ES2320766T3 - FOAM ARTICLES OF HYDROPHYL POLYURETHANE THAT INCLUDE AN ANTIMICROBIAL COMPOUND. - Google Patents

Abstract

Foamed polyurethane articles, such as a sponges, sheets, tapes or ribbons, blocks or other molded, extruded or cast article which foamed polyurethane articles comprising one or more quaternary ammonium compounds having germicidal properties and are particularly useful in the formation of cleaning articles. Processes for the manufacture of such cleaning articles based on hydrophilic polyurethane foams exhibit an antimicrobial benefit and their use are also described.

Description

Hydrophilic polyurethane foam articles that They comprise an antimicrobial compound.

The present invention relates to articles that They have an antimicrobial benefit. More specifically this invention relates to hydrophilic foam articles having a antimicrobial benefit

Cleaning items are notoriously Old in the art. Popular cleaning items that are know include, for example, sponges, cleaning supplies with a cloth, cloths, rags, disposable paper towels, and the like. Generally, these items can be used with or without the adding a cleaning composition to locally treat a stained surface. Very often, such a cleaning composition includes one or more detersive surfactants, and optionally can Contain, which are frequently used with cleaning supplies. Such products are widely known and used. As to its use, a consumer sprays, pours, or does not apply a useful amount of said cleaning composition to a surface usually in the place of a stained or dirty hard surface, and to  then use the cleaning item to clean by rubbing wipe the surface and thereby remove dirt and surface spots. In general thereafter, the cleaning item can be reused, or optionally, Discard.

A problem inherent in the articles of cleaning that are used several times is that, very often provide a breeding ground for bacteria and others undesirable microorganisms. Such include gram microorganisms positive as well as gram negative microorganisms. So, so quite unnoticed, the cleaning item can be, in fact, an incubator for such undesirable microorganisms. Generally, such cleaning items are kept in a state wet, in general in an environment of room temperature (approx. 20 ° C), such are also typically suitable conditions to maintain the viability of such microorganisms. Even worse, when it is left unattended for some time the growth of undesirable micro-organisms increases the amount of these microorganisms that may come into contact with the user and with the surface to be treated after the Next use of the cleaning item.

The prior art has proposed various methods to control the growth of microorganisms undesirable in cleaning supplies, and in particular in sponges. Rubber-foam sponges are very popular and are widely used, typically based on regenerated cellulose, or based on one or more of a variety of expanded polymers such as expanded polyurethane. The natural sponges are also notoriously old, and are widely used as cleaning articles. A more modern approach to control the growth of undesirable microorganisms is described, by example, in US Pat. 6228389 describing a sponge, especially a regenerated cellulose sponge that is provided with a biocidal composition of low aqueous solubility. Low aqueous solubility provides an antimicrobial activity expanded to the sponge, particularly between uses. Another sponge is described in US Pat. 6287584 in which a sponge, such as a regenerated cellulose sponge is injected with a mass carrier that is poorly soluble in water, and where in such carrier mass It incorporates a polarization signal. The low aqueous viability of the carrier mass acts to provide a controlled release of the biocide inside the sponge particularly when the Sponge is kept in a wet condition between uses. The articles described in US Pat. 6375964 B1 disclose items made of closed cell hydrophobic foam that include a support material as a source for the controlled release of silver ions, silver ions that provide a disinfectant effect to a treated surface. Certain foam sponge items hydrophobic are described in US Pat. 4476251 whose foam it is prepared by mixing together a selected prepolymer reactant and water, and adding to the mixture before the formation of the foam a non-phonic surfactant, a quaternary ammonium compound and a silicon based surfactant. U.S. Pat. 5091102 describes a substantially flexible dry matrix and the result and article capable of cleaning a surface by removing dust and / or the organic film and returning to the surface substantially free static, suitable for use as a garment, air filter or felt, in which the dry matrix is uniformly coated with a sufficient amount of treatment solution to allow the matrix retain its substantially dry characteristics, said treatment solution comprising between about 25% and 75% of at least one glycol compound, between approximately 0.2% and 60% of a cationic surfactant, and antimicrobial compound and optionally up to about 45% of a non-surfactant phonic. U.S. Pat. 4389448 describes a flexible substrate of polyurethane foam impregnated with an effective amount of a conditioning agent and having on at least one surface of the same a print that is substantially removed from the substrate during the drying cycle thus indicating the consumer or user of the article that the conditioning agent substantially has been completely removed from the article during the course of drying cycle The contents of these patents are incorporated as a reference herein.

I know these provide certain benefits technicians, there is nevertheless a real and continuous need in the technique to further improve cleaning supplies, especially flexible cleaning items like sponges that provide a residual antimicrobial effect, particularly which is effective after a significant number of uses by a consumer. Accordingly, the present invention relates to this need in the art as well as refers to other needs that will become more apparent from reading the following descriptive memory.

Figure 1 represents an embodiment of a molded cleaning article according to the invention.

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Figures 2A and 2B represent two views of a further embodiment of a cleaning article according to the invention in the form of a multilayer cleaning article.

Figures 3A, 3B and 3C represent several views of an additional embodiment more than one cleaning article according to the invention in the form of a cleaning article tri-layer

In one aspect of the invention a expanded polyurethane composition that exhibits a benefit antimicrobial, which can be used to form articles of expanded polyurethane, as well as cleaning supplies.

In another aspect of the present invention, provides a cleaning article comprising a composition of expanded polyurethane that exhibits an antimicrobial benefit, such as a sponge, sheet, strip or tape, block or other item molded, extruded or cast, cleaning items that exhibit a antimicrobial benefit

In a further aspect of the invention, provides a cleaning article comprising a composition of expanded polyurethane that exhibits an antimicrobial benefit, in which the cleaning article comprises at least one layer of a fibrous substrate attached to a sponge formed from the expanded polyurethane composition.

A further aspect of the invention relates to to a procedure for manufacturing cleaning supplies, such as sponges, sheets, strips or tapes, blocks or other items molded, extruded or cast, cleaning items exhibiting An antimicrobial benefit.

A further aspect of the invention is directs a procedure to provide a benefit residual antimicrobial to a cleaning article comprising a expanded polyurethane composition.

Still a further aspect of the invention is refers to a procedure to clean and / or sanitize a surface that needs treatment, procedure that contemplates the steps of: providing a cleaning article comprising an expanded polyurethane composition, for example, sponges, sheets, tapes, blocks and other molded, extruded or castings, expanded polyurethane composition that exhibits a antimicrobial benefit; and, contact the aforementioned surface with said cleaning item to provide thus a cleaning and / or sanitizing effect to it.

In a further aspect of the invention, provides a procedure for cleaning treatment and / or hard surface disinfectant that contemplates the use of a cleaning article as described herein, in the that said cleaning item applies to the site of a stain or to an area in which the presence of a microorganism is suspected undesirable, for example a bacterium or a virus, and it is put into contact said surface with the cleaning article to eradicate  the undesirable microorganism.

These and other aspects of the invention, especially the preferred aspects will be more evident from of reading the following descriptive report.

The expanded polyurethane composition of the The present invention is particularly adapted to be used as a cleaning item or be used in the construction of a cleaning item, cleaning items that exhibit a residual antimicrobial benefit.

In one aspect, the present invention provides an expanded polyurethane composition that exhibits a benefit antimicrobial, said polyurethane composition comprising expanded hydrophilic:

0.001-10% by weight of one or more quaternary ammonium compounds that have germicidal properties generally distributed throughout the composition,

a detersive surfactant constituent that consists of one or more nonionic, cationic surfactants, zwitterionic, and amphoteric in an amount that does not exceed approximately 10% by weight,

in which the non-phonic surfactant is Select condensates of alkyl poly (alkylene oxide) phenols, condensation products of aliphatic alcohols with 1 to approximately 60 moles of an alkylene oxide, ethoxylates of primary and secondary linear and branched alcohols, alkoxy block copolymers, alkylmonoglycosides, alkyl polyglucosides and amine oxides,

in which the polyurethane composition expanded hydrophilic exhibits a density of at least 0.25 g / cm3,

formed by a process that includes the stages procedure of:

provide a reaction mixture that comprises at least one polyurethane prepolymer, said quaternary ammonium compound that has germicidal properties, and said detersive surfactant constituent consisting of one or more  nonionic, cationic, zwitterionic, and amphoteric surfactants; and subsequently form the hydrophilic polyurethane composition expanded, which, after at least twenty-five (25) cycles rinsing / squeezing, exhibits an elution of at least approximately 100 parts per million, preferably at least approximately 150 parts per million germicidal compounds of quaternary ammonium in the squeezed or drained fluid of the Article.

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Preferably said polyurethane composition expanded exhibits a density in the range of approximately 0.3-0.4 g / cm3, most desirably a density in the range of approximately 0.3-0.36 g / cm3. The expanded polyurethane composition contains necessarily a sufficient amount of ammonium compounds quaternary that have germicidal properties to confer a Antimicrobial benefit to the expanded polyurethane composition. Said expanded polyurethane composition preferably contains from about 0.1-10% by weight, more preferably about 0.3-10% by weight and what more preferably about 0.5-10% by weight of at least one quaternary ammonium compound that has Germicidal properties generally uniformly distributed by everywhere. The expanded polyurethane composition can be use only as hydrophilic foams that provide a benefit antimicrobial, as well as in the formation of cleaning supplies which may consist entirely, or only partially, of the expanded polyurethane composition that exhibits a benefit antimicrobial The expanded polyurethane compositions of the invention are hydrophilic, and are capable of absorbing water, as well as contain and release a quaternary ammonium compound that has Germicidal properties

The expanded polyurethane composition is formed advantageously of a prepolymer composition of polyurethane that is used to form a spongy article, especially a fluffy article that has properties hydrophilic The selection of the polyurethane prepolymer is not critical and it is expected that you can use any of a variety of polyurethane prepolymers known and commercially available. Hydrophilic polyurethane foam compositions of the present invention are prepared using a prepolymer of isocyanate protected polyether. Polyether prepolymers protected with isocyanate such as those described in the patent of USA No. 4,137,200 are suitable for use herein. invention. These prepolymers have a functionality of defined average isocyanate greater than 2. These prepolymers can be protect with aromatic isocyanates, such as, isocyanate diphenylmethane (MDI), or mixtures of MDI with toluene diisocyanate (TDI) and / or forms MDI polymers. Polyether prepolymers protected with isocyanates that have been found suitable for use in Practice of the present invention include prepolymers sold by  Hampshire Chemical Company the registered trademark HYPOLO. The examples include HYPOL FHP 3000, HYPOL FHP 2002, HYPOL FHP 3000, HYPOL FHP 4000, HYPOL FHP 5000, HYPOL X6100, HYPOL JT 6000, and HYPOL hydrogel. HYPOL FHP 4000 and HYPOL FHP 5000 prepolymers are derived from methylene diisocyanate. These resins have molecular weights in the interval of approximately 1300-1400 and have approximately 1.5-2.6 mEq / g of isocyanate groups free. After being in contact with a molar excess of water, these Isocyanate groups are hydrolyzed to release dioxide gas from carbon, thus expanding the resin without the need to add catalysts or blowing agents. Free amino groups formed by the hydrolysis reaction react with groups unhydrolyzed isocyanate to form urea groups with crosslinking, with additional isocyanurate groups to form urethane and stabilize the foam while enclosing a part of the water in excess in cell walls, where it acts to confer hydrophilic properties to the foam.

In addition to MDI or MDI with TDI, poly isocyanate Polymeric can be incorporated into the polyurethane prepolymer. The commercially available PAPI series manufactured by Dow Chemical Company is a family of polymeric MDI produced by the reaction of carbonyl chloride with a condensate aniline-formaldehyde. The PAPI family consists of mixtures of MDI and polymeric forms of phenyl isocyanates which they form the MDI that are linked together by methylene groups. Other example of a prepolymer protected with isocyanate used preferably in the present invention is ISO 247, a product of BASF Corporation. This prepolymer is formed from approximately two thirds polyether polyol and one third of isocyanate The polyol is about 75 percent by weight of ethylene oxide and about 25% by weight of Propylene with a trifunctional initiator. The isocyanate comprises a combination of diphenylmethane diisocyanate (MDI) and another MDI polymeric ISO 247 prepolymers have a weight percentage of NCO of 10.15%.

