lost less than 15% of its strength after soaking for 1 hour in either deionized water or a 200 ppm divalent ionic solution. All of the base layers in Table 17 lost more tensile strength than Comparative Example 22 when immersed.

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 air-laid underlayers listed in Table 18. In each case, 20% binder solids were applied to the base layer with a blend of 75% SSB / 25% cobinder.

[0175]

Table 18 Tensile strength data for various cobinder systems Under the same test conditions, all three cobinders performed equally well. All base layers lost their tensile strength (S-CDWT-M) in 200 ppm divalent cation solution regardless of the type of cobinder.

Example 25 A measurement of the peel force required to unwind the product from the outer layer of a pre-moistened wipe coreless roll suitable for use as a moisturizing toilet paper product was made. The product was made according to Example 10 with an addition level of 200% of the wetting composition. The dry web was chopped to a width of 4.25 inches and the wetting compositions Q, R, listed in Table 19,
And a 200% addition of a wetting composition containing a 4% NaCl deionized aqueous solution containing a surfactant such as S and S, silicone, and lanolin. The wet web is 4.
The perforating knife was operated and perforated to perforate every 5 inches. The perforated web is rolled and 100 perforated sheets / rolls (approximately 3
(7.5 ft / roll) into a coreless roll and then sealed in a plastic cartridge for use in a pre-moistened wiper dispenser.

[0177]

Table 19 Other Additives in Three Wetting Compositions

The rolls are freely placed in a plastic tub with a rounded and ribbed bottom that pulls the rolls as they are unwound by pulling the end of the roll vertically upwards. Hold in place with minimal friction. Adjacent plies were attached to each other so that some force was required to separate the layers. The peel force required appeared to be less than the weight of the roll and substantially greater than the frictional resistance experienced by the tub as the roll rotated. This is evidenced, in part, by the angle between the web and roll at the point of separation. If there is no peeling force,
The angle between the web being pulled and the line perpendicular to the roll at the point of separation is 90 degrees, but when the moisturizing roll containing the salt sensitive binder is unwound, the angle is substantially 90 degrees.
Less than a degree, which resulted in a peel force to separate the web.

Peel force is measured by MTS Sin with TestWorks 3.10 software.
It was measured on a tech 1 / G test machine. All tests were performed in a conditioned laboratory under Tappi standard conditions. Grab the end of the roll with a 4.5-inch wide clamp with a rubber surface, position the roll directly under the clamp, and if the web does not wrap around a portion of the roll and deviate vertically from the end, Keeps it vertical when unwound from the roll. The clamps are attached to the crosshead, which pulls the tissue web upwards at 100 cm / min. The peeling force was measured with a 50N load cell. The average load of pulling 18 sheets off the roll was recorded by averaging two tests that each separated 4 sheets and two tests that each separated 5 sheets. Only the first 18 sheets of rolls were used for the measurements. The average peel force for the two rolls in each condition (overall average taken from 36 sheets total) is recorded in Table 20 below.

[0180]

[Table 20] Table 20 Peel force (grams) for removing the web from the wound moisturizing roll Width is between 7 and 15 cm (roll width tested in Table 20 is 10.8 cm
) The peel force for the roll is desirably less than 500 g, in particular less than 300 g,
More specifically less than about 200 g, more specifically less than about 160 g, and most specifically about 1 g.
Less than 20 g, typical range is from about 50 g to about 350 g, or about 80 g
To about 200 g. More generally, the peel force per 4 inch wide moisturizing roll can be any of the values in the above range.

Example 26 An additional sample was prepared according to Example 24 above except that 15% by weight of the fiber blend contained 6 mm crimped PET fiber (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 air-laid substrate. This property is listed in Table 21. In each case, 20% binder solids is 75
The base layer was coated with a blend of% SSB / 25% co-binder. The properties of such a base layer were measured after wetting with a 4% NaCl solution. All three co-binders have comparable performance. All base layers are 200pp regardless of the type of co-binder
Loss of tensile strength in divalent cation solution of m. Compared to the similar results of Example 24, the incorporation of synthetic fibers improves the strength from narrow to narrow (CDWT) and also improves the dry bulk.

[0182]

Table 21 Table 21 Substrate data with PET fibers and various co-binders

Example 27 An additional example was made according to Example 26 with increasing amount of synthetic fiber added to the fiber blend. 6 mm crimped PET fiber (KoSa) or 6 mm crimped 2.4 decitex Lyocel fiber as used in Table 22 below was used.

[0184]

Table 22 Data for base layers with PET fibers and various cobinders Non-zero wet CDWT tensile strength in 200 ppm divalent cations is a test combination containing 25% synthetic fiber (PET or Lyocell), which results in weaker water dispersibility at higher contents. Is suggested.

Example 28 All the base layers shown in Table 23 were made according to the method of Example 10 and prepared according to the method described in Example 23. All base layers in Table 23 were formed from air-laid pulp (CF405). All binder blends were 75% SSB and 25% cobinder. The dry thickness of the sheet was controlled by adjusting the level of web consolidation with two compaction rolls prior to the first spray application of binder. Table 15
SSB codes O and Q were used.

[0186]

Table 23 Table 23 Data for base layers with PET fibers and various co-binders It appears that consolidating the dry web prior to applying the binder can significantly increase the wet strength of the final sheet without sacrificing dispersibility. This surprising increase in strength allows the same wet tensile strength to be achieved in various combinations, including reduced basis weight and / or reduced% binder in the sheet.

Example 29 All substrates were prepared according to the method described in Example 27. All base layers contained 20% binder in the sheet and the fiber blends described in Table 24 with Dur-O-Set RB acting as a cobinder. Synthetic fiber crimped, 6 mm PE
T (KoSa) or 6 or 8 mm Lyocell with 1.7 or 2.4 decitex (A
cccordis).

[0188]

Table 24 Data for base layers with various fibers and binders

The example in Table 24 suggests that the combination of synthetic fiber length, SSB molecular weight and web compaction affects the product dispersibility as indicated by the S-CDWT-M value. All substrata containing 6 or 8 mm synthetic fibers were dispersible in low molecular weight SSB. As the molecular weight increased, the 8 mm Lyocell underlayer began to retain some of its strength after being immersed in the divalent cation solution for 1 hour. However, this base layer was dispersible in deionized water. Also, increasing the density of the dry web prior to applying the binder can affect the dispersibility of the base layer (codes 3015 and 3016) containing synthetic fibers. Code 3015 and Code 3016 were completely dispersible in deionized water. Sheet dispersibility can be controlled by selecting low molecular weight SSB in combination with synthetic fibers and dry web densification.

Example 30 Substrates listed in Table 25 were prepared, wetted with a 4% NaCl solution and tested according to the method described in Example 29. Each base layer comprised the fiber blends listed in Table 25 and the listed 20% SSB binder / cobinder blends. Dur-O-Set
RB was the cobinder used for all the samples listed in Table 25. All cords, except the last one, cord 2813, used 100% softwood fibers. Code 2813 contained 15% PET fiber (6 mm crimped fiber obtained from KoSa). Basis weight was generally constant at 60 gsm. The thickness of the air-laid web was controlled by adjusting the level of web compaction by the two compaction rolls before first spray coating the binder. The dry CD stiffness of selected base layers in Table 25 was measured using a Handle-O-Meter and recorded as stiffness.

