Patent Application
20050256020
This application claims the benefit of EP Patent Application No. 04252837.2, filed May 17, 2004, EP Patent Application No. 04252849.7, filed May 17, 2004, EP Patent Application No. 04252846.3, filed May 17, 2004, EP Patent Application No. 04252838.0, filed May 17, 2004, EP Patent Application No. 04252853.9, filed May 17, 2004, EP Patent Application No. 04252851.3, filed May 17, 2004, EP Patent Application No. 04252845.5 and U.S. application Ser. No. 10/967,757, filed Oct. 18, 2004.
Compositions for cleaning laundry as well as other substrates are well known in the art. There are cleaning compositions for cleaning items ranging from dishes to laundry and around the home use. While such cleaning compositions have nearly become ubiquitous, cleaning compositions still suffer from inadequacies, particularly toward stubborn stains and/or soils.
Hard water, or water containing high concentrations of minerals such as calcium, has been a problem for consumers. Problems associated with having hard water include decreased cleaning efficiency, hard water staining of materials, and poor water taste. While the problems associated with hard water are well known, solutions to these problems have been elusive.
One process used for improving the cleaning ability for certain compositions involves softening the water. Typically, water has been softened with water softening devices utilizing an ion-exchange resin. These resins typically replace ions that cause hardness, such as calcium ions, with other ions that result in less hardness, such as sodium ions.
An attempt at softening water includes the use of an ion exchange device. While ion exchange devices are capable of softening water, they do not do so without imparting their own unique problems. Ion exchange devices require large amounts of salts. These salts must be continually purchased by a user in order to maintain the ion exchange device. Also these salts are delivered to wastewater plants, where these salts can be difficult to remove.
Although there have been attempts at providing a softened water for use by a consumer, cleaning compositions for use in the softened water are lacking. Indeed, the vast majority of cleaning compositions are designed to perform cleaning in hard water. While these compositions are useful for cleaning in hard water environments, they prove to be inadequately designed for soft water environments.
It is highly desirable to achieve a softened water without the investment and time of utilizing a salt-based ion exchange device. Further, it is highly desirable to have a water softening device that works with a minimum of effort and time on the part of the user. It is also desirable to have a cleaning composition that is developed for used in soft water that provides maximized benefit to a consumer. This invention accomplishes these goals.
To be filled by MAC upon finalization of claims
While the specification concludes with the claims particularly pointing and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.
The compositions of the present invention can include, consist essentially of, or consist of, the components of the present invention as well as other ingredients described herein. As used herein, “consisting essentially of” means that the composition or component may include additional ingredients, but only if the additional ingredients do not materially alter the basic and novel characteristics of the claimed compositions or methods.
All percentages and ratios used herein are by weight of the total composition and all measurements made are at 25° C., unless otherwise designated. An angular degree is a planar unit of angular measure equal in magnitude to 1/360 of a complete revolution.
All measurements used herein are in metric units unless otherwise specified.
“System” as used herein means a unity formed of a plurality of parts subject to a common plan or serving a common purpose. The parts can be materials, compositions, devices, appliances, procedures, methods, or conditions. Diverse parts and/or diverse types of parts can characterize different systems.
The term “divalent” as used in phrases such as “divalent moiety” or “divalent hydrocarbyl” refers to a moiety having two covalent vanencies available for connecting it to the structure. For example, -(CH2)6- is such a moiety.
As used herein, “effective amount” of a material or composition is the amount needed to accomplish an intended purpose, for example, to impart a desired level of fabric care benefit to a fabric article/substrate.
As used herein, “feed water” includes water provided by a municapility, well, water purification system and the like.
It has now surprisingly been discovered that the composition of the present invention provides increased cleaning and washing efficacy in at least partially softened water. Further, the washing systems can be utilized for a variety of cleaning or washing duties.
According to a first aspect of the present invention, there is provided a composition for cleaning with a washing system comprising from about 15% to about 75% of at least one surfactant; from about 0.01% to about 10% of at least one enzyme; less than about 1% builder, less than about 1% chelant, and less than about 1% dispersant polymers.
The composition of the present invention, in one embodiment, is utilized with a water-softening zone capable of receiving a feed water and forming an at least partially softened water. The water-softening zone is also capable of fluidly transferring at least part of the at least partially softened water to the washing zone.
Optionally, the washing system can also include one or more of the following: a product dispensing zone (sometimes referred to herein as ‘the dispensing zone’); means for sonically or ultrasonically treating the soiled substrate in the washing zone or in a washing pre-treatment zone; an electrolysis zone for electrolysing the feed water or wash liquor; and a wash liquor disinfection zone. The washing zone can be dual purpose and also function as a post-wash rinsing zone; alternatively the wash system can optionally comprise a separate post-wash rinsing zone.
In one embodiment, it is contemplated that the washing systems of the present invention are contained substantially within one housing. Without wishing to be bound by theory, it is believed that by housing the washing systems of the present invention substantially within one housing minimizes any plumbing or fluid connections necessary among the elements of the washing system. Also, housing the washing systems of the present invention substantially within one housing minimizes the volume and/or space required by the washing systems of the present invention.
In another embodiment, it is contemplated that the washing zone and the water softening zone are independently housed. Such an embodiment is contemplated with washing systems that are at the point-of-use. In one non-limiting example, it is contemplated that the water-softening zone of the present invention is located in a different housing than the washing zone. The water-softening zone is fluidly connected between the inlet water stream and the inlet of the washing zone. In such an embodiment, its is contemplated that existing devices utilizing feed water, including washing zones comprising washing machines and automatic dishwashing machines, water heaters, as well as “whole-house” inlet streams may be retrofitted and/or adapted to have such water softening zones present to treat feed water.
Without wishing to be bound by theory, it is believed that the compositions of the present invention represent a major departure from compositions known in the art. Many components, and their amounts necessary for cleaning efficacy, are used to create compositions known in the art that are unnecessary in some embodiments while actually hurting cleaning efficacy in other embodiments when present in at least partially softened water. The compositions of the present invention synergistically function with at least partially softened water to improve performance. In one non-limiting example, the relatively small amounts of builder, chelant, and/or dispersant polymers in one embodiment results in improved cleaning in at least partially softened water. Further, a cost savings on raw materials is also realized.
According to the invention, the washing systems herein comprise a water-softening zone. In the systems and methods of the invention, the water-softening zone comprises one or more devices selected from nanofiltration, electrodeionization, electrodialysis, reverse-osmosis, ion-exchange, and capacitive deionization water-softening devices and combinations thereof. In one embodiment, the water-softening zones can include those disclosed in the commonly-assigned and co-filed patent application in the name of Baeck, Convents and Smets, applicant's reference number CM2849F, said application being incorporated by reference herein and described in detail below.