The amount of polyurethane prepolymer in the reaction mixture used to prepare the foam composition Hydrophilic polyurethane is not particularly critical, but it depends of a number of factors, which include the proportion of others components in the reactant composition as described in more detail later. However, there must be enough polyurethane prepolymer to form a polyurethane foam. Polyurethane prepolymers can be used alone or in combination.

The polyurethane prepolymer is sponged in the presence of an aqueous component, preferably water, in the conventional manner known in the art. The aqueous component may also be an aqueous porridge or suspension, an aqueous emulsion, or an aqueous solution having the water soluble materials disposed therein. Having the reaction mixture containing at least the polyurethane prepolymer and a quaternary ammonium compound, germicidal properties. The reaction mixture typically contains additional constituents that take part in the reaction through which polyurethane foams are formed that exhibit an antimicrobial benefit. During the reaction in which the polyurethane foam is formed, the amount of water present in the reaction mixture reacts with the free isocyanate groups to release carbon dioxide, which expands the polyurethane prepolymer into an open cell crosslinked foam that is It becomes hydrophilic by the integral entrapment of excess water in the cell walls of the foam matrix. When the reaction mixture is allowed to be in molds, a sturdy and flexible foam body is formed as desired. Alternatively, the reaction mixture can be applied to a substrate such as a sheet, plate, film but especially a removable sheet coated with silicone and allowed to be, which can provide a flexible resistant foam body in a generally flat or sheet form. . The reaction mixture, and the expanded polyurethane compositions ultimately formed therefrom, necessarily include one or more quaternary ammonium compounds having germicidal properties. Desirably the one or more quaternary ammonium compounds having germicidal properties are provided to provide a long-term antimicrobial benefit to the expanded polyurethane composition and particularly to the cleaning articles formed therefrom or with it. Per se , many quaternary ammonium compounds are known and are contemplated as being useful in the present inventive compositions.

Such quaternary ammonium compounds having germicidal properties are well known, and many of these are classified as cationic surfactants including those described for example in McCutcheon's Functional Materials, Vol. 2, 1998; Kirk-Othmer, Encyclopedia of Chemical Technology , 4th Ed., Vol. 23, p. 481-541 (1997), the content of which is incorporated herein by reference. Useful quaternary ammonium compounds having germicidal properties are also described in the respective product descriptions and literature available from the suppliers of these cationic surfactants.

Examples of surfactant compositions preferred cationic, useful in the practice of the present invention are those that provide a germicidal effect to the expanded polyurethane composition, and especially preferred are the quaternary ammonium compounds and salts thereof, which They can be characterized by the general structural formula:

one

in which at least one of R_ {1}, R 2, R 3 and R 4 is an alkyl, aryl or substituent alkylaryl of from 6 to 26 carbon atoms and the cationic portion The complete molecule has a molecular weight of at least 165. The alkyl substituents may be: long chain alkyl, long chain alkoxyaryl, long chain alkylaryl, long chain alkylaryl substituted with halogen, long chain alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on nitrogen atoms other than those alkyl substituents mentioned above are hydrocarbons which do not normally contain more than 12 carbon atoms. The substituents R 1, R 2, R 3 and R 4 may be of linear chain or can be branched, but are preferably of linear chain, and may include one or more amide, ether or ester. The counterion X can be any salt forming anion that allow water solubility of the ammonium complex quaternary.

Exemplary quaternary ammonium salts Within the above description include halides of alkylammonium, such as cetyltrimethylammonium bromide, halides of alkyl arylammonium, such as bromide octadecyl dimethylbenzylammonium halides N-alkylpyridinium, such as bromide N-cetylpyridinium and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains amide, ether or ester linkages, such as octyl chloride phenoxyethoxyethyl dimethyl benzylammonium chloride N- (laurylcocoaminoformylmethyl) -pyridinium and Similar. Other types of quaternary ammonium compounds very effective that are useful as germicides include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyl trimethylammonium chloride, Cetylaminophenyl trimethylammonium methosulfate, dodecylphenyl trimethylammonium, dodecylbenzyl chloride trimethylammonium, chlorinated dodecylbenzyl chloride and trimethylammonium Similar.

Preferred quaternary ammonium compounds that act as germicides and that have been found useful in expanded polyurethane composition include those that present the structural formula:

2

in which R_ {2} and R_ {3} are same or different C 8 -C 12 alkyl, or R 2 is C 12-16 alkyl, alkyl C 8-18 ethoxy, C 8-18 alkyl phenoletoxy and R 3 is benzyl and X is a halide, for example, chloride, bromide or iodide or is a methosulfate anion. The groups alkyl indicated in R2 and R3 may be straight chain or branched, but are preferably substantially linear

Useful quaternary germicides in particular include compositions that include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the trademarks BARDAC®, BARQUAT®, HYAMINEO, LONZABAC®, and ONYXIDE®, which are described more fully in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product bibliography of the suppliers identified below. For example, it is described that BARDAC® 205M is a liquid containing alkyl dimethyl benzylammonium chloride, octyl decyl dimethylammonium chloride; didecyl dimethylammonium chloride and dioctyl dimethylammonium chloride (50% active ingredient) (also available as 80% active ingredient (BARDAC® 208M)); generally described in McCutcheon's as a combination of alkyl dimethyl benzyl ammonium chloride and dialkyl dimethylammonium chloride); BARDAC® 2050 is described as a combination of octyl decyl dimethylammonium chloride / didecyl dimethylammonium chloride and dioctyl dimethylammonium chloride (50% active ingredient) (also available as 80% active ingredient (BARDAC® 2080)); BARDAC ® 2250 is described as didecyl dimethylammonium chloride (50% active ingredient); It is described that BARDAC® LF (or BARDAC® LF-80) is based on dioctyl dimethylammonium chloride (BARQUAT® MB-50, MX-50, OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are each described as an alkyl dimethyl benzyl ammonium chloride; BARDAC® 4250 and BARQUATO 4250Z (each with 50% active ingredient) or BARQUAT® 4280 and BARQUAT4280Z (each with 80% active ingredient ) are described as alkyl dimethyl benzylammonium chloride / alkyl dimethyl ethyl benzyl ammonium chloride Also, HYAMINE® 1622, described as diisobutyl phenoxyethoxyethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINE® 3500 (50% active ingredient), described as alkyl dimethyl benzylammonium chloride (also available as 80% active ingredient (HYAMINE® 3500-80)) and HYAMINE® 2389 described as being based on methyl dodecyl benzyl ammonium chloride and / or methyl dodecyloxylene bis-trimethylammonium chloride (BARDAC®, BARQUAT® and HYAMINE® are currently commercially available s in Lonza, Inc., Fairlawn, New Jersey). BTC® 50 NF (or BTC® 65 NF) is described as being alkyl dimethyl benzylammonium chloride (50% active ingredient); BTC® 99 is described as didecyl dimethylammonium chloride (50% active ingredient); BTC® 776 is described as being myrisalconium chloride (50% active ingredient); BTC® 818 is described as being octyl decyl dimethylammonium chloride, didecyl dimethylammonium chloride and dioctyl dimethylammonium chloride (50% active ingredient) (also available as 80% active ingredient (BTC® 818-80%)); BTC® 824 and BTC® 835 describe that each is alkyl dimethyl benzylammonium chloride (each 50% active ingredient); BTC® 885 is described as a combination of BTC® 835 and BTC® 818 (50% active ingredient) (also available as 80% active ingredient (BTC® 888)); BTC® 1010 is described as didecyl dimethylammonium chloride (50% active ingredient) (also available as 80% active ingredient (BTC® 1010-80)); BTC® 2125 (or BTC® 2125 M) is described as alkyl dimethyl benzylammonium chloride and alkyl dimethyl ethylbenzylammonium chloride (each 50% active substance) (also available as 80% active ingredient (BTC® 2125 80 or BTC® 2125 M )); BTC® 2565 is described as alkyl dimethyl benzylammonium chlorides (50% active ingredient) (also available as 80% active ingredient (BTC® 2568)); BTC® 8248 (or BTC® 8358) is described as alkyl dimethyl benzylammonium chloride (80% active ingredient) (also available as 90% active ingredient (BTC® 8249)); ONYXIDE® 3300 is described as n-alkyl dimethyl benzylammonium saccharinate (95% active ingredient). (BTC® and ONYXIDE® are commercially available at the present time at Stepan Company, Northfield, Illinois). Polymeric quaternary ammonium salts based on these monomeric structures are also considered desirable for the present invention. An example is POLYQUAT®, described as a 2-butenyldimethylammonium chloride polymer.

The inventors have observed that not all quaternary ammonium compound that have germicidal properties necessarily guarantee the optimal expansion of the prepolymer of polyurethane and the resulting expanded polyurethane composition which exhibits good strength, good flexibility and good integrity of the product, and for these reasons certain ammonium compounds Quaternary are preferred at this time over others. For example, such preferred quaternary ammonium compounds include the selected from the following: BTC® 65, BTC® 2125M90, BTC® 8358, CATIGENE® T50, and HYAMINE®1622. BTC® 65 is a preparation commercially available described that contains 50% in weight of a C 12 -C 16 alkyl chloride dimethyl benzyl ammonium provided in an aqueous alcoholic vehicle wherein the water comprises 46% by weight of the preparation commercial, and ethanol comprises the remaining 4% by weight of the commercial preparation BTC® 2125M90 in a preparation commercially available described as containing 45% by weight of a C 12 -C 16 alkyl dimethyl chloride Benzyl Ammonium, 45% by weight of an alkyl chloride C 12 -C 16 dimethyl (ethylbenzyl) ammonium, 4% by weight of water, 3% by weight of ethanol, and comprising the remaining balance of 3% by weight alkyl C 12 -C 16 methylamines. BTC® 8358 in one commercially available preparation described containing 80% by weight of an alkyl chloride C 12 -C 16 dimethyl benzyl ammonium, 17% by weight of ethanol, 2% by weight of water, and 1% by weight of alkyl C 12 -C 16 dimethyl amines. CATIGENE®T50 is a commercially available preparation containing 50% by weight of a C 8 -C 18 alkyl dimethyl chloride benzalkonium ammonium and 50% by weight of water. HYAMINE® 1622 Crystal is a commercially available preparation that describes that Contains 100% by weight of diisobutylphenoxyethoxyethyl chloride dimethyl benzyl ammonium. As is evident from the above, the concentration of active quaternary ammonium compounds in each of these commercial compositions varies, and the composition of the alcoholic / aqueous solution also varies.

Although you don't want to be limited by the text Next, one or more of the following factors may contribute to the advantages of preferred quaternary ammonium compounds about others. One possible factor is that ammonium compounds Preferred quaternary are provided in preparations commercials that may contain non-alkyldimethylamines quaternized in appreciable quantities. Another possible factor is that the preferred quaternary ammonium compounds provided in commercial preparations contain at least one benzyl moiety within the structure of quaternary ammonium compounds that It provides germicidal properties.

According to certain embodiments particularly preferred, preferred quaternary ammonium compounds are those only constituents that provide a germicidal effect to molded items.

Most preferably the articles and compositions of the invention, for their production, exclude sources of silver ions as described in US Pat. 6375964 the contents of which are incorporated herein as reference.

It will be appreciated that optionally they can be added additional constituents to the reaction mixture for ultimately instance, confer the desired properties to the composition of expanded polyurethane and / or cleaning articles comprising  The expanded polyurethane composition. If desired, the mixture of reaction may contain fillers, stabilizers, additives such as reinforcing agents, blowing agents auxiliaries, fragrances, deodorizers, dyes, one or more detersive surfactants, silicone oils, gums, powders abrasives and the like Preferably, all mentioned loading materials, stabilizers, additives and the like will be essentially non-reactive with isocyanate and hydroxyl groups under the conditions of foam formulation.

