JP2020169325A - Cleaning compositions containing branched alkyl sulfate surfactant and short-chain nonionic surfactant - Google Patents

Abstract

To solve the problem in which conventional laundry detergents may provide a laundering experience at one or more of these touch points but never realize any product providing consumers with an optimized sudsing profile at all four of these touch points (while also providing cleaning efficacy).SOLUTION: Cleaning compositions with improved sudsing profiles are provided. The cleaning compositions contain one or more branched unalkoxylated C6-C14 alkyl sulphate anionic surfactants in combination with one or more linear or branched C4-C11 alkyl or aryl alkoxylated alcohol nonionic surfactants. Such cleaning compositions are particularly suitable for use in hand-washing fabrics.SELECTED DRAWING: Figure 1

Description

The present invention relates broadly to cleaning compositions, particularly laundry or dishwashing detergent compositions, and more specifically to detergent compositions specifically designed for manual / manual or semi-automatic cleaning of fabrics or dishes. Regarding things.

Detergents containing anionic detergency surfactants for cleaning fabrics have been known for many years. Historically, washing laundry has been defined as a process that primarily involves the removal of stains. Following this historic approach to cleaning, laundry detergent designers have focused their efforts on formulating detergents with longer carbon chain surfactants, ensuring maximum surfactant activity and the most. Achieved effective dirt removal.

Such long-chain surfactants can generate large amounts of foam during the washing cycle of the fabric washing process. Therefore, consumers consider high foam volume to be the first and most desirable cleaning signal. For hand-washing consumers, who still make up the majority in most developing countries, high foam volume is especially desirable because consumers can directly feel and touch the foam generated during the hand-washing process. This is because the volume can be intuitively associated with sufficient washing of the fabric.

Paradoxically, a large amount of foam during the wash cycle usually leads to more foam during the subsequent rinse cycle. When consumers observe the foam during the rinse cycle, they immediately think from this foam that surfactant residue may still remain on the fabric. Surfactant residues remaining on the fabric can cause skin irritation and can leave the fabric "sticky" after drying, making it more responsive when worn. Easy to attract a lot of dust. As a result, the consumer will apply the fabric a few more times until the foam has completely or substantially disappeared from the rinse and the fabric is now "clean" and free of surfactant residues. It feels like it needs to be rinsed. However, in many cases, one or two rinses are sufficient to remove most or all of the surfactant residue from the fabric, even though a significant amount of foam remains in the rinse. is there. In other words, no additional rinsing is necessary and excessive. Such excessive rinsing requires additional time, effort, energy and water. Excessive rinsing is especially undesirable in resource-poor areas, especially in areas suffering from water shortages.

Therefore, the foaming properties of the detergent composition during both the washing and rinsing cycles of the fabric washing process are important to the overall consumer washing experience, especially the hand-washing consumer.

Consumers, in particular, wash the laundry completely manually (ie, completely manual / hand wash), or wash the laundry manually (ie, semi-automatically) in combination with mechanical washing. There is a need to provide an improved washing (ie, washing) experience to consumers who are habitual in any of these things. Specifically, this improved washing experience is made possible by the desirable lathering properties defined by at least four key points observed by the consumer (hereinafter referred to as "touch points"). Both of these points suggest to consumers that the laundry has been thoroughly washed and rinsed. The lack of any of these touchpoints can result in consumers having a less than ideal laundry experience.

These four touchpoints are referred to herein as "Flash Suds," "Suds Mileage," "Initial Rinse Suds," and "End Rinse Suds." These are referred to and described below with reference to FIG. 1, which shows a typical washing process with a washing cycle followed by a rinsing cycle.

Before the washing cycle, that is, during the pre-washing process, the consumer dissolves the laundry detergent product in a certain amount of water to form an aqueous washing solution and attempts to bring the laundry to be treated into contact with the washing solution.

The wash cycle is initiated by mechanically stirring the laundry with the wash solution, either in the washing machine or directly by the consumer's hands, thereby the first stage of the wash cycle, i.e. "W-1" shown in FIG. During the stage, it results in an early generation of foam, characterized by a significantly large amount of foam (measured by height), which occurs at a relatively high rate (within the first 2-3 minutes of the wash cycle). The initial generation of this foam, the so-called "flash foam", constitutes the first touch point and indicates that the surfactant in the laundry detergent is functioning effectively and washing the laundry. At the second touch point, the volume or height of the wash foam at a relative level, i.e. the "foam effect", over the second stage (the "W-2" stage shown in FIG. 1), which is the continuation of the wash cycle. Needs to be maintained or sustained.

These two early touchpoints show consumers that laundry detergents are effective in washing laundry and are maintained throughout the washing cycle. In the W-1 stage, if there is no flash foam or the flash foam volume is not large enough, consumers may interpret the laundry detergent product as ineffective. If the foam effect is not maintained over most of the W-2 stages of the washing cycle, the consumer is sufficient for the laundry detergent product to lose its cleaning effect or to effectively clean all bundles of laundry. It may be interpreted that the detergent is not in the detergent.

After the wash cycle, before the rinse cycle, i.e. in the intermediate steps, the well-washed laundry is separated from the wash liquor. The cleaning solution is drained or otherwise discarded. The laundry is squeezed or spun to remove excess wash solution, followed by contacting the laundry with clean water or rinse solution. The foam volume (measured by height) during this intermediate step is not measured as it is not important to the consumer and the dotted line is the approximate foam volume (height) during this step for illustration purposes. (Measured by) is shown only.

During the rinsing cycle, mechanical agitation (mechanical or manual) is used to wash in the rinsing solution when attempting to rinse any carry-over or residual surfactant, and dirt from the laundry. It also applies to things. In the first stage of the rinsing cycle, the "R-1" stage of FIG. 1, some initial bubbles may be observed in the rinsing solution, which are referred to as "initial rinse bubbles". A portion of such initial rinse foam, shown in FIG. 1, is carried over from the washing cycle by the laundry, i.e., residual foam adhering to the laundry. The rest of the initial rinse foam is produced by mechanical agitation of the rinse solution due to the presence of carry-over components or residual surfactant. Such initial rinse bubbles constitute a third touch point, which is preferably of medium volume (measured by height). Given the carry-over ingredients of the surfactant from the washed laundry, consumers expect some initial rinse foam. In the absence of any initial rinse foam, consumers may question the effectiveness of previous wash cycles.

At the fourth touch point, rapidly at the second continuation stage of the rinse cycle (“R-2 stage” in FIG. 1) leading to zero or near zero “final rinse foam” volume (measured by height). , And significantly requires the bubbles to disappear (indicated by the dotted arrow). Despite continued agitation, the rinse foam volume (measured by height) decreases significantly and rapidly to zero or near zero levels during this stage. It should be noted that in the R-2 stage, both the magnitude and rate of such foam reduction are important as they both indicate that laundry rinsing is effective. At the end of the R-2 stage, rinse foam is removed or almost removed, suggesting to consumers that most or all residual surfactant has been rinsed from the laundry. The consumer can move on to post-rinse processes (eg, drying and / or ironing the laundry). Therefore, consumers can rest assured that they can stop rinsing and end the washing process, which will help not only save water, but also save consumers time.

Washed laundry if the reduction of rinse foam during the R-2 stage is insufficient or not fast enough to reach the final rinse foam volume (measured by height) at or near zero. Or suggest to the consumer that the residual surfactant still remains in the rinse solution. As a result, the consumer feels that the rinse is not yet complete and unnecessarily further rinses and / or uses additional rinse water until all bubbles are removed or almost eliminated. You may spend time. Therefore, to suggest that the detergent product can be easily rinsed from the washed laundry, i.e. an easy rinse formulation that can provide a significant differentiation of the laundry detergent product. It is important that there are 4 touch points.

A laundry detergent product that provides optimized foaming properties at all four touch points described above suggests not only the high cleaning effect of the laundry detergent product, but also the advantage of easy rinsing. It can also help consumers save water and / or reduce the time it takes for users to rinse the laundry. Traditional laundry detergents can provide a washing experience at one or more of these touchpoints, but provide consumers with optimized foaming properties at all four touchpoints (while cleaning effect). There has never been a product (also offered).

Therefore, such laundry detergent products are needed.

The present invention provides a washing composition having a branched alkyl sulfate surfactant combined with a short chain nonionic surfactant, the composition spanning both the washing and rinsing cycles of the dishwashing or fabric washing process. , Shows excellent foaming properties. Specifically, the cleaning composition contains the following. That is, (a) one or more branched dealkoxylated C _{6 to} C ₁₄ alkyl sulfates (AS) of about 5% to about 50% (hereinafter, simply referred to as "% by weight") of the total weight of the cleaning composition. Surfactants, (b) one or more linear or branched C _{4 to} C ₁₁ alkyls having a weight average alkoxylation degree in the range of 1-10 from about 0.05% to about 10% by weight. Arylalkoxylated alcohol (AA) surfactant and (c) one or more additional components. Unless otherwise specified, when used herein and in the sections below, one or more additional ingredients are usually provided in an amount that makes up 100% of the total weight of each composition.

The cleaning compositions of the present invention are characterized by having optimized foaming properties at all four touch points described above during the cleaning and rinsing cycle, which is particularly comfortable for hand-washing consumers. is there.

Correspondingly, the present invention also relates to the use of the above cleaning compositions for hand-washing tableware or fabrics. Further, the present invention relates to a method for treating a dirty material, wherein the method is (a) a step of preparing the cleaning composition described above, (b) a step of bringing the cleaning composition into contact with at least a part of the dirty material, and (c). ) Includes the process of rinsing dirty materials. Preferably, steps (b) and (c) are both performed by hand, and the more soiled material is more preferably a soiled fabric.

In particular, the present invention relates to (a) about 1% to about 30% by weight, preferably about 2% to about 25% by weight, more preferably about 3% to about 20% by weight and the laundry detergent composition. Most preferably from about 5% to 15% by weight of branched non-alkoxylated C ₁₂ AS surfactant, (b) from about 1% to about 30% by weight, preferably from about 2% to about 25% by weight, more. A branched non-alkoxylated C ₁₃ AS surfactant, preferably from about 3% to about 20% by weight and most preferably from about 5% to 15% by weight, (c) from about 0.1% to about 15% by weight. , Preferably from about 0.5% to about 10% by weight, more preferably from about 1% to about 8% by weight and most preferably from about 2% to about 5% by weight, in the range of about 4 to about 6. having a weight average degree of ethoxylation, linear C ₆ AA surfactant, and (d) 1 or more additional ingredients, contains.

Furthermore, the present invention relates to a concentrated laundry detergent composition containing the following: That is, (a) branched non-alkoxylated C ₁₂ AS surface activity of about 20% by weight to about 50% by weight, preferably about 25% by weight to about 45% by weight, and more preferably about 30% by weight to about 40% by weight. Agent, (b) about 20% to about 50% by weight, preferably about 25% to about 45% by weight and more preferably about 30% to about 40% by weight of branched non-alkoxylated C ₁₃ AS surface activity. Agent, (c) weight in the range of about 4 to about 6, from about 5% to about 30% by weight, preferably from about 8% to about 20% by weight and more preferably from about 10% to about 15% by weight. having an average degree of ethoxylation, a linear C ₆ AA surfactant and (d) 1 or more additional ingredients.