In one embodiment, the water softening zone is effective to soften the water to a residual Ca2+/Mg2+ hardness of less than about 4 mmol/L, in another embodiment less than about 2 mmol/L, in yet another embodiment less than about 1 mmol/L, in still another embodiment from about 4 mmol/L to about 0.01 mmol/L, in yet still another embodiment from about 2 mmol/L to about 0.05 mmol/L, in even still another embodiment from about 1 mmol/L to about 0.1 mmol/L.
It is, however, well known that technologies for increasing water softness will remove ionic species, including, but not limited to cationic species, anionic species, zwitterionic species, amphoteric species and combinations thereof. Such cationic species include, but are not limited to, calcium, iron, magnesium, manganese, sodium and mixtures thereof. Such anionic species include, but are not limited to, chlorine, fluorine, carbonate and mixtures thereof.
Downstream of the water-softening zone and in fluid communication therewith, the washing system can additionally comprise an softened water reservoir for storing and delivering at least partially softened water to the washing zone.
Without wishing to be bound by theory, it is believed that the water-softening zone forms an at least a partially softened water. The partially softened water, when transferred to the washing zone, increases the efficacy of any product added to the washing zone. Further, it is believed that the at least partially softened water lengthens the usable life of components of the washing system, as the use of at least partially softened water reduces and/or prevents the build up of hard water deposits, scales, and the like resulting in cleaner washing system components.
In another embodiment, the water-softening zone utilizes capacitive deionization. Capacitive deionization units utilize charged electrodes for softening of the water. Capacitive deionization with electrodes is capable of removing ionic species and other impurities from water. Without wishing to be bound by theory, water is passed between electrodes kept at a low potential difference and/or voltage. When the electrodes become saturated with ionic species, the electrodes are electrostatically regenerated, and ionic species are expelled as a waste electrolyte stream. The electrodes are periodically purged of ionic species by reversing electrode polarity and flushing with water. Further, the electrodes can be regenerated of adsorbed materials by contacting the electrodes with acid streams or base streams. In one embodiment, acid streams and base streams are generated by an electrolysis zone, as discussed herein.
In one embodiment, the electrodes of the capacitive deionization units are made from carbon aerogels. Exemplary carbon aerogel electrodes are found in U.S. Pat. No. 6,309,532 to Tran et el. Carbon-aerogel electrodes have excellent chemical stability and a very high surface area.
In one embodiment, carbon aerogels are made utilizing various carbon systems. These systems are often, though not necessarily made by pyrolisis. These carbon systems include, but are not limited to, resorcinol/formaldehyde resorcinol/phenol/formaldehyde, hydroquinone/resorcinol/formaldehyde, phloroglucinol/resorcinotlformaldehyde, catecholresorcinol/formaldehyde, polyvinyl chloride, phenol/formaldehyde, epoxidized phenol/formaldehyde, polyvinyl chloride, phenolibenzaldehyde, oxidized polystyrene, polyfurfuryl alcohol, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride, cellulose, polybutylene, cellulose acetate, melamine/formaldehyde, polyvinyl acetate, ethyl cellulose, epoxy resins, acrylonitrile/styrene, polystyrene, polyamide, polyisobutylene, polyethylene, polymethyl-methacrylate, polyvinyl chloride/divinylbenzene, divinylbenzene/styrene, and combinations and mixtures thereof.
Other sources can be utilized for form electrodes for use in capacitive deionization units. In one embodiment, electrodes exemplified are U.S. Pat. No. 6,737,445 to Bell et al. and U.S. Application No. 20030153636 to Dietz et al. are utilized. Further, the electrodes may be arranged in a flow through fashion, as described in U.S. Pat. No. 6,462,935 to Shiue et al. and U.S. Application No. 20040095706 to Faris et al.
In one embodiment, the flow rate of feed water treated with capacitive deionization to make an at least partially softened water is from about 0.5 liters/min to about 20.0 liters/min, in another embodiment from about 0.75 liters/min to about 8 liters/min, in yet another embodiment from about 1 liters/minute to about 5 liters/min, in still another embodiment greater than about 1 liter/minute.
In one embodiment, the overall surface area of the electrodes utilized in the capacitive deionization unit is from about 200 to about 1500 m2/g; in another embodiment from about 400-1200 m2/g; in another embodiment from about 500-1000 m2/g.
In one embodiment the potential difference or voltage is from about 0.5 volts to about 10 volts; in another embodiment from about 0.75 to about 8 volts; in yet another embodiment from about 1 to about 5 volts.
In one embodiment, the capacitive deionization unit is capable of self-cleaning. In one self-cleaning embodiment, cleaning commences when the electrodes exhibit diminished adsorption of the ionic species from the solution as noted by the increase in the resistance across the electrode and a decrease in the level of hardness reduction. In one embodiment, the decreased performance of the electrodes is observed by a conductivity meter. One of ordinary skill in the art would readily be able to determine means of measuring the decrease in performance of the electrodes of the present invention. The decreased performance, in one embodiment, is measured by dividing the conductivity of the “dirty” electrode by the conductivity of the “clean” electrode to determine the conductivity fraction. When the conductivity fraction reaches a predetermined value, a self-cleaning cycle is initiated. In one embodiment, a self-cleaning cycle is initiated when the conductivity fraction is less than about 0.9, in another embodiment, the conductivity fraction is less than about 0.7, in yet another embodiment, the conductivity fraction is less than about 0.5.
Optionally, the capacitive deionization unit further comprises a prefilter. Without wishing to be bound by theory, it is believed that the prefilter is capable of extending the life of the electrodes, as well as delaying the frequency of the self-cleaning cycle of the electrodes. It is believed that the prefilter absorbs, blocks, or otherwise removes the neutrally charged species contained in feed water. Such neutrally charges species are minimally effected by the electrodes on the capacitive deionization unit and thus are capable of contaminating the adsorption sites on the electrodes. The prefilter of the present invention is made from any material that substantially absorbs, blocks, and/or otherwise removes neutrally charged species from feed water. Such materials include, but are not limited to, activated carbon, silica, paper, metallic mesh filters, membranes, gels, and combinations thereof.
To facilitate the use of the systems of the present invention, compositions, also called fabric care compositions, have been developed for synergistic use. The compositions of the present invention offer surprising benefits when utilized with the washing system as they are designed to complement the benefits produced by the washing system.
The compositions of the present invention, may be in any form, such as liquids (aqueous or non-aqueous), granules, pastes, powders, sprays, foams, tablets, gels, and the like. Encapsulated and/or unitized dose compositions are included, as are compositions which form two or more separate but combinedly dispensable portions. Granular compositions can be in “compact” or “low density” form and the liquid compositions can also be in a “concentrated” or diluted form. Fabric care compositions of the present invention include liquids, including heavy duty liquid fabric care compositions and liquid detergents for washing fine fabrics including silk, wool and the like. Compositions formed by mixing the provided compositions with water in widely ranging proportions are included.