[0191]

Table 25 Data for base layers with various binder blends

When the percentage of salt sensitive binder in the blend is reduced from 100% to 55%, the CDWT is only marginally reduced at constant dry bulk. With a composition of 65% salt sensitive binder in the binder blend, the base layer begins to retain more of its wet strength after 1 hour of immersion in 200 ppm divalent cation solution. When the web is densified before the binder is first applied and the salt sensitive binder in the blend is reduced to 65% or less, the same composition compared to a higher dry bulk However, the strength retained after being immersed in deionized water or a 200 ppm divalent cation solution for 1 hour is significantly increased. These examples suggest that increasing the cobinder content, whether or not additionally densifying the web, weakens the dispersibility of the base layer. The results in Table 25 also show that compacting the dry web thickness prior to applying the binder significantly increases the CDWT. Codes 3007 to 3010
As a result, under certain binder conditions, CDWT does not impair the dispersibility of the base layer,
It is shown to increase as a function of decreasing dry bulk. Based on the Handle-O-Meter results (stiffness), the CD stiffness of the base layer decreases as the percentage of salt sensitive binder in the blend decreases.

Example 31 Substrates listed in Table 26 were prepared according to the methods described in Example 10 and Example 23. Each base layer contained pulp (CF405) and 20% binder. The binder had the SSB / cobinder blend shown in Table 26. Dur-O-Set RB
Was the co-binder. The base layer was converted to roll form and wet with solution Q (solution D) of Table 19. Example 25 from the outer layer of a pre-wetted wipe coreless roll.
The peeling force required to unwind the product was measured by the method described in. The results of this test are recorded in Table 26 below.

[0194]

Table 26 Table 26 Results of peeling force of coreless rolls In this case, reducing the percentage of salt sensitive binder in the blend will reduce the peel force.

Example 32 A 75/25 blend of SSB binders according to the information in Table 27 below (see Table 15).
And Dur-O-Set RB cobinders (cobinders in Table 16) were used to make samples as in Example 10. The tensile strength results in Table 27 show good dispersibility over a range of product conditions.

[0196]

Table 27 Tensile strength results and base sheet properties for specific ranges of binders The samples recorded in Table 27 show several ranges of binder content, basis weight, and web thickness that can make a dispersible base layer.

Example 33 A sample was prepared as in Example 10 using a 75/25 blend of SSB binders (see Table 15) and a cobinder (see Table 16) as shown in Table 28. All base layers contained 6 mm crimped 2.4 decitex Lyocell (Accordis) as 15% of the fiber blend with 85% softwood pulp (CF405). All base layers contain 19% binder and 81% binder blend.

[0198]

Table 28 Tensile Strength Results and Base Sheet Properties for a Specific Range of Binders In Table 28, all samples lost at least 75% of their wet strength (S-CDWT) after being immersed in 200 ppm divalent cation solution for 1 hour. The main difference between these samples lies in the SSB composition, as shown in Table 15. The salt-sensitive binders L and E have the same composition but a different molecular weight than the salt-sensitive binders W and AB (see Table 15). The salt sensitive binders W and AB have the same composition but different molecular weights. The W / 1 treated and AB / 2 treated base layers appear to have less dispersibility than the L / 1 treated and E / 2 treated base layers, regardless of cobinder. Reducing the molecular weight of the salt sensitive binder can be used to increase the dispersibility of the base layer as shown in Base layer AB / 1. Alternatively, varying the composition of the salt sensitive binder can be used to increase the dispersibility of the base layer as shown by L / 1 and E / 2. Thus, by modifying the molecular composition of the salt sensitive binder or its molecular weight, a fully dispersible blend can be made. Alternatively, by selecting different cobinder chemistries that are highly compatible with salt sensitive binders, it is possible to make fully dispersible binder blends, as shown in the base layers AB / 2 and AB / 1. it can.

Example 34 A latex emulsion containing about 6% NMA crosslinker AirFlex 105 (Air Products, Allentown, PA) was 75%.
Combined with SSB Code H in Table 15, at a ratio of 1 part SSB to 25 parts latex solids, 8 bars having dimensions of 1 cm x 4 cm x 3 mm were molded as described in Example 9. Four bars were prepared by drying in air at 60 ° C overnight, the other four bars were dried at 167 ° C for 3 hours. 30m each for 2 bars of each group
It was placed in 1 l of 4% NaCl solution and left for 1 hour, after which the solubility was measured by weight. Both sets of bars (two dry conditions) were essentially completely insoluble in saline solution. The remaining bars of each set were each placed in 30 ml of hard water at about 23 ° C. containing 200 ppm calcium and magnesium ions in a 2: 1 ratio and left for 1 hour. The two bars, dried at 167 ° C. and placed in hard water, were essentially completely insoluble (0% soluble). The two bars dried at 60 ° C and placed in hard water were 54% and 53% soluble respectively, which is surprisingly low considering that the latex does not substantially crosslink when dried at this temperature. It was However, some agglomeration occurred when the latex was mixed with SSB, suggesting that there may be miscibility problems between the two mixtures, and thus poor solubility or some Aggregated particles may have failed to pass through the filter paper. It is also possible that the NMA crosslinker in the Airflex latex promoted crosslinking or gelation of the blend. While it is believed that a highly miscible latex emulsion will provide high solubility, it will be present in a relatively small amount in the crosslinker (eg less than 6% of crosslinker based on solids content, specifically It is also believed that the co-binder (less than 2%, more specifically less than 1%, most particularly less than 0.3%) helps maintain the high solubility of the dry polymer blend.

FIG. 1 shows the wet tensile strength results of treated air-laid basesheets,
In this case the test was carried out in different saline solutions or hard water. An air-laid base sheet was prepared according to Example 10 with the addition of 20% salt sensitive binder compositions designated Code X, Code Y, and Code Z. Code X is 60% acrylic acid, 10.
5% 2-ethylhexyl acrylate, 24.5% butyl acrylate, and 5% N
A binder polymer containing aAMPS, polymerized according to Example 1 with a molecular weight of 1.3 million and corresponds to Code B in Table 15. Code Y is similar, but has a molecular weight of about 550,000 and corresponds to code D in Table 15. Code Z is similar, but has 62% acrylic acid and 8.5% 2-ethylhexyl acrylate as monomers, has a molecular weight of approximately 1.2 million and corresponds to code G in Table 15. All binders were blended with Dur-O-Set RB co-binder in a 75:25 ratio. The treated web was dried as in Example 10 and then wet with either a 4% or 1.5% NaCl solution. Wet tensile testing was performed according to the CDWT protocol (eg, using a 1 inch wide strip and MTS tensile tester) with the exceptions described in Example 5.

Immersion CD tensile tests were performed on samples prepared with a 4% solution. The four columns shown in each code (some are not visible because the value is zero) correspond to the results of four different tests. The first two columns are the "as is" CDWT values for the web in either 4% or 1.5% NaCl solution. The third and fourth columns are 4%
1 is a 1 hour and 3 hour S-CDWT-M (hard water soak) result for each web wet with the solution. The results show that both 1.5% NaCl and 4% NaCl have good wet strength and the web treated with Code Y has excellent strength loss (100% hard water dispersibility).
, Code Z shows that good strength loss occurs, while code X still retains strength. Comparing Code X with Code Y suggests that lower molecular weight may promote dispersibility of the salt sensitive binder.