These features and other features of the present invention will become apparent to those skilled in the art by examining the following detailed description in conjunction with the appended claims.

FIG. 5 is a graph showing desirable foaming properties with four touch points at various stages of the washing and rinsing cycle of the washing process. It is a photograph which photographed the cleaning liquid and the first rinsing liquid formed using the powder laundry detergent composition of the present invention, and shows the washing foam and the rinsing foam volume during the hand washing washing process. It is a photograph of the cleaning liquid and the first rinsing liquid formed by using the liquid laundry detergent composition of the present invention, and shows the washing foam and the rinsing foam volume during the hand washing washing process.

Definitions As used herein, "foam" refers to a non-equilibrium dispersion of bubbles in a relatively small volume of liquid. The terms "suds" (foam), "foam" (foam) and "later" (foam) can be used interchangeably within the meaning of the present invention.

As used herein, the term "foaming properties" refers to the properties of detergent compositions with respect to foaming properties during cleaning and rinsing cycles. Foaming properties include the initial rate of foam formation when dissolved in the wash solution, the volume and retention of foam during the wash cycle, the appearance and feel of the foam produced, the amount of residual foam carried over to the rinse solution and during the rinse cycle. The rate of foam reduction or disappearance in, but is not limited to, is all related to the consumer's fabric washing experience. Preferably, the foaming characteristics include the initial cleaning foam volume (measured by centimeter height), foam effect (measured by centimeter height), and cleaning measured by using the foaming characteristic test described later. Foam retention (%), rinse foam at 0 minutes (volume measured by centimeter height), rinse foam at 1 minute (volume measured by centimeter height) and reduction of rinse foam The speed (% / min) can be mentioned. More preferably, the foaming properties of the detergent composition of the present invention are the initial cleaning foam volume (cm), foam effect (cm) and rinsing foam reduction rate (% /) measured by using the foaming property test described later. Minutes). These three parameters evaluate the four touch points mentioned above for the wash and rinse cycle. The foaming properties may further include other foam parameters.

As used herein, the term "cleaning composition" means, as a specific example, a liquid or solid composition for treating fabrics, hard surfaces and any other surface in the field of fabrics and home care. Cleaning and / or treatments for hard surfaces, including floor and bathroom cleaners (eg, toilet bowl cleaners); hand-washing dishwashers or light dishwashers, especially high Foam type; dishwasher cleaners; 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 may be in the form of a liquid, powder, paste, gel, single dose, pouch or tablet. In another embodiment, the cleaning composition is a dishwashing liquid composition, which can be in the form of a liquid, powder, paste, gel, single dose, pouch or tablet.

As used herein, the term "dirty material" is used non-specifically and is not limited to natural materials such as cotton, linen, wool, polyester, nylon, silk, acrylic and the like. It may refer to a network of natural or artificial fibers, including artificial and synthetic fibers, as well as any type of flexible material consisting of various blends and combinations. Dirty materials also include natural, artificial or synthetic surfaces, such as, but not limited to, glass, metal, plastic, porcelain or ceramic countertops or countertop surfaces, and tiles. It can refer to any type of hard surface, including granite, grout, composites, vinyl, broadleaf wood and the like, as well as tables, countertops or floor surfaces formed in blends and combinations.

As used herein, the term "laundry detergent composition" is part of the "cleaning composition" and is a versatile or "strong" cleaning agent for fabrics (especially liquids, powders, pastes, gels, once). Includes dosages, cleaning detergents in the form of pouches or tablets), and cleaning aids such as bleaching, rinsing aids, additives or pretreatment types. In one embodiment, the laundry detergent composition is a strong liquid laundry detergent, and in another embodiment, the laundry detergent composition is a free-flowing granular laundry detergent.

As used herein, the term "C ₄ -C ₁₁ alkyl or aryl alkoxylated alcohol", broadly, C ₄ of at least one linear or branched structure -C ₁₁ alkyl or C ₄ ~ C ₁₁ Refers to an alkoxylated alcohol containing an aryl group. In other words, C _{4 to} C ₁₁ specify the total carbon number of the alkyl or aryl group, not the total carbon number of the alkoxylated alcohol compound. The C _{4 to} C ₁₁ aryl groups may be unsubstituted or substituted with either linear or branched alkyl groups, provided that the total carbon number of this group does not exceed 11. If the C _{4 to} C ₁₁ aryl group contains an alkyl substituent, the C _{4 to} C ₁₁ aryl group can be attached to the alkoxylated alcohol via either a ring carbon or an alkyl substituent.

As used herein, the articles such as "a" and "an" used in the claims are understood to mean that there is more than one claim or description.

As used herein, "include" (including), "includes" (including) and "include" (including) are meant to be non-limiting. The term "consisting of" means to be limiting, i.e. to eliminate any component or component not specifically listed, unless they are present as impurities. To do. On the other hand, the term "consisting essentially of" refers to the presence of other components or components as long as they do not interfere with the function of the specifically listed components or components. Tolerate.

As used herein, the term "substantially free of or substantially free from" (substantially free of) is used in the composition to be 0.5% or less, preferably 0.% of the total weight of such composition. It means that there is an indicator of 2% or less, and more preferably 0.1% or less.

As used herein, the term "essentially free of" is not the intentional addition of the indicator to the composition, or preferably at a concentration detectable by analysis. It means that it does not exist. That means that the indicator material comprises a composition that is present only as an impurity in one of the other materials to which it was intentionally added.

The term "solid" as used herein includes product forms of granules, powders, bars and tablets.

The term "fluid" as used herein includes product forms of liquids, gels, pastes and gases.

As used herein, the term "liquid" refers to a fluid having a viscosity of about 1 to about 2000 mPa ^* s at 25 ° C. and a shear rate of 20 seconds- ¹ . In some embodiments, the viscosity of the liquid may range from about 200 to about 1000 mPa ^* s at a shear rate of 25 ° C., 20 seconds- ¹ . In some embodiments, the viscosity of the liquid may range from about 200 to about 500 mPa ^* s at a shear rate of 25 ° C., 20 seconds- ¹ . Viscosity can be measured at 60 RPM / s using a Brookfield viscometer, Spindle # 2.

All temperatures herein are in degrees Celsius (° C) unless otherwise noted. Unless otherwise specified, all measurements herein are made at 20 ° C. and atmospheric pressure.

In all embodiments of the invention, all ratios (%) are relative to the weight of the total composition unless otherwise stated. Unless otherwise stated, all ratios are weight ratios.

The dimensions and values disclosed herein should not be understood to be strictly limited to the exact numbers given. Rather, unless otherwise stated, each such dimension shall mean both the stated value and the functionally equivalent range around that value. For example, the dimension disclosed as "40 mm" shall mean "about 40 mm".

It is understood that the test methods disclosed in the Test Methods section of the present application must be used to measure the values of each of the parameters of the inventions described and claimed herein. Yeah.

Foam-Optimized Surfactant Systems The inventors of the present invention are short-chain nonionic surfactants of branched anionic surfactants (ie, branched nonalkoxylated C _{6 to} C ₁₄ alkyl sulfates). Cleaning compositions containing combinations with (ie, linear or branched C _{4 to} C ₁₁ alkyl or arylalkoxylated alcohols) have been found to exhibit improved foaming properties. Improved foaming properties are large "flash foam" volume at W-1 stage and good "foam effect" at W-2 stage in the wash cycle, moderate at R-1 stage in the rinse cycle. At the R-2 stage in the amount of "early rinse foam" and rinse cycle, the rinse foam is dramatically reduced and eliminated, and the "final rinse foam" is zero or nearly zero.

Such unique lathering properties provide hand-washing consumers with a comfortable washing and rinsing experience, especially during the rinsing stage. The volume of foam produced and its persistence / stability during the wash cycle are high enough to indicate to the consumer that effective washing is taking place. A moderate amount of foam is observed early in the rinse cycle. Consumers expect this because after observing a large amount of foam generated during the wash as a sign of effective wash. However, once the rinse cycle begins, the bubbles undergo a dramatic and rapid reduction and disappearance during the first minute or two of the rinse. Consumers, especially hand-washing, dramatically and quickly reduce and eliminate rinse foam, and finally, at the end of the first rinse cycle, the foam is slightly or absent, clear. You will have the opportunity to visually observe that it becomes a rinse solution. By visually recognizing that the foam has diminished and disappeared, the article to be cleaned has undergone effective cleaning and has been thoroughly rinsed, and now there are no stains or residual surfactant left. Show that clearly. Therefore, the consumer will rest assured to stop the washing process after the first rinse cycle. Therefore, the need for further rinsing is eliminated, and in some cases the concept of a single rinse becomes possible.

The surprising and unexpected foaming properties achieved by the cleaning compositions of the present invention are specifically the initial large cleaning foam volume, large foam effect and rinse measured by using the foaming property test described below. It is characterized by a fast depletion rate of foam. Specifically, the unique foaming characteristics are defined by the following. That is, a) initial cleaning foam volume of about 30 cm or more (measured by height), b) foam effect of about 30 cm or more (measured by height) and c) measured by using the foaming characteristic test described later. The rate of decrease of rinse foam is about 40% / min or more. The initial wash foam volume evaluates the first touch point. That is, the "flash foam" described above during the W-1 stage of the wash cycle. The foam effect evaluates the second touch point described above (hence, named after it) during the W-2 stage of the wash cycle. The rate of decrease of the rinse foam is the same as the above-mentioned "initial rinse foam" and "final rinse foam" between the third and fourth touch points, that is, the R-1 and R-2 stages in the rinse cycle. evaluate.

The initial wash foam volume can be as high as about 45 cm and may range from about 30 cm to about 45 cm. Preferably, the initial wash foam volume of the wash composition is about 35 cm or more and preferably about 40 cm or more. More preferably, the initial wash soap foam volume is in the range of about 33 cm to about 44 cm and preferably about 34 cm to about 43 cm.

The foam effect also has an upper limit of about 45 cm and may be in the range of about 30 cm to about 42 cm. Preferably, the foaming effect of the cleaning composition is about 31 cm or more, preferably about 32 cm or more and more preferably about 33 cm or more. More preferably, the foam effect ranges from about 31 cm to about 42 cm and preferably from about 32 cm to about 41 cm.

The retention of wash foam is calculated from the initial foam volume and foam effect and may range from 60% to 120%. Preferably, it is 65% or more, or 70% or more or 75% or more. More preferably, the wash foam retention is in the range of about 65% to about 100%.

The rate of decrease of rinse foam is preferably in the range of about 40% / min to 100% / min. Preferably, it is in the range of about 50% / min to 100% / min. More preferably, it is in the range of about 60% / min to 100% / min. Even more preferably, it is in the range of about 70% / min to 100% / min. Even more preferably, it is in the range of about 80% / min to 100% / min.