The detersive surfactant constituent consists of in one or more nonionic, cationic, zwitterionic surfactants, and amphoteric in an amount that does not exceed approximately 10% in weight,

in which the nonionic surfactant is Select condensates of alkyl poly (alkylene oxide) phenols, condensation products of aliphatic alcohols with 1 to approximately 60 moles of an alkylene oxide, ethoxylates of primary and secondary linear and branched alcohols, alkoxy block copolymers, alkylmonoglycosides, alkyl polyglucosides and amine oxides.

Suitable non-ionic surfactants that are used in the present invention include the following:

Condensates of poly (alkylene oxide) from alkyl phenols. These compounds include the products of condensation of alkylphenols having an alkyl group that it contains about 6 to 12 carbon atoms in a either straight chain or branched chain configuration with a alkylene oxide, especially an ethylene oxide, being present ethylene oxide in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkylphenol. The substituent alkyl in said compounds may, for example, come from propylene, diisobutylene and the like, polymerized. Examples of compounds of this type include nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol; dodecylphenol condensed with approximately 12 moles of oxide ethylene per mole of phenol; dinonylphenol condensed with approximately 15 moles of ethylene oxide per mole of phenol and diisooctylphenol condensed with approximately 15 moles of oxide ethylene per mole of phenol.

An additional class of non-ionic surfactants are the condensation products of aliphatic alcohols with about 1 to about 60 moles of an oxide of alkylene, especially an ethylene oxide. The alkyl chain of the aliphatic alcohol can be linear or branched, primary or secondary and usually contains between about 8 and approximately 22 carbon atoms. Examples of said alcohols ethoxylates include alcohol condensation product myristyl condensed with approximately 10 moles of oxide ethylene per mole of alcohol, and the condensation product of approximately 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with varying alkyl chains in its length between approximately 10 and 14 carbon atoms). Other examples are linear chain alcohols C_ {6} -C_ {11} that are ethoxylated with de about 3 to about 6 moles of ethylene oxide. its Bypass is well known in the art. Examples include Alfonic® 810-4.5, which is described in the Sasol product bibliography as a C8-10 that It has an average molecular weight of 356, an oxide content of ethylene of approximately 4.85 moles (approximately 60% in weight) and an HLB of about 12; Alfonic® 810-2, which is described in product literature as a C8-C10 that has an average molecular weight of 242, an ethylene oxide content of approximately 2.1 moles (approximately 40% by weight) and an HLB of approximately 12; and Alfonic® 610-3.5, which is described in bibliography of the product as with an average molecular weight of 276, a content in ethylene oxide of about 3.1 moles (about 50% by weight) and an HLB of 10. Other examples of ethoxylated alcohol they are oxo-alcohols of 10 carbon atoms, ethoxylates, available in BASF under the trade name Lutensol® ON. They are available in grades containing approximately 3 at about 11 moles of ethylene oxide (available with names Lutensol® ON 30; Lutensol® ON 50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70; Lutensol® ON 80 and Lutensol® ON 110). Other examples of ethoxylated alcohols include the available non-ionic surfactants of the Neodol® 91 series in Shell Chemical Company, which are described as alcohols ethoxylated C9-C11. The nonionic surfactants of The Neodol® 91 series of interest include: Neodol® 91-2.5, Neodol® 91-6 and Neodol® 91-8. Neodol® 91-2.5 has been described having approximately 2.5 ethoxy groups per molecule; the Neodol 95-6 has been described as having approximately 6 ethoxy groups per molecule; and Neodol 91-8 has described as having approximately 8 ethoxy groups per molecule.  Additional examples of ethoxylated alcohols include the non-ionic surfactants of Rhodia Rhodasurf® DA series which They are described as branched ethoxylates of isodecyl alcohol. Rhodasurf® DA-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5; Rhodasurf® DA-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5 and Rhodasurf® DA-639 It is a 90% solution of DA-630. More examples of ethoxylated alcohols include those from Tomah Products (Milton, WI) under the registered trademark Tomadol® with the formula RO (CH 2 CH 2 O) n H where R is the Primary linear alcohol and n is the total number of moles of oxide of ethylene. Tomah's ethoxylated alcohol series includes: 91-2.5; 91-6 91-8, where R is C 9 / C 10 / C 11 linear, and n is 2.5, 6 or 8; 1-3 1-5; 1-7; 1-73B; 1-9; where R is C_ {11} linear and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5; - where R is 12/13 carbon atoms, linear and n is 1; 3; 5 or 6.5; 25-3; 25-7; 25-9; 25-12; -where R is C 12 / C 13 / C 14 / C 15 linear and n is 3, 7, 9 or 12; Y 45-7; 45-13; - where R is 14/15 carbon atoms, linear and n is 7 or 13.

An additional class of non-ionic surfactants they are ethoxylates of primary and secondary linear alcohols and branched, such as those based on alcohols C_ {6} -C_ {18} which also include an average of 2 to 80 moles of ethoxylation per mole of alcohol. These examples include Genapol® UD (eg Clariant, Muttenz, Switzerland) described under the registered trademarks Genapol® UD 030, polyglycol ether of C 11 oxoalcohol with 3 EO; Genapol® UD, 050 polyglycol ether C 11 oxoalcohol with 5 EO; Genapol® UD 070, polyglycol ether of C 11 oxoalcohol with 7 EO; Genapol® UD 080, polyglycol ether of C 11 oxoalcohol with 8 EO; Genapol® UD 088, polyglycol ether C 11 oxoalcohol with 8 EO; and Genapol® UD 110, polyglycol ether of oxoalcohol of 11 carbon atoms, with 11 EO.

An additional class of non-ionic surfactants useful includes alkoxy block copolymers, and in particular, compounds based on ethoxy / propoxy block copolymers. The block copolymers of polymeric alkylene oxide include nonionic surfactants in which the main portion of the molecule is composed of alkylene oxides C_ {2} -C_ {4} block polymeric. Sayings nonionic surfactants, although they are preferably prepared at from an alkylene oxide chain initiator group, they can present almost any group as a starting nucleus contain active hydrogen including, without limitation, amides, phenols, thiols and secondary alcohols.

A group of said non-phonic surfactants useful containing alkylene oxide blocks characteristic are those that can be represented generally by the formula (A):

(A) R- (EO) x (PO) y (EO) z H

in where

R represents a hydroxyl group or a group I rent.

EO represents ethylene oxide,

PO represents propylene oxide,

and is equal to at least 15,

(EO) x + z is equal to 20 to 80% of the weight total of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000. These surfactants are available under the registered trademark PLURONIC® (eg BASF) where R is -OH, or when R is a group alkyl, EMULGEN® (eg Kao.).

An additional group of said surfactants does not Useful phonics containing alkylene oxide blocks characteristic are those that can be represented by the formula (TO):

(B) R (EO, PO) a (EO, PO) b H

in which R is an alkyl group, aryl or aralkyl, in which the group R contains 1 to 20 atoms of carbon, the percentage by weight of EO is in the range of 0 to 45% in one of the blocks a, b, and in the range of 60 to 100% in the another of blocks a, b, and the total number of moles of EO and PO combined is in the range of 6 to 125 moles, with 1 to 50 moles in the block rich in PO and 5 to 100 moles in the block rich in EO. Specific non-ionic surfactants that are included in generally by formula B, include butoxy derivatives of polymers in propylene oxide / ethylene oxide blocks having weights molecular in the range of approximately 2,000-5,000.

Even more examples of nonionic surfactants Useful include those that can be represented by formula (C) as follows:

(C) RO- (BO) n (EO) x -H

in where

EO represents ethylene oxide,

BO represents butylene oxide,

R is an alkyl group containing between 1 and 20 carbon atoms,

n is approximately 5-15 and x is approximately 5-15.

Additional useful non-ionic surfactants include those that can be represented by the formula (D) next:

(D) HO- (EO) x (BO) n (EO) y H

in where

EO represents ethylene oxide,

BO represents butylene oxide,

n is approximately 5-15, preferably about 15,

x is approximately 5-15, preferably about 15, and

and it's about 5-15, preferably about 15.

Other additional nonionic surfactants Exemplary useful block copolymers include derivatives ethoxylated ethylene diamine propoxylated, which can be represented by the following formula:

3

in the that

(EO) represents ethoxy,

(PO) represents propoxy,

the amount of (PO) x is as to provide a molecular weight prior to ethoxylation of about 300 to 7,500, and the amount of (EO) y is such as to provide approximately 20% to 90% of the total weight of said compound.

Particularly preferred for use as nonionic surfactants include those marketed in this moment under the registered name Pluronic® (eg BASF). The Compounds are formed by condensing ethylene oxide with a base hydrophobic formed by the condensation of propylene oxide with propylene glycol, and it is described by its manufacturer that they have the following general structure:

4

in which x, y and z are selected such that the molecular weight of block polymers varies from at least about 7,000 to about 15,000, preferably about 11,000 to about 15,000 and the poly (ethylene oxide) content may comprise 5% to 90% in block polymer weight. Preferably, these surfactants they are in liquid form and surfactants particularly satisfactory are available as marketed as Pluronic® F88 described as having a molecular weight of approximately 11400, Pluronic® F98 described as having a weight molecular of approximately 13000, Pluronic® F108 described that It has a molecular weight of approximately 14600, and Pluronic® F127 described that has a molecular weight of approximately 12600

In certain preferred embodiments there is therefore minus a non-ionic surfactant present, non-ionic surfactant which is based on ethoxy / propoxy units; according to certain preferred embodiments the only nonionic surfactant present is a non-ionic block copolymer as described above within of the Pluronic® series of surfactants, especially the non-ionic surfactant described as Pluronic® F88.

Alkylmonoglycosides and alkylpolyglycosides which can also be found in the present compositions Inventive include known non-phonic surfactants that are alkaline and stable electrolytes. Alkylmonoglycosides and alkyl polyglycosides are generally prepared by reacting a monosaccharide, or a hydrolysable compound to a monosaccharide with a alcohol such as a fatty alcohol in an acidic medium. Miscellaneous glycoside and polyglycoside compounds that include glycosides alkoxylates and the processes for manufacturing them are described in U.S. patents No. 2,974,134; 3,219,656; 3,598,865; 3,640,998; 3,707,535; 3,772,269; 3,839,318; 3,974,138; 4,223,129 and 4,528,106 the contents of which are incorporated as reference.

An exemplary group of such alkyl polyglycosides Useful includes those according to the formula:

R 2 O- (C_ H 2n O) i - (Z) x

in the that:

R2 is a hydrophobic group selected from alkyl groups, alkylphenyl groups, hydroxyalkylphenyl groups as well as mixtures thereof, in which the alkyl groups can be linear or branched chain, and containing from about 8 to about 18 carbon atoms,

n has a value of 2-8, especially a value of 2 or 3;

r in an integer from 0 to 10, but it is preferably 0,

Z is derived from glucose; Y

x is a value from about 1 to 8, preferably from about 1.5 to 5.

Preferably the alkyl polyglycosides are nonionic fatty alkyl polyglycosides containing a group C 8 -C 15 alkyl straight chain or branched chain, and have an average of about 1 to 5 glucose units per molecule of fatty alkyl polyglucoside. Plus preferably, non-phonic fatty alkyl polyglucoside contain the C 8 -C 15 branched or branched alkyl group linear chain, and have an average of about 1 to approximately 2 glucose units per molecule of fatty alkyl polyglucoside.