FIG. 2 shows that a 68 gsm softwood air-laid web containing an ion-sensitive binder was dipped in a solution containing calcium ions to obtain wet tensile strength (CDWT in grams / 2.54 cm over a range of soaking times). Is a graph showing how it can change over time. Wet webs were prepared from Lion (Tokyo, Japan) 85% SSB-3b acrylic acid based terpolymer and 15% Dur-OS.
20 by weight including et RB (National Starch) co-binder
Prepared with% binder. After drying, the web was wetted with a solution containing 0.9% NaCl, 0.5% phospholipid CDM (Mona), and 0.5% Mackstat H-66 at about 400 g / inch (or g / 2.54 cm). ) Of wet strength.
The treated web is then loaded with calcium ions at 0, 13, 29, and 109 pp.
Immersion in water containing m levels and no NaCl produced four curves of wet tensile strength vs. time as shown in FIG. At 109 ppm calcium ion, there is essentially no loss of strength. The strength exceeding 100 g / inch is maintained even in 29 ppm ion. Even small amounts of calcium in water appear to interfere with the dispersibility of webs treated with Lion's SSB-3b product.

FIG. 3 shows two data sets for the Lion SSB-3b product of FIG.
Code 3300) and a sulfonated salt sensitive binder blended with Dur-O-Set RB polymer in a 75/25 ratio. The data set referred to as Code 2102 is a 65 gsm web with sulfonate salt sensitive binder, which corresponds to SSB Code H in Table 15. The web was wet with the solutions listed in Table 4. Solution loading was 225% based on the dry weight of the web. This binder formulation has a calcium ion concentration of 257 p when immersed in hard water.
Even at pm, there was a sharp drop in tensile strength—and thus good triggerability. Thus, the sulfonate salt sensitive binders of the present invention show a dramatic improvement in their ability to disperse in hard water compared to conventional acrylic acid based terpolymers.

Tensile strength results for the data in FIGS. 2 and 3 are shown in Testworks ™ 3
． MTS5, which is an MTS tensile tester, using 10 Windows version software
00 / S unit (MTS System at Research Park, NC)
s). Instead of the usual 3 inch strip for testing, a 1 inch wide strip cut into 6 inches long was used. The gauge length between the rubber coated jaws of the test equipment was 3 inches. The test was run at a specific crosshead speed of 12 inches / minute. The foregoing description relates only to the particular disclosed embodiments of the invention, which are subject to numerous modifications or changes without departing from the spirit and scope of the invention as set forth in the appended claims. It should be understood, of course, that you will get.

[Brief description of drawings]

FIG. 1 is a graph depicting wet strength data for three binder formulations as a function of ionic environment and soak time.

FIG. 2: Wet tensile strength (C over a range of soak times) when a fabric containing a 68 gsm softwood air-laid web and an ion-sensitive binder was immersed in a solution containing calcium ions.
DWT recorded in grams / 2.54 cm) is a graph showing how it can change over time.

3 shows two data sets (Code 3 for the Lion SSB-3b product of FIG. 2).
300)) and 75/2 Dur-O-Set® RB polymer.
5 is a graph comparing a sulfonated salt sensitive binder blended in a 5 ratio.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 33/02 A61F 13/18 307G D04H 1/58 (81) Designated country EP (AT, BE, CH, CY) , DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR), OA (BF, BJ, CF, CG, CI, CM, GA, GN , GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA CH, CN, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Branham Kelly D., USA Wisconsin 54986 Winnicon Crossroads 6661 (72) Inventor Lang Frederick Jay United States Wisconsin 54956 Nina Whitetail Drive 1541 (72) Inventor Mumic Pavneet S. United States New Jersey 08502 Bellmead Taggart Drive 1202 (72) Inventor Pumplan William Es United States North Carolina 27376 West End Fox Run Court 117 Seven Lakes North 928 (72) Inventor Chen Franklin Mc United States Wisconsin 54914 Appleton West Glendale Avenue 1820 (72) Inventor Jackson David M United States Georgia 30076 Roswell Summer Oak Drive 9825 (72) Inventor Johnson Eric Dee United States Wisconsin 54947 Larsen Grandview Road 5255 (72) Inventor Lindsey Jeffrey Dee United States Wisconsin 54913 Appleton Diane Lane 20 (72) Inventor Thick Kim Gee United States Wis Consin 54952 Menash First Street 527 (72) Inventor Santon United States Wisconsin 54956 Nina Gulf Bridge Drive 1715 Number 7 (72) Inventor Schulz Walter Tee United States Wisconsin 65915 Appleton Shepherd Lane North 9560 (72) Invention Inventor One Kennis Wye, United States of America 30005 Alpharetta Cutty Sarkway 292 (72) Inventor Serence Dave A, United States of America Georgia 30075 Roswell Brook Lane 191 F Term (Reference) 4C003 AA19 HA04 4C098 AA09 CC01 CE06 DD05 DD10 DD23 4J002 BB06X BC06X BG01W BG02W BG13W BN14X GK02 4J100 AJ02P AK12Q AL02R AM00R AM15R AM17R AM19R CA03 CA05 DA25 JA11 4L047 AA08 AA12 AA17 AA21 AA23 BA15 BA21 BC07 CB01 CB07 CB10 CC04 CC05 CC16

Claims (188)

