Patent Application
20170137745
The present invention relates generally to cleaning compositions, particularly to laundry or dish detergent compositions, and more particularly to detergent compositions specifically designed for manual/hand washing or semi-automatic washing of fabric or dishware.
Detergents comprising anionic detersive surfactants for cleaning fabrics have been known for many years. Historically, cleaning laundry was defined primarily as a process that involved removal of stains. Consistent with this historical approach to cleaning, laundry detergent designers focused on formulating detergents with surfactants with longer carbon chains to ensure maximum surface activity of the surfactants to achieve the most effective soil removal.
Such long-chain surfactants can generate copious suds during wash cycles of the fabric laundering process. Therefore, consumers view high suds volume as the primary and most desirable signal of cleaning. For hand-washing consumers, who are still the dominating majority in most developing countries, high suds volume are especially desirable, since the consumers can directly feel and touch suds generated during the hand-washing process and intuitively correlate high suds volume with sufficient fabric cleaning.
Paradoxically, high volume of suds during the wash cycle will typically translate to more suds in the subsequent rinse cycle. When consumers observe suds during the rinse cycle, they immediately infer from it that there may still be surfactant residue on the fabrics. Surfactant residue remaining on the fabrics may cause irritation to the skin, and it may also render the fabrics “sticky” after drying, thereby likely to attract more dirt upon wearing. Consequently, the consumers will feel the need to rinse the fabric a few more times, until suds are completely or substantially disappeared from the rinse solution, signaling that the fabrics are now “clean” and free of surfactant residue. However, oftentimes one or two rinses are sufficient to remove most or all of surfactant residue from the fabrics, despite a significant amount of suds remaining in the rinse solution. In other words, the additional rinses are unnecessary and excessive. Such excessive rinsing requires additional time, labor, energy and water. For regions where resources are scarce, especially those regions suffering from water shortage, excessive rinsing is particularly undesirable.
Therefore, a sudsing profile of a detergent composition during both wash and rinse cycles of the fabric laundering process is important for the overall consumer laundering experience, particularly for hand-washing consumers.
There is a need to provide consumers with an improved laundry cleaning (i.e., laundering) experience, especially those consumers who are accustomed to manually washing their laundry, either entirely (i.e., full manual/hand laundering) or in conjunction with machine washing (i.e., semi-automatic laundering). Specifically, this improved laundering experience is enabled by a desired sudsing profile defined by at least four (4) key points of consumer observation (hereinafter “touch points”), which jointly connote to the consumer that the laundry is sufficiently cleaned and rinsed. A failure at any one of these touch points may result in the consumer having a less than an ideal laundering experience.
These four touch points, which are hereby labeled as “Flash Suds,” “Suds Mileage,” “Initial Rinse Suds,” “End Rinse Suds,” are explained hereinafter with reference to
Prior to the wash cycle, i.e., during a pre-wash step, a consumer will dissolve a laundry detergent product in a specific amount of water to form aqueous wash liquor, and the laundry to be treated will be brought into contact with the wash liquor.
The wash cycle starts with mechanical agitation of the laundry with the wash liquor, either in a washing machine or directly by the hands of the consumer, which leads to an initial bloom of suds that is characterized by a significantly high volume of suds (measured by height) generated at a relatively high speed (within the first 2-3 minutes of the wash cycle) during a first stage of the wash cycle, i.e., the “W-1” stage shown in
These two initial touch points indicate to the consumer that the laundry detergent is efficacious in cleaning the laundry and remains so throughout the entire wash cycle. If there are no flash suds or if the flash suds volume is not high enough at the W-1 stage, then the consumer may interpret that the laundry detergent product as not being efficacious. If the suds mileage is not maintained throughout a significant portion of the W-2 stage of the wash cycle, the consumer may interpret that the laundry detergent product is losing cleaning efficacy or that there is not enough surfactant in the detergent to effectively clean the entire laundry bundle.
After the wash cycle and before the rinse cycle, i.e., during an in-between step, the sufficiently washed laundry is separated from the wash liquor. The wash liquor is drained or otherwise disposed. The laundry is wrung or spun to remove any excess wash liquor, followed by contacting the laundry with clean water or a rinse solution. The suds volume (measured by height) during this in-between step is inconsequential to the consumer, so it is not measured, and the dotted line only indicates the approximate suds volume (measure by height) during this step for illustration purposes.
During the rinse cycle, mechanical agitation (either by machine or by hand) is also applied to the laundry in the rinse solution, in attempt to rinse any carry-over or residue surfactant and soil off the laundry. At a first stage of the rinse cycle, i.e., the “R-1” stage in
The fourth touch point calls for fast and significant withering of suds (indicated by the dotted arrowhead) at a second, subsequent stage of the rinse cycle (the “R-2” stage of
During the R-2 stage, if the rinse suds decrease is not significant or fast enough to lead to zero or near-zero End Rinse Suds volume (measured by height), it connotes to the consumer that there is still residue surfactant in the washed laundry or the rinse solution. Consequently, the consumer feels that the rinse is not completed yet and may needlessly spend additional time rinsing and/or using additional rinse water until all of the suds are eliminated or nearly eliminated. Therefore, it is important that the fourth touch point is present to connote that the detergent product can be easily rinsed away from the washed laundry, i.e., it is an easy-rinse formulation, which can provide a key point of differentiation for laundry detergent products.
A laundry detergent product that provides an optimized sudsing profile at all four touch points discussed hereinabove connotes high cleaning efficacy as well as the easy rinse benefits of the laundry detergent product. It may also help the consumer to save water and/or may reduce the time the user takes in rinsing the laundry. Conventional laundry detergents may provide a laundering experience at one or more of these touch points, but never has a product provided consumers with an optimized sudsing profile at all four of these touch points (while also providing cleaning efficacy). Accordingly, there is a need for such a laundry detergent product.
The present invention provides a cleaning composition having a branched alkyl sulfate surfactant in combination with a short-chain nonionic surfactant, which demonstrate superior sudsing profile through both the wash and rinse cycles of a dish washing or fabric laundering process. Specifically, the cleaning composition contains: (a) from about 5% to about 50%, by total weight of the cleaning composition (hereinafter referred to simply as “by weight”), of one or more branched, unalkoxylated C6-C14 alkyl sulfate (AS) surfactants; (b) from about 0.05% to about 10% by weight of one or more linear or branched C4-C11 alkyl or aryl alkoxylated alcohol (AA) surfactants having a weight average degree of alkoxylation ranging from about 1 to about 10; and (c) one or more additional ingredients. Unless otherwise specified, the one or more additional ingredients as used herein and in sections hereinafter typically are provided in an amount that makes up for 100% of the total weight of the respective composition.
The cleaning composition of the present invention is characterized by with an optimized sudsing profile at all of the above-mentioned four touch points during wash and rinse cycles, which is particularly delightful to hand-washing consumers.
Correspondingly, the present invention also relates to use of the above-mentioned cleaning composition for hand-washing dishes or fabrics. Further, the present invention relates to a method of treating a soiled material, including the steps of: (a) providing a cleaning composition as mentioned hereinabove; (b) contacting the cleaning composition with at least a portion of the soiled material; and (c) rinsing the soiled material. Preferably, the steps (b) and (c) are both conducted by hand, and the soiled material is more preferably soiled fabric. Particularly, the present invention relates to a laundry detergent composition containing:
(a) from about 1% to about 30%, preferably from about 2% to about 25%, more preferably from about 3% to about 20%, and most preferably from about 5% to about 15% by weight of a branched, unalkoxylated C12 AS surfactant; (b) from about 1% to about 30%, preferably from about 2% to about 25%, more preferably from about 3% to about 20%, and most preferably from about 5% to about 15% by weight of a branched, unalkoxylated C13 AS surfactant; (c) from about 0.1% to about 15%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 8%, and most preferably from about 2% to about 5% by weight of a linear C6 AA surfactant having a weight average degree of ethoxylation ranging from about 4 to about 6; and (d) one or more additional ingredients.
Still further, the present invention relates to a concentrated laundry detergent composition containing: (a) from about 20% to about 50%, preferably from about 25% to about 45%, and more preferably from about 30% to about 40% by weight of a branched, unalkoxylated C12 AS surfactant; (b) from about 20% to about 50%, preferably from about 25% to about 45%, and more preferably from about 30% to about 40% by weight of a branched, unalkoxylated C13 AS surfactant; (c) from about 5% to about 30%, preferably from about 8% to about 20%, and more preferably from about 10% to about 15% by weight of a linear C6 AA surfactant having a weight average degree of ethoxylation ranging from about 4 to about 6; and (d) one or more additional ingredients.