The fabric care compositions and/or perfume compositions of the present invention may be in the form of spray compositions, preferably contained within a suitable spray dispenser. In one embodiment, the fabric care compositions have a residual hardness (Ca2+, Mg2+, or combinations thereof) of less than about 4 mmol/L, in another embodiment less than about 2 mmol/L, in yet another embodiment less than about 1 mmol/L, in still another embodiment from about 4 mmol/L to about 0.01 mmol/L, in yet still another embodiment from about 2 mmol/L to about 0.05 mmol/L, in even still another embodiment from about 1 mmol/L to about 0.1 mmol/L.
In one embodiment, the liquor containing fabric care compositions and at least partially softened water have an overall residual Ca2+-Mg hardness of less than about 4 mmol/L, in another embodiment less than about 2 mmol/L, in yet another embodiment less than about 1 mmol/L, in still another embodiment from about 4 mmol/L to about 0.01 mmol/L, in yet still another embodiment from about 2 mmol/L to about 0.05 mmol/L, in even still another embodiment from about 1 mmol/L to about 0.1 mmol/L wherein the concentration of fabric care composition to at least partially softened water is from about 0.01% to about 30%, in another embodiment from about 0.1% to about 20%, in another embodiment from about 1% to about 10%, in another embodiment greater that 0.01%, in another embodiment greater than 0.1%, in another embodiment greater than 1%, in another embodiment greater than 5%.
The specific conductance depends on the total concentration of the dissolved ionized substances, i.e., the ionic strength of a water sample. As used herein, it is an expression of the ability of the water to conduct an electric current. For example, freshly distilled water has a conductance of 0.5-2 μS/cm, whereas that of potable water generally is 50-1500 μS/cm. The method of determining the specific conductance in the present invention utilizes the following test: ASTM D5391-99 (2005): Standard Test Method for Electrical Conductivity of Flowing High Purity Water Samples.
In one embodiment, the liquor containing fabric care compositions and at least partially softened water has a specific conductance of less than about 200 μS/cm, in another less than about 150 μS/cm, in yet another embodiment less than about 100 μS/cm, in another less than 75 μS/cm, in another less than 50 μS/cm, in still another embodiment from about 0.01 μS/cm to about 200 μS/cm, in yet still another embodiment from about 0.1 μS/cm to about 100 μS/cm, in even still another embodiment from about 1 μS/cm to about 50 μS/cm.
As used herein, “fabric care compositions” include fabric care compositions for handwash, machine wash and other purposes including fabric care additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics.
The compositions of the present invention may contain one or more of the following ingredients.
In one embodiment, the perfume compositions of the present invention are incorporated into the fabric care compositions of the present invention. For example, the perfume compositions of the present invention may be premixed prior to adding to the fabric care compositions of the present invention. In another embodiment, the perfume compositions of the present invention are added to the washing zone concurrently with the fabric care compositions. In yet another embodiment, the perfume components are added after the fabric care compositions are added to the washing zone.
In one embodiment, the level of perfume composition in the fabric care composition is from about 0.0001% to about 2% or higher, e.g., to about 10%; in another embodiment from about 0.0002% to about 0.8%, in another embodiment from about 0.003% to about 0.6%, in another embodiment from about 0.005% to about 0.5% by weight of the fabric care composition.
In one embodiment, the level of fabric substantive perfume ingredients in the perfume compositions of the present invention is from about 0.0001% to about 99%, in another embodiment from about 0.01% to about 50%, in another embodiment from about 0.2% to about 30%, in another embodiment from about 1% to about 20%, in another embodiment from about 2% to about 10% by weight of the composition of the perfume composition.
In one embodiment, compositions of the present invention include a stabilizer. Suitable levels of this component are in the range from about 0.01% to about 20%, more preferably from about 0.1% to about 10% by weight of the composition. In another embodiment, the stabilizers when present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10% of the composition.
Stabilizers suitable for use herein can be selected from thickening stabilizers. These include gums and other similar polysaccharides, for example gellan gum, carrageenan gum, and other known types of thickeners and rheological additives other than highly polyanionic types; thus conventional clays are not included.
Suitable stabilizers also include hydroxyl-containing stabilizing agent, including a trihydroxystearin, hydrogenated oil or a variation thereof.
The crystalline, hydroxyl-containing stabilizing agent typically is present in the compositions of the present invention at a level of from about 0.1% to about 10%, in another embodiment from about 0.1% to about 3%, in another embodiment from about 0.3% to about 2% by weight of the composition.
Crystalline, hydroxyl-containing stabilizing agents can be fatty acid, fatty ester or fatty soap water-insoluble wax-like substance.
The crystalline, hydroxyl-containing stabilizing agents in accordance with the present invention in one embodiment are derivatives of castor oil, especially hydrogenated castor oil derivatives such as castor wax. Commercially available crystalline, hydroxyl-containing stabilizing agents include THIXCIN® from Rheox, Inc.
Other stabilizers useful herein include gum-type polymers (e.g. xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof and tamarind gum (preferably consisting of xyloglucan polymers), guar gum, locust bean gum (preferably consisting of galactomannan polymers), and other industrial gums and polymers, which include, but are not limnited to, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psyllium seed, quince seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, schizophyllan, chitin, hydroxyalkyl cellulose, arabinan (preferably from sugar beets), de-branched arabinan (preferably from sugar beets), arabinoxylan (preferably from rye and wheat flour), galactan (preferably from lupin and potatoes), pectic galactan (preferably from potatoes), galactomannan (preferably from carob, and including both low and high viscosities), glucomannan, lichenan (preferably from icelandic moss), mannan (preferably from ivory nuts), pachyman, rhamnogalacturonan, acacia gum, agar, alginates, carrageenan, chitosan, clavan, hyaluronic acid, heparin, inulin, cellodextrins, carboxymethylcellulose (CMC), dextrans, dextrins, ethylhydroxyethylcellulose (EHEC), guar, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxybutylcellulose (HBC), karaya, larch, methylcellulose (MC), tamarind, scleroglucan, xanthan, carboxymethylhydroxyethylcellulose (CMHEC), methoxypropyl methyl cellulose (MPMC), hexylcarboxymethyl cellulose, C12-C20 alkyl carboxymethylcellulose, methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose (MHPC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), hydroxybutylmethylcellulose (HBMC) and mixtures thereof.
The stabilizer is in one embodiment present at a level of from 0.01% to 10%, most preferably from 0.1% to 3%.
Surfactants, as used herein, include anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants. In one embodiment, the surfactants are present at greater than 10%, in another embodiment greater than 15%, in another embodiment from about 15% to about 60%, in another embodiment, from about 17% to about 55%, in another embodiment from about 20% to about 50% of the composition. Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term “alkyl” is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil.