[Claims] 1. A polymer formulation comprising a salt sensitive binder and a cobinder, the polymer formulation comprising at least about 1 monovalent ion.
A polymer formulation having wet strength in a neutral salt solution containing weight percent salt and dispersible in hard or soft water. 2. A polymer formulation comprising a salt sensitive binder and a co-binder, the polymer formulation being insoluble in water that does not contain a sufficient amount of the first salt,
A polymer formulation that is soluble in water containing a solubilizing amount of a second salt that is different from the first salt. 3. A polymer preparation comprising an ion-sensitive polymer and a cobinder polymer dispersed in the ion-sensitive polymer, the polymer preparation being adapted to be ion-sensitive. Polymer formulation. 4. The polymer formulation according to claim 3, wherein each of the polymers has a Tg, and the Tg of the cobinder polymer is lower than the Tg of the ion-sensitive polymer. 5. The polymer formulation of claim 3, wherein the cobinder polymer is of a type that renders the polymer formulation sprayable and is present in a sprayable amount. 6. The ion-sensitive polymer is a terpolymer made of monomers capable of free radical polymerization into terpolymers, the monomers being selected from acrylic acid monomers and alkyl acrylate monomers. The polymer preparation according to claim 3, which is characterized in that 7. The polymer formulation according to claim 3, wherein the acrylic acid monomer is selected from acrylic acid and methacrylic acid. 8. The alkyl acrylate monomer has 1 to 1 carbon atoms.
The polymer preparation according to claim 6, which is selected from acrylic acid esters and methacrylic acid esters having an alkyl group which is 8 or a cycloalkyl group which has 3 to 18 carbon atoms. 9. Polymer formulation according to claim 6, characterized in that the acrylic ester monomer is selected from acrylamide and methacrylamide based monomers. 10. The acrylic ester monomer is acrylamide and N, N-dimethylacrylamide and N-ethylacrylamide and N-isopropylacrylamide and hydroxymethylacrylamide, N-vinylpyrrolidinone, N-vinylformamide, and hydroxy acrylic acid. Polymer formulation according to claim 6, characterized in that it is selected from alkyl and hydroxyalkyl methacrylate. 11. The polymer formulation according to claim 6, wherein the acrylate ester monomer is selected from hydroxyethyl methacrylate and hydroxyethyl acrylate. 12. The polymer preparation according to claim 3, wherein the ion-sensitive polymer is a terpolymer containing acrylic acid, butyl acrylate, and 2-ethylhexyl acrylate. 13. The polymer preparation according to claim 3, wherein the cobinder polymer is non-crosslinked. 14. The polymer formulation of claim 3, wherein the cobinder polymer is not water soluble. 15. The co-binder polymer is selected from non-crosslinked poly (ethylene-vinyl acetate), non-crosslinked poly (styrene-butadiene), and non-crosslinked poly (styrene-acrylic). The polymer preparation according to item 3. 16. Polymer formulation according to claim 3, characterized in that the cobinder polymer is in the form of an emulsion. 17. The polymer formulation of claim 3, wherein the co-binder polymer has a molecular weight of about 500,000 to about 200,000,000. 18. 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. The polymer preparation according to claim 3. 19. The polymer formulation is insoluble in a neutral salt solution containing at least about 1 weight percent salt containing one or more monovalent ions, up to about 200 ppm of one or The ion-sensitive polymer preparation according to claim 3, which is soluble in water containing more polyvalent ions. 20. The ion sensitive polymer formulation of claim 19, wherein the polymer formulation is soluble in water containing from about 15 ppm to about 200 ppm of one or more polyvalent ions. . 21. The ion-sensitive polymer formulation of claim 19, wherein the polymer formulation is soluble in water containing from about 15 ppm to about 150 ppm of one or more polyvalent ions. . 22. The ion-sensitive polymer formulation of claim 19, wherein the polymer formulation is soluble in water containing from about 15 ppm to about 100 ppm of one or more polyvalent ions. . 23. The ion-sensitive polymer formulation of claim 19, wherein the polymer formulation is soluble in water containing from about 15 ppm to about 50 ppm of one or more multivalent ions. . 24. The ion-sensitive polymer formulation of claim 19, wherein the polymer formulation is soluble in water containing less than about 10 ppm of one or more polyvalent ions. 25. The ion-sensitizer of claim 19, wherein the polymer formulation is insoluble in a neutral salt solution containing from about 1 weight percent to about 5.0 weight percent salt. Polymer formulation. 26. The polymer is from about 1 weight percent to about 3.0 weight percent.
20. Insoluble in a neutral salt solution containing up to 18 salts.
The ion-sensitive polymer preparation according to 1. 27. The ion-sensitive polymer preparation according to claim 19, wherein the polyvalent ions include Ca ²⁺ ions, Mg ²⁺ ions, Zn ²⁺ ions, or a combination thereof. 28. The ion-sensitive polymer preparation according to claim 19, wherein the monovalent ions include Na ⁺ ions, Li ⁺ ions, K ⁺ ions, NH ₄ ⁺ ions, or a combination thereof. . 29. The ion-sensitive polymer preparation according to claim 3, wherein the ion-sensitive polymer comprises a sulfonate anion-modified acrylic acid terpolymer. 30. The sulfonate anion-modified acrylic acid terpolymer,
Formed from four monomers: acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal and organic amine salts, butyl acrylate, and 2-ethylhexyl acrylate. 30. The ion-sensitive polymer preparation according to claim 29. 30. The sulfonate anion-modified acrylic acid terpolymer,
About 35 to less than 80 mole percent acrylic acid, more than 0 to about 20 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal salts and organic amine salts, more than 0 to about Up to 65 mole percent butyl acrylate and greater than 0 up to about 45 mole percent acrylic acid 2-
30. The ion-sensitive polymer preparation according to claim 29, which contains ethylhexyl. 31. The sulfonate anion-modified acrylic acid terpolymer,
From about 50 to less than 67 mole percent acrylic acid, from greater than 0 to about 10 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal and organic amine salts, from about 15 to about Up to 28 mole percent butyl acrylate and about 7 to about 15 mole percent acrylic acid 2
-Ion-sensitive polymer formulation according to claim 29, characterized in that it comprises ethylhexyl. 32. The sulfonate anion-modified acrylic acid terpolymer,
About 57 to less than 66 mole percent acrylic acid, about 1 to about 6 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal and organic amine salts, about 15 to about Up to 28 mole percent butyl acrylate and about 7 to about 13 mole percent acrylic acid 2-
30. The ion-sensitive polymer preparation according to claim 29, which contains ethylhexyl. 33. An ion sensitive polymer formulation comprising a sulfonate anion modified acrylic acid copolymer and a latex, wherein the polymer formulation comprises at least 1 weight percent salt comprising one or more monovalent cations. An ion-sensitive polymer preparation characterized in that it is insoluble in a salt solution containing and is soluble in water containing 50 ppm of calcium and magnesium ions in a 2: 1 ratio. 34. The ion-sensitive polymer preparation according to claim 33, wherein the latex is non-crosslinked. 35. The ion-sensitive polymer preparation according to claim 33, wherein less than 50% of the latex is crosslinked. 36. The ion-sensitive polymer formulation of claim 33, wherein less than 20% of the latex is crosslinked. 37. The latex is uncrosslinked poly (ethylene-vinyl acetate).