An additional exemplary group of surfactants from alkyl glycoside suitable for use in the practice of this Invention can be represented by the following formula (A):

(A) RO- (R1O) y (G) x Z_b

in the that:

R is a monovalent organic radical that contains from about 6 to about 30, preferably from about 8 to 18 carbon atoms,

R1 is a divalent hydrocarbon radical containing from about 2 to about 4 atoms of carbon,

and is a number that has an average value from about 0 to about 1 and is preferably 0,

G is a residue derived from a saccharide reducer containing 5 or 6 carbon atoms; Y

x is a number that has an average value from about 1 to 5 (preferably from 1.1 to 2);

Z is O2M1, 100 , O (CH2), CO2M1, OSO3M1, or O (CH2) SO3M1, R2 is (CH2) CO 2 M 1 or CH = CHCO 2
M1; (with the proviso that Z can be O 2 M 1 1 only if Z is at the site of a primary hydroxyl group in which the carbon atom carrying the primary hydroxyl, CH 2 } OH, oxidizes to form a group 101 ).

b is a number from 0 to 3x + 1 preferably a average from 0.5 to 2 per glycosal group; p is 1 to 10, M1 is H + or an organic or inorganic counterion, particularly cations such as, for example, an alkali metal cation, ammonium cation, monoethanolamine cation or calcium cation. How has it defined in Formula (A) above, R is generally a residue of a fatty alcohol that has from about 8 to 30 and preferably 8 to 18 carbon atoms.

Examples of such alkyl glycosides as described above include, for example APG 325 CS Glycoside® which is described as what is an alkyl C 9 -C 11 50% polyglycoside, also commonly referred to as D-glucopyranoside, (commercially available from KGaA) and Glucopon® 625 CS which describes what a C 10 -C 16 alkyl is like 50% polyglycoside, also commonly referred to as D-glucopyranoside, (eg Henkel).

Inventive compositions can also include a constituent of non-phonic amine oxide. Oxides of Exemplary amine include:

(A) Alkyldi (alkyl) oxides lower) amine in which the alkyl group has about 10-20 and preferably 12-16 carbon atoms, and can be chain linear or branched, saturated or unsaturated. Alkyl groups Lower include between 1 and 7 carbon atoms. The examples include lauryl dimethylamine oxide, myristyldimethylamine oxide and those in which the alkyl group is a mixture of oxide of different amine, dimethylcocoamine oxide, dimethyl (hydrogenated tallow) amine and oxide myristyl / palmityldimethylamine;

(B) Alkyl di (hydroxyalkyl) oxides lower) amine in which the alkyl group has approximately 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated Examples are oxide of bis (2-hydroxyethyl) cocoamine oxide bis (2-hydroxyethyl) seboamine; and rust from bis (2-hydroxyethyl) stearylamine;

(C) Alkylamidopropyl oxides (alkyl lower) amine in which the alkyl group has about 10-20 and preferably 12-16 carbon atoms, and can be chain linear or branched, saturated or unsaturated. Examples are oxide of cocoamidopropyldimethylamine and tallowamidopropyl dimethylamine oxide Y

(D) Alkylmorpholine oxides in which the alkyl group has about 10-20 and preferably 12-16 carbon atoms, and it can be linear or branched chain, saturated or unsaturated.

Preferably, the oxide constituent of amine is an alkyldi (lower alkyl) amine oxide as indicated above and that can be represented by the following structure:

5

in which every:

R1 is an alkyl group C 1 -C 4 straight chain, preferably both R1 are methyl groups and

R2 is an alkyl group C 8 -C 18 straight chain, preferably it is a C 10 -C 14 alkyl group, the most preferably it is an alkyl group of 12 carbon atoms. Every one of the alkyl groups can be linear or branched, but the most Preferably, they are linear. Most preferably the Constituent of amine oxide is lauryl dimethylamine oxide. Be they can use technical grade mixtures of two or more amine oxides, in which amine oxides of variable chains of the group R2. Preferably, the amine oxides used in The present invention includes R2 groups comprising the less 50% by weight, preferably at least 60% by weight of groups C 12 alkyl and at least 25% by weight of C 14 alkyl groups, with no more than 15% by weight of C 16, C 18 or alkyl groups higher, such as the R2 group.

Of course the surfactant constituent does not ionic, when present, can comprise two or more nonionic surfactants. When present, the surfactant does not ionic is present in the compositions of the present invention in an amount of about 0.1% to about 10% in weight, more preferably it is present in an amount of approximately 1-5% by weight, and most preferably in an amount of approximately 1-3.5% by weight.

The compositions according to the present invention may include one or more additional detersive surfactants particularly those selected from amphoteric surfactants and zwitterionic, particularly those that can provide a detersive effect to the compositions. As an example, no limiting, zwitterionic surfactants and surfactants Amphoteric can include one or more of the following.

For example the compositions according to the invention they may optionally further comprise an alkyl surfactant ethoxylated carboxylate. In particular, the ethoxylated alkyl carboxylate comprises compounds and mixtures of compounds that are They can represent by the formula:

R 1 (OC 2 H 4) n -OCH 2 COO - M +

in which R1 is an alkyl C 4 -C 18, n is about 3 to about 20, and M is hydrogen, a solubilizing metal, preferably an alkali metal such as sodium or potassium, or ammonium or lower alkyl ammonium, such as triethanolammonium, monoethanolammonium, or diisopropanolammonium. He Lower alkanol of such alkanolammonium will normally be 2 to 4 carbon atoms and ethanol is preferable. Preferably R 1 is C 12 -C 15 alkyl, n is of about 7 to about 13, and M is a counterion of metal alkaline.

Examples of alkyl ethoxylated carboxylates which are contemplated to be useful in the present invention include, but not necessarily limited to, buteth-3 sodium carboxylate, hexeth-4 carboxylate sodium, laureth-5 sodium carboxylate, laureth-6 sodium carboxylate, laureth-8 sodium carboxylate, laureth-11 sodium carboxylate, laureth-13 sodium carboxylate, sodium trideceth-3 carboxylate, sodium trideceth-6 carboxylate, sodium trideceth-7 carboxylate, sodium trideceth-19 carboxylate, caprileth-4 sodium carboxylate, caprileth-6 sodium carboxylate, caprileth-9 sodium carboxylate, caprileth-13 sodium carboxylate, ceteth-13 sodium carboxylate, C_ {15-15} pareth-6 carboxylate sodium, C 12-15 pareth-7 sodium carboxylate, C 14-15 pareth-8 sodium carboxylate, isosteareth-6 sodium carboxylate as well as the form acid. Sodium laureth-8 carboxylate is preferred, laureth-13 sodium carboxylate, acid pareth-25-7 carboxylic. A laureth-13 sodium carboxylate particularly Preferred can be obtained from Finetex Inc. under the registered trademark Surfine® WLL or Clariant Corp. under the trademark Sandopan® LS-24

       \ newpage
    

As a non-limiting example, the Exemplary amphoteric surfactants include one or more surfactants. water soluble betaines that can be represented by the General Formula:

       \ vskip1.000000 \ baselineskip
    

6

in which: R_ {1} is a group alkyl containing from 8 to 18 carbon atoms, or the radical amido that can be represented by the general formula next:

       \ vskip1.000000 \ baselineskip
    

7

in which R is an alkyl group that it has 8 to 18 carbon atoms, a is an integer that has a value from 1 to 4 inclusive, Y

R2 is an alkylene group C1-C4. Examples of such surfactants Water soluble betaines include dodecyl dimethyl betaine, as well like cocoamidopropyl betaine.

When present, any surfactant amphoteric and / or zwitterionic present in the compositions of the The present invention is desirably included in an amount of about 0.1% to about 10% by weight.

The total amount of detersive surfactants present in the inventive compositions does not exceed approximately 10% by weight, more preferably does not exceed approximately 5% by weight of the total weight of the composition inventiveness. Detersive surfactants can be used alone, or in mixtures of two or more surfactants.

An additional constituent that is optionally included, but in certain cases desirably, in the expanded polyurethane compositions of the invention is one or more organic solvents that provide both a solvency function, as well as an anti-foaming function. By way of non-limiting example, such solvents can be virtually any organic solvent material. By way of non-limiting example, exemplary useful organic solvents that may be included in the compositions of the invention include those that are at least partially miscible with water, such as alcohols (eg, low molecular weight alcohols, such as by eg ethanol, propanol, isopropanol, and the like), glycols (such as, for example, ethylene glycol, propylene glycol, hexylene glycol, and the like), water miscible ethers (eg, diethyl ether of diethylene glycol, dimethyl ether of diethylene glycol and dimethyl ether of propylene glycol ), water-miscible glycol ethers (for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether) lower monoalkyl ethers of ethylene glycol or propylene glycol (for example monomethyl ether acetate propylene glycol) and mixtures thereof. Glycol ethers having the general structure R a -R b -OH, in which R a is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms, and R b is a condensed ether of propylene glycol and / or ethylene glycol having one to ten glycol monomer units. Of course, mixtures of two or more organic solvents can be used in the organic solvent constituent. Desirably, when present, the organic solvent is selected to aid in the miscibility of one or more of the other constituents used to make the expanded polyurethane composition, and at the same time confer at least a minimal anti-foaming effect. This latter effect is often desired as during the in situ formation of the expanded polyurethane composition that a limited or controlled degree of foaming is achieved. Excessive or turbulent foaming is usually avoided because it typically degrades the ultimate structural integrity of the expanded polyurethane composition as well as the cleaning articles formed therefrom. Uncontrolled foam formation may result in uneven or poor distribution of gas bubbles within the expanded polyurethane composition which in turn, deleteriously affects the structural integrity of the expanded polyurethane composition as well as any cleaning article formed. from it. The preferred organic solvents are glycol ethers, of which a particularly preferred glycol ether solvent is the commercially available n-butyl ether of dipropylene glycol, ie as Dowanol DPnB (eg Dow Chemical).

As an additional organic solvent, the mixture reaction may include a lower amount of a low alcohol boiling point such as one of the monohydric alcohols C 1 -C 4, such as methanol, ethanol or propanol Of these, the use of methanol is particularly preferred. C 1 -C 4 monohydric alcohols reduce the reaction rate between the prepolymer protected with isocyanate and water present in the reaction mixture. A reduction of the reaction rate, that is, in the polymerization and formation of polyurethane foam is frequently desirable to facilitate mixing of the various constituents used to produce polyurethane foams, and to allow subsequent handling of the reaction mixture such as in a mold, cavity or spreading it in a thick layer suitable for curing. Monohydric alcohols serve to protect some of the terminal NCO groups, preventing the reaction with water to form the urea bond. Such alcohols too They provide a more flexible polyurethane foam composition. Generally good results are observed when mixed approximately one part by weight of the prepolymer protected with isocyanate with water in the presence of 0.05 to 0.25 parts by weight of methanol or 0.1 to 0.3 parts by weight of ethanol. When is present, any organic solvent present in the composition of the present invention is desirably included in a amount from about 0.01 to about 10% by weight.

An optional constituent that can also be include in the reaction mixture used to form the Expanded polyurethane composition is a rubber, which can be or natural or synthetic This has the effect of increasing the time of Cured for polyurethane, and increases extensibility, resistance and adhesion. Preferably, the gum is added in the form of a latex, ie a suspension or emulsion of the gum in an aqueous medium. The latex generally comprises 40 to 70% solids  by weight, preferably 50 to 60% by weight. They prefer particularly acrylic based gums. These are commercially available in latex form, such as PRIMAL® B-15J and RHOPLEX® N-560 (eg Rohm & Haas). When present, any gum present in the Composition of the present invention is desirably included in an amount of about 0.1 to about 5% in weight.

An additional constituent that is optionally included, but in certain cases desirably, in the reaction mixture used to form the expanded polyurethane composition are silane-based coupling agents, especially alkoxysilane coupling agents. Such coupling agents are per se , known in the art and include silane coupling agents of both the amino type and the glycidyl type. Alkoxysilane coupling agents are currently available under the registered trademark SILQUEST®. When present, silane-based coupling agents are desirably included in an amount of about 0.1 to about 1.0% by weight, or alternatively in an amount of about 0.01% by weight to about 4% by weight based on the weight of any of the loading agents that may be present.