Other anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 24 (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C8-18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water-soluble salts of esters of α-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and β-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Particularly preferred anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula:
RO(C2H4O)xSO3−M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is 15 carbon atoms or less on the average, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x is from 1 to about 15. The surfactant component of the present compositions preferably comprises from about 60% to about 100%, by weight of the surfactant component, of an alkyl polyethoxylate sulfate, preferably at least about 70%, more preferably at least about 80%.
Other preferred anionic surfactants are the non-ethoxylated C12-15 primary and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than about 65° F. (18.3° C.), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates.
Mixtures of the alkyl sulfates with the above-described paraffin sulfonates, alkyl glyceryl ether sulfonates and esters of a α-sulfonated fatty acids, are also preferred.
The anionic surfactant component herein may comprise low levels of alkyl benzene sulfonates, but must comprise no more than about 6%, preferably less than about 3%, more preferably less than about 2% of alkyl benzene sulfonates. Most preferably, the detergent compositions herein contain no alkyl benzene sulfonates. These include alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pat. No. 2,220,099 and U.S. Pat. No. 2,477,383. Especially troublesome are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to about 14.
The laundry detergent compositions of the present invention may further contain an ethoxylated nonionic surfactant. The compositions of the present invention may contain up to about 30%, in one embodiment from about 0.01% to about 20%, alternatively from about 0.1% to about 10%, by weight of the detergent composition, of an ethoxylated nonionic surfactant. These materials are described in U.S. Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981. In one embodiment, the nonionic surfactant is selected from the ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4)n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. These surfactants are more fully described in U.S. Pat. No. 4,284,532, Leikhim et al, issued Aug. 18, 1981. In one embodiment, the nonionic surfactant is selected from ethoxylated alcohols having an average of from about 10 to about 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 3 to about 12 moles of ethylene oxide per mole of alcohol.
Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid and/or solid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.
Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula: R1(CmH2mO)nOH wherein R1 is a C8-C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably R1 is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, alternatively from about 3 to 10 ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol materials useful in the detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. In one embodiment, the HLB of this material will range from about 6 to 15, alternatively from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are materials which are often referred to in the art as “semi-polar” nonionics. Amine oxides have the formula: R(EO)x(PO)y(BO)zN(O)(CH2R′)2.qH2O. In this formula, R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, in one embodiment from 10 to 16 carbon atoms, and is alternatively a C12-C16 primary alkyl. R′ is a short-chain moiety, and may be selected from hydrogen, methyl and —CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C12-14 alkyldimethyl amine oxide.
Non-limiting examples of nonionic surfactants useful herein include: a) C12-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed in U.S. Pat. No. 6,150,322; e) C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x 1-30, as discussed in U.S. Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,093,856; f) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 26, 1986; specifically alkylpolyglycosides as discussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; g) Polyhydroxy fatty acid amides as discussed in U.S. Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.
In another embodiment, surfactants and surfactant compositions, including anionic, nonionic, and zwitterionic surfactants, that are highly hydrophobic and/or hardness intolerant are preferred. Such preferred surfactants and surfactant compositions can be described by a hydrophilic index (HI) value of 10 or lower, more preferably 8 or lower, and most preferably 6 or lower.
The Hydrophilic Index for a system of mixed surfactants can be calculated as follows:
HIS is calculated for each of the individual surfactants in the mixture as follows:
HIS=20×(the molecular weight of the head group)/(the molecular weight the surfactant). (2)
In the case of ionic surfactants, the HIS in equation (2) are calculated for the surfactant ions and the weight percents in equation (1) are for the corresponding surfactant ions.
Examples of said highly hydrophobic surfactants include, but are not limited to, C12-C20 fatty acids, C12-C24 linear and branched alkylbenzene sulfonates, C14-C24 linear and branched alkyl polyethoxylate sulfates, C12-C24 linear and branched alkyl sulfates, C12-C24 linear and branched amine oxides, C12-C24 linear and branched alkyl ethoxylates and propoxylates.
Suitable levels of this component, when present, are in the range from about 0.01% to about 20%, in another embodiment from about 0.1% to about 15%, typically from about 1% to about 10% by weight of the composition. The nitrogen-containing detersive surfactant herein is in one embodiment selected from cationic nitrogen-containing detersive surfactants, amine oxide surfactants, amine and amide-functional detersive surfactants (including fatty amidoalkylamines) and mixtures thereof. Different surfactants of this type can be combined in varying proportions.
i) Cationic nitrogen containing detersive surfactants—Cationic nitrogen-containing detersive surfactants suitable for use in the compositions of the present invention are typically water-soluble and have at least one quaternized nitrogen and one long-chain hydrocarbyl group. Examples of such cationic surfactants include the water-soluble alkyltrimethylamrnonium salts or their hydroxyalkyl substituted analogs, including compounds having the formula R1R2R3R4N+X− wherein R1 is C8-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4O)xH where x has a value from 2 to 5, and X is an anion. In one embodiment, not more than one of R2, R3 or R4 is a benzyl. In one embodiment the alkyl chain length for R1 is C12-C15. Groups for R2, R3 and R4 include methyl and hydroxyethyl and the anion X may be selected from halide, methosulfate, acetate and phosphate.
ii) Amine Oxide Surfactants—These surfactants have the formula: R(EO)x(PO)y(BO)zN(O)(CH2R′)2.qH2O (I). R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from about 8 to about 20, in another embodiment from about 10 to about 16 carbon atoms, and is in another embodiment from C12-C16 primary alkyl. R′ is a short-chain moiety selected from hydrogen, methyl and —CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C12-14 alkyldimethyl amine oxide.
iii) Amine and Amide Functional Detersive Surfactants—One embodiment of these surfactants is amine surfactants, another embodiment includes an amine surfactant having the formula RX(CH2)xNR2R3 wherein R is C6-C12 alkyl; X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; x is from 2 to 4; R2 and R3 are each independently selected from H, C1-C4 alkyl, or (CH2—CH2—O(R4)) wherein R4 is H or methyl. Yet another embodiment of surfactants of this type include those selected from the group consisting of decyl amine, dodecyl amine, C8-C12 bis(hydroxyethyl)amine, C8-C12 bis(hydroxypropyl)amine, C8-C12 amido propyl dimethyl amine, and mixtures thereof.
This group of surfactants also includes fatty acid amide surfactants having the formula RC(O)NR′2 wherein R is an alkyl group containing from about 10 to about 20 carbon atoms and each R′ is a short-chain moiety preferably selected from the group consisting of hydrogen and C1-C4 alkyl and hydroxyalkyl. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 92/06154. Other sugar-derived nitrogen-containing nonionic surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide.