34. The ion-sensitive polymer preparation according to claim 33, comprising: 38. An ion-sensitive polymer formulation comprising a sulfonate anion-modified acrylic acid copolymer and a latex, wherein the polymer formulation comprises at least about 1 weight percent comprising one or more monovalent cations. An ion-sensitive polymer formulation, characterized in that it is insoluble in salt solutions containing salts and soluble in water containing 100 ppm of calcium and magnesium ions in a 2: 1 ratio. 39. An ion-sensitive polymer formulation comprising a sulfonate anion-modified acrylic acid copolymer and a latex, wherein the polymer formulation comprises at least about 1 weight percent comprising one or more monovalent cations. An ion-sensitive polymer formulation, characterized in that it is insoluble in a salt solution containing salts and soluble in water containing 150 ppm of calcium and magnesium ions in a 2: 1 ratio. 40. An ion sensitive polymer formulation comprising a sulfonate anion modified acrylic acid copolymer and a latex, wherein the polymer formulation comprises at least about 1 weight percent comprising one or more monovalent cations. An ion-sensitive polymer formulation, characterized in that it is insoluble in a salt solution containing salts and soluble in water containing 200 ppm of calcium and magnesium ions in a 2: 1 ratio. 41. The ion-sensitive polymer of claim 38, wherein the polymer formulation is soluble in water containing from about 15 ppm to about 100 ppm of one or more polyvalent cations. Formulation. 42. The ion sensitive polymer formulation of claim 33, wherein the polymer formulation is soluble in water containing less than about 10 ppm of one or more polyvalent cations. 43. The polymer formulation is insoluble in a salt solution containing from about 1 weight percent to about 5 weight percent salt.
3. The ion-sensitive polymer preparation according to item 3. 44. The polymer formulation is insoluble in a salt solution containing from about 3 weight percent to about 5 weight percent salt.
3. The ion-sensitive polymer preparation according to item 3. 45. The ion-sensitive polymer formulation of claim 33, wherein the polymer formulation is insoluble in a salt solution containing about 4 weight percent sodium chloride. 46. The ion-sensitive polymer formulation of claim 33, wherein the polymer formulation is insoluble in salt solution over a pH range of about 3 to about 8. 47. The ion-sensitive polymer formulation of claim 33, wherein the polymer formulation is insoluble in salt solution over a pH range of about 4 to about 7. 48. The ion-sensitive polymer preparation according to claim 33, wherein the polymer preparation is insoluble in a salt solution having a pH of 5. 49. The ion-sensitive polymer formulation of claim 33, wherein the salt solution has a pH of about 3.5 to about 7. 50. The ion-sensitive polymer preparation according to claim 33, wherein the salt solution has a pH of 4.2 to 6.1. 51. The polymer of claim 3, wherein the polymer is insoluble in a salt solution containing from about 1 weight percent to about 3.0 weight percent salt.
3. The ion-sensitive polymer preparation according to item 3. 52. The ion sensitive polymer of claim 33, wherein the copolymer is prepared by sulfonation of a polymer having a molecular weight greater than about 100,000. 53. The ion-sensitive polymer formulation of claim 33, wherein the copolymer is prepared by polymerizing monomers, including sulfonate-containing monomers. 54. The ion-sensitive polymer preparation according to claim 33, wherein the copolymer is a terpolymer. 55. The sulfonate-containing monomer is acrylamidopropanesulfonic acid, 2-methyl-2-propanesulfonic acid, vinyl sulfonate, styrenesulfonic acid, 2-sulfopropyl methacrylate and 3-sulfopropyl acrylate, And selected from organic salts or inorganic salts thereof.
3. The ion-sensitive polymer preparation according to item 3. 56. A latex that is one of a sulfonate anion-modified acrylic acid copolymer and one prepared without the addition of a cross-linking agent, one that is non-cross-linked, or one that is substantially cross-linked dried. An ion-sensitive polymer formulation comprising and wherein the polymer formulation is insoluble in a salt solution containing at least about 1 weight percent salt containing one or more monovalent cations and at least 50 ppm. An ion-sensitive polymer preparation characterized in that it is soluble in water containing a divalent cation. 57. The latex is uncrosslinked poly (ethylene-vinyl acetate).
57. The ion-sensitive polymer preparation according to claim 56, wherein 58. The divalent cation is Ca ²⁺ ion, Mg ²⁺ ion, Z.
^57. The ion-sensitive polymer formulation of claim 56, comprising ^{n2 +} ions, or a combination thereof. 59. The divalent cation contains Ca ²⁺ ions and Mg ²⁺ ions in a 2: 1 ratio, and the monovalent cation is Na ^+. The ion-sensitive polymer preparation according to 1. 60. The monovalent cation is Na ⁺ ion, Li ⁺ ion, K ⁺
57. Ions, NH ₄ ⁺ ions, or combinations thereof.
The ion-sensitive polymer preparation according to 1. 61. The method of claim 56, wherein the acrylic acid copolymer is a terpolymer prepared with acrylic acid or methacrylic acid or a combination thereof and one or more alkyl acrylates. Ion-sensitive polymer formulation. 62. The sulfonate anion-modified acrylic acid terpolymer,
Formed from four monomers: acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal and organic amine salts, butyl acrylate, and 2-ethylhexyl acrylate. 62. An ion sensitive polymer according to claim 61. 63. The sulfonate anion modified acrylic acid terpolymer
62. The ion-sensitive polymer formulation of claim 61, which is formed from four monomers: acrylic acid, AMPS or NaAMPS, butyl acrylate, and 2-ethylhexyl acrylate. 64. The sulfonate anion-modified acrylic acid terpolymer,
About 57 to less than 66 mole percent acrylic acid, about 1 to about 6 mole percent AMPS or NaAMPS, about 15 to about 28 mole percent butyl acrylate, and about 7 to about 13 mole percent acrylic. Acid 2-
62. The ion-sensitive polymer formulation of claim 61, which comprises ethylhexyl. 65. The ion-sensitive polymer preparation according to claim 56, wherein the ion-sensitive polymer is an acrylic acid terpolymer. 66. The ion-sensitive polymer formulation of claim 65, wherein the acrylic acid terpolymer comprises acrylic acid or methacrylic acid or a combination thereof and one or more alkyl acrylates. . 67. The acrylic acid terpolymer comprises three monomers, namely:
66. The ion-sensitive polymer formulation of claim 65, formed from acrylic acid, butyl acrylate, and 2-ethylhexyl acrylate. 68. The acrylic terpolymer comprises from about 35 to less than 80 mole percent acrylic acid, greater than 0 to about 65 mole percent butyl acrylate, and greater than 0 to about 45 mole percent acrylic acid. 66. The ion-sensitive polymer formulation according to claim 65, comprising 2-ethylhexyl. 69. The acrylic acid terpolymer comprises from about 50 to less than 67 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 15 mole percent acrylic acid. 66. The ion-sensitive polymer formulation according to claim 65, comprising 2-ethylhexyl. 70. The acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 13 mole percent acrylic acid. 66. The ion-sensitive polymer formulation according to claim 65, comprising 2-ethylhexyl. 71. The ion sensitive polymer formulation of claim 56, wherein the sulfonate anion modified acrylic acid copolymer comprises about 65 to 75 weight percent. 72. The ion sensitive polymer formulation of claim 56, wherein the latex comprises about 25 to 35 weight percent. 73. The method of claim 56, wherein the sulfonate anion modified acrylic acid copolymer comprises about 55 to 99 weight percent and the latex comprises about 1 to 45 weight percent. Ion-sensitive polymer formulation. 74. A binder composition for bonding fibrous materials into a unitary web, the binder composition comprising the ion-sensitive polymer formulation of claim 56. A binder composition comprising: 75. A non-woven fabric comprising a fibrous material and a binder material, the binder material comprising the ion-sensitive polymer formulation of claim 56. 76. An ion sensitive polymer formulation comprising an acrylic acid terpolymer and uncrosslinked poly (ethylene-vinyl acetate), wherein the polymer formulation comprises at least about 0 monovalent ions. Ion-sensitive polymer characterized by being insoluble in a neutral salt solution containing 3 weight percent salt and soluble in water containing less than about 10 ppm of one or more polyvalent ions. Formulation. 77. The polymer formulation comprises from about 0.3 weight percent to about 5.
77. The ion-sensitive polymer formulation of claim 76, which is insoluble in a neutral monovalent salt solution containing up to 0 weight percent salt. 78. The method of claim 76, wherein the polymer is insoluble in a neutral monovalent salt solution containing from about 0.5 weight percent to about 3.0 weight percent salt. The ion-sensitive polymer preparation described. 79. The ion-sensitive polymer preparation according to claim 76, wherein the polyvalent ions include Ca ²⁺ ions, Mg ²⁺ ions, Zn ²⁺ ions, or a combination thereof. 80. The ion-sensitive polymer preparation according to claim 76, wherein the monovalent ions include Na ⁺ ions, Li ⁺ ions, K ⁺ ions, NH ₄ ⁺ ions, or a combination thereof. . 81. The ion-sensitive polymer formulation of claim 76, wherein the acrylic acid terpolymer comprises acrylic acid or methacrylic acid or a combination thereof and one or more alkyl acrylates. . 82. The acrylic acid terpolymer comprises three monomers, namely:
77. The ion-sensitive polymer formulation of claim 76, formed from acrylic acid, butyl acrylate, and 2-ethylhexyl acrylate. 83. The acrylic terpolymer comprises from about 35 to less than 80 mole percent acrylic acid, from greater than 0 to about 65 mole percent butyl acrylate, and from greater than 0 to about 45 mole percent acrylic acid. 77. The ion-sensitive polymer formulation according to claim 76, comprising 2-ethylhexyl. 84. The acrylic acid terpolymer comprises from about 50 to less than 67 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 15 mole percent acrylic acid. 77. The ion-sensitive polymer formulation according to claim 76, comprising 2-ethylhexyl. 85. The acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 13 mole percent acrylic acid. 77. The ion-sensitive polymer formulation according to claim 76, comprising 2-ethylhexyl. 86. The ion-sensitive polymer formulation of claim 76, wherein the acrylic acid terpolymer comprises about 65 to about 75 weight percent. 87. The ion-sensitive polymer formulation of claim 76, wherein the uncrosslinked poly (ethylene-vinyl acetate) comprises about 25 to about 35 weight percent. 88. The uncrosslinked poly (ethylene-vinyl acetate) is about 1 to 4
77. The ion-sensitive polymer formulation of claim 76, which comprises 5 weight percent. 89. The acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 13 mole percent acrylic acid. Including 2-ethylhexyl, wherein the acrylic acid terpolymer comprises about 65 to about 75 weight percent and the uncrosslinked poly (ethylene-vinyl acetate) comprises about 25 to about 35 weight percent. 77. The ion-sensitive polymer formulation of claim 76. 90. A binder composition for bonding fibrous materials into a unitary web, the binder composition comprising the ion-sensitive polymer formulation of claim 76. A binder composition comprising: 91. A non-woven fabric comprising a fibrous material and a binder material, the binder material comprising the ion-sensitive polymer formulation of claim 76. 92. Three monomers, namely acrylic acid, butyl acrylate,
And a first polymer formed from 2-ethylhexyl acrylate and a second polymer containing uncrosslinked poly (ethylene-vinyl acetate), wherein the polymer preparation is one Or more monovalent ions insoluble in a neutral salt solution containing at least about 0.3 weight percent salt, wherein the polymer is less than about 10 ppm of one or more polyvalent ions. An on-sensitive polymer preparation characterized by being soluble in water containing 93. The first polymer comprises about 35 to less than 80 mole percent acrylic acid, greater than 0 to about 65 mole percent butyl acrylate,
93. The ion-sensitive polymer formulation of claim 92, further comprising greater than 0 up to about 45 mole percent 2-ethylhexyl acrylate. 94. The first polymer comprises about 50 to less than 67 mole percent acrylic acid, about 15 to about 28 mole percent butyl acrylate, and about 7 to about 15 mole percent acrylic acid. 93. The ion-sensitive polymer formulation according to claim 92, which comprises 2-ethylhexyl. 95. The first polymer comprises about 57 to less than 66 mole percent acrylic acid, about 15 to about 28 mole percent butyl acrylate, and about 7 to about 13 mole percent acrylic acid. 93. The ion-sensitive polymer formulation according to claim 92, which comprises 2-ethylhexyl. 96. The second polymer of claim 92, wherein the second polymer comprises from about 25 to about 35 weight percent uncrosslinked poly (ethylene-vinyl acetate).
The ion-sensitive polymer preparation according to 1. 97. The ion-sensitive polymer formulation of claim 92, wherein the second polymer comprises from about 1 to about 45 weight percent uncrosslinked poly (ethylene-vinyl acetate). 98. The acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 13 mole percent acrylic acid. 94. The compound of claim 92, comprising 2-ethylhexyl, wherein the first polymer comprises about 65 to about 75 mole percent and the second polymer comprises about 25 to about 35 weight percent. The ion-sensitive polymer preparation described. 99. A binder composition for bonding fibrous materials into a unitary web, the binder composition comprising the ion-sensitive polymer formulation of claim 92. A binder composition comprising: 100. A non-woven fabric comprising a fibrous material and a binder material, the binder material comprising the ion-sensitive polymer formulation of claim 92. 101. A neutral salt comprising an acrylic acid terpolymer in combination with an uncrosslinked poly (ethylene-vinyl acetate) containing at least about 0.3 weight percent salt containing one or more monovalent ions. Is insoluble in the salt solution of
A method of making an ion-sensitive polymer formulation that is soluble in water containing less than ppm of one or more polyvalent ions. 102. The method of claim 101, wherein the acrylic acid terpolymer comprises acrylic acid or methacrylic acid or a combination thereof and one or more alkyl acrylates. 103. The method of claim 101, wherein the acrylic acid terpolymer is formed from three monomers: acrylic acid, butyl acrylate, and 2-ethylhexyl acrylate. 104. The acrylic acid terpolymer comprises from about 35 to less than 80 mole percent acrylic acid, from greater than 0 to about 65 mole percent butyl acrylate, and from greater than 0 to about 45 mole percent acrylic acid. 102. The method of claim 101, comprising 2-ethylhexyl. 105. The acrylic acid terpolymer comprises from about 50 to less than 67 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 15 mole percent acrylic acid. 102. The method of claim 101, comprising 2-ethylhexyl. 106. The acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 13 mole percent acrylic acid. 102. The method of claim 101, comprising 2-ethylhexyl. 107. The method of claim 101, wherein the acrylic acid terpolymer comprises about 65 to 75 weight percent. 108. The method of claim 101, wherein the uncrosslinked poly (ethylene-vinyl acetate) comprises about 25 to about 35 weight percent. 109. The method of claim 101, wherein the uncrosslinked poly (ethylene-vinyl acetate) comprises about 1 to about 45 weight percent. 110. The acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 15 to about 28 mole percent butyl acrylate, and from about 7 to about 13 mole percent acrylic acid. Including 2-ethylhexyl, the acrylic acid terpolymer comprises about 65 to about 75 weight percent, and the uncrosslinked poly (ethylene-vinyl acetate) comprises about 25 to about 35.
102. The method of claim 101, which comprises a weight percentage. 111. A fibrous material; and a binder composition comprising an acrylic acid terpolymer and uncrosslinked poly (ethylene-vinyl acetate) for bonding the fibrous material into a unitary web. The binder composition comprises at least about 0.1 of one or more monovalent ions.
Is insoluble in a neutral salt solution containing 3 weight percent salt and the polymer is soluble in water containing less than about 10 ppm of one or more polyvalent ions. Fiber base layer. 112. The binder composition comprises from about 0.3 weight percent to about 5 weight percent.
． 112. The fibrous base layer of claim 111, which is insoluble in a neutral monovalent salt solution containing up to 0 weight percent salt. 113. A water dispersible article comprising the fibrous base layer of claim 111. 114. A method of making an ion-sensitive polymer formulation, comprising the step of dispersing a cobinder polymer in the ion-sensitive polymer, thereby rendering the polymer formulation ion-sensitive. And how to. 115. The polymer formulation is insoluble in a neutral salt solution containing at least about 1 weight percent salt containing one or more monovalent ions, up to about 200 ppm of one or 115. The method of claim 114, wherein the method is soluble in water containing more multivalent ions. 116. The method of claim 114, wherein each of the polymers has a Tg, and the Tg of the cobinder polymer is lower than the Tg of the ion-sensitive polymer. 117. The method of claim 114, wherein the cobinder polymer is of a type that renders the polymer formulation sprayable and is present in a sprayable amount. 118. The method of claim 114, wherein the cobinder polymer is uncrosslinked. 119. The method of claim 114, wherein the cobinder polymer is not water soluble. 120. The co-binder polymer is uncrosslinked poly (ethylene-
115. The method of claim 114, wherein the method is selected from vinyl acetate), non-crosslinked poly (styrene-butadiene), and non-crosslinked poly (styrene-acrylic). 121. The molecular weight of the cobinder polymer is about 500,000.