These and other features of the present invention will become apparent to one skilled in the art upon review of the following detailed description when taken in conjunction with the appended claims.
As used herein, “suds” indicates a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of a liquid. The terms like “suds”, “foam” and “lather” can be used interchangeably within the meaning of the present invention.
As used herein, “sudsing profile” refers to the properties of a detergent composition relating to suds character during the wash and rinse cycles. The sudsing profile may include, but is not limited to: the initial speed of suds generation upon dissolution in a washing solution, the volume and retention of suds during the wash cycle, the look and feel of suds generated, the amount of residue suds carried over to the rinse solution, and the speed of suds reduction or disappearance during the rinse cycle, which are all connected with the fabric laundering experience of the consumers. Preferably, the sudsing profile may include Initial Wash Suds Volume (measured by height in centimeters), Suds Mileage (measured by height in centimeters), Wash Suds Retention Percentage (%), Rinse Suds at 0 Minute (volume measured by height in centimeters), Rinse Suds at 1 Minute (volume measured by height in centimeters), and Rinse Suds Reduction Rate (%/min), as measured by using the Sudsing Profile Test described hereinafter. More preferably, the sudsing profile of detergent compositions according to the present invention is defined by the Initial Wash Suds Volume (cm), the Suds Mileage (cm), and the Rinse Suds Reduction Rate (%/min), as measured by using the Sudsing Profile Test described hereinafter. These three parameters evaluate the four touch points as discussed hereinabove for the wash and rinse cycles. The sudsing profile may further include additional suds-related parameters.
As used herein, the term “cleaning composition” means a liquid or solid composition for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, and includes hard surface cleaning and/or treatment including floor and bathroom cleaners (e.g., toilet bowl cleaners); hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents; personal care compositions; pet care compositions; automotive care compositions; and household care compositions. In one embodiment, the cleaning composition of the present invention is a laundry detergent composition, which can be in liquid, powder, paste, gel, unit dose, pouch, or tablet form. In another embodiment, the cleaning composition is dish detergent composition, which also can be in liquid, powder, paste, gel, unit dose, pouch, or tablet form.
As used herein, the term “soiled material” is used non-specifically and may refer to any type of flexible material consisting of a network of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations. Soiled material may further refer to any type of hard surface, including natural, artificial, or synthetic surfaces, such as, but not limited to, surfaces of glass, metal, plastic, porcelain or ceramic cooking articles or utensils, and table, countertop or floor surfaces formed of tile, granite, grout, composite, vinyl, hardwood, and the like, as well as blends and combinations.
As used herein, the term “laundry detergent composition” is a subset of “cleaning composition”, and includes all-purpose or “heavy-duty” washing agents for fabric, especially cleaning detergents in liquid, powder, paste, gel, unit dose, pouch, or tablet form, as well as cleaning auxiliaries such as bleach, rinse aids, additives or pre-treat types. In one embodiment, the laundry detergent composition is a heavy duty liquid laundry detergent; and in another embodiment, the laundry detergent composition is a free-flowing granular laundry detergent.
As used herein, the term “C4-C11 alkyl or aryl alkoxylated alcohol” refers broadly to alkoxylated alcohol that contains at least one C4-C11 alkyl group with a linear or branched structure, or a C4-C11 aryl group. In other words, C4-C11 defines the total carbon number of the alkyl or aryl group, not the total carbon number of the alkoxylated alcohol compound. The C4-C11 aryl group can be either unsubstituted or substituted with an alkyl group that is either linear or branched, provided that the total carbon number of this group does not exceed 11. If the C4-C11 aryl group contains an alkyl substitution, the C4-C11 aryl group can be connected to the alkoxylated alcohol either through a ring carbon or through the alkyl substitution.
As used herein, articles such as “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
As used herein, the terms “comprising,” “comprises,” “include”, “includes” and “including” are meant to be non-limiting. The term “consisting of” is meant to be limiting, i.e., excluding any components or ingredients that are not specifically listed except when they are present as impurities. The term “consisting essentially of,” on the other hand, allows the presence of other components or ingredients as long as they do not interfere with the functions of those components or ingredients that are specifically listed.
As used herein, the term “substantially free of” or “substantially free from” refers to the presence of no more than 0.5%, preferably no more than 0.2%, and more preferably no more than 0.1%, of an indicated material in a composition, by total weight of such composition.
As used herein, the term “essentially free of” means that the indicated material is not deliberately added to the composition, or preferably not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity of one of the other materials deliberately added.
As used herein, the term “solid” includes granular, powder, bar and tablet product forms.
As used herein, the term “fluid” includes liquid, gel, paste and gas product forms.
As used herein, the term “liquid” refers to a fluid having a liquid having a viscosity of from about 1 to about 2000 mPa*s at 25° C. and a shear rate of 20 sec-1. In some embodiments, the viscosity of the liquid may be in the range of from about 200 to about 1000 mPa*s at 25° C. at a shear rate of 20 sec-1. In some embodiments, the viscosity of the liquid may be in the range of from about 200 to about 500 mPa*s at 25° C. at a shear rate of 20 sec-1. The viscosity can be determined using a Brookfield viscometer, No. 2 spindle, at 60 RPM/s.
All temperatures herein are in degrees Celsius (° C.) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20° C. and under the atmospheric pressure.
In all embodiments of the present invention, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise. The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
It is understood that the test methods that are disclosed in the Test Methods Section of the present application must be used to determine the respective values of the parameters of Applicants' inventions are described and claimed herein.
Inventors of the present invention has discovered that cleaning compositions containing the combination of a branched anionic surfactant (i.e., branched, unalkoxylated C6-C14 alkyl sulfate) with a short-chain nonionic surfactant (i.e., linear or branched C4-C11 alkyl or aryl alkoxylated alcohol) demonstrate an improved sudsing profile, which is characterized by a high “Flash Suds” volume at the W-1 stage and good “Suds Mileage” at the W-2 stage of the wash cycle, a moderate amount of “Initial Rinse Suds” at the R-1 stage of the rinse cycle, and a drastically faster reduction and disappearance of rinse suds leading to zero or near-zero “End Rinse Suds” at the R-2 stage of the rinse cycle.
Such a unique sudsing profile provides hand-wash consumers with delightful washing and rinsing experience, especially during the rinse stage. The volume of suds generated and sustainability/stability thereof during the wash cycle are sufficiently high, thereby signaling to the consumer that effective cleaning is occurring. A moderate amount of suds is observed at the beginning of the rinse cycle, which is expected by the consumer after observing a large amount of suds generated during the wash as a sign of effective cleaning. However, once the rinse cycle starts, the suds undergo drastic and fast reduction and disappearance during the first one or two minutes of rinsing. Consumers, especially the ones conducting hand-wash, will have the chance to visually observe the drastic and fast reduction and disappearance of rinse suds, eventually resulting in a clear rinse solution with little or no suds at the end of the first rinse cycle. The visual perception of suds reduction and disappearance by the consumers provides a clear signal that the article to be cleansed has gone through effective cleaning and sufficient rinsing, and is now free of soil as well as residue surfactant. Therefore, the consumers will confidently stop the laundering process after the first rinse cycle, thus eliminating the need for additional rinses and potentially enabling the concept of single rinse.
The surprising and unexpected sudsing profile achieved by the cleaning compositions of the present invention is specifically characterized by a high Initial Wash Suds Volume, a high Suds Mileage, and a high Rinse Suds Reduction Rate, as measured by using the Sudsing Profile Test described hereinafter. Specifically, the unique sudsing profile is defined by: a) an Initial Wash Suds Volume (measured by height) of no less than about 30 cm; b) a Suds Mileage (measured by height) of no less than about 30 cm; and c) a Rinse Suds Reduction Rate of no less than about 40%/min, which are measured using the Sudsing Profile Test described hereinafter. The Initial Wash Suds Volume evalutes the first touch point, i.e, the “Flash Suds” as discussed hereinabove, during W-1 stage of the wash cycle. The Suds Mileage evalues the second touch point as discussed hereinabove (therefore named after it) during W-2 stage of the wash cycle. The Rinse Suds Reduction Rate jointly evalutes the third and fourth touch points, i.e., the “Initial Rinse Suds” and “End Rinse Suds,” as discussed hereinabove during R-1 and R-2 stages of the rinse cycle.