Coupling agents suitable for use herein include fatty amines other than those which have marked surfactant character or are conventional solvents (such as the lower alkanolamines). Examples of these coupling agents include hexylamine, octylamine, nonylamine and their C1-C3 secondary and tertiary analogs. Levels of this component, when present, are suitably in the range of from about 0.1% to about 20%, in another embodiment from about 0.5% to about 5% by weight of the composition.
A particularly useful group of coupling agents is selected from the group consisting of molecules which consist of two polar groups separated from each other by at least 5, in another embodiment 6, aliphatic carbon atoms; in another embodiment compounds in this group are free from nitrogen and include
1,4 Cyclo Hexane Di Methanol (CHDM), 1,6 Hexanediol, 1,7 Heptanediol and mixtures thereof.
1,4 Cyclo Hexane Di Methanol may be present in either its cis configuration, its trans configuration or a mixture of both configurations.
In general any known detergent builder is useful herein, including inorganic types such as zeolites, layer silicates, and phosphates such as the alkali metal polyphosphates, and organic types including especially the alkali metal salts of citrate, 2,2-oxydisuccinate, carboxymethyloxysuccinate, nitrilotriacetate and the like. Phosphate-free, water-soluble organic builders which have relatively low molecular weight, e.g., below about 1,000, are highly preferred for use herein. Other suitable builders include sodium carbonate and sodium silicates having varying ratios of SiO2:Na2O content, e.g., 1:1 to 3:1 with 2:1 ratio being typical.
The detergent compositions herein may also optionally contain low levels of an organic detergent builder material which serves to counteract the effects of calcium, or other ion, water hardness encountered during laundering/bleaching use of the compositions herein. Detergent builders are described in U.S. Pat. No. 4,321,165, Smith et al, issued Mar. 23, 1982. Examples of such materials include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids C10-C22 fatty acids and citric acid. Other examples are organic phosphonate type sequestering agents such as those which have been sold by Monsanto under the Dequest tradename and alkanehydroxy phosphonates. Citrate salts and C12-C18 fatty acid soaps are highly preferred. Preferred builders for use in liquid detergents herein are described in U.S. Pat. No. 4,284,532, Leikhim et al, issued Aug. 18, 1981. A particularly preferred builder is citric acid.
Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the Sokalan trademark.
If utilized, the composition may comprise up to 30%, in another embodiment from about 1% to about 20%, in another embodiment from about 3% to about 10%, by weight of the composition, of the builder materials. In another embodiment, the composition should comprise less than about 5%, in another embodiment less than about 2%, in another embodiment, less than 1%, of the builder materials. While all manner of detergent builders known in the art can be used in the detergent compositions of the present invention, the type and level of builder should be selected such that the final composition has an initial pH of from about 7.0 to about 9.0 at a concentration of from about 1% to about 10% by weight in water at 20° C.
The detergent compositions herein may also optionally contain low levels of materials which serve as phase stabilizers and/or co-solvents for the liquid compositions herein. Materials of this type include C1-C3 lower alkanols such as methanol, ethanol and/or propanol. Lower C1-C3 alkanolamines such as mono-, di- and triethanolamines can also be used, by themselves or in combination with the lower alkanols. If utilized, phase stabilizers/co-solvents can comprise from about 0.1% to 5.0%by weight of the compositions herein. In one embodiment, the phase stabilizers and/or co-solvents are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10% of the composition.
The compositions of the present invention may comprise at least about 0.001%, in another embodiment from about 0.5% to about 10%, in another embodiment to about 5% by weight, of one or more scavenger agents. Scavenger agents suitable for use herein are selected from scavengers selected to capture fugitive dyes and/or anionic surfactants and/or soils.
Preferred scavenger agents are selected from the group consisting of fixing agents for anionic dyes, complexing agents for anionic surfactants, clay soil control agents and mixtures thereof. These materials can be combined at any suitable ratio. Suitable compounds are included in commonly patents to Gosselink et al and are commercially available from BASF, Ciba and others.
i) Fixing Agents for Anionic dyes—Dye fixing agents, “fixatives”, or “fixing agents” are well-known, commercially available materials which are designed to improve the appearance of dyed fabrics by minimizing the loss of dye from fabrics due to washing. Not included within this definition are components which can in some embodiments serve as fabric softener actives.
Many fixing agents for anionic dyes are cationic, and are based on quaternized nitrogen compounds or on nitrogen compounds having a strong cationic charge.
Fixing agents are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) ex Crosfield; INDOSOL E-50 (Feb. 27, 1984, Ref. No. 6008.35.84; polyethyleneimine-based) ex Sandoz; SANDOFIX TPS, ex Sandoz. Additional non-limiting examples include SANDOFIX SWE (a cationic resinous compound) ex Sandoz, REWIN SRF, REWIN SRF-O and REWIN DWR ex CHT-Beitlich GMBH; Tinofix® ECO, Tinofix® FRD and Solfin® ex Ciba-Geigy and described in WO 99/14301. Other fixing agents for use in the compositions of the present invention are CARTAFIX CB® ex Clariant and the cyclic amine based polymers, oligomers or copolymers described in WO 99/14300.
Other fixing agents useful herein are described in “Aftertreatments for Improving the Fastness of Dyes on Textile Fibres”, Christopher C. Cook, Rev. Prog. Coloration, Vol. XII, (1982). Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid-diamine condensates, inter alia the hydrochloride, acetate, methosulphate and benzyl hydrochloride salts of diamine esters. Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamine methosulphate, and monostearylethylene diaminotrimethylammonium methosulphate. In addition, N-oxides other than surfactant-active N-oxides, more particularly polymeric N-oxides such as polyvinylpyridine N-oxide, are useful as fixing agents herein. Other useful fixing agents include derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates, and aminated glycerol dichlorohydrins.
Dye transfer inhibiting agents also include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R—Ax —Z; wherein Z is a polymerizable unit to which an N—O group can be attached or the N—O group can form part of the polymerizable unit or the N—O group can be attached to both units; A is one of the following structures: —NC(O)—, —C(O)O—, —S—, —O—, —N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N—O group can be attached or the N—O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N—O group can be represented by the following general structures: [Figure] wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N—O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa<10, preferably pKa<7, more preferred pKa<6.
Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as “PVNO”.
The most preferred polyamine N-oxide useful in the rinse added compositions and processes herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as “PVPVI”) are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. “Modern Methods of Polymer Characterization”, the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2: 1, more preferably from 0.8:1 to 0.3: 1, most preferably from 0.6:1 to 0.4: 1. These copolymers can be either linear or branched.
The present compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50: 1, and more preferably from about 3:1 to about 10:1.
ii) Scavenger agents for anionic surfactants and/or soils—Suitable scavenger agents for anionic surfactants and/or soils include alkoxylated polyalkyleneimines and/or quaternized derivatives thereof.