115. The method of claim 114, wherein the method is from about 200,000,000 to about 200,000,000. 122. 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. The method of claim 114. 123. The method of claim 114, wherein the ion sensitive polymer is selected from acrylic acid terpolymers and sulfonate anion modified acrylic acid terpolymers. 124. The method of claim 114, wherein the ion sensitive polymer is a sulfonate anion modified acrylic acid terpolymer. 125. The sulfonate anion-modified acrylic acid terpolymer is acrylic acid or methacrylic acid or a combination thereof, 2-acrylamido-2-
125. The method of claim 124, comprising methyl-1-propanesulfonic acid and its alkaline earth metal salts and organic amine salts, and one or more alkyl acrylates. 126. The sulfonate anion modified acrylic terpolymer is formed from four monomers: acrylic acid, AMPS or NaAMPS, butyl acrylate, and 2-ethylhexyl acrylate. The method of claim 124. 127. The co-binder polymer is an uncrosslinked poly (ethylene-
115. The method of claim 114, wherein the method is selected from vinyl acetate), non-crosslinked poly (styrene-butadiene), and non-crosslinked poly (styrene-acrylic). 128. The co-binder polymer is an uncrosslinked poly (ethylene-
115. The method of claim 114, wherein the method is vinyl acetate). 129. Four monomers, namely acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal salts and organic amine salts, butyl acrylate, and 2-ethylhexyl acrylate. And a second polymer selected from non-crosslinked poly (ethylene-vinyl acetate), non-crosslinked poly (styrene-butadiene), and non-crosslinked poly (styrene-acrylic). An ion-sensitive polymer formulation, wherein the polymer formulation is insoluble in a neutral salt solution containing at least about 1 weight percent salt containing one or more monovalent ions, wherein the polymer is , An on-sensitive polymer, characterized by being soluble in water containing up to about 200 ppm of one or more polyvalent ions Agent. 130. A binder composition for bonding fibrous materials into a unitary web, the binder composition comprising the ion-sensitive polymer formulation of claim 129. A binder composition comprising: 131. A non-woven fabric comprising a fibrous material and a binder material, the binder material comprising the ion-sensitive polymer formulation of claim 129. 132. A first polymer formed from four monomers, acrylic acid, butyl acrylate, and 2-ethylhexyl acrylate, and non-crosslinked poly (ethylene-vinyl acetate), non-crosslinked poly (styrene-). Butadiene) and a second polymer selected from non-crosslinked poly (styrene-acrylic), the ion-sensitive polymer formulation comprising at least one monovalent ion. Characterized by being insoluble in a neutral salt solution containing about 1 weight percent salt, the polymer being soluble in water containing up to about 200 ppm of one or more polyvalent ions. On-sensitive polymer formulation. 133. A binder composition for bonding fibrous materials into a unitary web, the binder composition comprising the ion-sensitive polymer formulation of claim 132. A binder composition comprising: 134. A non-woven fabric comprising a fibrous material and a binder material, the binder material comprising the ion-sensitive polymer formulation of claim 132. 135. A method of making an ion-sensitive polymer formulation, the method comprising:
A first polymer formed from one monomer, namely acrylic acid, butyl acrylate, and 2-ethylhexyl acrylate, and non-crosslinked poly (ethylene-vinyl acetate), non-crosslinked poly (styrene-butadiene), and non-crosslinked Neutral in combination with a second polymer selected from poly (styrene-acrylic), whereby said polymer formulation contains at least about 1 weight percent salt containing one or more monovalent ions. Of the polymer is insoluble in a salt solution of about 200 p
A method comprising rendering soluble in water containing up to pm one or more multiply charged ions. 136. A fibrous material; a binder composition for bonding the fibrous material into an integrated web comprising an ion-sensitive polymer and a cobinder polymer dispersed in the ion-sensitive polymer; The binder composition is insoluble in a neutral salt solution containing at least about 1 weight percent salt containing one or more monovalent ions, the polymer comprising:
A fibrous base layer, which is soluble in water containing up to about 200 ppm of one or more multiply charged ions. 137. The binder composition comprises from about 1 weight percent to about 5.0.
138. The fibrous base layer of claim 136, which is insoluble in a neutral monovalent salt solution containing up to weight percent salt. 138. A fibrous material; and a binder composition comprising a salt sensitive polymer for binding the fibrous material into a unitary web, wherein the binder composition comprises one or more thereof. Insoluble in neutral salt solutions containing at least about 1 weight percent salt containing the above monovalent ions and soluble in water containing up to about 200 ppm of one or more polyvalent ions. , A fiber base layer. 139. The fibrous base layer of claim 138, wherein the binder composition further comprises a cobinder polymer. 140. The fibrous base layer of claim 138, wherein the cobinder polymer is dispersed in the salt sensitive polymer. 141. A fiber material, a sulfonate anion-modified acrylic acid terpolymer and an uncrosslinked poly (ethylene-
A binder composition for binding said fibrous material into a unitary web, comprising vinyl acetate), said binder composition comprising at least about one or more monovalent ions. A fibrous base layer which is insoluble in a neutral salt solution containing 1 weight percent salt and soluble in water containing up to about 200 ppm of one or more polyvalent ions. 142. The binder composition comprises from about 15 ppm to about 200 ppm.
144. The fibrous base layer of claim 141, which is soluble in water containing one or more multivalent ions up to. 143. The binder composition comprises from about 15 ppm to about 150 ppm.
144. The fibrous base layer of claim 141, which is soluble in water containing one or more multivalent ions up to. 144. The binder composition comprises from about 15 ppm to about 100 ppm.
144. The fibrous base layer of claim 141, which is soluble in water containing one or more multivalent ions up to. 145. The fibrous base layer of claim 141, wherein the binder composition is soluble in water containing from about 15 ppm to about 50 ppm of one or more multiply charged ions. 146. 141. The binder composition of claim 141, wherein the binder composition is soluble in water containing less than about 10 ppm of one or more multiply charged ions.
The fiber base layer according to 1. 147. The binder composition comprises from about 1 weight percent to about 5.0.
142. The fibrous base layer of claim 141, which is insoluble in neutral salt solutions containing up to weight percent salt. 148. The binder composition comprises from about 1 weight percent to about 3.0.
142. The fibrous base layer of claim 141, which is insoluble in neutral salt solutions containing up to weight percent salt. 149. The fiber base layer of claim 141, wherein the polyvalent ions include Ca ²⁺ ions, Mg ²⁺ ions, Zn ²⁺ ions, or a combination thereof. 150. The monovalent ion is Na ⁺ ion, Li ⁺ ion, K ⁺
Ion, NH ₄ ⁺ ion, or a combination thereof.
The fiber base layer according to 1. 151. The fibrous base layer of claim 141, wherein the acrylic acid terpolymer comprises at least one of acrylic acid and methacrylic acid and one or more alkyl acrylates. 152. The sulfonate anion-modified acrylic acid terpolymer comprises acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal salts and organic amine salts, butyl acrylate, and 144. The fibrous base layer of claim 141, formed from at least four monomers selected from 2-ethylhexyl acrylate. 153. The sulfonate anion-modified acrylic acid terpolymer is acrylic acid, AMPS, NaAMPS, butyl acrylate, and acrylic acid 2
144. The fibrous base layer of claim 141 formed from at least four monomers selected from ethylhexyl. 154. The sulfonate anion-modified acrylic acid terpolymer comprises from about 35 to less than 80 mole percent acrylic acid, greater than 0 to about 20 mole percent 2-acrylamido-2-methyl-1-propane sulfone. Acids and their alkaline earth metal and organic amine salts, greater than 0 up to about 65 mole percent butyl acrylate, and greater than 0 up to about 45 mole percent acrylic acid 2