The Initial Wash Suds Volume can be as high as about 45 cm, so it may range from about 30 cm to about 45 cm. Preferably, the Initial Wash Suds Volume of the cleaning composition is no less than about 35 cm, and preferably no less than about 40 cm. More preferably, the Initial Wash Suds Volume ranges from about 33 cm to about 44 cm, and preferably from about 34 cm to about 43 cm.
The Suds Mileage also has an upper limit of about 45 cm, so it may also range from about 30 cm to about 42 cm. Preferably, the Suds Mileage of the cleaning composition is no less than about 31 cm, preferably no less than about 32 cm, and more preferably no less than about 33 cm. More preferably, the Suds Mileage ranges from about 31 cm to about 42 cm, and preferably from about 32 cm to about 41 cm.
The Wash Suds Retention Percentage, which is calculated from the Initial Suds Volume and the Suds Mileage may range from 60% to 120%. Preferably, it is no less than 65%, or no less than 70%, or no less than 75%. More preferably, the Wash Suds Retention Percentage ranges from about 65% to about 100%.
The Rinse Suds Reduction Rate preferably ranges from about 40%/min to 100%/min. Preferably it ranges from about 50%/min to 100%/min. More preferably, it ranges from about 60%/min to 100%/min. Still more preferably, it ranges from about 70%/min to 100%/min. Yet more preferably, it ranges from about 80%/min to 100%/min.
This sudsing profile can be achieved by the combination of one or more branched, unalkoxylated C6-C14 alkyl sulfate (AS) surfactants with one or more linear or branched C4-C11 alkyl or aryl alkoxylated alcohol (AA) surfactants having a weight average degree of alkoxylation ranging from about 1 to about 10. When combined together, these two surfactants are found to interact with each other and achieve an improved and desired sudsing profile as described hereinabove.
The surfactant system of the present invention may contain one or more additional surfactants, other than the branched, unalkoxylated C6-C14 AS surfactants and the linear or branched C4-C11 alkyl or aryl AA surfactants, as long as such additional surfactants do not adversely affect the optimized sudsing profile established by the AS and AA surfactants, or otherwise interfere with functionalities of the AS and AA surfactants. Such additional surfactants may be selected from other anionic surfactants, other nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
The anionic surfactants suitable for the practice of the present invention are branched, unalkoxylated C6-C14 alkyl sulfates (hereinafter “AS”). EP2119764 discloses in Example 12 of Table 4 a combination of relatively short-chain nonionic surfactants (i.e., alkylene glycol ether 1 with a C8 alkyl group and PO2.3) with alkoxylated AS surfactants (i.e., sodium polyoxyethylene lauryl ether sulfate). However, it has been found that alkoxylation of the branched AS surfactants, even at a relatively low degree (e.g., a weight average degree of about 1), can adversely affect the sudsing profile of the cleaning composition. Specifically, there is a significantly higher amount of suds observed at the beginning of the rinse cycle, which undergoes little or no reduction through the rinse, leaving a significant amount of suds at the end of the first rinse cycle that can only be removed by one or more additional rinses. Therefore, it is desirable to employ unalkoxylated branched AS surfactants instead. Preferably, but not necessarily, the cleaning composition of the present invention is substantially free of alkoxylated alkyl sulfate surfactants, either linear or branched. More preferably, the cleaning composition of the present invention is essentially free of any alkoxylated alkyl sulfate surfactant.
Further, branching of the C6-C14 alkyl chain in the AS surfactants is important for ensuring stability of the suds generated during the wash cycle of the laundry process. US20050124738 discloses in Example 18 a combination of a mid-chain nonionic surfactant (a C10 alcohol ethoxylate) with an AS surfactant having a linear C12-C14 alkyl chain. However, it has been found that the use of linear AS, instead of branched AS, leads to poor suds stability during the wash cycle, and the resulting cleaning composition exhibits a sudsing profile with undesirably low suds mileage. Preferably, but not necessarily, the cleaning composition of the present invention is substantially free of linear alkyl sulfate surfactants.
Still further, the branched AS surfactants of the present invention are characterized by relatively short alkyl chains, i.e., with from about 6 to about 14 carbon atoms. Preferably, the branched AS surfactants of the present invention have branched alkyl moieties of different carbon chain lengths, while the weight average carbon number of all branched alkyl moieties ranges from about 9 to about 14, more preferably from about 10 to about 13, and most preferably from about 11 to about 13. WO9739088 discloses mid-chain branched alkyl sulfates that contain branched alkyl moieties with total carbon numbers ranging from 14 to 20 and an average total carbon number of greater than 14.5 (see WO9739088, page 11, lines 8-12). Specifically, Example 11 of WO9739088 discloses the combination of a mid-chain branched AS having an average total carbon number of 16.5 with a C9-C11 alcohol ethoxylate nonionic surfactant. However, it has been found that branched AS surfactants with longer alkyl chains, e.g., with more than 14 carbon atoms in total or with an average total carbon number of 14 or more, have adverse effect on the sudsing profile of the cleaning composition. Specifically, the amount of carried-over suds from the wash cycle to the rinse cycle increases significantly, in comparison with that of branched AS surfactants with shorter alkyl chains. Moreover, the carried-over suds undergoes little or no reduction during the rinse, and at the end of the first rinse there is still a significant suds left on the surface of the rinse solution that can only be removed by additional rinses. Therefore, it is desirable to employ branched AS surfactants with relatively short alkyl chains (i.e., C6-C14), and preferably their branched alkyl moieties are characterized by a weight average carbon number ranging from about 9 to about 14, more preferably from about 10 to about 13, and most preferably from about 11 to about 13. Preferably, but not necessarily, the cleaning composition of the present invention is substantially free of longer chain (i.e., C15 or above) alkyl sulfate surfactants, either linear or branched.
The branched, unalkoxylated AS surfactants of the present invention may exist in an acid form, while the acid form may be neutralized to form a salt. Typical agents for neutralization include metal counterion bases, such as hydroxides, e.g., NaOH or KOH. Further suitable agents for neutralizing anionic surfactants in their acid forms include ammonia, amines, or alkanolamines. Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; suitable alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may be done to a full or partial extent, e.g., part of the anionic surfactant mix may be neutralized with sodium or potassium and part of the anionic surfactant mix may be neutralized with amines or alkanolamines.
In a preferred but not necessary embodiment of the present invention, the branched, unalkoxylated C6-C14 AS surfactants have the general formula (I):
while M is a cation of alkali metal, alkaline earth metal, ammonium, amine or alkanolamine; x and y are independently selected from integers ranging from 0 to about 10; z is an integer ranging from about 1 to about 4; the sum of x+y is equal to or greater than z; and the sum of x+y+z ranges from about 3 to about 11. Preferably, z is about 1, and the sum of x+y is from about 8 to about 9.
Non-limiting examples of suitable branched, unalkoxylated AS surfactants of the present invention include those having the following chemical structures:
It is particularly preferred that the cleaning composition of the present invention contains a mixture of two or more branched, unalkoxylated C6-C14 AS surfactants. More preferably, such a mixture includes: (1) a branched, unalkoxylated C12 AS surfactant in the amount ranging from about 20% to about 80%, preferably from about 30% to about 70%, and more preferably from about 35% to about 50%, by total weight of the mixture; and (2) a branched, unalkoxylated C13 AS surfactant in the amount ranging from about 20% to about 80%, preferably from about 30% to about 70%, and more preferably from about 35% to about 50%, by total weight of the mixture. Most preferably, the mixture is consisting of or consisting essentially of the branched, unalkoxylated C12 AS surfactant and the branched, unalkoxylated C13 AS surfactant.
Branched, unalkoxylated AS surfactants are commercially available as a mixture of linear isomer and branched isomer with a variety of chain lengths and degrees of branching, which include but are not limited to sulphated Isalchem® 123 from Sasol with C12-13 chain length distribution and about 95% branching, and Neodol® 123 AS from Shell with C12-13 chain length distribution and about 20% branching.
The cleaning composition of the present invention may contain the branched, unalkoxylated C6-C14 AS surfactants as described hereinabove in an amount ranging from about 5% to about 50%, preferably from about 6% to about 40%, more preferably from about 8% to about 30%, and most preferably from about 10% to about 20%, by total weight of the cleaning composition. In more concentrated formulations with 2×, 3×, or 4× compaction ratios, the branched, unalkoxylated C6-C14 AS surfactants may be present in higher amounts ranging from 30% to 50%, preferably from 35% to 45%, and more preferably from 40% to 45% by weight of the concentrated formulations.