This foaming property is one or more linear non-alkoxylated C _{6 to} C ₁₄ alkyl sulfate (AS) surfactants having a weight average alkoxylation degree in the range of about 1 to about 10. Alternatively, it can be achieved in combination with a branched C _{4 to} C ₁₁ alkyl or arylalkoxylated alcohol (AA) surfactant. When combined together, these two surfactants interact to achieve the above-mentioned improved and desirable foaming properties.

The surfactant system of the present invention is one or more additions other than the branched non-alkoxylated C _{6 to} C ₁₄ AS surfactant and the linear or branched C _{4 to} C ₁₁ alkyl or aryl AA surfactant. Surfactants, such additional surfactants adversely affect the optimized foaming properties achieved by AS and AA surfactants or otherwise interact with the functionality of AS and AA surfactants. It may be contained as long as it does not act. Such additional surfactants are selected from other anionic surfactants, other nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof. You can do it.

Anionic Surfactant: Branched Non-alkoxylated Alkoxy Sulfate A suitable anionic surfactant for carrying out the present invention is branched non-alkoxylated C _{6 to} C ₁₄ alkyl sulfate (hereinafter “AS”). In EP 2119764, in Example 12 of Table 4, relatively short-chain nonionic surfactant (i.e., alkylene glycol ethers 1 having a C ₈ alkyl group and PO2.3), alkoxylated AS The combination with a surfactant (ie, sodium polyoxyethylene lauryl ether sulfate) is disclosed. However, it has been found that the alkoxylation of branched AS surfactants can adversely affect the foaming properties of the cleaning composition, even at relatively low levels (eg, a weight average of about 1). .. Specifically, a significantly higher amount of foam is observed early in the rinse cycle. This leaves little or no reduction throughout the rinse, leaving a significant amount of foam at the end of the first rinse cycle. Foam can only be removed by one or more further rinses. Therefore, it is desirable to use a non-alkoxylated branched AS surfactant instead. Although not essential, preferably, the cleaning compositions of the present invention are substantially free of either linear or branched alkoxylated alkyl sulfate surfactants. More preferably, the cleaning compositions of the present invention are substantially free of any alkoxylated alkyl sulfate surfactant.

In addition, the branching of the C _{6 to} C ₁₄ alkyl chains in the AS surfactant is important to ensure the stability of the foam produced during the washing cycle of the washing process. In U.S. Patent Application Publication No. 2005/01/24738, in Example 18, an AS surfactant having a linear C _{12 to} C ₁₄ alkyl chain of a medium chain nonionic surfactant (C ₁₀ alcohol ethoxylate) The combination of is disclosed. However, by using a linear AS instead of a branched chain AS, the foam stability during the cleaning cycle becomes insufficient, and the resulting cleaning composition unfortunately exhibits a foaming property of less foaming effect. Was found. Although not essential, preferably, the cleaning compositions of the present invention are substantially free of linear alkyl sulfate surfactants.

Further, the branched AS surfactant of the present invention is characterized by a relatively short alkyl chain (ie, having about 6 to about 14 carbon atoms). Preferably, the branched AS surfactant of the present invention has branched alkyl moieties of different carbon chain lengths and the weight average carbon number of the total branched alkyl moieties is in the range of about 9 to about 14, more preferably about. It is 10 to about 13, and most preferably about 11 to about 13. WO 9739088 discloses medium-chain branched alkyl sulfates containing branched alkyl moieties in the range of 14-20 with an average total carbon number of greater than 14.5 (International). See Publication No. 9739088, page 11, lines 8-12). Specifically, Example 11 of International Publication No. 9739088 combines a medium-chain branched AS with an average total carbon number of 16.5 with C _{9 to} C ₁₁ alcohol ethoxylate nonionic surfactants. It is disclosed. However, branched AS surfactants with longer alkyl chains (eg, having more than 14 total carbon atoms or having an average total carbon number of 14 or more) have an adverse effect on the foaming properties of the cleaning composition. Was found. Specifically, the amount of foam carried over from the wash cycle to the rinse cycle is significantly increased compared to branched AS surfactants with shorter alkyl chains. Moreover, the carry-over foam is little or no reduction during the rinse, and at the end of the first rinse, a significant amount of foam remains on the surface of the rinse solution. This foam can only be removed by further rinsing. Therefore, it is desirable to use branched AS surfactants with relatively short alkyl chains (ie, C _{6 to} C ₁₄ ), preferably those branched alkyl moieties have a weight average carbon number of about 9 to about 14. It is more preferably in the range of about 10 to about 13 and most preferably in the range of about 11 to about 13. Although not essential, preferably, the cleaning compositions of the present invention are substantially free of alkylsulfate surfactants, either linear or branched, with longer molecular chains (ie, C _{15 and} above). ..

The branched non-alkoxylated AS surfactant of the present invention may exist in the acid form, and the acid form may be neutralized to form a salt. Typical neutralizers include hydroxides, such as metal counterionic bases such as NaOH or KOH. Further preferred neutralizers for anionic surfactants in the acid form 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 carried out completely or partially, for example, some of the anionic surfactant mixture may be neutralized with sodium or potassium, and some of the anionic surfactant mixture may be amine. Alternatively, it may be neutralized with an alkanolamine.

In a non-essential, but preferred embodiment of the invention, the branched, non-alkoxylated C _{6 to} C ₁₄ AS surfactants have the general formula (I).

式中、Ｍはアルカリ金属、アルカリ土類金属、アンモニウム、アミン又はアルカノールアミンのカチオンであり、ｘ及びｙは０〜約１０の範囲の整数から独立して選択され、ｚは約１〜約４の範囲の整数であり、ｘ＋ｙの和はｚ以上であり、及びｘ＋ｙ＋ｚの和は約３〜約１１の範囲である。好ましくはｚは約１、及びｘ＋ｙの和は約８〜約９である。

In the formula, M is an alkali metal, alkaline earth metal, ammonium, amine or alkanolamine cation, x and y are independently selected from integers in the range 0 to about 10, and z is about 1 to about 4. The sum of x + y is greater than or equal to z, and the sum of x + y + z is in the range of about 3 to about 11. Preferably z is about 1 and the sum of x + y is about 8 to about 9.

Non-limiting examples of suitable branched non-alkoxylated AS surfactants of the present invention include those having the following chemical structures.

The cleaning compositions of the present invention, it is particularly preferably contains two or more branched non-alkoxylated C ₆ ~ ₁₄ AS surfactant. More preferably, such mixtures include: That is, (1) branched dealkenylation in an amount in the range of about 20% to about 80%, preferably about 30% to about 70% and more preferably about 35% to about 50% of the total weight of the mixture. An amount in the range of about 20% to about 80%, preferably about 30% to about 70% and more preferably about 35% to about 50% of the total weight of the C ₁₂ AS surfactant and (2) mixture. A branched, non-alkenylated C ₁₃ AS surfactant. Most preferably, the mixture comprises or consists essentially of a branched, non-alkoxylated C ₁₂ AS surfactant and a branched, non-alkoxylated C ₁₃ AS surfactant.

Branched non-alkoxylated AS surfactants are commercially available as a mixture of linear isomers and branched isomers having various molecular chain lengths and degrees of branching, and have a molecular chain length distribution of C _{12 to 13} of Sasol. And Sulfated Isalchem® 123 with about 95% bifurcation and Neodol® 123 As with C _12-13 molecular chain distribution of Shell and 20% bifurcation, but not limited to these. ..

The cleaning composition of the present invention contains the above-mentioned branched non-alkoxylated C _{6 to} C ₁₄ AS surfactants in an amount of about 5% to about 50%, preferably about 6% to about 40% of the total weight of the cleaning composition. , More preferably in the range of about 8% to about 30% and most preferably in the range of about 10% to about 20%. At higher concentrations with 2-fold, 3-fold or 4-fold compression ratios, branched non-alkoxylated C _{6 to} C ₁₄ AS surfactants are from 30% by weight of the high concentration formulation. It may be present in higher amounts, ranging from 50% by weight, preferably 35% to 45% by weight and more preferably 40% to 45% by weight.

Nonionic Surfactants: Short Chain Alkoxylated Alcohol Suitable nonionic surfactants for the practice of the present invention are either linear or branched alkyl or arylalkoxylated alcohols (alcohol alkoxylates or simply AA). (Sometimes referred to as), (1) a relatively short carbon chain or a relatively small aromatic ring, i.e. a C _{4 to} C ₁₁ alkyl or aryl moiety, preferably a C _{4 to} C ₁₀ alkyl or aryl moiety, more preferably. Contains C _{4 to} C ₈ alkyl or aryl moieties and most preferably C _{4 to} C ₆ alkyl or aryl moieties, further (2) about 1 to about 10, preferably about 2 to about 8, more preferably about 3 to. It has a weight average degree of alkoxylation in the range of about 7 and most preferably about 4 to about 6, that is, the weight average number of alkoxylated moieties contained in the AA. The C _{4 to} C ₁₁ aryl moieties of the AA surfactant may be unsubstituted or substituted with either linear or branched alkyl groups, provided that the total carbon number of this group is Does not exceed 11. If the C _{4 to} C ₁₁ aryl moiety contains an alkyl substituent, the C _{4 to} C ₁₁ aryl moiety can be attached to the alkoxylated alcohol via either a ring carbon or an alkyl substituent. Preferably, the AA surfactant used in the practice of the present invention contains a C _{4 to} C ₁₁ alkyl moiety.

Nonionic AA surfactants with longer carbon chains (eg, C _12- C ₂₀ alkyl moieties, etc.) are known in the art for use in cleaning compositions, including laundry detergent compositions. However, short chain AA surfactants, such as those having a C _{4 to} C ₁₁ alkyl moiety, are much less commonly used in this embodiment due to their poor foaming properties. When used alone, such short chain AA surfactants produce little or no wash foam.

Thus, such short chain AA surfactants interact with the branched C _6- C ₁₄ AS anionic surfactants described above to provide more stable (ie, better foaming) foam during the wash cycle. Is generated in a larger volume, while simply carrying a moderate amount of foam into the rinse solution, which also disappears almost completely during a minute or two of the first rinse cycle. It is a surprising and unexpected finding in the present invention that at the end of the first rinse cycle it is possible to produce a cleaning composition that results in a rinse solution with little or no foam remaining.

Furthermore, when combined with branched C _6- C ₁₄ AS anionic surfactants, longer chain AA surfactants (eg, having C ₁₂ and / or C ₁₄ alkyl moieties) are short chains of the invention. It has been found to exhibit inadequate rinse foam properties compared to AA surfactants. Specifically, a much larger amount of wash foam is carried from the wash cycle to the rinse cycle, with little or no reduction in foam during the rinse. In addition, such longer chain AA surfactants, when combined with branched C _6- C ₁₄ AS anionic surfactants, are shorter chain nonionic AA surfactants of the invention during the wash cycle. Shows less foam stability and significantly less foam effect as compared to. Therefore, in practicing the present invention, it is desirable to use a short chain nonionic AA surfactant having a C _{4 to} C ₁₁ alkyl or aryl moiety. Although not essential, preferably, the cleaning compositions of the present invention substantially contain either linear or branched, longer chain AA surfactants (ie, having an alkyl moiety of C ₁₂ or higher). Not included in.