Fabric softeners, when present, are suitably at levels of up to about 30% by weight of the composition, more typically from about 1% to about 20%, in another embodiment from about 2% to about 10% in certain embodiments. In one embodiment, the fabric softeners are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10% of the composition. Suitable fabric softeners for use in the present invention include all the current commercial quaternary long-chain softeners, especially at least partially unsaturated esterquats with varying iodine value. Suitable fabric softeners more generally include fabric softening compounds which are cationic, water insoluble quaternary ammonium compounds comprising a polar head group and two long hydrocarbyl moieties, in one embodiment selected from alkyl, alkenyl and mixtures thereof, wherein each such hydrocarbyl moiety has an average chain length equal to or greater than C12, in another embodiment greater than C14, in another embodiment greater than C16, In another embodiment, at least 50% of each long chain alkyl or alkenyl group is predominantly linear. In one embodiment, an overall chain length is about C18, though mixtures of chainlengths having non-zero proportions of lower, e.g., C14, C16 and some higher, e.g., C20 chains can be quite desirable. The cationic softener can suitably be distearyl dimethyl ammonium chloride or unsaturated analogs thereof, in another embodiment for the environment, the quaternary ammonium fabric softener is selected to be biodegradable. This property is present, for example, in the common commercial esterquat fabric softeners such as di(tallowyloxyethyl)dimethyl ammonium chloride.
In one embodiment, the fabric softening compound is a quaternary ammonium esterquat compound having two C12-22 alkyl or alkenyl groups connected to a quaternary ammonium moiety via at least one ester moiety, in another embodiment two such ester moieties. One esterquat ammonium fabric softener for use in the present compositions has the formula:
{(R1)2N((CH2)nER2)2}+X− wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2-4 alkenyl; and wherein each R2 is independently selected from C8-28 alkyl or alkenyl groups; E is an ester moiety i.e., —OC(O)- or —C(O)O—, n is an integer from 0-5, and X− is a suitable anion, for example chloride, methosulfate and mixtures thereof.
A second type of quaternary ammonium material can be represented by the formula: {(R1)3N(CH2)nCH(O(O)CR2)CH2O(O)CR2}+X− wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2-4 alkenyl; each R2 is independently selected from C8-28 alkyl or alkenyl groups; n is an integer from 0-5; and X− is a suitable anion, for example chloride, methosulfate and mixtures thereof. This latter class can be exemplified by 1,2 bis[hardened tallowoyloxy]-3-trimethylammonium propane chloride.
Esterquat fabric softeners as available in commerce include materials comprising varying proportions of monoester in addition to diester.
Suitable fabric softeners herein include softening compounds having a solubility less than 1×10−3 wt %, in another embodiment less than 1×10−4 wt %, in another embodiment, from 1×10−6 wt % to 1×10−8 wt %, in demineralised water at 20 degrees C.
Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and/or for fabric restoration. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and known amylases, or combinations thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. A preferred enzyme combination comprises a cocktail of conventional detersive enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase. Detersive enzymes are described in greater detail in U.S. Pat. No. 6,579,839.Particularly preferred compositions herein contain from about 0.05% to about 2% by weight of detersive enzymes.
Enzymes, when present, comprise from about 0.001% to about 10%, in another embodiment form about 0.01% to 8%, in another embodiment form about 0.1% to 6% in another embodiment form about 1% to 5% by weight of the composition. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Proteases useful herein include those like subtilisins from Bacillus [e.g. subtilis, lentus, licheniformis, amyloliquefaciens (BPN, BPN′), alcalophilus,] e.g. Esperase®, Alcalase®, Everlase® and Savinase® (Novozymes), BLAP and variants [Henkel]. Further proteases are described in EP130756, WO91/06637, WO95/10591 and WO99/20726.
Amylases (α and/or β) are described in WO 94/02597 and WO 96/23873. Commercial examples are Purafect Ox Am® [Genencor] and Termamyl®, Natalase®, Ban®, Fungamyl® and Duramyl® [all ex Novozymes]. Amylases also include, for example, α-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc.
The cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307, Barbesgoard et al, issued Mar. 6, 1984. Cellulases useful herein include bacterial or fungal cellulases, e.g. produced by Humicola insolens, particularly DSM 1800, e.g. 50 Kda and −43 kD [Carezyme®]. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum.
Suitable lipases include those produced by Pseudomonas and Chromobacter groups. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 41,947) is a preferred lipase for use herein. Also preferred are e.g., Lipolase Ultra®, Lipoprime® and Lipex® from Novozymes. Also suitable are cutinases [EC 3.1.1.50] and esterases. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on Feb. 24, 1978. This lipase is available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P “Amano,” hereinafter referred to as “Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
Carbohydrases useful herein include e.g. mannanase (for example, those disclosed in U.S. Pat. No. 6,060,299), pectate lyase (for example, those disclosed in PCT Application WO99/27083), cyclomaltodextringlucanotransferase (for example, those disclosed in PCT Application WO96/33267), xyloglucanase (for example, those disclosed in PCT Application WO99/02663).
Bleaching enzymes useful herein with enhancers include e.g. peroxidases, laccases, oxygenases, (e.g. catechol 1,2 dioxygenase, lipoxygenase (for example, those disclosed in PCT Application WO 95/26393), (non-heme) haloperoxidases.
A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Pat. No. 3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978, and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No. 3,600,319, issued Aug. 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published Oct. 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Pat. No. 3,519,570.
In one embodiment, the liquid compositions of the present invention are substantially free of (i.e. contain no measurable amount of) wild-type protease enzymes.
If an enzyme or enzymes are included in the compositions of the present invention, it is preferred that the composition also contain an enzyme stabilizer. Enzymes can be stabilized using any known stabilizer system like calcium and/or magnesium compounds, boron compounds and substituted boric acids, aromatic borate esters, peptides and peptide derivatives, polyols, low molecular weight carboxylates, relatively hydrophobic organic compounds [e.g. certain esters, diakyl glycol ethers, alcohols or alcohol alkoxylates], alkyl ether carboxylate in addition to a calcium ion source, benzamidine hypochlorite, lower aliphatic alcohols and carboxylic acids, N,N-bis(carboxymethyl) serine salts; (meth)acrylic acid-(meth)acrylic acid ester copolymer and PEG; lignin compound, polyamide oligomer, glycolic acid or its salts; poly hexa methylene bi guanide or N,N-bis-3-amino-propyl-dodecyl amine or salt; and mixtures thereof.
Additional stability can be provided by the presence of various other an-disclosed stabilizers, especially borate species. See Severson, U.S. Pat. No. 4,537,706. Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition. This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions. Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts. A small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water. In solid detergent compositions the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal performance. Accordingly, as a general proposition the compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.
In a liquid composition, the degradation by the proteolytic enzyme of second enzymes can be avoided by protease reversible inhibitors [e.g. peptide or protein type, in particular the modified subtilisin inhibitor of family VI and the plasminostrepin; leupeptin, peptide trifluoromethyl ketones, peptide aldehydes.