The nonionic surfactants suitable for the practice of the present invention are either linear or branched alkyl or aryl alkoxylated alcohols (which are also sometimes referred to as alcohol alkoxylates or simply “AA”) containing: (1) relatively short carbon chains or relatively small aromatic rings, i.e., C4-C11 alkyl or aryl moieties, preferably C4-C10 alkyl or aryl moieties, more preferably C4-C8 alkyl or aryl moieties, and most preferably C4-C6 alkyl or aryl moieties, and (2) having a weight average degree of alkoxylation, i.e., the weight average number of alkoxylated moieties contained by said AA, ranging from about 1 to about 10, preferably from about 2 to about 8, more preferably from about 3 to about 7, and most preferably from about 4 to about 6. The C4-C11 aryl moiety of the AA surfactant can be either unsubstituted or substituted with an alkyl group that is either linear or branched, provided that the total carbon number of this group does not exceed 11. If the C4-C11 aryl moiety contains an alkyl substitution, the C4-C11 aryl moiety can be connected to the alkoxylated alcohol either through a ring carbon or through the alkyl substitution. Preferably, the AA surfactant used in the practice of the present invention contains a C4-C11 alkyl moiety.
Nonionic AA surfactants with longer carbon chains, such as those with C12-C20 alkyl moieties, are known in the art for their uses in cleaning compositions, including laundry detergent compositions. However, short chain AA surfactants, e.g., those with C4-C11 alkyl moieties, are much less commonly used in this manner, because of their poor suds performance. When used alone, such short chain AA surfactants produce little or no wash suds at all.
Therefore, it has been a surprising and unexpected discovery of the present invention that such short chain AA surfactants can interact with the above-described branched C6-C14 AS anionic surfactants to produce a cleaning composition capable of generating higher volumes of suds that are more stable (i.e., better suds mileage) during the wash cycle, while carrying over only a moderate amount of suds into the rinse solution, which almost completely disappears within a minute or two of the first rinse cycle, resulting in a rinse solution with little or no residue suds at the end of the first rinse cycle.
Further, it has been discovered that in comparison with short chain AA surfactants of the present invention, longer chain AA surfactants (e.g., with C12 and/or C14 alkyl moieties) exhibit poorer rinse suds performance when combined with the branched C6-C14 AS anionic surfactants. Specifically, a significantly higher amount of wash suds is carried over from the wash cycle to the rinse cycle, with little or no suds reduction during the rinse. Further, such longer chain AA surfactants, when combined with the branched C6-C14 AS anionic surfactants, exhibit poorer suds stability and noticeably lower suds mileage during the wash cycle, in comparison with that of shorter chain nonionic AA surfactants of the present invention. Therefore, it is desirable to employ short chain nonionic AA surfactants with C4-C11 alkyl or aryl moieties for practice of the present invention. Preferably, but not necessarily, the cleaning composition of the present invention is substantially free of longer chain AA surfactants (i.e., with C12 or longer alkyl moieties), either linear or branched.
The Short Chain AA surfactants of the present invention may comprise one or more alkoxylated moieties. Such alkoxylated moieties may be either linear or branched. Each of such alkoxylated moieties may contain from 1 to 10 carbon atoms. Preferably, the alkoxylated moieties are selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and mixtures thereof.
In a particularly preferred embodiment of the present invention, the short chain AA surfactants have the following general formula:
R1—O—(CH2—CHR2—O)n—(CH2—CH2—O)m—R3 (II),
wherein R1 is linear or branched C4-C11 alkyl or aryl, such as phenyl or substituted phenyl; R2 is linear or branched C1-C8 alkyl; R3 is hydrogen, linear or branched C1-C6 alkyl, benzoyl, acetyl, acryloyl or methacryloyl; n has a weight average value ranging from 0 to about 5; m has a weight average value ranging from about 1 to about 10; m>n and n+m is less than or equal to about 10.
Preferably, R1 is C4-C11 alkyl, more preferably C4-C10 alkyl, and still more preferably C4-C8 alkyl, and most preferably C4-C6 alkyl. In a particularly preferred embodiment of the present invention, R1 is linear C4-C11 alkyl, more preferably linear C4-C10 alkyl, and still more preferably linear C4-C8 alkyl, and most preferably linear C4-C6 alkyl.
In an alternative embodiment of the present invention, R1 is preferably phenyl or substituted phenyl. Substitutes on the phenyl radical can be linear or branched C1-C5 alkyls, which can optionally be further substituted with one or more function groups selected from the group consisting of amido, imido, carboxylic ester, halide and ether. Preferably, the substitute on the phenyl radical is an unsubstituted C1-C5 alkyl group.
Particularly preferred R1 radicals are derived from the following alcohols: hexanol, phenol, butanols (especially n-butanol and isobutanol), pentanols, ter-amyl alcohol, heptanols, octanols (specially n-octanols and 2-ethylhexanol), isononanol, decanol, isodecanol, 2-propylheptanol, and mixtures thereof. In addition, it is possible to use a mixture of a C4-C8 alcohol cut or a C5-C9 alcohol cut.
R2 is preferably C1-C4 alkyl, more preferably either methyl or ethyl, and most preferably methyl.
R3 is preferably hydrogen or C1-C4 alkyl, and more preferably hydrogen, methyl or ethyl, and most preferably hydrogen. The radical R3, if it is other than hydrogen, serves as what is typically referred to as an end group cap in order to stabilize the AA surfactants, when it is in an alkaline solution, for example.
The values n and m represent weight average values, since in the alkoxylation of alcohols, generally a distribution of the degree of alkoxylation is obtained. The sum of n+m is preferably from about 2 to about 8, more preferably from about 3 to about 7, and most preferably from about 4 to about 6. This means that the total weight average degree of alkoxylation in the short chain AA surfactants of the present invention may range from about 2 to about 8, preferably from about 3 to about 7, and more preferably from about 4 to about 6.
In a preferred embodiment, n has a weight average value (hereinafter simply referred to as the value of n) of less than or equal to about 2, and m has a weight average value (hereinafter simply referred to as the value of m) ranging from about 3 to about 10. In a particularly preferred embodiment of the present invention, n is 0, which means that the short chain AA surfactants of the present invention are primarily ethoxylated. In this event, m may preferably range from 2 to about 8, more preferably from about 3 to about 7, and most preferably from about 4 to about 6.
In a further preferred embodiment, n is 0 and m ranges from about 3 to about 9 when R1 is phenyl. In a still further preferred embodiment, n is less than or equal to about 2, and m ranges from about 3 to about 6 when R1 is a C4-C6 alkyl.
If both alkoxylation groups, i.e., the CH2—CHR2—O— and the CH2—CH2—O— groups, are present in such short chain AA surfactants, they can be distributed either randomly or in blocks. These alkoxylation groups are introduced into the short chain AA surfactants of the present invention by reaching the corresponding alcohols R1—OH with an alkylene oxide compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and the like. Preferably, the compound is selected from the group consisting of ethylene oxide, propylene oxide, and mixture thereof. When different alkylene oxides are used, the reaction can be carried out with the different alkylene oxides arranged in blocks (successively or alternately) or simultaneously (random or mixed).
The following are exemplary short chain AA surfactants for practice of the present invention: ethoxylated butanol with a weight average EO value of about 3; ethoxylated butanol with a weight average EO value of about 4; ethoxylated butanol with a weight average EO value of about 5; ethoxylated butanol with a weight average EO value of about 6; ethoxylated hexanol with a weight average EO value of about 3; ethoxylated hexanol with a weight average EO value of about 4; ethoxylated hexanol with a weight average EO value of about 5; ethoxylated hexanol with a weight average EO value of about 6; ethoxylated phenol with a weight average EO value of about 3; ethoxylated phenol with a weight average EO value of about 4; ethoxylated phenol with a weight average EO value of about 5; ethoxylated phenol with a weight average EO value of about 6; and the like. The stated EO values are rounded. Particularly preferred are the AA surfactants based on hexanol and phenol.
Commercially available short chain AA surfactants that can be used for practicing the present invention include, but are not limited to: Emulan® HE50 from BASF, which is a C6 alcohol with a weight average number of ethoxylation of about 5; and EcoSurf® 6 from Dow Chemical, which is a C8 alcohol with a weight average number of ethoxylation of about 6.