The short chain AA surfactant of the present invention may contain one or more alkoxylated moieties. The alkoxylated portion may be either linear or branched. Each of such alkoxylated moieties may contain 1 to 10 carbon atoms. Preferably, the alkoxylated moiety is selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy and mixtures thereof.

In a particularly preferred embodiment of the invention, the short chain AA surfactant has the following general formula:

式中、Ｒ¹は直鎖状又は分岐状Ｃ₄〜Ｃ₁₁アルキル又はアリール（例えば、フェニル又は置換フェニル）であり、Ｒ²は直鎖状又は分岐状Ｃ₁〜Ｃ₈アルキルであり、Ｒ³は水素、直鎖状又は分岐状Ｃ₁〜Ｃ₆アルキル、ベンゾイル、アセチル、アクリロイル又はメタクリロイルであり、ｎは０〜約５の範囲の重量平均値を有し、ｍは約１〜約１０の範囲の重量平均値を有し、ｍ＞ｎであり、更にｎ＋ｍは約１０以下である。

In the formula, R ¹ is a linear or branched C _{4 to} C ₁₁ alkyl or aryl (eg, phenyl or substituted phenyl), R ² is a linear or branched C _{1 to} C ₈ alkyl, and R ³ is hydrogen, linear or branched C _{1 to} C ₆ alkyl, benzoyl, acetyl, acryloyl or methacryloyl, n has a weight mean value in the range of 0 to about 5, and m is about 1 to about 10. It has a weight average value in the range of, m> n, and n + m is about 10 or less.

Preferably, R ¹ is C _{4 to} C ₁₁ alkyl, more preferably C _{4 to} C ₁₀ alkyl and even more preferably C _{4 to} C ₈ , and most preferably C _{4 to} C ₆ alkyl. In a particularly preferred embodiment of the invention, R ¹ is a linear C _{4 to} C ₁₁ alkyl, more preferably a linear C _{4 to} C ₁₀ alkyl and even more preferably a linear C _{4 to} C ₈ alkyl. And most preferably linear C _{4 to} C ₆ .

In an alternative embodiment of the invention, R ¹ is preferably phenyl or substituted phenyl. Substituents on the phenyl group can be linear or branched C _1- C ₅ alkyl, optionally one or more functional groups selected from the group consisting of amides, imides, carboxyl esters, halides and ethers. It may be further replaced with. Preferably, the substituent on the phenyl group is an unsubstituted C _{1 to} C ₅ alkyl group.

Particularly preferred R ¹ groups are the following alcohols: hexanol, phenol, butanol (particularly n-butanol and isobutanol), pentanol, ter-amyl alcohol, heptanol, octanol (particularly n-octanol and 2-ethylhexanol). , Isononanol, decanol, isodecanol, 2-propylheptanol and mixtures thereof. In addition, a mixture of C _{4 to} C ₈ alcohol cuts or C _{5 to} C ₉ alcohol cuts can be used.

R ² is preferably C _{1 to} C ₄ alkyl, more preferably methyl or ethyl and most preferably methyl.

R ³ is preferably hydrogen or C ₁ -C ₄ alkyl and more preferably hydrogen, methyl or ethyl and most preferably hydrogen. R ³ groups, if it is other than hydrogen, in order to stabilize the AA surfactants, for example when in alkaline solution, and functions as what are termed normal end group cap.

Generally, in alcoholification of alcohols, the degree of alkoxylation is distributed, so the values of n and m represent weight average values. The sum of n + m is preferably about 2 to about 8, more preferably about 3 to about 7, and most preferably about 4 to about 6. This means that the total weight average of the degree of alkoxylation of the short chain AA surfactant of the present invention is in the range of about 2 to about 8, preferably about 3 to about 7, and more preferably about 4 to about 6. It means good.

In a preferred embodiment, n has a weight average value of about 2 or less (hereinafter simply referred to as the value of n), and m is a weight average value in the range of about 3 to about 10 (hereinafter simply referred to as the value of m). Have. In a particularly preferred embodiment of the invention, n is 0, which means that the short chain AA surfactant of the invention is predominantly ethoxylated. In this situation, 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 more preferred embodiment, when R ¹ is phenyl, n is 0 and m is in the range of about 3 to about 9. In a more preferred embodiment, when R ¹ is C _{4 to} C ₆ alkyl, n is about 2 or less and m is in the range of about 3 to about 6.

If both alkoxylation groups, namely CH _2- CHR ^2- O- and CH _2- CH _2- O- groups, are present in such short chain AA surfactants, they are randomly or blocked. Can be distributed. These by reaching the corresponding alcohol R ^1- OH with an alkylene oxide compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like. The alkoxyl group is introduced into the short chain AA surfactant of the present invention. Preferably, the compound is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof. With different alkylene oxides, the reaction can be triggered by placing different alkylene oxides in blocks (continuously or alternately) or simultaneously (randomly or mixedly).

The following are exemplary short chain AA surfactants for carrying out the present invention. That is, ethoxylated butanol having a weight average EO value of about 3, ethoxylated butanol having a weight average EO value of about 4, ethoxylated butanol having a weight average EO value of about 5, and a weight average EO value of about 6. Butanol ethoxylated, ethoxylated hexanol having a weight average EO value of about 3, ethoxylated hexanol having a weight average EO value of about 4, ethoxylated hexanol having a weight average EO value of about 5, weight average EO value of about 6 Hexanol ethoxylated, ethoxylated phenol having a weight average EO value of about 3, ethoxylated phenol having a weight average EO value of about 4, ethoxylated phenol having a weight average EO value of about 5, weight average EO value is about 5. Approximately 6 ethoxylated phenols and the like. The EO values listed are rounded values. AA surfactants based on hexanols and phenols are particularly preferred.

Commercially available short-chain AA surfactants that can be used in the practice of the present invention include, but are not limited to: That is, BASF's Emulan (registered trademark) HE50, which is a C ₆ alcohol having a weight average ethoxylate of about 5, and EcoSurf (registered trademark) of Dow Chemical, which is a C ₈ alcohol having a weight average ethoxylate of about 6. It is 6.

The cleaning composition of the present invention contains the above-mentioned short-chain AA surfactant in an amount of about 0.05% to about 10%, preferably about 0.1% to about 6%, more preferably about the total weight of the cleaning composition. It may be contained in the range of about 0.5% to about 5% and most preferably about 1% to about 4%. At higher concentrations with 2-fold, 3-fold or 4-fold compression ratios, short-chain AA surfactants are 15% to 30% by weight and preferably 20% to 25% by weight of the high concentration formulations. May be present in higher amounts, in the range of.

Weight Ratio of Branched AS Surfactant and Short Chain AA Surfactant The weight ratio of the above-mentioned branched C _{6 to} C ₁₄ AS surfactant to the linear or branched C _{4 to} C ₁₁ AA surfactant is Preferably, it is about 20: 1 to about 1: 2, more preferably about 10: 1 to about 1: 1, even more preferably about 8: 1 to about 2: 1 and most preferably 5: 1 to 4: 1. Is the range of.

It was found that different weight ratios of the branched AS surfactant to the short chain AA surfactant had different effects on the foaming properties of the resulting cleaning composition. Such weight ratios are greater than 1: 1 (ie, more branched AS surfactants are present in the cleaning composition than short chain AA surfactants), preferably greater than 2: 1 and more preferably. When it is about 4: 1 to about 5: 1, the wash foam stability is improved and a better foam effect is achieved during the wash cycle.

Additional Surfactants In addition to the above-mentioned branched AS surfactants and short-chain AA surfactants, the surfactant system of the present invention includes other anionic surfactants (with the above-mentioned branched AS surfactants). (Different), other nonionic surfactants (different from the short chain AA surfactants described above), cationic surfactants, biionic surfactants, amphoteric surfactants and mixtures thereof. It may contain one or more additional surfactants of choice. Such additional surfactants in the cleaning composition of the present invention are about 1% to about 75%, preferably about 2% to about 35%, more preferably about 5% to about 5% to the total weight of the composition. It may be present in a total amount in the range of 10%.

Other Anionic Surfactants In some embodiments, the additional surfactant may comprise one or more other anionic surfactants. In some embodiments, the additional surfactant may consist essentially of one or more other anionic surfactants, or may consist of one or more other anionic surfactants. Good.

Specific and non-limiting examples of other suitable anionic surfactants include any conventional anionic surfactants. For example, conventional soaps, which are water-soluble salts of fatty acids, can be used as other anionic surfactants. Suitable soaps include alkali metal (eg sodium, potassium, etc.) salts, ammonium salts, and alkylammoniums of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 12 to about 18 carbon atoms. Salt is mentioned. Particularly useful are sodium and potassium salts of a mixture of fatty acids derived from coconut oil and tallow, ie sodium or potassium tallow and coconut soap.

Non-soap synthetic anionic surfactants, such as, but not limited to, are also suitable for use herein. That is, alkyl sulfonates, alkyl benzene sulfonates, alkoxylated alkyl sulphates (also known as alkyl ether sulphates or alkyl polyethoxylate sulphates), linear alkyl sulphates, alkyl ester sulphates, alkyl ester sulfonates, alkyl phosphates or phosphonates, alkyl Carboxylates, alkyl ether carboxylates and the like. Other preferred non-soap anionic surfactants are selected from the group consisting of: That is, (1) linear C _{10 to} C ₂₀ alkylbenzene sulfonates, (2) linear or branched C _{10 to} C ₂₀ alkylalkoxysulfates having an average degree of alkoxylation of 0.1 to 5.0, ( 3) Linear or branched C _10- C ₂₀ alkyl ester sulfates or sulfonates, (4) Linear or branched C _10- C ₂₀ alkyl sulfonates, phosphates, phosphonates or carboxylates and combinations thereof.

In addition to the above-mentioned branched AS surfactant and short chain AA surfactant, a surfactant system containing one or more linear C _{10 to} C ₂₀ alkylbenzene sulfonates (LAS) is used for carrying out the present invention. preferable. LAS is 0% to about 50%, preferably about 1% to about 45%, more preferably about 5% to about 40% and most preferably about 10% to about 35% of the total weight of the surfactant system. Can be present in a range of quantities. One or more linear or branched C _{10 to} C ₂₀ alkylalkoxysulfates (AxS) having an average degree of alkoxylation ranging from about 0.1 to about 5 and preferably from about 0.5 to about 3. Further contained surfactant systems are also preferred. AxS is 0% to about 30%, preferably about 1% to about 20%, more preferably about 2% to about 15% and most preferably about 5% to about 10% of the total weight of the surfactant system. Can be present in a range of quantities. Further suitable other anionic surfactants include methyl ester sulfonates and alkyl ether carboxylates.