-146. The fibrous base layer of claim 141, comprising -ethylhexyl. 155. The sulfonate anion modified acrylic acid terpolymer comprises from about 50 to less than 67 mole percent acrylic acid, greater than 0 to about 10 mole percent 2-acrylamido-2-methyl-1-propane sulfone. An acid and its alkaline earth metal and organic amine salts, about 15 to about 28 mole percent butyl acrylate, and about 7 to about 15 mole percent 2-ethylhexyl acrylate. Item 141. The fiber base layer according to Item 141. 156. The sulfonate anion-modified acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 1 to about 6 mole percent 2-acrylamido-2-methyl-1-propane sulfone. Acids and their alkaline earth metal and organic amine salts, about 15 to about 28 mole percent butyl acrylate, and about 7 to about 13 mole percent acrylic acid 2
-146. The fibrous base layer of claim 141, comprising -ethylhexyl. 157. The fibrous base layer of claim 141, wherein the binder composition comprises from about 65 to about 75 weight percent sulfonate anion-modified acrylic acid terpolymer. 158. 141. The binder composition of claim 141, wherein the binder composition comprises from about 55 to 99 weight percent uncrosslinked poly (ethylene-vinyl acetate).
The fiber base layer according to 1. 159. The binder composition of claim 14, wherein the binder composition comprises from about 25 to about 35 weight percent uncrosslinked poly (ethylene-vinyl acetate).
The fiber base layer according to 1. 160. The sulfonate anion modified acrylic acid terpolymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 1 to 6 mole percent AMPS or NaAMPS, from about 15 to about 28 mole percent. Butyl acrylate and about 2 to about 13 mole percent acrylic acid 2-
Comprising ethylhexyl, wherein the binder composition comprises from about 65 to 75 weight percent of the sulfonate anion modified acrylic acid terpolymer and from about 25 to 35 weight percent of the uncrosslinked poly (ethylene-vinyl acetate). 146. The fiber base layer according to claim 141. 161. The fibrous base layer of claim 141, wherein the fibrous material comprises one or more layers of woven, non-woven, knit, or combinations thereof. 162. The fibrous base layer of claim 141, wherein the fibrous material comprises one or more layers of non-woven fabric. 163. The fibrous base layer of claim 141, wherein the fibrous material comprises fibers having a length of about 15 mm or less. 164. The fibrous base layer of claim 141, wherein the fibrous material comprises natural fibers, synthetic fibers, or combinations thereof. 165. One or more fibers wherein the fibrous material comprises cotton, flax, jute, hemp, wool, wood pulp, viscose rayon, cupra rayon, cellulose acetate, polyester, polyamide, and polyacrylic. 146. The fiber base layer according to claim 141, comprising: 166. The fibrous base layer of claim 141, wherein the fibrous material comprises wood pulp. 167. A fiber material, selected from acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and its alkaline earth metal salts and organic amine salts, butyl acrylate, and 2-ethylhexyl acrylate. For bonding the fibrous material into a unitary web comprising a first polymer formed from at least four monomers and a second polymer comprising uncrosslinked poly (ethylene-vinyl acetate). Agent composition,
Wherein the binder composition is insoluble in a neutral salt solution containing at least about 1 weight percent salt containing one or more monovalent ions, up to about 200 ppm of one or A fiber base layer, which is soluble in water containing more polyvalent ions. 168. The first polymer comprises about 35 to less than 80 mole percent acrylic acid, greater than 0 to about 20 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth thereof. 168. The compound of claim 167, comprising a group metal salt and an organic amine salt, greater than 0 to about 65 mole percent butyl acrylate, and greater than 0 to about 45 mole percent 2-ethylhexyl acrylate. Fiber base layer. 169. The first polymer comprises about 50 to less than 67 mole percent acrylic acid, greater than 0 to about 10 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth thereof. 168. The compound of claim 167, comprising a group metal salt and an organic amine salt, about 15 to about 28 mole percent butyl acrylate, and about 7 to about 15 mole percent 2-ethylhexyl acrylate. Fiber base layer. 170. The first polymer comprises from about 57 to less than 66 mole percent acrylic acid, from about 1 to about 6 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth thereof. Metal salts and organic amine salts, about 15 to about 28 mole percent butyl acrylate, and about 7
165. The fiber base layer of claim 167, comprising from 2 to about 13 mole percent 2-ethylhexyl acrylate. 171. The fibrous base layer of claim 167, wherein the first polymer is present in an amount of about 65 to about 75 weight percent. 172. The fibrous base layer of claim 167, wherein the second polymer is present in an amount of about 1 to 45 weight percent. 173. The binder composition of claim 16, wherein the binder composition comprises from about 25 to about 35 weight percent uncrosslinked poly (ethylene-vinyl acetate).
7. The fiber base layer according to 7. 174. The first polymer comprises about 57 to less than 66 mole percent acrylic acid, about 1 to about 6 mole percent AMPS or NaA.
MPS, about 15 to about 28 mole percent butyl acrylate, and about 7
To about 13 mole percent 2-ethylhexyl acrylate, wherein the binder composition comprises about 65 to about 75 weight percent of the first polymer and about 25 to about 35 weight percent of the second polymer. 166. The fibrous base layer of claim 167, comprising a polymer. 175. The binder composition comprises from about 1 weight percent to about 5.0.
168. The fibrous base layer of claim 167, which is insoluble in a neutral monovalent salt solution containing weight percent salt. 176. The fibrous base layer of claim 167, wherein the fibrous material comprises one or more layers of woven, non-woven, knit, or combinations thereof. 177. The fibrous base layer of claim 167, wherein the fibrous material comprises one or more layers of non-woven fabric. 178. The fibrous base layer of claim 167, wherein the fibrous material comprises fibers having a length of about 15 mm or less. 179. The fibrous base layer of claim 167, wherein the fibrous material comprises natural fibers, synthetic fibers, or combinations thereof. 180. One or more fibers wherein the fibrous material comprises cotton, flax, jute, hemp, wool, wood pulp, viscose rayon, cupra rayon, cellulose acetate, polyester, polyamide, and polyacrylic. 166. The fiber base layer of claim 167, comprising: 181. The fibrous base layer of claim 167, wherein the fibrous material comprises wood pulp. 182. A water dispersible article comprising the fibrous base layer of claim 167. 183. A water dispersible article comprising the fibrous base layer of claim 167. 184. A fiber material and four monomers, namely acrylic acid, butyl acrylate, and acrylic acid 2-.
A first polymer formed from ethylhexyl and non-crosslinked poly (ethylene-vinyl acetate), non-crosslinked poly (styrene-butadiene), and non-crosslinked poly (styrene-
A second polymer selected from acrylics) and a binder composition for binding the fibrous material into an integrated web, the binder composition comprising one or more Wherein the polymer is insoluble in a neutral salt solution containing at least about 1 weight percent salt containing monovalent ions, said polymer comprising:
A fibrous base layer, which is soluble in water containing up to about 200 ppm of one or more polyvalent ions. 185. A water dispersible article comprising the fibrous base layer of claim 184. 186. A method of making a fibrous base layer, the method comprising: combining an ion-sensitive polymer and a cobinder polymer dispersed in the ion-sensitive polymer to bond a fibrous material into a unitary web. Applying a binder composition to the fibrous material, wherein the binder composition comprises at least about 1 ion containing one or more monovalent ions.
A method which is insoluble in a neutral salt solution containing weight percent salt and wherein the polymer is soluble in water containing up to about 200 ppm of one or more polyvalent ions. . 187. The method of claim 186, wherein the binder composition is applied to the fiber material in the form of foam and is drawn into the fiber material by the action of reduced pressure air. 188. The binder composition is sprayed, applied by foaming, dipping the fiber material in a binder composition bath, curtain coating, passing the fiber material through a wet nip, the pre-weighed binder Applied in liquid form to the fibrous material by one of contacting a wet roll coated with the composition, pressing the fibrous material onto a deformable carrier containing the binder composition, and printing. 187. The method of claim 186, wherein the method is performed.