In accordance with certain aspects of the invention, a filler, usually a solid filler, is incorporated into the reaction mixture and thus ultimately into the expanded polyurethane composition. While this is not essential, it is often desirable to include such a loading agent to the reaction mixture particularly when it is a larger three-dimensional spongy article to be part of the cleaning article according to the present invention. Such fillers are, per se , known in the art and especially are known in the relevant technical field in relation to the formation of polyurethane foam articles. By way of non-limiting examples, such fillers include inorganic oxides and inorganic silicates, for example, wollastonite, pumice stone, feldspar, diatomaceous earth, garnet, and the like. When present, the total amount of filler present in the composition of the present invention is desirably included in an amount of about 0.1 to about 50% by weight.

As previously indicated, when incorporate such loading agents, it is also preferred that also at least one silane compound is included in the mixture of reaction containing the polymer precursor. The silanes are useful as coupling agents for loading agents, particularly when such fillers are minerals and of this way they facilitate the incorporation of the agents of load to the three-dimensional structure of polyurethane foams.

In accordance with certain embodiments particularly preferred polyurethane compositions expanded of the present invention and the articles comprising said expanded polyurethane compositions are essentially free of silicon-based surfactants, such as oils silicone and the oxyalkylene siloxane block copolymers that it is described that they are an essential constituent in the patent of USA 4476251.

Still an additional constituent that can be include in the expanded polyurethane compositions of the The present invention is an acid constituent that is an acid water soluble inorganic, or a water soluble organic acid or its combination. By way of non-limiting example, inorganic acids Useful include hydrochloric acid, phosphonic acid, and acid sulfuric. With respect to water soluble organic acids, they usually include at least one carbon atom, and include at least one carboxyl group (-COOH) in its structure. Be prefer water-soluble organic acids that contain 1 at about 6 carbon atoms, and at least one group Carboxyl as indicated. Particularly preferred among Such organic acids are: formic acid, citric acid, acid sorbic, acetic acid, boric acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid and their mixtures However, according to certain embodiments preferred, the acid constituent is a combination of acid citrus in combination with at least one additional acid selected from the group consisting of sorbic acid, acid acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, and glycolic acid. The more preferably, the acid constituent is lactic acid. When present, any acid present in the composition of the present invention is desirably included in an amount of  about 0.1 to about 10% by weight.

The expanded polyurethane composition of the present invention may optionally include one or more additional constituents that can help improve the appearance and / or handling characteristics of the articles of cleaning of the invention. Such constituents can be incorporated to the reaction mixture and thus incorporated into the foam of polyurethane. Although optional, they are frequently included for help to improve the appeal of a cleaning item according to the invention. By way of non-limiting examples, such Additional constituents include, coloring agents such as dyes and pigments, fragrances derived from natural sources, or produced synthetically or both, agents directed towards the neutralization of the treatment of undesirable odors, and Similar.

As indicated above, the expanded polyurethane composition described herein can be used to form any of a number of cleaning items. The cleaning article produced according to the present inventive teaching can take any number of shapes and configurations. In fact, it should be understood that the ultimate physical form of the cleaning article can be varied according to the desired form of the commercial product. By way of non-limiting example, the cleaning articles according to the invention can take any form or conformation to address a particular need in a cleaning and / or disinfection application. Exemplary forms of the cleaning articles of the invention can be any molded three-dimensional shape, particularly in the form of a sponge, a sponge head such as for a mop, as well as a sponge head that can be removable or permanently attached to a handle That can be grabbed by a consumer. In said latter configuration, such a sponge head attached to a handle can be used in a variety of specialized cleaning purposes such as for example dishes, pots and pans, and when produced in a large size, surfaces such as the surfaces of the Bathroom included inside the toilets. Alternatively, the cleaning article according to the invention can be of a generally flat configuration such as in the form of a flexible sheet which can then be used as an article for cleaning by rubbing. Such a flexible sheet is desirably sized so that it can be conveniently used by a consumer to contact a surface such as a kitchen surface, bathroom surface, or other hard surfaces. Alternatively polyurethane foams that exhibit an antimicrobial benefit can be configured in the form of a tape or strip, and such a tape or strip can be used as a cleaning article, or it can be used in the construction of a cleaning article. For example, a series of loops can be formed from a single piece, or from discrete pieces of such a tape or strip and fixed to a handle in such a way, a "mop" can be formed. Said mop can be conveniently fixed to a handle and used in the manner described above in the cleaning of hard surfaces particularly surfaces of kitchens, dishes, and sinks. An advantage of such mops is that unlike a solid three-dimensional fluffy article, the mop shows
a greater degree of flexibility and that is perhaps more appropriate for certain cleaning functions than others.

With respect to cleaning articles, it should be contemplated that additional materials and / or additional articles may be associated with the expanded polyurethane composition that exhibits an antimicrobial benefit. Such alternative materials may have any shape or conformation and may include, for example handles, gripping instruments, and the like. Additional materials that are particularly advantageously used in certain configurations of cleaning items that are considered within the scope of the present invention are pads, woven sheets, nonwoven sheets, abrasive pads, and the like. For example, according to certain particularly preferred embodiments of a cleaning article according to the present invention, a nonwoven abrasive material, generally in the form of a pad, is attached to the expanded polyurethane composition that exhibits an antimicrobial benefit. While any joining means, among others, sewn, adhesive, and the like, can be used, said abrasive article is conveniently bonded to the polyurethane foam during in-situ polymerization of the expanded polyurethane composition according to the invention. Such a technique is preferred since a physical bond is formed between the polyurethane foam and the abrasive article that obviates the need to sew, or the need for an intermediate adhesive, or other additional means that can unnecessarily increase the cost, or require a Additional manufacturing stage to produce the cleaning items.

According to one aspect particularly preferred of the invention, a cleaning article is provided which exhibits an antimicrobial benefit, in which the article of expanded polyurethane comprises at least one layer of a substrate  fibrous bonded to a sponge formed from the composition of expanded polyurethane, and preferably comprises a layer of the expanded polyurethane composition stratified on record and between two layers of fibrous substrate.

By way of non-limiting examples, the substrates Useful fibrous can be of a woven or non-woven nature, and They can take a variety of forms. Useful fibrous substrates copies may include woven or nonwoven materials (fabrics), and such substrates may be resin bonded, hydroentangled, thermally bonded, microfiber cast, punched or any combination of the first. Such substrates can be formed at from virtually any material including materials fibrous obtained from synthetic sources as well as from sources that are They give naturally. Non-woven fibrous substrates are typically prefer from a cost point of view however, nothing should be understood that also prevents the use of substrates fibrous tissues.

Nonwoven fibrous substrates can be a combination of paper pulp fibers and long textile fibers Synthetic formed by well-known lamination procedures wet or dry molding. Synthetic fibers can be used such as rayon, nylon, orlón and polyester as well as their mixtures, with or without fibers obtained from natural sources, for example, wood pulp fibers, cellulose and the like. In certain embodiments, wood pulp fibers should comprise about 30 to about 60 percent by weight of the nonwoven fabric, preferably about 55 to approximately 60 percent by weight, the rest being fibers synthetic The pulp fibers provide the absorbency, abrasion and dirt retention while synthetic fibers provide the strength and elasticity of substratum.

Examples of fibrous substrates Commercially available and particularly useful include: Dexter® 10494 described as a mixture of 70% viscose / 30% polyolefin; Dexter® 5608 described as a 45% mixture cellulose / 55% polyester and polypropylene; Dexter® 12086 that is describes that it is a mixture of 65% cellulose / 30% rayon / 5% fiber synthetic; Dexter® 8553-55 described as being approximately a mixture of 80% cellulose, 20% rayon; Dexter® 12131  described as a mixture of 65% cellulose / 30% polyester that contains an additional 5% of a binder material; Dexter® 10471 which is described as a mixture of 75% cellulose / 7% rayon / 10% polyester and 8% polyolefin; Spuntech® A080 described as a 70% cellulose / 30% polyester blend; Fiberlla® 4300 described as  a mixture of 50% cellulose / 50% polyester; Vicotex® D6M-45 described which is a mixture of viscose / polyester; as well as Albad® SP50 described as a mixture 70% cellulose / 30% polyester. Additional and preferred examples of Useful fibrous substrates are listed with reference to one or more of the examples.

Fibrous substrates are supplied typically in the form of sheets or wide ribbons that are generally flat. Certain fibrous substrates that include those between preferred embodiments are constructed to provide a abrasive effect when applied to surfaces. Others fibrous substrates that include those that are also among the preferred embodiments include those with a pattern "padding" in which regions of the fibrous substrate are extend outward from the plane of the fibrous substrate thereby giving it a three-dimensional appearance.

A particularly preferred embodiment of a cleaning article according to the invention is a cleaning article multilaminate comprising a layer of the composition of expanded polyurethane that provides an antimicrobial benefit stratified on record and between two layers of fibrous substrate, particularly where one of said layers of fibrous substrate is builds to provide an abrasive effect while the another said fibrous substrate layer includes a quilting pattern. Such an embodiment provides a dual function because the layer abrasive can be used to improve the removal of dirt or other materials on hard surfaces, while the opposite layer provides good water absorption and a attractive appearance

While any joining means, among others, sewn, adhesive, and the like, can be used conveniently, the two layers of fibrous substrate bind to the intermediate polyurethane foam layer during in-situ polymerization of the polyurethane foam.

In a particular aspect the present invention provides a polyurethane based foam composition, and articles formed from it, which exhibit a benefit residual antimicrobial. Said residual antimicrobial benefit is a very significant improvement over the cleaning items of the known technique The inventors have found that according to preferred aspects of the invention, cleaning articles comprising the expanded polyurethane composition exhibit a residual antimicrobial benefit even after the article  cleaning has been saturated with water, specifically tap water, and rinsed a number of times. Embodiments of the Invention particularly preferred are those in which a residual antimicrobial benefit even after the cleaning item has been "rinsed / squeezed" a large number times. The term "rinse / squeeze" means that the cleaning article contacts water until saturation (especially under a stream of running water from tap, or deionized water) and subsequently squeezed or drained manually to remove a significant proportion of the water (generally in excess of approximately 40% by weight) that has been absorbed. The present inventors have surprisingly found that good antimicrobial efficacy is preserved residual in the cleaning articles according to the present invention.

According to a particularly preferred aspect of the invention, a cleaning article is provided such that comprises an expanded polyurethane composition as describes herein that it exhibits, after at least fifty (50) rinse / squeeze cycles, an elution of at minus 100 parts per million, preferably an elution of at least minus 150 parts per million of germicidal ammonium compounds quaternary in the squeezed or drained fluid of the article.

According to another particularly preferred aspect of the invention, a cleaning article is provided comprising the expanded polyurethane composition described herein memory that it exhibits, after at least twenty (20) cycles of rinse / squeeze, preferably after at least forty (40) rinse / squeeze cycles of an elution of at least 300 parts per million of quaternary ammonium germicidal compounds in the squeezed or drained water of the article.

According to a still additional aspect particularly preferred of the invention, a article comprising the expanded polyurethane composition as described herein that it exhibits, after at least fifty (50) cycles of rinsing / squeezing an elution from at least 200 parts per million of the germicidal compounds of quaternary ammonium in the water squeezed or drained from Article.

According to a particularly preferred aspect In addition to the invention, a cleaning article is provided. in which the maximum thickness of the composition layer of expanded polyurethane present in a cleaning article is not in excess of approximately 10 millimeters, cleaning item that exhibits, after at least ten (10) cycles of rinse / squeeze, more preferably after at least twenty (20) rinse / squeeze cycles, an elution of at least approximately 200 parts per million, preferably at least 300 parts per million, but more preferably an elution of by at least 400 parts per million of the germicidal compounds of quaternary ammonium in the squeezed or drained fluid of the Article.

Desirably, antimicrobial efficacy effective can be expressed as the concentration of compounds quaternary ammonium germicides eluted from the article of cleaning during the crushing stage. The concentration of eluted quaternary ammonium compounds can be determined by routine analytical methods.