Other Nonionic Surfactants In some embodiments, the additional surfactant comprises one or more other nonionic surfactants. In some embodiments, the cleaning composition comprises such other nonionic surfactants from about 0.1% to about 40%, preferably about 0.5% to about 10%, more preferably of the total weight of the cleaning composition. May be included in an amount of about 1% to about 5%.

Other suitable nonionic surfactants may include any conventional nonionic surfactant. These include, for example, longer chain alkoxylated alcohols with C _{12 to} C ₂₀ alkyl or aryl moieties, medium chain, branched C _{14 to} C ₂₂ alcohols, alkyl polysaccharides (specifically, alkyl polyglycosides). ), Amine oxide, Polyhydroxy fatty acid amide.

Cationic Surfactants In some embodiments, the additional surfactant comprises one or more cationic surfactants. In some embodiments, the cleaning compositions of the present invention add such cationic surfactants to about 0.1% to about 10%, preferably about 0.1% to about 5%, more preferably of the total weight of the composition. Is included in a total amount of about 0.1% to about 2%.

Non-limiting examples of cationic surfactants include the following. That is, a quaternary ammonium surfactant containing a functional group having 26 or less carbon atoms (alkenylated quaternary ammonium (AQA) surfactant or alkyl quaternary ammonium surfactant, dimethylhydroxyethyl quaternary ammonium or dimethyl. (Hydroxyethyl lauryl ammonium chloride, etc.), polyamine cationic surfactants, cationic ester surfactants and amino surfactants, specifically amidopropyl dimethylamine (APA). Suitable quaternary ammonium compounds have the general formula _{(R) (R 1) (} R 2) (R 3) N + X - is such as to have a. Wherein, R is a linear or branched, substituted or unsubstituted C _{6 ~ 18} alkyl or alkenyl moiety, R ₁ and R ₂ are, independently of one another, are selected from methyl or ethyl moieties, R ₃ is It is a hydroxy, hydroxymethyl or hydroxyethyl moiety, where X is an anion that provides electrical neutrality. Suitable anions include, for example, halides such as chloride, sulfates and sulfonates. Suitable cationic detersive surfactants are mono--C 6 _{~ 18} alkyl mono - methyl quaternary ammonium chloride - hydroxyethyl di. Highly preferred cationic detersive surfactants are mono--C 8 _{~ 10} alkyl mono - hydroxyethyl di - methyl quaternary ammonium chloride, mono--C _{10 ~ 12} alkyl mono - hydroxyethyl di - methyl quaternary ammonium chloride , And mono-C ₁₀ alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.

Suitable cationic surfactants may also include alkyl pyridinium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds and mixtures thereof.

Zwitterionic Surfactants Suitable zwitterionic surfactants include the following. That is, betaines containing secondary and tertiary amine derivatives, quaternary ammonium, quaternary phosphonium or tertiary sulfonium compound derivatives alkyldimethylbetaine and cocodimethylamide propyl betaine, C _{8 to} C ₁₈ (eg, C _{12 to} C _18). ) Amine oxides and sulfos and hydroxybetaines such as N-alkyl-N, N-dimethylammino-1-propanesulfonate. The alkyl group may be C _{8 to} C ₁₈ , and in some embodiments C _{10 to} C ₁₄ .

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 the above-mentioned aliphatic derivative, the aliphatic group may be a straight chain or a branched chain, and one of the aliphatic substituents has at least about 8 carbon atoms, typically about 8 to about 18. It contains a carbon atom and at least one of the aliphatic substituents contains an anionic water-soluble group such as carboxy, sulfonate, sulfate. Examples of compounds that fall into this definition are sodium 3- (dodecylamino) propionate, sodium 3- (dodecylamino) propan-1-sulfonate, sodium 2- (dodecylamino) ethylsulfate, sodium 2- (dimethylamino) octadeca. Noate, disodium 3- (N-carboxymethyl dodecylamino) propan1-sulfonate, disodium octadecyl-iminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N, N-bis (2-) Hydroxyethyl) -2-sulfato-3-dodecoxypropylamine. Suitable amphoteric surfactants also include sarcosinate, glycosinate, taurinate, and mixtures thereof.

Cleaning Compositions As used herein, the phrase "cleaning composition" or "detergent composition" includes compositions and formulations designed to clean dirty materials. Such compositions include laundry and cleaning compositions and detergents (having normal surfactant activity or, in high concentration form, significantly higher surfactant activity), fabric softening compositions, fabric strengthening compositions. , Cloth deodorant composition, laundry prewash solution, laundry pretreatment agent, laundry additive, spray product, dry cleaning agent or composition, laundry rinsing additive, cleaning additive, post-rinsing fabric treatment agent, iron From the viewpoint of auxiliaries, dishwashing compositions, hard surface cleaning compositions, single dose formulations, delayed delivery formulations, detergents contained on or within porous substrates or non-woven sheets and as taught herein. , Other suitable forms that may be obvious to those skilled in the art, but are not limited to these. Such compositions may be used as pre-wash, post-wash treatments, or may be added during the rinsing or washing cycle of the washing operation. The cleaning composition can have a form selected from liquids, powders, single-phase or polyphase single doses, pouches, tablets, gels, pastes, bars, or flakes.

The cleaning compositions of the present invention do not require any defoaming agents such as silicone defoaming agents or suds collapsing polymers, as the surfactant system itself provides the desired lathering effect. Acts to minimize the manufacturing and processing costs associated with such cleaning compositions. In a preferred embodiment of the invention, the cleaning composition is substantially free of, more preferably essentially free of, a silicone foam suppressant. In a more preferred embodiment of the invention, the cleaning composition is substantially free or essentially free of any antifoaming agent.

The cleaning composition of the present invention may be formulated or designed as either an automatic mechanical cleaning detergent product, a semi-automatic detergent product, or a hand-washing detergent product. The improved lathering properties of such compositions are most perceived by consumers during hand washing, so detergent products can be designed specifically for hand washing to emphasize their lathering effect and please consumers. preferable.

The cleaning composition can be a laundry detergent composition. Although not essential, preferably such laundry detergent compositions have conventional surfactant activity levels and include: That is, (1) about 1% by weight to about 30% by weight, preferably about 2% by weight to about 25% by weight, more preferably about 3% by weight to about 20% by weight, and most preferably about 5% by weight to about 15% by weight. By weight% branched C ₁₂ AS surfactant, (2) from about 1% to about 30% by weight, preferably from about 2% to about 25% by weight, more preferably from about 3% to about 20% by weight and Most preferably about 5% to about 15% by weight of branched C ₁₃ AS surfactant and (3) about 0.1% to about 15% by weight, preferably about 0.5% to about 10% by weight. Linear C ₆ AA, having a weight average ethoxylation degree in the range of about 4 to about 6, more preferably from about 1% to about 8% by weight and most preferably from about 2% to about 5% by weight. It is a surfactant.

Alternatively, such laundry detergent compositions, in high concentration form, have, for example, twice, three or four times the activity of ordinary surfactants. Preferably, the concentrated laundry detergent composition contains the following: That is, (1) a branched C ₁₂ AS surfactant of about 20% by weight to about 50% by weight, preferably about 25% by weight to about 45% by weight, and more preferably about 30% by weight to about 40% by weight. (2) About 20% to about 50% by weight, preferably about 25% to about 45% by weight, and more preferably about 30% to about 40% by weight of branched C ₁₃ AS surfactant and (3). ) Weight average ethoxylation in the range of about 4 to about 6, from about 5% to about 30% by weight, preferably from about 8% to about 20% by weight and more preferably from about 10% to about 15% by weight. It is a linear C ₆ AA surfactant having.

The cleaning compositions of the present invention do not require any defoaming agents such as silicone defoaming agents or suds collapsing polymers, as the surfactant system itself provides the desired lathering effect. Acts to minimize the manufacturing and processing costs associated with such cleaning compositions. Specifically, in a preferred embodiment of the invention, the cleaning composition is substantially free of, and more preferably essentially free of, any antifoaming agent.

In a preferred but not essential embodiment of the invention, the cleaning composition is a granule or powder detergent composition, more preferably 250 g / l to about 1000 g / l, more preferably about 300 g / l to about 900 g / l and most. A granular or powder laundry detergent composition having a density in the range of about 400 g / l to about 850 g / l is preferable. The powder or granular detergent may include: (a) 0.1% to 40%, preferably 0.5% to 30% and more preferably 3% of the total weight of such granular detergent composition. ~ 25% water-soluble alkali metal carbonate (sodium carbonate, etc.) and / or (b) 10% to 95%, preferably 20% to 90%, and more preferably 30% to 80% of the total weight of the granular detergent composition. % Of the total weight of the water-soluble alkali metal sulfate (sodium sulfate, etc.) and / or (c) such granular detergent composition, from about 10% to about 95%, preferably from about 20% to about 90% and more preferably from about. 30% to about 80% water-soluble alkali metal chloride (sodium chloride, etc.). Such a granular laundry detergent composition is one or more auxiliary component (for example, builder, carrier, structuring agent, aggregating aid, chelating agent, dye transfer inhibitor) generally used in the formulation of the granular laundry detergent composition. , Enzymes, enzyme stabilizers, catalyst materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymer dispersants, clay stain removers / anti-redeposition agents, whitening agents, foam suppressors Agents, dyes, fragrances, structural softeners, fabric softeners, hydrotropes, processing aids, pigments and / or aesthetic particles, etc.) may be further included.

The powder or granular detergent composition preferably contains only slightly lower concentrations of phosphate or zeolite builder, or more preferably substantially free of phosphate or zeolite builder, or most preferably completely phosphate or Does not contain zeolite builder.

In another embodiment of the invention, the cleaning composition is a liquid detergent composition, preferably having a viscosity in the range of about 200 to about 800 mPa · s, measured at 25 ° C., 20 seconds- ¹ shear rate. A liquid laundry detergent composition. The liquid detergent composition may be packaged in a single-phase or polyphase single dose form. That is, it is contained in a single compartment or multi-compartment water-soluble pouch formed of, for example, a water-soluble polymer (polyvinyl alcohol (PVA) and / or polyvinylpyrrolidone (PVP), etc.).

The liquid detergent composition of the present invention has about 0.1% to about 10%, preferably about 0.5% to about 8%, and more preferably about 1% of the total weight of the liquid detergent composition in addition to the above components. It may further contain ~ about 5% of one or more acids (citric acid, boric acid and mixtures thereof, etc.). Preferably, the liquid detergent composition contains from about 1% to about 3% by weight citric acid and / or from about 1% to about 3% by weight boric acid. Further, fatty acids, particularly C _12- C ₁₈ fatty acids or salts thereof, may be included in the liquid laundry detergent compositions of the present invention. The total amount of such fatty acids or salts ranges from about 0.1% to about 5% by weight, preferably from about 0.5% to about 4% by weight and more preferably from about 0.7% to about 3% by weight. It may be.