The cleaning composition of the present invention may contain the short chain AA surfactants as described hereinabove in an amount ranging from about 0.05% to about 10%, preferably from about 0.1% to about 6%, more preferably from about 0.5% to about 5%, and most preferably from about 1% to about 4%, by total weight of the cleaning composition. In more concentrated formulations with 2×, 3×, or 4× compaction ratios, the short chain AA surfactants may be present in higher amounts ranging from 15% to 30%, and preferably from 20% to 25%, by weight of the concentrated formulations.
The weight ratio of the above-described branched C6-C14 AS surfactants to the linear or branched C4-C11 AA surfactants is preferably in the range of from about 20:1 to about 1:2, more preferably from about 10:1 to about 1:1, still more preferably from about 8:1 to about 2:1, and most preferably from 5:1 to 4:1.
It has been discovered that different weight ratios of the branched AS surfactants to the short chain AA surfactants have different impact on the sudsing profile of the resulting cleaning composition. When such weight ratio is above 1:1 (i.e., there are more branched AS surfactants in the cleaning composition than the short chain AA surfactants), preferably above 2:1, more preferably from about 4:1 to about 5:1, the wash suds stability improves, and better suds mileage is achieved during the wash cycle.
In addition to the above-described branched AS surfactants and short chain AA surfactants, the surfactant system of the present invention may comprise one or more additional surfactants selected from the group consisting of other anionic surfactants (different from the branched AS surfactants described hereinabove), other nonionic surfactants (different from the short AA surfactants described hereinabove), cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Such additional surfactants may be present in the cleaning composition of the present invention in a total amount ranging from about 1% to about 75% by total weight of the composition, preferably from about 2% to about 35%, more preferably from about 5% to about 10%.
Other Anionic Surfactants
In some examples, the additional surfactants may comprise one or more other anionic surfactants. In some examples, the additional surfactants may consist essentially of, or even consist of one or more other anionic surfactants.
Specific and non-limiting examples of suitable other anionic surfactants include any conventional anionic surfactants. For example, conventional soaps, which are water-soluble salts of fatty acids, can be used as the other anionic surfactants. Suitable soaps include alkali metal salts, such as the sodium, potassium, ammonium, and alkyl ammonium salts, of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Also suitable for use herein are non-soap synthetic anionic surfactants, which include but are not limited to: alkyl sulfonates, alkyl benzene sulfonates, alkoxylated alkyl sulfates (also known as alkyl ether sulfates or alkyl polyethoxylate sulfates), linear alkyl sulfates, alkyl ester sulfates, alkyl ester sulphonates, alkyl phosphates or phosphonates, alkyl carboxylates, alkyl ether carboxylates, and the like. Preferred other non-soap anionic surfactants are selected from the group consisting of: (1) C10-C20 linear alkyl benzene sulphonates; (2) C10-C20 linear or branched alkylalkoxy sulfates having an average degree of alkoxylation ranging from 0.1 to 5.0; (3) C10-C20 linear or branched alkyl ester sulfates or sulphonates; (4) C10-C20 linear or branched alkyl sulphonates, phosphates, phosphonates, or carboxylates; and combinations thereof.
Preferred for the practice of the present invention are surfactant systems that contain one or more C10-C20 linear alkyl benzene sulphonates (LAS), in addition to the branched AS surfactants and the short chain AA surfactants described hereinabove. The LAS can be present in an amount ranging from 0% to about 50%, preferably from about 1% to about 45%, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%, by total weight of the surfactant system. Also preferred are surfactant systems further containing one or more C10-C20 linear or branched alkylalkoxy sulfates (AxS) having an average degree of alkoxylation ranging from about 0.1 to about 5, and preferably from about 0.5 to about 3. The AxS can be present in an amount ranging from 0% to about 30%, preferably from about 1% to about 20%, more preferably from about 2% to about 15%, and most preferably from about 5% to about 10%, by total weight of the surfactant system. Further suitable other anionic surfactants include methyl ester sulfonates and alkyl ether carboxylates.
Other Nonionic Surfactants
In some aspects, the additional surfactants comprise one or more other nonionic surfactants. In certain aspects, the cleaning composition may comprise such other nonionic surfactants in an amount ranging from about 0.1% to about 40%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 5%, by total weight of the cleaning composition.
Suitable other nonionic surfactants can comprise any conventional nonionic surfactant. These can include, for e.g., longer chain alkoxylated alcohols with C12 to C20 alkyl or aryl moieties, C14-C22 mid-chain branched alcohols, alkyl polysaccharides (specifically alkyl polyglycosides), amine oxides, polyhydroxy fatty acid amides.
Cationic Surfactants
In some examples, the additional surfactants comprise one or more cationic surfactants. In certain aspects, the cleaning composition of the present invention comprises such cationic surfactants in a total amount ranging from about 0.1% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.1% to about 2%, by total weight of the composition.
Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants containing functional groups with up to 26 carbon atoms, such as alkoxylated quaternary ammonium (AQA) surfactants or alkyl quaternary ammonium surfactants, dimethyl hydroxyethyl quaternary ammonium or dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; cationic ester surfactants; and amino surfactants, specifically amido propyldimethyl amine (APA). Suitable quaternary ammonium compounds are those having the general formula of (R)(R1)(R2)(R3)N+X−, wherein R is a linear or branched, substituted or unsubstituted C6-18 alkyl or alkenyl moiety, R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, suitable anions include: halides, for example chloride; sulphate; and sulphonate. Suitable cationic detersive surfactants are mono-C6-18 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highly suitable cationic detersive surfactants are mono-C8-10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C10-12 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-C10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
Suitable cationic surfactants may also include alkyl pyridinium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
Zwitterionic Surfactants
Examples of suitable zwitterionic surfactants include: derivatives of secondary and tertiary amines; derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds; betaines, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine; C8 to C18 (for example from C12 to C18) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group can be C8 to C18 and in certain embodiments from C10 to C14.
Amphoteric Surfactants
Examples of suitable amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight or branched-chain and where one of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. Examples of compounds falling within this definition are sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino) propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino) octadecanoate, disodium 3-(N-carboxymethyldodecylamino)propane 1-sulfonate, disodium octadecyl-imminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis (2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof.
As used herein the phrase “cleaning composition” or “detergent composition” includes compositions and formulations designed for cleaning soiled material. Such compositions include but are not limited to, laundry cleaning compositions and detergents (either with the typical surfactant activity or in a concentrated form with significantly higher surfactant activity), fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation. The cleaning compositions may have a form selected from liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, bar, or flake.
Because the surfactant system itself provides the desired sudsing benefit, the cleaning composition of the present invention does not require any suds suppressors, such as silicone antifoam or suds collapsing polymers, which functions to minimize the manufacturing and processing costs associated with such cleaning composition. In a preferred embodiment of the present invention, the cleaning composition is substantially free of, and preferably is essentially free of, silicone suds suppressor. In a more preferred embodiment of the present invention, the cleaning composition is substantially free of, or essentially free of, any suds suppressor.
The cleaning composition of the present invention can be formulated or designed either as an automatic machine wash detergent product, or a semi-automatic detergent product, or a hand-wash detergent product. Due to the improved sudsing profile of such composition, which is most visible to the consumers during hand-wash, it is preferred that it is a detergent product specifically designed for hand-wash, in order to highlight its sudsing benefit and delight the consumer.
The cleaning composition can be a laundry detergent composition. Preferably, but not necessarily, such laundry detergent composition has a normal surfactant activity level, and it contains: (1) from about 1% to about 30%, preferably from about 2% to about 25%, more preferably from about 3% to about 20%, and most preferably from about 5% to about 15% by weight of a branched C12 AS surfactant; (2) from about 1% to about 30%, preferably from about 2% to about 25%, more preferably from about 3% to about 20%, and most preferably from about 5% to about 15% by weight of a branched C13 AS surfactant; and (3) from about 0.1% to about 15%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 8%, and most preferably from about 2% to about 5% by weight of a linear C6 AA surfactant having a weight average degree of ethoxylation ranging from about 4 to about 6.
Alternatively, such laundry detergent composition is in a concentrated form having, for example, 2×, 3×, or 4× of the normal surfactant activity. Preferably, the concentrated laundry detergent composition contains: (1) from about 20% to about 50%, preferably from about 25% to about 45%, and more preferably from about 30% to about 40% by weight of the branched C12 AS surfactant; (2) from about 20% to about 50%, preferably from about 25% to about 45%, and more preferably from about 30% to about 40% by weight of the branched C13 AS surfactant; and (3) from about 5% to about 30%, preferably from about 8% to about 20%, and more preferably from about 10% to about 15% by weight of the linear C6 AA surfactant having a weight average degree of ethoxylation ranging from about 4 to about 6.