The present inventors surprisingly discovered that, in addition to exhibiting a residual antimicrobial property in the cleaning articles, those of the preferred embodiments of the cleaning articles of the invention also exhibit good "contact death" when exposed to an undesirable microorganism, particularly gram negative bacteria for example, Salmonella choleraesuis and / or gram positive bacteria for example Staphylococcus aureus . Preferred embodiments of the invention demonstrate good antimicrobial efficacy against Enterobacter aerogenes . Said "contact to kill" is an important feature in a cleaning article, as rapid destruction of undesirable micro-organisms can be achieved. Such as a technical feature particularly useful in a cleaning article in which it is contemplated that, frequently, the same cleaning article is used to treat a variety of surfaces within a particular environment. For example, in a kitchen it is easy to foresee that a cleaning article can be used to, for example wash a cutting board or cutting surface, after that it is rinsed, and subsequently used to hand wash one or more dishes by example in a kitchen sink. The benefits of rapid death are that unwanted micro-organisms that are trapped or dragged on the surface of the cleaning article after treatment of the cutting surface are quickly destroyed, and this substantially reduces the possibility of cross contamination of any micro-organism. on the cutting board or cutting surface with the surfaces of the dishes to be washed by hand. And such an application, and according to preferred embodiments of the cleaning article, the cleaning article would first be moistened with water or with any other cleaning composition and would be used to clean by rubbing the cutting board or the cutting surface, subsequently it is contemplated that rinse in water, drain to remove a majority of the water carried inside the sponge, and after that it would be used to hand wash the dishes. Due to the rapid contact death, most, if not all, of the unwanted micro-organisms that may come into contact from the cutting board or the cutting surface and in the cleaning article would be destroyed or deactivated before coming into contact with the dishes to be washed by hand, particularly when the protocol of an intermediate rinsing stage is practiced as discussed above.

According to certain embodiments of the invention, expanded polyurethane compositions exhibiting an antimicrobial benefit provide three concurrent technical functions namely, that of an absorbent vehicle, at the same time as a controlled release, and as a reservoir for the quaternary ammonium compound that It has germicidal properties. When contacted with a fluid, particularly water, the solubility exhibited by the quaternary ammonium compound is limited and thus, only a proportion of the quaternary ammonium compound leaches from the expanded polyurethane composition. Compared to prior art cleaning articles in which most of any germicidal or sanitizing agent leaches quickly after a relatively small number of rinse / squeeze cycles, surprisingly quaternary ammonium compounds, particularly quaternary ammonium compounds Preferred seem to exhibit a strong affinity for polyurethane foam. It is believed that this strong affinity is a significant factor that provides a surprisingly long lifespan of cleaning items containing expanded polyurethane compositions and residual antimicrobial benefits. Although it is not desired to be bound by the following text, it is believed that there is such an affinity, and that said affinity between the polyurethane of the expanded polyurethane composition, and the quaternary ammonium compound having germicidal properties is responsible for the ability of the Expanded polyurethane compositions exhibit a useful antimicrobial benefit, even after fifty (50) or even more rinse / squeeze cycles, and in some cases even after one hundred (100) rinse / squeeze cycles. Although it is not desired to be bound by the following text, it is assumed that during the production of the polyurethane foam the quaternary ammonium compound having germicidal properties is physically trapped within the walls of the polyurethane foam cells and this physical entrapment It is responsible for the affinity between the polyurethane foam on the one hand and the quaternary ammonium compound on the other. Such physical entrapment is relatively long lasting, and contributes to the surprisingly long lifespan of the cleaning article formed from or formed using the polyurethane foams taught herein and the residual antimicrobial benefit observed.
by the inventors

In addition, although you do not want to be bound by the following text, it is assumed that the inclusion of a copolymer non-phonic block based on ethoxy / propoxy polymer units, especially PLURONIC® F88 can act to slow down, or slow down  the release of the quaternary ammonium compound that has germicidal properties from within the foam of polyurethane.

The following examples below illustrate exemplary polyurethane formulations and compositions expanded preferred according to certain aspects of the invention. Be You should understand that these examples are presented only as illustration and what additional useful formulations, compositions of expanded polyurethane fall within the scope of this invention and the claims can be easily elaborated by an expert in the technique without going beyond the scope and spirit of the invention. Throughout this specification and in the claims attached, the weight percentages of any constituent should be understood as a percentage by weight of the active part of the constituent referred to, unless indicated another way.

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Examples

In Table 1 they are described in more detail exemplary formulations illustrating certain embodiments preferred of expanded polyurethane compositions exhibiting a antimicrobial benefit according to the invention. You are below They were generally formulated according to the following protocol.

A reaction mixture is formed from two components, the first component being the composition of polyurethane prepolymer, for example, HYPOL JT6000, and being the second component a premix of the remaining constituents. The second component was conveniently formed by combining its constituents in appropriate measured amounts in a glass of standard laboratory glass precipitate using a conventional laboratory shaker to ensure homogeneity of the second component. Then quantities were mixed together measures of the first component and the second component using a standard laboratory shaker using a vane propeller that rotates at approximately 1000-9000 rpm for a period of approximately 1-30 seconds, especially between about 1-10 seconds to ensure a good mix of the two components. Immediately after that, the mixed mixture was poured into a cavity mold and allowed to react to form an article of expanded polyurethane that exhibits an antimicrobial benefit. Optionally a nonwoven abrasive sheet material was applied to the upper open end of the cavity mold and at least one part of the surface of the expanded polyurethane article growing polymerized entangled abrasive sheet material not tissue and formed a physical union with it. Subsequently, the expanded polyurethane article was removed from the cavity mold and It was ready for use.

Table 1 describes the proportions, in percentage by weight of each of the constituents used to produce the respective polyurethane foams that exhibit an antimicrobial benefit. The amounts mentioned Constituents used in each Example are indicated in the amount "as supplied" of the product / material cited. This amount may be less than or equal to the amount of "active principles" provided in the said constituent. The current amount of active ingredients is indicated in Table 2 which identifies the materials used in Table 1.

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The identity of the specific constituents named in Table 1 is identified in Table 2, below:

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12

The shape of the sponges produced from the expanded polyurethane compositions described in Table 1 is illustrated in Figure 1. As is visible, the sponge 10 comprises two parts, a body 12 of a polyurethane foam formed to starting from the compositions described in Table 1, having said body 12 a curved upper surface 13 stratified in registration with a layer of a nonwoven abrasive sheet material 14 which is in contact with a lower flat surface 15 of the body 12.

Elution of quaternary ammonium germicidal compounds from of cleaning supplies

Several test sponges that had compositions such as those described in Table 1, were saturated in water keeping them under a stream of deionized water and subsequently each test sponge was squeezed or drained manually to remove a significant proportion of the water (generally in excess of approximately 40% by weight, preferably at least 50% by weight, more preferably by at least about 75% by weight) that had been absorbed. Every one of these operations was a "squeeze / drain cycle". Each test sponge was evaluated for a sequence of cycles of Squeeze / drain and the amount of quaternary ammonium compound in the eluted water was evaluated according to conventional methods from laboratory. The results are presented below; the quantities of the quaternary ammonium compound in the eluted water are indicate in parts per million (ppm) after the indicated number of squeeze / rinse cycles.

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Antimicrobial evaluation Test Microorganism

The microorganism used for the antimicrobial evaluation of cleaning supplies was Enterobacter aerogenes (ATCC # 13048).

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Preparation of test sponges

Each of the cleaning items tested they were molded sponges that had a mass of approximately 31-37 grams The sponge compositions of test are described in Table 1. Each test sponge was removed aseptically from its container and stored in a petri dish large and sterile Each petri dish (also referred to as "plates" herein) was uniquely labeled to identify the test sponge contained inside. Between trials, and when it was not in use for testing, the plates of Large petri dishes that contained each of the test sponges were stored in a laminar flow cabinet.

For the antimicrobial evaluation of test sponges, three replicates were used (3 sponges separated) from a test sponge composition.

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Preparation of the test system (transfer of culture)

From a stock culture (for example a frozen culture), a transfer was carried out in a suitable culture medium, and incubated at 35 + 2.5 ° C overnight. This transfer was labeled To for Enterobacter aerogenes , and the cultures were incubated at 30 ° C.

Three transfers were made consecutive 24-hour culture, and were labeled sequentially as T1, T2, and T3.

After this third transfer, a daily broth transfer was skipped. For transfers beyond the third transfer "T3" for example, up to and including an eighth transfer identified as "T8", an aliquot (for example 100 mL bottle, 350 mL flask) of culture broth was inoculated in a proportion of 1: 1000. Likewise, the transfers were inoculated and incubated overnight at 30 + 1.0 ° C to obtain the test inoculum of E. aerogenes .

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Preparation of the Test Culture (s)

The test inoculum was poured through a sterile funnel containing a thick filtration medium (for glass wool example) to remove any particles strange.

An appropriate amount of the culture was pipetted filtered in a sterile container and sufficient volume was added of organic soil, horse serum, to reach a final concentration of 5% (v / v). It was considered acceptable any organic crop / soil combination (for example 9.5 mL / 0.5 mL) which resulted in a final concentration of 5% soil organic. The mixtures were stirred in vortex; after that you are prepared mixtures were referred to as "test culture" (or "test cultures").

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Inoculation of the Test Surface

On each day of analysis, for each sponge tested, four sterile 100 mm Petri dishes were used. A 2½ square was inscribed outside the bottom of each petri dish. For each test sponge replicate, it labeled each of the four Petri dishes with the identification of the test sponge, and a 1, 2, 3 or R.

Plate 1 was inoculated with 00.1 to 0.03 mL of test system and dried, and was used to dirty the sponge test.

Plate 2 was inoculated with 0.01 to 0.03 mL of test system and was used to assess the effectiveness of the sanitization of the eluted liquid from the test sponge.

Plate 3 was inoculated with 0.01 to 0.03 mL of test system and was used to assess the effectiveness of the sanitizing the test sponge after it is used to Clean by rubbing the test surface.

The R plate was not inoculated and was used to assess the amount of redeposited bacteria after cleaning the test sponge after carrying out the stages previous.

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For each test system, it is also inoculated and dried 3 additional plates marked with a square of 2½. These plates serve as "counting plates of dry recovery. "

(For example, if 8 replicates of tested cleaning items are being tested, for Enterobacter aerogenes , then a total of 27 plates would be inoculated, that is, 3 plates per replicated cleaning item tested plus 3 dry recovery count plates ).

The total number of plates per test system that may have been inoculated and dried all at once, or dried in sets that depend on the test plan or program. The Dry recovery count plates are usually valued at last place to truly reflect the number of organisms survivors of the incubator drying as well as any additional drying that occurs while remaining on the countertop from the lab table.

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Carrier Drying

The inoculated test plates were dried at 35 + 2.5 ° C for 15-20 minutes. Temperatures of dried out of this interval, and for a longer period of time long, they were considered acceptable if the recovery counts of control of the analysis were within the expected intervals and acceptable. After this drying period, the complete drying of the test culture on all plates (Petri dishes).

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Treatment of the test system with the test sponge

Each test sponge was tested the way Next on each analysis date.

Using a new set of sterile gloves For each cleaning item tested, the analyst (technician) held the test sponge under warm running water (approximately 26.7 at 40.5 ° C / 80 at 105 ° F) provided by a Municipal water source, that is, tap water. Then The test sponge was squeezed to remove any excess Water. This rinsed and squeezed (rinse / squeeze cycle) simulated wetting the test sponge and draining excess water before use in the house. This rinsing / crushing sequence is He performed 3 times.

After the third crush, the sponge of test was used to clean by rubbing the inoculated bottom of Plate 1 (Petri dish) for 2-3 seconds.  This stage represented a periodic exposure to a shit Microbiological bacterial (viable dried test bacteria on surfaces / carriers that are cleaned by rubbing).

An additional sequence of 7 was carried out rinsed / squeezed with tap water. After he took After the tenth rinsed / crushed daily, the liquid was eluted from the test sponge on the inoculated surface of Plate 2; after that this inoculated plate did not clean by rubbing.

After that, then the surface inoculated from Plate 3 was cleaned by rubbing with the test sponge for 5 seconds

A contact time of "X" started at from Plate 3 and Plate 3.