The liquid detergent composition of the present invention typically contains one or more carriers such as water. The liquid detergent composition can contain water alone as a carrier or a mixture of organic solvents (s) with water as carriers. Suitable organic solvents include linear or branched lower molecular weight amine solvents such as lower C _{1 to} C ₈ alcohols, diols, glycerol or glycols, C _{1 to} C ₄ alkanolamines, and lower molecular weight amine solvents. It is a mixture of these. Particularly preferred organic solvents include 1,2-propanediol, ethanol, glycerol, monoethanolamine and triethanolamine. Carriers are typically present in the liquid detergent compositions of the present invention in concentrations ranging from about 10% to about 95%, preferably about 25% to about 75% of the total weight of the liquid detergent compositions. .. In certain embodiments, water is about 85 to about 100% by weight of the carrier. In other embodiments, water is absent and the composition is anhydrous. A highly preferred composition obtained by the present invention is a clear isotropic liquid.

In a preferred but not essential embodiment of the invention, the cleaning composition is in single dose form and comprises a liquid laundry detergent encapsulated in a water soluble film. Preferred film materials are preferably polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, cellulose ester, celluloseamide, polyvinyl acetate, polycarboxylic acid and salt, polyamino acid or peptide, polyamide, A polymer material selected from natural gums such as polyacrylamide, maleic acid / acrylic acid copolymers, polysaccharides including starch and gelatin, xanthan and cara gum. More preferred polymers are selected polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methylcellulose (HPMC) and combinations thereof.

The cleaning composition of the present invention may also contain one or more cleaning auxiliary additives. Suitable cleaning aids include builder, filler, carrier, structuring agent or thickener, clay stain remover / anti-redeposition agent, polymer stain release agent, polymer dispersant, polymer grease cleaner, enzyme, enzyme stabilizer. Chemicals, amines, bleaching compounds, bleaching agents, bleaching activators, bleaching catalysts, whitening agents, dyes, fabric colorants, dye transfer inhibitors, chelating agents, softeners or conditioners (eg cationic polymers or silicones, etc.) ), Fragrances (including perfume inclusions), hygiene and malodor treatment agents, and the like.

More specifically, the cleaning auxiliary additives include transition metal catalysts, imine bleaching accelerators, amylases, carbohydrases, cellulase, lacquerse, lipases, bleaching enzymes such as oxidase and peroxidase, proteases, pectatetriases, and mannanases. Peroxygen sources such as enzymes, percarbonates and / or perborates (sodium percarbonate is preferred; peroxygen sources are carbonates, sulfates, silicates, borosilicates or mixtures containing these. It is preferable that the coating component is at least partially coated with a coating component such as (), a bleaching activator such as tetraacetylethylenediamine, or an oxybenzenesulfonate bleaching activator such as nonanoyloxybenzenesulfonate. , Caprolactam bleaching activator, imide bleaching activator such as N-nonanoyl-N-methylacetamide, preformed excess such as N, N-phthaloylaminoperoxycaproic acid, nonylamide peroxyadiponic acid or dibenzoyl peroxide. Acids, whitening agents, hue agents, photobleaching agents, clays, silicones, and / or fabric softeners such as quaternary ammonium compounds, flocculants such as polyethylene oxide, polyvinylpyrrolidone, poly4-vinylpyridine N-oxide, and / Or dye transfer inhibitors such as copolymers of vinylpyrrolidone and vinylimidazole, fabric-integrating components such as oligomers produced by condensation of imidazole and epichlorohydrin, stains such as alkoxylated polyamines and ethoxylated ethyleneimine polymers Dispersants and stain anti-adhesion aids, anti-re-adhesion ingredients such as polyester and / or terephthalate polymers, vinyl alcohol and / or polyethylene glycol containing polyethylene glycol substituted with vinyl acetate pendant groups, fragrance microcapsules, Schiff base fragrances / Polymer composites, fragrances such as polymer auxiliary fragrance delivery systems containing starch-encapsulated fragrance accords, soap rings, colored noodles and / or aesthetic particles including acicular particles, dyes, fillers such as sodium percarbonate (provided) , The composition may preferably be substantially free of fillers), carbonates such as sodium percarbonate and / or sodium percarbonate, sodium silicate containing 1.6R and 2.0R sodium silicate, or catalyst. Quayates such as sodium acidate, copolyester of dicarboxylic acid and diol, methyl cellulo Cellulose polymers such as cellulosic, carboxymethyl cellulose, hydroxyethoxycellulose, or other alkyl or alkylalkoxy celluloses, and hydrophobically modified cellulose, carboxylic acids and / or salts thereof containing citric acid and / or sodium citrate, and Any combination of these can be mentioned.

A wide variety of other ingredients may be used in the cleaning compositions herein, including: That is, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, liquid solvents and solid or other liquid fillers, erythrosin, colloidal silica, waxes, probiotics, surfactins, aminocellulose polymers, ricinol. Zinc Acid Acid, Perfume Microcapsules, Ramnolipide, Sophorolipide, Glycopeptides, Methylester Sulfonates, Methyl ester ethoxylates, Sulfated Estrides, Degradable Surfactants, Biopolymers, Silicones, Modified Silicones, Amino Silicones, Deposition Aids, Locust Beans Gum, cationic hydroxyethyl cellulose polymer, cationic guar, hydrotropes (particularly cumene sulfonate salt, toluene sulfonate salt, xylene sulfonate salt and naphthalene salt), antioxidants, BHT, PVA particle encapsulating dyes or fragrances, pearl brighteners. , Foaming agent, color change system, silicone polyurethane, opalescent agent, tablet disintegrant, biomass filler, quick-drying silicone, glycol distearate, hydroxyethyl cellulose polymer, hydrophobic modified cellulose polymer or hydroxyethyl cellulose polymer, starch fragrance encapsulant, Emulsifying oils, bisphenol antioxidants, microfibrous cellulose structuring agents, pre-fragrances, styrene / acrylate polymers, triazines, soaps, superoxide dismutase, benzophenone protease inhibitors, functionalized TiO2, dibutyl phosphate, silica fragrance capsules and other Auxiliary components, silicate salts (eg, sodium silicate, potassium silicate), choline oxidases, pectate triases, polymers, titanium dioxide coated polymers, bismuth oxychloride and other activators.

The cleaning compositions described herein also include vitamins and amino acids such as water-soluble vitamins and derivatives thereof, water-soluble amino acids and salts and / or derivatives thereof, insoluble amino acid viscosity regulators, dyes, non-volatile solvents or dilutions. Agents (water-soluble and insoluble), pearl luster aids, additional surfactants or non-ionic auxiliary surfactants, shavings, pH regulators, fragrances, preservatives, chelating agents, proteins, skin activators, It may contain sunscreens, UV absorbers, vitamins, niacinamides, caffeine and minoxidil.

The cleaning composition of the present invention is described in C.I. I. Nitroso, monoazo, disazo, carotenoids, triphenylmethanes, triarylmethanes, xanthenes, quinolines, oxazines, azines, anthraquinones, indigoides, thionindigoids, quinacridones, phthalocianines, including water-soluble ingredients such as those named Pigment materials such as plant colorants and natural colorants may also be included. The cleaning composition of the present invention may also contain an antibacterial agent.

Methods of Use The present invention includes methods for cleaning dirty materials using the cleaning compositions of the present invention. As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are suitable for use in pre-washing applications, washing and cleaning applications, and home care applications.

Preferably, such a method is a method of cleaning a soiled material using the detergent composition of the present invention, and is not limited to the following steps, that is, preparing (diluting) the detergent composition described above. No form or diluted in cleaning solution), such detergent composition is in contact with at least a portion of the soiled material, followed by rinsing the soiled material.

For use in laundry pretreatment applications, the method may include contacting the cleaning composition described herein with a soiled fabric. After the pretreatment, the dirty fabric may be machine washed or otherwise rinsed.

The cleaning composition of the present invention is particularly suitable for hand-washing applications or applications that combine hand-washing with a semi-automatic washing machine. Specifically, the consumer cleans the soiled material with direct contact with the composition, manually or semi-manually cleans the soiled material, and subsequently rinses the soiled material with one or more rinse cycles. Rinse at.

Alternatively, the washing composition of the present invention is suitable for a machine washing method, and the machine washing method is a dirty laundry in a washing machine in which an effective amount of the washing composition for machine washing according to the present invention is dissolved or administered. May include treating with a wash solution.

Another method involves contacting a non-woven substrate impregnated with one embodiment of the cleaning composition with a dirty material. As used herein, a "nonwoven fabric substrate" may include any conventional non-woven fabric sheet or web with suitable weighing, caliper (thickness), absorbency, and strength properties. Non-limiting examples of suitable commercially available non-woven fabric base materials are described by DuPont under the trade names SONTARA® and James River Corp. Examples thereof include those commercially available under the trade name POLYWEB (registered trademark).

The "effective amount" of the cleaning composition means that about 10 g to about 300 g of the product is dissolved or dispersed in a volume of about 5 L to about 65 L of the cleaning solution. The water temperature can range from about 5 ° C to about 100 ° C. The ratio of water to dirty material (eg, fabric) can be from about 1: 1 to about 30: 1. The composition may be used in solution at a concentration of about 500 ppm to about 15,000 ppm, preferably about 1000 ppm to about 10,000 ppm and more preferably about 3000 ppm to about 5000 ppm. In the context of fabric washing compositions, the concentration used is also the type and degree of stains and stains, as well as the temperature of the wash water, the volume of the wash water, and the type of washing machine (eg, top-load, front-load). , Top-loading type, vertical axis type Japanese type automatic washing machine).

The cleaning compositions herein can be used to wash fabrics at low temperature cleaning temperatures. These methods of washing fabrics include delivering the washing and washing composition to water to form a washing liquid and adding the washing fabric to the washing liquid. The cleaning liquid has a temperature of about 0 ° C to about 20 ° C, about 0 ° C to about 15 ° C, or about 0 ° C to about 9 ° C. The fabric may be contacted with water before, after, or at the same time the cleaning composition is contacted with water.

Test Method Various techniques for determining the properties of the composition containing the branched AS surfactant and the short chain nonionic AA surfactant of the present invention are known in the art. However, the following assays must be used to fully understand the invention described and claimed herein.

Test 1: Foaming property test (for determining various foaming parameters)
In the present specification, the foaming characteristics of the test detergent composition are measured using a foam cylinder tester (SCT). The SCT has a set of eight cylinders. Each cylinder is a plastic cylinder about 66 cm long, has a uniform inner diameter of 50 mm over its length, and can be covered or sealed with a rubber stopper during rotation. All eight cylinders have the central part of each cylinder mounted on a horizontal axis. All eight cylinders are perpendicular to the horizontal axis but are arranged parallel to each other. The cylinders are evenly spaced between them and rotate together around a horizontal axis at a speed of 20 to 22 revolutions per minute (rpm) along a vertical plane perpendicular to the horizontal axis. be able to.