Because the surfactant system itself provides the desired sudsing benefit, the cleaning composition of the present invention does not require any suds suppressors, such as silicone antifoam or suds collapsing polymers, which functions to minimize the manufacturing and processing costs associated with such cleaning composition. Specifically, in a preferred embodiment of the present invention, the cleaning composition is substantially free of, and preferably is essentially free of, any suds suppressors.
In a preferred but not necessary embodiment of the present invention, the cleaning composition is a granular or powder detergent composition, more preferably a granule or powder laundry detergent composition, having a density ranging from 250 g/l to about 1000 g/1, more preferably from about 300 g/l to about 900 g/1, and most preferably from about 400 g/l to about 850 g/l. The powder or granular detergent may comprise: (a) from 0.1% to 40%, preferably from 0.5% to 30%, and more preferably from 3% to 25%, of a water-soluble alkali metal carbonate (such as sodium carbonate), by totally weight of such granular detergent composition; and/or (b) from 10% to 95%, preferably from 20% to 90%, and more preferably from 30% to 80%, of a water-soluble alkali metal sulfate (such as sodium sulfate), by total weight of the granular detergent composition; and/or (c) from about 10% to about 95%, preferably from about 20% to about 90%, and more preferably from about 30% to about 80%, of a water-soluble alkali metal chloride (such as sodium chloride), by totally weight of such granular detergent composition. Such a granule laundry detergent composition may further comprise one or more adjunct ingredients commonly used for formulating granular laundry detergent compositions, such as builders, carriers, structurants, flocculating aid, chelating agents, dye transfer inhibitors, enzymes, enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, hydrotropes, processing aids, pigments and/or aesthetic particles.
The powder or granular detergent composition preferably comprises only low levels of phosphate or zeolite builders, or more preferably it is substantially free of, or most preferably it is completely free of, phosphate or zeolite builders.
In another embodiment of the present invention, the cleaning composition is a liquid detergent composition, preferably a liquid laundry detergent composition, having a viscosity ranging from about 200 to about 800 mPa·s measured at 25° C. at a shear rate of 20 sec−1. The liquid detergent composition may be packaged in a single phase or multiphase unit dose form, i.e., it is contained in a single compartment or multi-compartment water-soluble pouch formed, for example, by a water-soluble polymer such as polyvinvyl alcohol (PVA) and/or polyvinylpyrrolidone (PVP).
The liquid detergent composition of the present invention may further comprise, in addition to the ingredients described hereinabove, from about 0.1% to about 10%, preferably from about 0.5% to about 8%, and more preferably from about 1% to about 5% of one or more acids, such as citric acid, boric acid, and mixture thereof, by total weight of the liquid detergent composition. Preferably, the liquid detergent composition contains from about 1 wt % to about 3 wt % of citric acid and/or from about 1 wt % to about 3 wt % of boric acid. In addition, fatty acids, particularly C12-C18 fatty acids, or salts thereof can be included in the liquid laundry detergent composition of the present invention. The total amount of such fatty acids or salts may range from about 0.1 wt % to about 5 wt %, preferably from about 0.5 wt % to about 4 wt %, and more preferably from about 0.7 wt % to about 3 wt %.
The liquid detergent composition of the present invention typically contains one or more carriers, such as water. It can contain either water alone as the sole carrier, or mixtures of organic solvent(s) with water as carriers. Suitable organic solvents are linear or branched lower C1-C8 alcohols, diols, glycerols or glycols; lower amine solvents such as C1-C4 alkanolamines, and mixtures thereof. Particularly preferred organic solvents include 1,2-propanediol, ethanol, glycerol, monoethanolamine and triethanolamine. The carriers are typically present in the liquid detergent composition of the present invention at levels in the range of from about 10% to about 95%, preferably from about 25% to about 75%, by total weight of the liquid detergent composition. In some embodiments, water is from about 85 to about 100 wt % of the carrier. In other embodiments, water is absent and the composition is anhydrous. Highly preferred compositions afforded by the present invention are clear, isotropic liquids.
In a further preferred but not necessary embodiment of the present invention, the cleaning composition is in a unit dose form, which contains a liquid laundry detergent encapsulated within a water-soluble film. Preferred film materials are preferably polymeric materials selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers are selected polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof.
The cleaning compositions of the invention may also contain one or more adjunct cleaning additives. Suitable adjunct cleaning additives include builders, fillers, carriers, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, polymeric dispersing agents, polymeric grease cleaning agents, enzymes, enzyme stabilizing systems, amines, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibiting agents, chelating agents, softeners or conditioners (such as cationic polymers or silicones), perfumes (including perfume encapsulates), hygiene and malodor treatment agents, and the like.
More specifically, the adjunct cleaning additives may include: transition metal catalysts; imine bleach boosters; enzymes such as amylases, carbohydrases, cellulases, laccases, lipases, bleaching enzymes such as oxidases and peroxidases, proteases, pectate lyases and mannanases; source of peroxygen such as percarbonate salts and/or perborate salts, preferred is sodium percarbonate, the source of peroxygen is preferably at least partially coated, preferably completely coated, by a coating ingredient such as a carbonate salt, a sulphate salt, a silicate salt, borosilicate, or mixtures, including mixed salts, thereof; bleach activator such as tetraacetyl ethylene diamine, oxybenzene sulphonate bleach activators such as nonanoyl oxybenzene sulphonate, caprolactam bleach activators, imide bleach activators such as N-nonanoyl-N-methyl acetamide, preformed peracids such as N,N-pthaloylamino peroxycaproic acid, nonylamido peroxyadipic acid or dibenzoyl peroxide; brighteners; hueing agents; photobleach; fabric-softening agents such as clay, silicone and/or quaternary ammonium compounds; flocculants such as polyethylene oxide; dye transfer inhibitors such as polyvinylpyrrolidone, poly 4-vinylpyridine N-oxide and/or co-polymer of vinylpyrrolidone and vinylimidazole; fabric integrity components such as oligomers produced by the condensation of imidazole and epichlorhydrin; soil dispersants and soil anti-redeposition aids such as alkoxylated polyamines and ethoxylated ethyleneimine polymers; anti-redeposition components such as polyesters and/or terephthalate polymers, polyethylene glycol including polyethylene glycol substituted with vinyl alcohol and/or vinyl acetate pendant groups; perfumes such as perfume microcapsules, polymer assisted perfume delivery systems including Schiff base perfume/polymer complexes, starch encapsulated perfume accords; soap rings; aesthetic particles including coloured noodles and/or needles; dyes; fillers such as sodium sulphate, although it may be preferred for the composition to be substantially free of fillers; carbonate salt including sodium carbonate and/or sodium bicarbonate; silicate salt such as sodium silicate, including 1.6 R and 2.0 R sodium silicate, or sodium metasilicate; co-polyesters of di-carboxylic acids and diols; cellulosic polymers such as methyl cellulose, carboxymethyl cellulose, hydroxyethoxycellulose, or other alkyl or alkylalkoxy cellulose, and hydrophobically modified cellulose; carboxylic acid and/or salts thereof, including citric acid and/or sodium citrate; and any combination thereof.
A wide variety of other ingredients may be used in the cleaning compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and solid or other liquid fillers, erythrosine, colliodal silica, waxes, probiotics, surfactin, aminocellulosic polymers, zinc ricinoleate, perfume microcapsules, rhamnolipids, sophorolipids, glycopeptides, methyl ester sulfonates, methyl ester ethoxylates, sulfonated estolides, cleavable surfactants, biopolymers, silicones, modified silicones, aminosilicones, deposition aids, locust bean gum, cationic hydroxyethylcellulose polymers, cationic guars, hydrotropes (especially cumenesulfonate salts, toluenesulfonate salts, xylenesulfonate salts, and naphalene salts), antioxidants, BHT, PVA particle-encapsulated dyes or perfumes, pearlescent agents, effervescent agents, color change systems, silicone polyurethanes, opacifiers, tablet disintegrants, biomass fillers, fast-dry silicones, glycol distearate, hydroxyethylcellulose polymers, hydrophobically modified cellulose polymers or hydroxyethylcellulose polymers, starch perfume encapsulates, emulsified oils, bisphenol antioxidants, microfibrous cellulose structurants, properfumes, styrene/acrylate polymers, triazines, soaps, superoxide dismutase, benzophenone protease inhibitors, functionalized TiO2, dibutyl phosphate, silica perfume capsules, and other adjunct ingredients, silicate salts (e.g., sodium silicate, potassium silicate), choline oxidase, pectate lyase, mica, titanium dioxide coated mica, bismuth oxychloride, and other actives.