Suitable chelants for use herein include nitrogen-containing, P-free aminocarboxylates such as EDDS, EDTA and DTPA; aminophosphonates such as diethylenetriamine pentamethylenephosphonic acid and, ethylenediamine tetramethylenephosphonic acid; nitrogen-free phosphonates e.g., HEDP; and nitrogen or oxygen containing, P-free carboxylate-free chelants such as compounds of the general class of certain macrocyclic N-ligands such as those known for use in bleach catalyst systems. Levels of chelant are typically lower than about 20%, in another embodiment, chelants, when present, are at levels of from about 1% to about 15%. In another embodiment, the chelants are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10% of the composition.
The solvent system in the present compositions can be anhydrous or hydrous; and can include water alone or mixtures of organic solvents with water. Organic solvents include 1,2-propanediol, ethanol, glycerol and mixtures thereof. Other lower alcohols, C1-C4 alkanolamines such as monoethanolamine and triethanolamine, can also be used. Solvent systems can be absent, for example from anhydrous solid embodiments of the invention, but more typically are present at levels in the range of from about 0.1% to about 98%, in another embodiment at least about 10% to about 95%, in another embodiment from about 25% to about 75%.
The liquid detergent compositions according to the present invention also contain an aqueous, non-surface active liquid carrier. Generally the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be relatively large. Preferably, the compositions of the present invention comprise from about 40% to about 80% of an aqueous liquid carrier.
The most cost effective type of aqueous, non-surface active liquid carrier is, of course, water itself. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, for purposes of the present invention, the utilization of such water-miscible liquids should be minimized to hold down compsotion cost. Accordingly, the aqueous liquid carrier component of the liquid detergent products herein will generally comprise water present in concentrations ranging from about 30% to 70%, more preferably from about 35% to about 50%, by weight of the composition.
Effervescent systems suitable herein include those derived by combining an acid and a bicarbonate or carbonate, or by combining hydrogen peroxide and catalase, or any other combination of materials which release small bubbles of gas. The components of the effervescent system may be combinedly dispensable to form the effervescence when they are mixed, or can be formulated together provided that conventional coatings or protection systems are used. Levels of effervescent system can vary very widely, for example effervescent components together can range from about 0.1% to about 30% of the composition. Hydrogen peroxide and catalase are very mass efficient and can be at much lower levels with excellent results.
Any suitable coatings or encapsulating agents can be applied to all or a part of the present compositions. Suitable examples include polyvinylalcohol film or other suitable variations; carboxymethylcellulose, cellulose derivatives, starch, modified starch, sugars, PEG, waxes, or combinations thereof. Coatings can have one or a plurality of layers. The amount of coating material, for any material coated, can range from about 5% to about 50% by weight of the material to be coated or encapsulated.
The detergent compositions of the present invention further may comprise an effective amount of an opacifying agent, substantially suspended within the composition. As used herein, the term “opacifying agent” refers to a material which, when added to a formulation having a transmittance of from about 55% to 100% when measured at 440 nm wavelength, is capable of producing a formulation having a transmittance reading of about 20% or less when measured at a 440 nm wavelength. The amount and type of opacifier used will depend on the particular formulation and how much is necessary to produce a formulation with a transmittance of less than about 20%, preferably from about 15% to about 0.1%.
Preferably, the composition comprises from about 0.02% to about 0.5%, by weight of the composition, of the opacifying agent, more preferably from about 0.05% to about 0.4%, more preferably from about 0.1% to about 0.25%.
Preferred opacifying agents for use herein include particles have a mean particle size of from about 50 nanometers to about 300 microns, preferably from about 100 nanometers to about 200 microns, more preferably from about 100 nanometers to about 500 nanometers, more preferably from about 150 nanometers to about 300 nanometers. Preferred opacifying agents are selected from polymer particles, more preferably acrylic or styrene-based polymers, more preferably polyacrylate/polystyrene copolymers.
The compositions of the present invention may optionally contain from about 0.01% to about 10%, preferably from about 2% to about 7%, more preferably from about 3% to about 5%, by weight the composition, of a fatty acid containing from about 8 to about 20 carbon atoms. The fatty acid can also contain from about 1 to about 10 ethylene oxide units in the hydrocarbon chain.
Suitable fatty acids are saturated and/or unsaturated and can be obtained from natural sources such a plant or animal esters (e.g., palm kernel oil, palm oil, coconut oil, babassu oil, safflower oil, tall oil, castor oil, tallow and fish oils, grease, and mixtures thereof), or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher Tropsch process). Examples of suitable saturated fatty acids for use in the compositions of this invention include captic, lauric, myristic, palmitic, stearic, arachidic and behenic acid. Suitable unsaturated fatty acid species include: palmitoleic, oleic, linoleic, linolenic and ricinoleic acid. Examples of preferred fatty acids are saturated C12 fatty acid, saturated C12-C14 fatty acids, and saturated or unsaturated C12 to C18 fatty acids, and mixtures thereof.
In the detergent compositions herein containing a fatty acid component, the weight ratio of quaternary ammonium softening agent to fatty acid is preferably from about 1:3 to about 3:1, more preferably from about 1:1.5 to about 1.5:1, most preferably about 1:1.
The compositions of the present invention may contain a dye to either provide a particular color to the composition itself (non-fabric substantive dyes) or to provide a hue to the fabric (hueing dyes). In one embodiment, the compositions of the present invention may contain from about 0.0001 to about 0.01% of a non-fabric substantive dye and/or a hueing dye.
Examples of hueing dyes useful herein include Basic Violet 3 (Cl 42555) and Basic Violet 4 (Cl 42600), both commercially available from Standard Dyes. In one embodiment, the hueing dyes are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10%, of the composition.
The compositions of the present invention may contain a bleaching agent. In one embodiment, the compositions of the present invention may contain from about 0.10% to about 10%, by weight of the composition, of a bleaching agent.
Bleaching agents useful herein include hydrogen peroxide or peroxyacids such as 6-phthalimidoperoxyhexanoic acid.
The compositions of the present invention may contain a radical scavenger which may be used with liquid hydrogen peroxide to provide stability. Radical scavengers useful herein include trimethoxybenzoic acid.
The compositions of the present invention may contain a fluorescent whitening agent. Fluorescent whitening agents useful herein include those that are compatible with an acidic environment such as Tinopal CBS-X.
The compositions of the present invention may contain a suds suppressor. In one embodiment, the suds suppressor is a non-fatty acid suds suppressor. Examples of non-fatty acid suds supressors useful herein include silica/silicone type, silicone oil, branched alcohols, and mixtures thereof. In one embodiment, the suds supressors are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10%, of the composition.