Next the sterile surface of the part Bottom of Plate R was cleaned by rubbing with the test sponge to evaluate any redeposition. Twenty may have been added (20) mL of neutralizer to Plate R immediately after clean by rubbing.

At the contact time of "X", it they poured 20 mL of neutralizer onto the test surfaces of Plates 2 and 3. A cell scraper was used to resuspend any organism that remains on the surface of the Plates 2 and 3. After that serial dilutions were carried out at from each plate (Plates 2, 3 and R), and the appropriate dilutions they were seeded, in a conventional way.

This sequence was repeated several times. using the same test sponge, so that it could evaluate the performance of a test sponge during a sequence of days, with 10 rinse / squeeze cycles taken to out on each day of analysis. The sequence was carried out in days natural sequential, as well as non-sequential natural days in which days were omitted, for example, in which the test does not it took place during the two days of the weekend, but it resumed during the following work week.

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Serial dilutions and planting

Test Plates 2, 3 and R were considered the dilution 100. Dilutions of 100, 101 and 102 were seeded to Each replica of the cleaning item tested. The seeds were sown dilutions of 100, 101 and 102 for the replicates of the substances test. The dilutions of 101, 102 and 103 were seeded to Any replicated "control." Dilutions were seeded 101,102 and 103 for replicates dry recovery control. Be aliquots of one (1) mL of each dilution were seeded, and poured with Soy Tripticasa Agar ("TSA") English).

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Incubation

The test surfaces contacted with E. aerogenes were incubated at 30 + 1.0 ° C for two nights; incubation in excess of 2 nights is acceptable as long as the culture medium was not dehydrated.

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Quantification of the results

The number of survivors present on the plates was quantified and the result was recorded. The results indicated below indicate the average results for the 3 replicates of the test sponges. The sequence of days is indicated in order of calendar days, which may not be sequential. In the tables below, the results in the column indicated as "L" indicated the number of surviving Enterobacter aerogenes colonies present in the plate (Plate 2) on which the test sponge liquid was eluted, the results in the column indicated as "W" indicated the number of survivors present in the plate (Plate 3) that was cleaned by rubbing with the test sponge, the results in the column indicated as "R" indicated the number of survivors present in the plate ( Plate R) that was cleaned by rubbing to analyze the redeposition of Enterobacter aerogenes . The minimum threshold for determining the number of survivors present on a plate was 20 survivors; Any value less than 20 ("<20") indicated an extremely effective eradication of Enterobacter aerogenes on a plate.

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As you can see from the above, the Proven cleaning items (test sponges) produced according to inventive teaching exhibited a good benefit residual antimicrobial that is retained even after the cleaning item has undergone rinse / squeeze cycles A large number of times.

Multilayer Cleaning Item

A multi-layer cleaning article was produced as depicted in Figures 2A and 2B comprising a layer of an expanded polyurethane composition according to the invention laminated on record with a first layer of fibrous substrate abrasive.

A first sheet of a non-material was applied abrasive fabric on a flat laboratory table top and it was sprayed with approximately 10-12 grams of release agent, LPS Heavy Duty Silicone Lubricant. The purpose of the release agent was to make sure that the first sheet of abrasive nonwoven material could ultimately peel off molded cleaning article. Then it it forms a reaction mixture from two components, the first component the polyurethane prepolymer composition, by example, HYPOL JT6000, and the second component being a premix of the remaining constituents, all those identified in the Table 3 below. The second component was conveniently formed combining its constituents in appropriate measured amounts in a standard laboratory glass beaker using a conventional laboratory shaker to ensure the homogeneity of the second component. Advantageously the second component is formed first by first providing water to a suitable container, using a laboratory stirrer is added Wollastonite 325 until a suspension is formed, followed by the Silquest 1120 that is allowed to mix approximately 10-20 minutes until a mixture is reached homogeneous, followed by Tomadol 91-6, to then Pluronic F88, then fragrance, then coloring, followed by the Dowanol DPnB, and finally the BTC 65 and after the adding the final constituent the mixture is allowed to continue for 20 more minutes. Then measured quantities of the mixture were mixed together first component and the second component using a stirrer of standard laboratory using a vane propeller that rotates to approximately 1000-9000 rpm over a period of approximately 1-30 seconds, especially between approximately 1-10 seconds to ensure a Good mix of the two components.

Immediately after that the mixed mixture it is poured and spread evenly using a thin sheet flat on the surface of sprayed nonwoven abrasive material. Foam formation begins and approximately 5-30 seconds after the start of the expansion but before the end of the foam formation reaction, He removed the excess foam using the thin flat sheet and then of that a non-woven fibrous substrate material (SAB was applied 36D-45-B) additional directly to exposed polyurethane foam and subsequently applied a flat plate over the layer of nonwoven fibrous substrate material additional. The flat plate was separated from said flat surface which the nonwoven fibrous substrate material is in contact via a series of spacer elements that ensured that the surface flat outside approximately parallel to the plate. After the end of the foaming reaction (approximately 3-7 minutes) the plate was removed; took off the first sheet of a nonwoven abrasive material to expose the surface of the polyurethane foam opposite to that of the material of additional non-woven fibrous substrate. After that, the first resulting multilayer construction was cut into squares of approximately 13.34 cm by 13.34 cm (5¼ inches by 5¼ inches) with a final thickness of these flexible cleaning items of double layer of approximately 2-10 mm.

The final composition of the layer of the expanded polyurethane composition of the cleaning article Multilayer was as follows:

twenty-one

The identity of the specific constituents It is described in Table 2, above.

The multi-layer cleaning article described in the This memory can also be produced by continuous molding procedure instead of the procedure by lots mentioned above.

Now with reference to Figures 2A and 2B, it represents a preferred embodiment of a cleaning article multilayer 20 which is represented in two views, illustrating the ratio of the laminated polyurethane foam layer 22 on record with a layer of a non-woven fibrous substrate material 24. I do not know requires no intermediate layer or adhesive material, and the shape Hexagonal provides a comfortable grip surface, facilitating its convenient use by a consumer. A preferred embodiment differs from multilayer construction result described immediately above just because of the fact that is cut into a hexagonal shape instead of a shape square.

Elution of germicidal compounds of quaternary ammonium in the squeezed or drained water of the Flexible double layer cleaning items of 13.34 cm by 13.34 cm (5¼ inches by 5¼ inches) formed according to the procedure described above was evaluated according to the general protocol next. For the evaluation, three samples were tested (replicated), "A", "B" and "C" respectively of the flexible double-layer cleaning items formed as described above and which include the composition of the Table 3.

The test of each sample was according to the protocol General following: First each sample was moistened by a five-second contact with a flow to deionized water at ambient temperature (approximately 20 ° C) flowing from a 18.9 L (5 gallon) laboratory dispenser. After the 5-second exposure, the sample was withdrawn and held by a edge so that the replicate was oriented vertically and it was let it drain, after that the sample was squeezed by hand to remove at least 50% of the absorbed water and the eluted liquid released was collected and subsequently analyzed in it the content of eluted quaternary ammonium compounds. This procedure is repeated using the same sample of cleaning items flexible double layer for 100 such cycles of squeeze / drain and collected samples of the eluted liquid released in the squeeze / drain cycles 1st, 10th, 20th, 30th, 40th, 50º, 60º, 70º, 80º, 90º and 100º.

The amount of germicidal compounds was evaluated of quaternary ammonium eluted by an analytical technique standard via titration using a solution of tetraphenylborate Of course, other techniques can be used analytical and expected to provide comparable results.

The amount of germicidal ammonium compounds eluting quaternary expressed as parts per million (ppm) of each one of the samples A, B, and C are indicated in Table 4 below. which indicates the individual results after the cycle of squeeze / drain indicated respectively as well as the results Average for all three samples.

22

As you can see from the above, the samples of flexible double layer cleaning items provide excellent and long-lasting elution of germicidal quaternary ammonium compounds.

Tri-layer cleaning article (1)

A cleaning item was produced tri-layer as depicted in Figures 3A, 3B and 3C comprising a layer of a polyurethane composition expanded laminated on record and between a first substrate layer Abrasive fibrous and a second layer of abrasive fibrous substrate which includes a quilting pattern.

First, a sheet of a material of non-woven fibrous substrate (Dexter® 10494 that had a surface "padded") to a flat worktop of the laboratory table. Subsequently a reaction mixture formed from two components, the first component being the composition of polyurethane prepolymer, for example, HYPOL JT6000, and being the second component a premix of the remaining constituents, all those identified in Table 4 below. The second component was conveniently formed by combining its constituents in appropriate measured amounts in a beaker of standard laboratory glass using a laboratory shaker conventional to ensure the homogeneity of the second component. Advantageously the second component is formed first first providing water to a suitable container, using a laboratory stirrer is added the VVoilastonite 325 until a suspension is formed, followed by the Silquest 1120 that is left mix approximately 10-20 minutes until it is reaches a homogeneous mixture, followed by the Taken) 91-6, then Pluronic F88, after fragrance, then coloring, followed by Dowanol DPnB, and finally BTC 65 and after the addition of the final constituent the mixture is allowed to continue for 20 more minutes. Later mixed together measured quantities of the first component and the second component using a standard laboratory shaker which uses a vane propeller that rotates to approximately 1000-9000 rpm for a period of approximately 1-30 seconds, especially between approximately 1-10 seconds to ensure a good mix of two components

Immediately after that the mixed mixture it is poured and spread evenly using a thin sheet flat on the surface of the abrasive nonwoven fibrous substrate. Foam formation begins and approximately 5-30 seconds after the start of the expansion but before the end of the foam formation reaction, He removed the excess foam using the thin flat sheet and then of that a sheet of nonwoven fibrous substrate material was applied (VICOTEX D6M-45) directly to the foam of polyurethane exposed and then a flat plate was applied on the second layer of nonwoven fibrous substrate material. The flat plate separated from said flat surface that is in contact the nonwoven fibrous substrate material via a series of spacer elements that ensured that the flat surface was approximately parallel to the plate. After the end of the foaming reaction (approximately 5-7 minutes) the plate was removed; the resulting three-layer construction is cut into hexagons of approximately 12.70 cm by 15.24 cm (5 inches by 6 inches), and the final thickness of the article of Flexible cleaning was approximately 2-8 millimeters The final composition of the composition layer of expanded polyurethane of the multilayer cleaning article was like follow:

2. 3

The identity of the specific constituents It is described in Table 2, above.

The multi-layer cleaning article described in the This memory can also be produced by continuous molding procedure instead of the procedure by lots mentioned above.

A further embodiment of the article of tri-layer cleaning 30 is depicted in the Figures 3A, 3B and 3C. In this flat side view a layer of expanded polyurethane 32 laminated in registration and between a first Abrasive fibrous substrate layer 34 and a second substrate layer fibrous 36 comprising a quilting pattern having regions high 38 bounded by sunken regions 40, sunken regions that bind to expanded polyurethane layer 32 while the elevated regions 38 do not. Such a construction defines cavities 42 between the surface of the polyurethane layer expanded 32 and elevated regions 38, as delimited by the portion of the sunken regions 40 of the fibrous layer 36 not adhered to the expanded polyurethane layer. One is preferred realization as it provides the consumer with two types different from surfaces, for example, a cleaning surface non-woven abrasive, and a non-woven cleaning surface "padded" more absorbent as integral parts of the article cleaning, providing a choice to the consumer that surface is more appropriately used for particular use by example, for the treatment of a particular surface or the removal of a particular type of stain. For example, more difficult to use inorganic deposits such as salts minerals can be removed in a more aggressive way using the layer 34 of abrasive fibrous substrate while the treatment General unstained surface or liquid absorption spilled could be treated more appropriately using the side Obverse and use of non-woven cleaning surface "padded" more absorbent. It should be understood that although not visible in Figure 3, the preferred shape of the cloth represented is a hexagonal format such as that shown in the Figures 2A and 2B, as well as Figures 3A, 3B and 3C but also other formats and configurations are considered to be also suitable for use.