The cleaning compositions described herein may also contain vitamins and amino acids such as: water soluble vitamins and their derivatives, water soluble amino acids and their salts and/or derivatives, water insoluble amino acids viscosity modifiers, dyes, nonvolatile solvents or diluents (water soluble and insoluble), pearlescent aids, additional surfactants or nonionic cosurfactants, pediculocides, pH adjusting agents, perfumes, preservatives, chelants, proteins, skin active agents, sunscreens, UV absorbers, vitamins, niacinamide, caffeine, and minoxidil.
The cleaning compositions of the present invention may also contain pigment materials such as nitroso, monoazo, disazo, carotenoid, triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine, anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine, botanical, and natural colors, including water soluble components such as those having C.I. Names. The cleaning compositions of the present invention may also contain antimicrobial agents.
The present invention includes methods for cleaning soiled material using the cleaning compositions of the present invention. As will be appreciated by one skilled in the art, the cleaning compositions of the present invention are suited for use in laundry pretreatment applications, laundry cleaning applications, and home care applications.
Preferably, such a method is a method of using the detergent compositions of the present invention to clean soiled material, which includes, but are not limited to, the steps of providing a detergent composition as described hereinabove (either in neat form or diluted in a wash liquor), contacting such detergent composition with at least a portion of a soiled material, and then rinsing the soiled material.
For use in laundry pretreatment applications, the method may include contacting the cleaning compositions described herein with soiled fabric. Following pretreatment, the soiled fabric may be laundered in a washing machine or otherwise rinsed.
The cleaning compositions of the present invention are particular suitable for hand washing applications, or combined hand washing with semi-automatic washing machines. Specifically, the consumers directly bring the soiled material into contact with the cleaning compositions, manually or semi-manually clean the soiled material, and then rinse off the soiled material in one or more rinse cycles.
Alternatively, the cleaning compositions of the present invention are suitable for machine laundry methods, which may comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry cleaning composition in accord with the invention.
Another method includes contacting a nonwoven substrate impregnated with an embodiment of the cleaning composition with soiled material. As used herein, “nonwoven substrate” can comprise any conventionally fashioned nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those marketed under the tradenames SONTARA® by DuPont and POLYWEB® by James River Corp.
An “effective amount” of the cleaning composition means from about 10 g to about 300 g of product dissolved or dispersed in a wash solution of volume from about 5 L to about 65 L. The water temperatures may range from about 5° C. to about 100° C. The water to soiled material (e.g., fabric) ratio may be from about 1:1 to about 30:1. The compositions may be employed at concentrations of from about 500 ppm to about 15,000 ppm, preferably from about 1000 ppm to about 10,000 ppm and more preferably from about 3000 ppm to about 5000 ppm, in solution. In the context of a fabric laundry composition, usage levels may also vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water, as well as the type of washing machine (e.g., top-loading, front-loading, top-loading, vertical-axis Japanese-type automatic washing machine).
The cleaning compositions herein may be used for laundering of fabrics at reduced wash temperatures. These methods of laundering fabric comprise the steps of delivering a laundry cleaning composition to water to form a wash liquor and adding a laundering fabric to said wash liquor, wherein the wash liquor has a temperature of from about 0° C. to about 20° C., or from about 0° C. to about 15° C., or from about 0° C. to about 9° C. The fabric may be contacted to the water prior to, or after, or simultaneous with, contacting the laundry cleaning composition with water.
Various techniques are known in the art to determine the properties of the compositions of the present invention comprising the branched AS surfactant and the short-chain nonionic AA surfactant. However, the following assays must be used in order that the invention described and claimed herein may be fully understood.
Sudsing profile of test detergent compositions herein is measured by employing a suds cylinder tester (SCT). The SCT has a set of eight (8) cylinders. Each cylinder is a plastic cylinder about 66 cm long that has uniform inner diameter of 50 mm through its length and can be capped or sealed by a rubber stopper during rotation. The 8 cylinders are all attached to a horizontal axis at the middle part of each cylinder. All 8 cylinders are arranged perpendicular to the horizontal axis but parallel to one another. The cylinders are spaced apart with equal distances in between, and they may be rotated together the around the horizontal axis along a vertical plan that is perpendicular to the horizontal axis at a speed of 20-22 revolutions per minute (rpm).
The following factors may affect the measurement results and therefore should be controlled carefully: (a) concentration of the test detergent composition in the washing solution and rinsing solution; (b) hardness of the water used to form the washing and rinsing solution; (c) water temperature; (d) speed and number of rotations of the SCT cylinders; (e) type of soil used and the total soil load used in the wash; and (f) cleanness of the interior of the SCT cylinders.
Following steps are followed to obtain the suds measurements for each test detergent composition:
Preparation of Fabric Loaded with BJ Clay:
Preparation of Fabric Loaded with DCO:
An inventive powder laundry detergent formulation containing a branched AS surfactant and a short-chain AA nonionic surfactant is prepared according to the present invention. Following is the detailed compositional breakdown of this formulation:
1Isalchem ® 123 commercially available from Sasol, containing more than 40% of C12 AS and more than 40% of C13 AS, both branched and unalkoxylated and having at least 90% branching.
2Emulan ® HE50 commercially available from BASF.
The inventive powder laundry detergent formulation is used to form a wash solution by dissolving 15 grams of the detergent in 3 liters of tap water at a temperature of about 20° C. The wash solution is then used to manually treat 300 g of dry fabric, which include half piece of a dirty shirt and clean pieces of cotton fabric to balance the weight. The treatment involves hand-scrubbing the half piece of the dirty shirt for 20 times and each cotton fabric piece for 10 times. The treated fabric is then wringed 2-3 times to reach a wet weight of about 900 g. Subsequently, a rinse solution is formed by diluting the wash solution carried over through the wet treated fabric into 4 liters of tap water.
An inventive liquid laundry detergent formulation containing a branched AS surfactant and a short-chain AA nonionic surfactant is prepared according to the present invention. Following is the detailed compositional breakdown of this formulation:
1Isalchem ® 123 commercially available from Sasol. It is provided as a 75% active raw material with 0.6% of NaOH, 0.8% of sodium sulfate, 1-1.3% C12-C13 residue alcohol carried over from the synthesis of the alkyl sulfate, and balance water.
2Emulan ® HE50 commercially available from BASF. It is provided as a 100% active raw material.
The inventive powder laundry detergent formulation is used to form a wash solution by dissolving 15 grams of the detergent in 3 liters of tap water at a temperature of about 20° C. The wash solution is then used to manually treat 300 g of dry fabric, which include half piece of a dirty shirt and clean pieces of cotton fabric to balance the weight. The treatment involves hand-scrubbing the half piece of the dirty shirt for 20 times and each cotton fabric piece for 10 times. The treated fabric is then wringed 2-3 times to reach a wet weight of about 900 g. Subsequently, a rinse solution is formed by diluting the wash solution carried over through the wet treated fabric into 4 liters of tap water.
Four powder laundry detergent compositions are prepared, which include: (1) a control composition containing no branched AS surfactant and no short-chain AA surfactant (“Control 1”); (2) a comparative composition A similar in formulation to the control composition but with an additional 12 wt % of branched C12-C13 AS surfactants, which is commercially available as Isalchem® 123 from Sasol (“Comparative Example A”); (3) a comparative composition B similar in formulation to the control composition but with an additional 3 wt % of a linear C6 alkylethoxylated alcohol with a weight average degree of ethoxylation of about 5, which is commercially available as Emulan® HE50 from BASF (“Comparative Example B”); and (4) an inventive composition similar in formulation to the control composition, but with an additional 12 wt % of the branched C12-C13 AS surfactants and an additional 3 wt % of the linear C6 alkylethoxylated alcohol (“Inventive Example 1”).
The detailed compositional breakdowns of the above-described four powder laundry detergent compositions are as follows:
1Isalchem ® 123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
The above-described four powder laundry detergent compositions are subject to the Suds Profile Test described in Test 1, with the following test results:
The Inventive Example 1 generates more initial suds during the beginning of the wash cycle and also has better Suds Mileage through the wash than both the Comparative Examples A and B, either considered alone or added together. Further, the rinse suds of the Inventive Example 1 during the first rinse cycle is sufficiently low (comparable with that of Comparative Example A). Therefore, the Inventive Example 1, by combining the branched C12-C13 AS surfactants with the linear C6 AA alcohol, provides a sudsing profile that is desirable for powder laundry detergent application.