The following factors can affect the measurement results and should be carefully controlled. That is, (a) the concentration of the test detergent composition in the cleaning liquid and the rinsing liquid, (b) the hardness of the water used to form the cleaning and rinsing liquid, (c) the water temperature, and (d) the rotation speed of the SCT cylinder. And the number of revolutions, (e) the type of dirt used and the amount of dirt used in cleaning, and (f) the cleanliness inside the SCT cylinder.

Follow the steps below to achieve foam measurements for each test detergent composition.
1.1.5 g of the test detergent composition (granular or liquid form) is weighed and at room temperature its hardness is about 274 mg / L (16 gpg) (Ca / Mg 4: 1 and 21.9 mg / L CaCl2 Dissolve in 300 mL of reverse osmosis (RO) water (formed by mixing 2H2O and 111.3 mg / L MgCl2.6H2O).
2. The mixture is stirred for at least 15 minutes to form a cleaning solution sample containing the test detergent composition at 5000 ppm.
3. 3. Pour the test solution into the SCT cylinder and close it tightly using a rubber stopper to secure the cylinder in place and prepare for rotation. To perform foam measurements of different test detergent compositions at the same time, other SCT cylinders can be filled with sample solutions formed by using other test detergent compositions.
4. Power on the SCT and rotate the cylinder 10 times at a speed of 22 rpm.
5. The rotation by the SCT is stopped, and the SCT cylinder is fixed in the upright position.
6. Wait 1 minute before recording the foam volume (represented by absolute foam height) in each SCT. This is taken as the foam volume produced by the test detergent composition rotated 10 times. Since all SCT cylinders have the same inner diameter, the foam volume at any given point can simply be expressed in absolute height of foam (centimeters (cm)) within each SCT cylinder, which is the cleaning solution. Alternatively, the height of the rinse solution is measured by subtracting the total height of the foam and the wash solution or rinse solution.
7. The SCT is powered on, the cylinder continues to rotate 20 more times at a speed of 22 rpm, the SCT is stopped, and the foam volume is recorded as the foam volume at 30 revolutions.
8. Step 7 is repeated and the foam volume at 50 and 70 revolutions at a rate of 22 rpm is recorded.
9. Stop the SCT rotation, remove the rubber stopper from the cylinder, and put a piece of fabric with Beijing viscosity (BJ viscosity) and a piece of fabric with dirty cooking oil (DCO) into each SCT cylinder. And place it. The preparation of these fabrics will be described below.
Preparation of fabric with BJ clay attached ● 20 g BJ viscosity (collected from 15 cm below the surface of Beijing, China, dried at room temperature for 1-2 weeks, then blended in a strong blender and sieved 150-200 # (Through) is dispersed in 80 mL of deionized water by stirring to obtain a viscosity suspension. Alternatively, Arizona clay (ie, Arizona Test Dust with a median particle size of about 0.889 micrometers and an average particle size of about 0.942 micrometers, by Power Technology Inc. of the United States) can be used in place of the BJ viscosity.
● While continuing to stir the viscosity suspension, place 2 g of such clay suspension in the center of a piece of 10 cm x 10 cm, CW98 white cotton knitted (100%) fabric (supplied from DaXinFangZHi (Beijing, China)). Apply to form a circular stain with a diameter of about 5 cm.
● Subsequently, the cotton fabric is allowed to stand and dried at room temperature before use.
Preparation of DCO-attached fabric ● Using 100 g of peanut oil, 20 g of salty fish was fried at 150-180 ° C for 2 hours to form DCO.
● 0.6 mL of DCO is dropped onto the center of the 10 cm × 10 cm cotton fabric described above to form a circular stain with a diameter of about 5 cm.
● Cut the cotton fabric into two equal pieces and use one piece for each performance evaluation.
10. Return the rubber stopper to the SCT cylinder.
11. The SCT is powered on, the cylinder continues to rotate 40 more times at a speed of 22 rpm, the SCT is stopped, and the foam volume is recorded as the foam volume at 110 revolutions.
12. Steps 9-11 are repeated and the foam volume is recorded as the foam volume at 150 revolutions. Further addition of the soiled fabric to the cleaning liquid in the SCT cylinder mimics the actual cleaning conditions, and as the cleaning cycle continues, more dirt is gradually dissolved from the fabric into the cleaning liquid. Therefore, this test relates to the measurement of the initial foam formation by the test detergent composition and the foam effect maintained over the cleaning cycle while more dirt gradually dissolves in the cleaning solution.
Gently pour a 13.37.5 mL wash solution sample (without any treated fabric pieces) from the SCT cylinder into a 300 mL beaker. 262.5 mL of RO water having a hardness of 274 mg / L (16 gpg) (Ca / Mg 4: 1) was added to the beaker to form a diluted solution (referred to as "rinse solution") having a total volume of 300 mL. To do. Clean up any residual test solution and all stained fabric shavings from the SCT cylinder and wash the SCT cylinder with tap water. Pour 300 mL of rinse back from the beaker into the washed SCT cylinder. These steps are repeated for the test solution in each of the remaining SCT cylinders.
14. The power is turned on to the SCT, the cylinder is continuously rotated at a speed of 22 rpm for another 20 times, and the SCT is stopped. A picture is taken immediately after the SCT is stopped and the bubble height is read from the picture (in the sample of the present invention, the bubbles collapse very rapidly, so this is done to ensure the accuracy of the data). This is recorded as the bubble volume at 0 minutes after 170 rotations. This foam data, measured after the wash solution, replaces the rinse solution. Therefore, it is recorded as "rinse foam in 0 minutes".
15. Another reading of the foam volume in the SCT cylinder is performed 1 minute after the SCT is stopped at 170 revolutions (this is referred to as "rinse foam in 1 minute").
16. The rate of reduction of foam from 0 minutes to 1 minute using the rinse solution during the first rinse is calculated as follows.

１７．以下は、本試験方法により記録された泡データである。

17. The following is the bubble data recorded by this test method.

Example 1: Powder Laundry Detergent Formulation The powder laundry detergent formulation containing the branched AS surfactant and the short chain AA nonionic surfactant of the present invention is prepared according to the present invention. The following is a breakdown of the detailed composition of this formulation.

¹Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。４０％を上回るＣ₁₂ ＡＳ及び４０％を上回るＣ₁₃ ＡＳを含有する。いずれも分岐状、非アルコキシル化であり、少なくとも９０％の分岐を有する。
²ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol. It contains more than 40% C ₁₂ AS and more than 40% C ₁₃ AS. Both are branched, dealkoxylated and have at least 90% bifurcation.
² Emulan® HE50 commercially available from BASF.

The powder laundry detergent formulation of the present invention is used to form a cleaning solution by dissolving 15 g of detergent in 3 liters of tap water at a temperature of about 20 ° C. Subsequently, 300 g of dry fabric is manually processed using the cleaning solution. The fabric includes half a dirty shirt and a clean piece of cotton fabric to adjust the weight. The treatment involves hand scrubbing half of the dirty shirt 20 times and each piece of cotton fabric 10 times. Then, the treated fabric is squeezed 2-3 times to a wet weight of about 900 g. The rinse solution is then formed by diluting the wash solution carried over to 4 liters of tap water with a damp treated fabric.

On the left hand side of FIG. 2, a photograph of a cleaning solution formed by using the powder laundry detergent formulation of the present invention is shown, and a photograph of a rinsing solution corresponding to the right hand side is shown. The powder laundry detergent composition of the present invention is capable of producing a sufficient amount of stable wash foam during the wash cycle of the hand wash wash process, but at the end of the first rinse cycle of the hand wash wash process. It is clear that there is little or no rinsing foam left.

Example 2: Liquid laundry detergent formulation that produces "zero rinse foam" by hand washing The liquid laundry detergent formulation containing the branched AS surfactant and short-chain AA nonionic surfactant of the present invention is: Prepared according to the present invention. The following is a breakdown of the detailed composition of this formulation.

^*特に記載がない限り、本実施例及び全ての他の実施例の成分濃度は、最終組成物中の純粋な材料の濃度であり、添加した原材料の濃度ではないことに留意。
¹Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。０．６％のＮａＯＨ、０．８％の硫酸ナトリウム、アルキルサルフェートの合成から持ち越された１〜１．３％のＣ₁₂〜Ｃ₁₃残留アルコール及び残部の水を有し、７５％が有効な原材料として提供される。
²ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。１００％が有効な原材料として提供される。

^* Note that unless otherwise stated, the component concentrations in this example and all other examples are the concentrations of the pure material in the final composition, not the concentration of the added raw material.
¹ Isalchem® 123 commercially available from Sasol. It has 0.6% NaOH, 0.8% sodium sulphate, 1-1.3% C _12- C ₁₃ residual alcohol carried over from the synthesis of alkyl sulfate and the rest of the water, 75% effective. Provided as a raw material.
² Emulan® HE50 commercially available from BASF. 100% is provided as an effective raw material.

The powder laundry detergent formulation of the present invention is used to form a cleaning solution by dissolving 15 g of detergent in 3 liters of tap water at a temperature of about 20 ° C. Subsequently, 300 g of dry fabric is manually processed using the cleaning solution. The fabric includes half a dirty shirt and a clean piece of cotton fabric to adjust the weight. The treatment involves hand scrubbing half of the dirty shirt 20 times and each piece of cotton fabric 10 times. Then, the treated fabric is squeezed 2-3 times to a wet weight of about 900 g. The rinse solution is then formed by diluting the wash solution carried over to 4 liters of tap water with a damp treated fabric.

A photograph of the cleaning liquid formed by the liquid laundry detergent formulation of the present invention is shown on the left hand side of FIG. 3, and a photograph of the rinsing liquid corresponding to the right hand side is shown. The liquid laundry detergent compositions of the present invention are capable of producing a sufficient amount of stable wash foam during the wash cycle of the hand wash wash process, but at the end of the first rinse cycle of the hand wash wash process. It is clear that there is little or no rinsing foam left behind.

Example 3: Comparative Example showing Improved Foaming Characteristics of The Powder Laundry Detergent Composition of the Invention Four kinds of powder laundry detergent compositions including the following were prepared. A control composition (“Control 1”) that does not contain a branched AS surfactant and a short chain AA surfactant, (2) similar in composition to the control composition, but with an additional 12% by weight. Comparative Composition A (“Comparative Example A”) having a branched C _{12 to} C ₁₃ AS surfactant (commercially available from Sasol as Isalchem® 123), (3) Similar to the control composition. Comparison with 3% by weight of linear C ₆ alkyl ethoxylated alcohol (commercially available from BASF as Emulan® HE50) with an additional weight average ethoxylation of about 5 Compositions B (“Comparative Example B”) and (4) are similar in composition to the control composition, but with an additional 12% by weight of branched C _12- C ₁₃ AS surfactants and an additional 3% by weight. The composition of the invention having the linear C ₆ alkyl ethoxylated alcohol of the above ("Invention Example 1").

The breakdown of the detailed composition of the above four powder laundry detergent compositions is shown below.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.