The inventors have also found that the formation of a cleaning item that requires training in a mold, such as the embodiment of Figure 1 avoids the probability that during the foaming reaction the region of the  polyurethane sponge that is in contact with a smooth surface of the mold do not unduly densify next to said smooth surface of the mold and form a dense outer layer, conveniently referred to as a "skin" layer. It is generally due avoid the presence of such a layer of skin, as such it resists both absorption as to the elution of liquids through said layer of skin that can inhibit elution of germicidal compounds quaternary ammonium cleaning article. In addition the inventors have observed that during prolonged use this layer of skin often breaks and fractures which gives an ugly appearance to the product.

Thus, the shapes of the articles of multilayer cleaning shown in Figures 2A and 2B as well as in Figures 3A, 3B and 3C. According to the protocol for the manufacture of the article represented in Figures 2A and 2B the use of a first layer of a nonwoven material coated with a mold release lubricant allows removal of said non-woven material after the end of the formation reaction of the foam which removes any layer of skin that may have formed. Of course, other techniques can also be practiced such as separating or cutting the skin layer, also with effect similar beneficial. The embodiment according to Figures 3A, 3B and 3C it will be even more preferred since the presence of two layers of non-woven material that are in contact with the foam of polyurethane during the foam formation reaction rejects the formation of a layer of skin, rather polyurethane expanded joins the nonwoven material thus avoiding need for any intermediate adhesive and rejecting the formation of a layer of skin.

Tri-layer cleaning article (2)

A further embodiment of the article of tri-layer cleaning comprising a layer of the Composition of expanded polyurethane laminated in registration and between a first layer of abrasive fibrous substrate and a second layer of fibrous substrate using the protocol described above with reference to the tri-layer cleaning article (1), and using the same formulation described in Table 4. In the present tri-layer cleaning article, was used a first sheet of a nonwoven fibrous substrate material (Ahlstrom 150 GMS) which had an embossed padded surface with raised regions, and an additional sheet of a substrate material Abrasive nonwoven fibrous (SAB D6-MB50B) instead of the respective substrate materials named with reference to the tri-layer cleaning article (1). The article of resulting tri-layer cleaning formed was cut in hexagons of approximately 12.70 cm by 17.78 cm (5 inches per 7 inches), and the final thickness of the flexible cleaning article it was approximately 2-8 millimeters, as represented in Figures 3A, 3B and 3C.

Tri-layer cleaning article (3)

A further embodiment of the article of tri-layer cleaning comprising a layer of the Composition of expanded polyurethane laminated in registration and between a first layer of abrasive fibrous substrate and a second layer of fibrous substrate using the protocol described above with reference to the tri-layer cleaning article (1), and using the same formulation described in Table 4. In the present tri-layer cleaning article, was used a first sheet of a nonwoven fibrous substrate material (supplied by ADS Texel) and an additional sheet of a material Abrasive nonwoven fibrous substrate (SAB D6-MB50B) instead of the respective substrate materials named with reference to the tri-layer cleaning article (1). He resulting tri-layer cleaning article formed is cut into hexagons of approximately 12.70 cm by 17.78 cm (5 inches by 7 inches), and the final thickness of the article of Flexible cleaning was approximately 2-8 millimeters, as depicted in Figures 3A, 3B and 3C.

Tri-layer cleaning article (4)

A further embodiment of the article of tri-layer cleaning comprising a layer of the expanded laminated polyurethane composition in record between a first layer of abrasive fibrous substrate and a second layer of fibrous substrate using the protocol described above with reference to the tri-layer cleaning article (1), and using the same formulation described in Table 4. In the present tri-layer cleaning article, was used a first sheet of a nonwoven fibrous substrate material (Ahlstrom 125 GMS, LSW Substrate, thermally bonded with a additional non-woven pad) and an additional sheet of a material Abrasive nonwoven fibrous substrate (SAB D6-MB50B) instead of substrate materials respective named with reference to the cleaning article tri-layer (1). Cleaning item resulting tri-layer formed was cut into hexagons symmetrical measuring 12.70 cm (5 inches) between vertices opposites, and the final thickness of the flexible cleaning article was approximately 2-8 millimeters, as depicted in Figures 3A, 3B and 3C.

Tri-layer Cleaning Article (5)

A further embodiment of the article of tri-layer cleaning comprising a layer of the Composition of expanded polyurethane laminated in registration and between a first layer of abrasive fibrous substrate and a second layer of fibrous substrate using the protocol described above with reference to the tri-layer cleaning article (1), and using the same formulation described in Table 4. In the present tri-layer cleaning article, was used a first sheet of a nonwoven fibrous substrate material (Ahlstrom 125 GMS, LSW Substrate, thermally bonded with a additional non-woven pad) and an additional sheet of a Abrasive nonwoven fibrous substrate material (SAB D6-MB50B) instead of substrate materials respective named with reference to the cleaning article tri-layer (1). Cleaning item resulting tri-layer formed was cut into a shape hexagonal measuring 12.70 cm (5 inches) maximum width, and 15.24 cm (6 inches) maximum height, and the final thickness of the item Flexible cleaning was approximately 2-8 millimeters, as depicted in Figures 3A, 3B and 3C.

Tri-layer Cleaning Article (6)

A further embodiment of the article of tri-layer cleaning comprising a layer of the Composition of expanded polyurethane laminated in registration and between a first layer of abrasive fibrous substrate and a second layer of fibrous substrate described above with reference to the article of tri-layer cleaning (1), and using the same formulation described in Table 4. In this article of tri-layer cleaning, a first layer of a non-woven fibrous substrate material (Ahlstrom 125 GMS, LSW substrate, thermally bonded with a non-woven pad additional) and an additional layer of a fibrous substrate material non-woven abrasive (SAB D6-MB50B) instead of respective substrate materials named with reference to tri-layer cleaning article (1). The article of Tri-layer cleaning (6) was produced using a continuous manufacturing process in which a amount of a first and second constituents used to forms the expanded polyurethane layer to the surface of a fabric in motion of the first layer of a fibrous substrate material non-woven, and then the additional layer was applied to it of the abrasive nonwoven fibrous substrate material to form the tri-layer cleaning article. After the end of the expansion of the polyurethane layer, the cleaning article resulting tri-layer was subsequently cut into a hexagonal shape measuring 12.70 cm (5 inches) maximum width, and 15.24 cm (6 inches) maximum height, and the final thickness of the flexible cleaning item was approximately 2-8 millimeters, as depicted in the Figures 3A, 3B and 3C.

The elution of the compounds was evaluated quaternary ammonium germicides in squeezed or drained water of tri-layer flexible cleaning supplies formed and described immediately above as the articles tri-layer cleaning (2), (3), (4), (5), and (6), according to the following general protocol. For the evaluation, it was used a single sample of each cleaning item Tri-layer mentioned above.

The test of each sample was according to the protocol General following: First each sample was moistened by a five-second contact with a flow to deionized water at ambient temperature (approximately 20 ° C) flowing from a 18.9 L (5 gallon) laboratory dispenser. After the 5-second exposure, the sample was withdrawn and held by a edge so that the sample was oriented vertically and it was let it drain, after that the sample was squeezed by hand to remove at least 50% by weight of absorbed water and liquid eluted released was collected and subsequently analyzed in it content of eluted quaternary ammonium compounds. This procedure was repeated using the same sample of flexible double layer cleaning items for 100 such squeeze / drain cycles and liquid samples were collected eluted released in the squeeze / drain cycles 1st, 2nd, 10th, 20th, 30th, 40th, 50th, 60th, 70th, 80th, 90th and 100th.

The amount of germicidal compounds was evaluated of quaternary ammonium eluted by an analytical technique standard via titration using a solution of tetraphenylborate

Of course, other techniques can be used analytical and expected to provide comparable results.

The amount of germicidal ammonium compounds eluted quaternary expressed as parts per million (ppm) is indicate in Table 4 below, which indicates the results individual after the squeeze / drain cycle indicated respectively for each sample tested.

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As you can see from the above, the samples of flexible cleaning items tri-layer provide excellent elution and of long duration of germicidal ammonium compounds quaternary.

Although the invention is susceptible to various modifications and alternative forms, it should be understood that they have shown specific embodiments thereof by way of example in the drawings, which are not intended to limit the invention to particular forms described; on the contrary, the intention is to cover all the modifications, equivalents and alternatives that fall within the scope and spirit of the invention as expressed in the attached claims.

Claims (11)

1. A hydrophilic polyurethane composition expanded comprising: 0.001-10% by weight of one or more quaternary ammonium compounds that have germicidal properties generally distributed throughout the composition, a detersive surfactant constituent that consists of one or more nonionic, cationic surfactants, zwitterionic, and amphoteric in an amount that does not exceed approximately 10% by weight, in which the nonionic surfactant is Select condensates of alkyl poly (alkylene oxide) phenols, condensation products of aliphatic alcohols with 1 to approximately 60 moles of an alkylene oxide, ethoxylates of primary and secondary linear and branched alcohols, alkoxy block copolymers, alkylmonoglycosides, alkyl polyglycosides and amine oxides, in which the polyurethane composition expanded hydrophilic exhibits a density of at least 0.25 g / cm3, formed by a process that includes the stages procedure of: provide a reaction mixture that comprises at least one polyurethane prepolymer, said quaternary ammonium compound that has germicidal properties, and said detersive surfactant constituent consisting of one or more  nonionic, cationic, zwitterionic, and amphoteric surfactants; and subsequently form the hydrophilic polyurethane composition expanded, which, after at least twenty-five (25) cycles rinsing / squeezing, exhibits an elution of at least approximately 100 parts per million, preferably at least approximately 150 parts per million of germicidal compounds of quaternary ammonium in the squeezed or drained fluid of the Article. 2. A hydrophilic polyurethane composition expanded according to claim 1, which after at least Fifty (50) rinse / squeeze cycles exhibit an elution of at least about 200 parts per million compounds quaternary ammonium germicides in the squeezed or drained fluid from the article. 3. A hydrophilic polyurethane composition expanded according to claim 1, which after at least forty (40) rinse / squeeze cycles exhibit an elution of by at least about 300 parts per million compounds quaternary ammonium germicides in the squeezed or drained fluid from the article. 4. A cleaning article comprising a expanded hydrophilic polyurethane composition according to any preceding claim. 5. A cleaning article according to claim 4, wherein the cleaning article comprises at least one layer of a fibrous substrate bonded to a sponge formed from the expanded hydrophilic polyurethane composition
dido 6. A cleaning item according to the claim 4, wherein the cleaning article comprises at least two layers of a fibrous substrate attached to a sponge formed from the hydrophilic polyurethane composition expanded. 7. A cleaning item according to any of claims 4, 5 or 6, which exhibits, after at least fifty (50) rinse / squeeze cycles, an elution of at minus approximately 200 parts per million of the compounds quaternary ammonium germicides in squeezed or drained water from the article. 8. A cleaning item according to any of claims 4 to 7, wherein the maximum thickness of the layer of polyurethane foam present in a cleaning item has a dimension of maximum thickness not exceeding approximately 10 mm, cleaning item that displays, after at least ten (10) rinse / squeeze cycles, preferably at least twenty-five (25) rinse / squeeze cycles, an elution of at minus approximately 200 parts per million compounds quaternary ammonium germicides in the squeezed or drained fluid from the article. 9. A procedure to clean and / or sanitize a surface that needs treatment, a procedure that It includes the stages of: provide a polyurethane item expanded according to any one of claims 1 to 3 or a cleaning article according to any of claims 4 to 8 and, contacting said surface with said article of expanded hydrophilic polyurethane to provide an effect cleaner and / or sanitizer to it.

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10. A procedure for the manufacture of a cleaning article according to any of claims 4 to 8, procedure comprising the procedural steps of: provide a reaction mixture that comprises at least one polyurethane prepolymer, an ammonium quaternary that has germicidal properties and a constituent detersive surfactant, and subsequently form the composition of expanded hydrophilic polyurethane used in the article of cleaning. 11. A cleaning item formed by the method according to claim 10.