Four liquid laundry detergent compositions are prepared, which include: (1) a control composition containing no branched AS surfactant and no short-chain AA surfactant (“Control 2”); (2) a comparative composition A similar in formulation to the control composition but with an additional 12 wt % of the same branched C12-C13 AS surfactants as described hereinabove in Example 3 (“Comparative Example C”); (3) a comparative composition B similar in formulation to the control composition but with an additional 3 wt % of the same linear C6 AA alcohol as described hereinabove in Example 3 (“Comparative Example D”); and (4) an inventive composition similar in formulation to the control composition, but with an additional 12 wt % of the branched C12-C13 AS surfactants and an additional 3 wt % of the linear C6 AA alcohol (“Inventive Example 2”).
The detailed compositional breakdowns of the above-described four liquid laundry detergent compositions are as follows:
1Isalchem ® 123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
The above-described four liquid laundry detergent compositions are subject to the Suds Profile Test described in Test 1, with the following test results:
The Inventive Example 2 generates more initial suds during the beginning of the wash cycle and also has better Suds Mileage through the wash than both the Comparative Examples C and D, either considered alone or added together. Further, the rinse suds of the Inventive Example 1 during the first rinse cycle is sufficiently low (comparable with that of Comparative Example C). Therefore, the Inventive Example 1, by combining the branched C12-C13 AS surfactants with the linear C6 AA alcohol, provides a sudsing profile that is also desirable for liquid laundry detergent application.
An inventive powder laundry detergent composition (“Inventive Example 3”) is compared with a comparative composition E, which is similar in formulation to the Inventive Example 3 except that it contains a linear C12-C14 AS surfactant instead of the branched C12-C13 AS surfactant (“Comparative Example E”). The compositional breakdowns of Inventive Example 3 and Comparative Example E are provided below side-by-side:
1Isalchem ® 123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
The above-mentioned two powder laundry detergent formulations are subjected to the Sudsing Profile Test described in Test 1, and following are the results:
The Inventive Example 3 of the present invention (which contains the branched C12-C13 AS surfactant) exhibits significantly better Suds Mileage and higher Wash Suds Retention Percentage during the wash than the Comparative Example E (which contains the linear C12-C14 AS surfactant), while the rinse suds results of the two formulations are relatively comparable.
The same inventive powder laundry detergent composition described in Example 5 (“Inventive Example 3”) is further compared with a comparative composition F, which is similar in formulation to the Inventive Example 3 except that it contains a longer chain C12-C14 AA nonionic surfactant instead of the short chain C6 AA nonionic surfactant (“Comparative Example F”). The compositional breakdown of the Comparative Example F is provided hereinafter side-by-side with Inventive Example 3:
1Isalchem ® 123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
The above-mentioned two powder laundry detergent formulations are subjected to the Sudsing Profile Test described in Test 1, and following are the results:
The Inventive Example 3 of the present invention (which contains the short chain AA nonionic surfactant) exhibits significantly better Rinse Suds Reduction Rate than the Comparative Example F (which contains the longer chain C12-C14 AA nonionic surfactant). The wash suds results of these two formulations are relatively comparable, while the Inventive Example 3 has slightly better Suds Mileage and higher Wash Suds Retention Percentage during the wash than the Comparative Example F.
The same inventive powder laundry detergent composition described in Example 5 (“Inventive Example 3”) is further compared with a comparative composition G, which is similar in formulation to the Inventive Example 3 except that it contains an alkoxylated branched C12-C13 AS surfactant with an average degree of ethoxylation of about 1 instead of the unalkoxylated branched C12-C13 AS surfactant (“Comparative Example G”). The compositional breakdown of the Comparative Example G is provided hereinafter side-by-side with Inventive Example 3:
1Isalchem ® 123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
The above-mentioned two powder laundry detergent formulations are subjected to the Sudsing Profile Test described in Test 1, and following are the results:
The Inventive Example 3 of the present invention (which contains the unalkoxylated branched AS surfactant) exhibits significantly better Rinse Suds Reduction Rate than the Comparative Example G (which contains the ethoxylated branched AS surfactant).
The same inventive powder laundry detergent composition described in Example 5 (“Inventive Example 3”) is further compared with a comparative composition H, which is similar in formulation to the Inventive Example 3 except that it contains a branched AS surfactant with a longer C14-C15 alkyl chain instead of the C12-C13 branched AS surfactant (“Comparative Example H”). The compositional breakdown of the Comparative Example H is provided hereinafter side-by-side with Inventive Example 3:
1Isalchem ®123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
3Isalchem ®145 commercially available from Sasol.
The above-mentioned two powder laundry detergent formulations are subjected to the Sudsing Profile Test described in Test 1, and following are the results:
The Inventive Example 3 of the present invention (which contains the C12-C13 branched AS surfactant) exhibits significantly better Rinse Suds Reduction Rate than the Comparative Example H (which contains the longer chain C14-C15 branched AS surfactant).
The same inventive powder laundry detergent composition described in Example 5 (“Inventive Example 3” or “IE 3”) is further compared with several other inventive powder detergent compositions (“Inventive Examples 4-7” or “IE 4-7”) that are similar in formulations, except for the different weight ratios of the branched AS surfactant to the short chain AA nonionic surfactant. Specifically, Inventive Examples 4-7 have AS:AA weight ratios of 1:2, 1:1, 2:1, and 5:1, while Inventive Example 3 has an AS:AA weight ratio of 4:1. The compositional breakdowns of the Inventive Examples 4-7 are provided hereinafter side-by-side with Inventive Example 3:
1Isalchem ®123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
All the above-mentioned five inventive powder laundry detergent formulations are subjected to the Sudsing Profile Test described in Test 1, with the following results:
All Inventive Examples 3-7 of the present invention exhibits significant suds reduction during the first rinse cycle, e.g., having a Rinse Suds Reduction Rate of 70% or more. However, Inventive Examples 3, 6 and 7 with higher AS:AA weight ratios (e.g., 2:1, 4:1 and 5:1) exhibit better Suds Mileage through the wash. Therefore, it is preferred (although not necessary) for the detergent compositions of the present invention to have a higher AS:AA weight ratio, e.g., of from 2:1 to 5:1 and more preferably from 4:1 to 5:1.
Powder laundry detergent compositions 10A-10F are formulated according to the present invention, by mixing together ingredients listed hereinbelow:
0-0.5
1Isalchem ®123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
Liquid laundry detergent compositions 11A-11F are formulated according to the present invention, by mixing together ingredients listed hereinbelow:
0-1.2
0-1.2
0-0.5
0-0.5
0-0.5
1Isalchem ®123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
3Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g., Purafect Prime ®, Excellase ®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase ®, Coronase ®).
4Available from Novozymes, Bagsvaerd, Denmark (e.g., Natalase ®, Mannaway ®).
5Available from Novozymes (e.g., Whitezyme ®).
6Polyethyleneimine (MW = 600) with 20 ethoxylate groups per —NH.
7Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units, available from BASF as Sokalan PG101 ®.
8A compound having the following general structure: bis((C2H5O)(C2H4O)n)(CH3)—N+—CxH2x—N+—(CH3)-bis((C2H5O)(C2H4O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof, available from BASF as Lutenzit Z 96 ®
9DTPA is diethylenetriaminepentaacetic acid supplied by Dow Chemical, Midland, Michigan, USA.
10Suitable Fluorescent Whitening Agents are for example, Tinopal ® AMS, Tinopal ® CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland. It can be provided in the amount ranging from 0-5%.
11Suitable preservatives include methylisothiazolinone (MIT) or benzisothiazolinone (BIT), which can be provided in the amount ranging from 0-1%.
The following concentrated liquid laundry detergent compositions 12A-12E are prepared and then each encapsulated in a multi-compartment pouch formed by a polyvinyl alcohol-film.
1Isalchem ®123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
Dish wash detergent composition 13A-13F are formulated according to the present invention by mixing together with ingredients listed.
1Isalchem ®123 commercially available from Sasol.
2Emulan ® HE50 commercially available from BASF.
All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated. It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
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 |
|---|---|---|---|
| PCT/CN2015/094510 | Nov 2015 | CN | national |