The compositions of the present invention may contain a soil suspension polymer. In one embodiment, the soil suspension polymer is selected from PEI ethoxylates, HMDA diquate ethoxylates, sulfonated derivatives, hydrophobically modified anionic copolymers. Particularly preferred are PEI with MW=182 and an average degree of ethoxylation=15, PEI with MW=600 and an average degree of ethoxylation=20, hexamethylenediamine dimethyquat with an average degree of ethoxylation=24, and hexamethylenediamine dimethyquat with an average degree of ethoxylation=24 (disulfonated). Examples of hydrophobically modified anionic copolymers useful herein include Acusol 480 ®, commercially available from Rohm and Haas and Alcosperse® 725 and 747, commercially available from Alco Chemical. In one embodiment, the soil suspension polymers are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10% of the composition.
The compositions of the present invention may contain a soil release polymer. In one embodiment, the soil release polymer is a PET alkoxylate short block copolymer, anionic derivative, or mixture thereof. In one embodiment, the soil release polymers are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10% of the composition.
The compositions of the present invention may contain a rheology modifier. Rheology modifiers useful herein include methylcellulose, hydroxypropylmethylcellulose, xanthan gum, gellan gum, guar gum and hydroxypropyl guar gum, succinoglycan, and trihydroxystearin. Particularly preferred are methylcellulose and hydroxypropylmethylcellulose thickeners available under the Methocel® trade name from Dow Chemical. When used herein, the detergent compositions of the present invention contain from about 0.01 to about 1%, by weight of the composition, of a rheology modifier. In one embodiment, the compositions herein contain from about 0.02 to about 0.75%, alternatively from about 0.05% to about 0.5%, by weight of the composition, of the rheology modifier.
Examples of other suitable cleaning adjunct materials include, but are not limited to, fatty acids, alkoxylated benzoic acids or salts thereof such as trimethoxy benzoic acid or a salt thereof (TMBA), conventional (not fabric substantive) perfumes and pro-perfumes, anionic surfactants, including but not limited to linear alkylbenzene sulfonates, alkyl sulfates, alkyl ethoxysulfates and mixtures thereof, including also linear and branched (including mid-chain branched forms) of such surfactants, zwitterionic and/or amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzyme stabilizing systems, optical brighteners or fluorescers, soil release polymers, dispersants or polymeric organic builders including water-soluble polyacrylates, acrylate/maleate copolymers and the like, suds suppressors, dyes, colorants, filler salts such as sodium sulfate, hydrotropes such as toluenesulfonates, cumenesulfonates and naphthalenesulfonates, photoactivators, hydrolyzable surfactants, preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, color speckles, colored beads, spheres or extrudates, sunscreens, fluorinated compounds, clays, pearlescent agents, luminescent agents or chemiluminescent agents, anti-corrosion and/or appliance protectant agents, alkalinity sources or other pH adjusting agents, solubilizing agents, carriers, processing aids, pigments, free radical scavengers, and pH control agents. Suitable materials include those described in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. In one embodiment, the any one of these adjuncts are present at less than 10%, in another embodiment less than 5%, in another embodiment less than 2%, in another embodiment, less than 1%, in another embodiment, less than 0.1%, in another embodiment from about 0.01% to about 2%, in another embodiment form about 1% to 10% of the composition.
Due to the nature of the single liquid detergent composition containing dual benefits (softening & cleaning), it may be desirable to co-brand the liquid detergent compositions of the present invention with two or more tradenames, at least one recognizable by consumers as a detergent brand and another recognizable by consumers as a fabric softening brand. Examples of such co-branding include “Tide® with Downy®; “Wisk® with Snuggle®”; and the like. Co-branding may include the dual use of standard marketing materials for each of the brands, such as utilizing the colors associated with a laundry detergent brand in conjunction with the colors associated with a fabric softening brand. Similarly, both tradenames could be used or tradedress of each of the brands.
Such co-branding is useful to provide the consumer with the knowledge that the liquid laundry detergent composition will provide both cleaning and fabric softening benefits, similar to that of their previously recognizable cleaning detergent brand and fabric softening brand.
The detergent compositions of the present invention have a viscosity in the range of from about 30 to about 12,000 mPa.s (milli Pascal seconds), alternatively in the range of from about 150 to about 5,000 mPa.s. Preferably, the detergent compositions of the present invention have a viscosity in the range of from about 100 to about 1,500 mPa.s, alternatively from about 150 to about 400 mPa.s. The detergent compositions herein may be in the form of a gel, pourable gels, non-pourable gels, or heavy-duty liquids.
“Gel” as used herein includes a shear thinning gel with a pouring viscosity in the range of from 1,000 to 5,000 mPa.s, in one embodiment less than 3,000 mPa.s, alternatively less than 1,500 mPa.s. Gels may include thick liquids. More generally, a thick liquid may be a Newtonian fluid, which does not change its viscosity with the change in flow condition, such as honey or syrup. This type of thick liquid is very difficult and messy to dispense. A different type of liquid gel is shear-thinning, i.e. it is thick under low shear (e.g., at rest) and thin at high flow rates. The rheology of shear-thinning gels is described in more detail in the literature, see for example WO 04\027010A1 Unilever.
Other compositions according to the present invention are pourable gels having a viscosity of at least 1,500 mPa.s but no more than 6,000 mPa.s, in one embodiment no more than 4,000 mPa.s, alternatively no more than 3,000 mPa.s, alternatively no more than 2,000 mPa.s.
Yet other compositions according to the present invention are non-pourable gels having a viscosity of at least 6,000 mPa.s but no more than 12,000 mPa.s, in one embodiment no more than 10,000 mPa.s, alternatively no more than 8,000 mPa.s and especially no more than 7,000 mPa.s.
Preferred liquid or gel form laundry treatment compositions herein include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing-machines and liquid finewash and/or color care detergents; these suitably have the following rheological characteristics: viscosity of no more than 1,500 mPa.s, in one embodiment no more than 1,000 mPa.s, alternatively, no more than 500 mPa.s. Very suitable compositions have viscosity of from 150 to 400 mPa.s and are either Newtonian or shear-thinning.
In these definitions and unless specifically indicated to the contrary, all stated viscosities are those measured at a shear rate of 21 sec−1 and at a temperature of 25° C. Viscosity herein can be measured with any suitable viscosity-measuring instrument, e.g., a Carrimed CSL2 Rheometer at a shear rate of 21 sec−1.
All documents cited in the Detailed Description of the Invention are, are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 04252837.2 | May 2004 | EP | regional |
| 04252849.7 | May 2004 | EP | regional |
| 04252846.3 | May 2004 | EP | regional |
| 04252838.0 | May 2004 | EP | regional |
| 04252853.9 | May 2004 | EP | regional |
| 04252851.3 | May 2004 | EP | regional |
| 04252845.5 | May 2004 | EP | regional |