The above-mentioned four kinds of powder laundry detergent compositions have the following test results after undergoing the foaming property test described in Test 1.

^*本試験では、０分での１／８すすぎ液の泡と、すすぎ泡減少速度のデータを記録しない。

^{* In} this test, 1/8 rinse solution foam at 0 minutes and data on rinse foam reduction rate are not recorded.

Example 1 of the invention produces more initial foam during the early stages of the wash cycle and more throughout the wash than both Comparative Examples A and B (when considered alone or in combination). It also has a good foaming effect. Furthermore, the rinse foam of Invention Example 1 during the first rinse cycle is sufficiently small (similar to Comparative Example A). Therefore, Example 1 of the invention provides desirable foaming properties for powder laundry detergent applications by combining branched C _12- C ₁₃ AS surfactants with linear C ₆ AAA alcohols.

Example 4: Comparative Example showing Improved Foaming Characteristics of the Liquid Laundry Detergent Composition of the Invention Four kinds of liquid laundry detergent compositions including the following were prepared. A control composition (“Control 2”) that does not contain a branched AS surfactant and a short chain AA surfactant, (2) similar in composition to the control composition, but with an additional 12% by weight. , (“Comparative Example C”), which has the same branched C _{12 to} C ₁₃ AS surfactants as described above in Example 3, and (3) similar formulation to the control composition. to have, but an additional 3 wt.%, the same as those described above in example 3, comparative composition B having a linear C ₆ AA alcohol ( "Comparative example D") and (4) Compositions of the invention similar in formulation to the control composition, but with an additional 12% by weight branched C _12- C ₁₃ AS surfactant and an additional 3% by weight linear C ₆ AAA alcohol. "Invention Example 2").

The detailed composition of the above four liquid laundry detergent compositions is shown below.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.

The above-mentioned four kinds of liquid laundry detergent compositions have the following test results after undergoing the foaming property test described in Test 1.

^*本試験では、０分での１／８すすぎ液の泡と、すすぎ泡減少速度のデータを記録しない。

^{* In} this test, 1/8 rinse solution foam at 0 minutes and data on rinse foam reduction rate are not recorded.

Example 2 of the invention produces more initial foam during the early stages of the wash cycle than both Comparative Examples C and D (considering when added alone or together), and It also has a better foaming effect throughout the wash. Furthermore, the rinse foam of Invention Example 1 during the first rinse cycle is sufficiently small (similar to Comparative Example C). Therefore, Example 1 of the invention also provides desirable foaming properties for liquid laundry detergent applications by combining branched C _12- C ₁₃ AS surfactants with linear C ₆ AAA alcohols.

Example 5. Comparative Example of the Powdered Laundry Detergent Composition of the Invention, which shows improved foaming characteristics as compared with a comparative composition containing a linear AS surfactant ("Invention Example 3") ”) Is similar in formulation to Example 3 of the Invention, except that it contains a linear C _{12 to} C ₁₄ AS surfactant rather than a branched C _{12 to} C ₁₃ AS surfactant. Compare with the comparative composition E (“Comparative Example E”). The breakdown of the compositions of Example 3 and Comparative Example E of the invention is given side by side below.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.

The above-mentioned two kinds of powder laundry detergent formulations go through the foaming property test described in Test 1. The following are the test results.

Example 3 of the present invention (containing a branched C _{12 to} C ₁₃ AS surfactant) is more than Comparative Example E (containing a linear C _{12 to} C ₁₄ AS surfactant) during washing. Also shows a significantly better foam effect and a higher wash foam retention rate. On the other hand, the results of rinsing foam of the two formulations are relatively similar.

Example 6. Comparative Examples Examples of the powder laundry detergent composition of the present invention showing improved foaming properties as compared with a comparative composition containing a longer chain (C _{12 to} C ₁₄ ) AA nonionic surfactant. The same invention powder laundry detergent composition described in No. 5 (“Invention Example 3”) was used in a longer chain, C _{12 to} C ₁₄ AA, rather than a short chain C ₆ AA nonionic surfactant. It is further compared with Comparative Composition F (“Comparative Example F”), which has a similar composition to Example 3 of the invention, except that it contains a nonionic surfactant. The breakdown of the composition of Comparative Example F is given below along with Example 3 of the invention.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.

The above-mentioned two kinds of powder laundry detergent formulations go through the foaming property test described in Test 1. The following are the test results.

Example 3 of the present invention (containing a short chain AA nonionic surfactant) is significantly more than Comparative Example F (containing a longer chain C _{12 to} C ₁₄ AA nonionic surfactant). Shows a better rinsing foam reduction rate. The results of the cleaning foam of these two formulations are relatively similar. On the other hand, Example 3 of the invention has a slightly better foam effect and a higher cleaning foam retention rate than Comparative Example F during cleaning.

Example 7. Comparative Example of the Powder Laundry Detergent Composition of the Invention Showing Improved Foaming Characteristics Compared with a Comparative Composition Containing an Alkenylated Branched AS Surfactant The same invention powder washing described in Example 5 Detergent composition for use (“Example 3 of the invention”) is not a branched non-alkoxylated C _{12 to} C ₁₃ AS surfactant, but a branched alkenylated C _{12 to} C ₁₃ having an average degree of ethoxylation of about 1. It is further compared with Comparative Composition G (“Comparative Example G”), which has a similar composition to Example 3 of the invention, except that it contains an AS surfactant. The breakdown of the composition of Comparative Example G is given below along with Example 3 of the invention.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.

The above-mentioned two kinds of powder laundry detergent formulations go through the foaming property test described in Test 1. The following are the test results.

Example 3 of the present invention (containing a branched non-alkoxylated AS surfactant) has a significantly better rinsing foam reduction rate than Comparative Example G (containing a branched ethoxylated AS surfactant). Shown.

Example 8 A comparative example of the powder laundry detergent composition of the present invention showing improved foaming properties as compared with a comparative composition containing a longer chain (C _{14 to} C ₁₅ ) branched AS surfactant. The same invention powder laundry detergent composition described in Example 5 (“Invention Example 3”) was used in a longer chain of branched C ₁₄ to C ₁₃ instead of a C _{12 to} C ₁₃ branched AS surfactant. Further comparison is made with Comparative Composition H (“Comparative Example H”) having a formulation similar to that of Example 3 of the invention, except that it contains a C ₁₅ AS surfactant. The breakdown of the composition of Comparative Example H is given below along with Example 3 of the invention.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。
³ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１４５である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.
³ Isalchem® 145 commercially available from Sasol.

The above-mentioned two kinds of powder laundry detergent formulations go through the foaming property test described in Test 1. The following are the test results.

Example 3 of the present invention (containing a branched C _{12 to} C ₁₃ AS surfactant) is described in Comparative Example H (containing a longer chain branched C _{14 to} C ₁₅ AS surfactant). Remarkably better rinsing foam reduction rate.

Example 9. Comparative Example with Different AS: A Weight Ratios Exhibiting Foaming Properties of the Powdered Laundry Detergent Composition of the Invention The same powdered laundry detergent composition of the invention described in Example 5 (“Invention Example 3” or "IE3") is a powder detergent composition of the invention having a similar formulation, except that some other branched AS surfactants differ in weight ratio to short chain AA nonionic surfactants. ("Invention Examples 4 to 7" or "IE 4 to 7") was further compared. Specifically, Invention Example 3 has an AS: AA weight ratio of 4: 1, while Invention Examples 4 to 7 have an AS: AA of 1: 2, 1: 1, 2: 1 and 5: 1. Has a weight ratio. The breakdown of the compositions of Invention Examples 4 to 7 is given below along with Invention Example 3.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.

The powder laundry detergent formulations of all five inventions described above have the following results after undergoing the foaming property test described in Test 1.

All of Invention Examples 3-7 of the present invention show a significant reduction in foam during the first rinse cycle. For example, it has a rinsing foam reduction rate of 70% or more. However, Examples 3, 6 and 7 of the invention having a higher AS: A weight ratio (eg 2: 1, 4: 1 and 5: 1) show a better foaming effect throughout the wash. Therefore, it is preferable (but not essential) to have a higher AS: A weight ratio (eg, 2: 1-5: 1 and more preferably 4: 1-5: 1) for the detergent composition of the present invention. ..

Example 10: Illustrative powder laundry detergent formulation The powder laundry detergent compositions 10A to 10F are blended by integrally mixing the components listed below according to the present invention.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.

Example 11: Illustrative Liquid Laundry Detergent Formulation Liquid laundry detergent compositions 11A to 11F are blended in accordance with the present invention by integrally mixing the components listed below.

¹ Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
² ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。
³ プロテアーゼは、Ｇｅｎｅｎｃｏｒ Ｉｎｔｅｒｎａｔｉｏｎａｌ（Ｐａｌｏ Ａｌｔｏ，Ｃａｌｉｆｏｒｎｉａ，ＵＳＡ）から（例えばＰｕｒａｆｅｃｔ Ｐｒｉｍｅ（登録商標）、Ｅｘｃｅｌｌａｓｅ（登録商標））、又はＮｏｖｏｚｙｍｅｓ（Ｂａｇｓｖａｅｒｄ，Ｄｅｎｍａｒｋ）から（例えばＬｉｑｕａｎａｓｅ（登録商標）、Ｃｏｒｏｎａｓｅ（登録商標））供給され得る。
⁴ Ｎｏｖｏｚｙｍｅｓ（Ｂａｇｓｖａｅｒｄ，Ｄｅｎｍａｒｋ）から入手可能（例えば、Ｎａｔａｌａｓｅ（登録商標）、Ｍａｎｎａｗａｙ（登録商標））。
⁵ Ｎｏｖｏｚｙｍｅｓから入手可能（例えば、Ｗｈｉｔｅｚｙｍｅ（登録商標））。
⁶ −ＮＨにつき、２０個のエトキシレート基を有するポリエチレンイミン（ＭＷ＝６００）。
⁷ ランダムグラフトコポリマーは、ポリエチレンオキシド骨格と複数のポリ酢酸ビニル側鎖とを有する、ポリ酢酸ビニルグラフト化ポリエチレンオキシドコポリマーである。ポリエチレンオキシド主鎖の分子量は、約６０００であり、ポリエチレンオキシドとポリ酢酸ビニルの重量比は、約４０対６０であり、５０エチレンオキシド単位あたり１グラフト点を超えず、ＢＡＳＦからＳｏｋａｌａｎ ＰＧ１０１（登録商標）として入手可能である。
⁸ 次の一般構造、ビス（（Ｃ₂Ｈ₅Ｏ）（Ｃ₂Ｈ₄Ｏ）_n）（ＣＨ₃）−Ｎ⁺−Ｃ_xＨ_2x−Ｎ⁺−（ＣＨ₃）−ビス（（Ｃ₂Ｈ₅Ｏ）（Ｃ₂Ｈ₄Ｏ）_n）（式中、ｎ＝２０〜３０、ｘ＝３〜８）を有する化合物又はその硫酸化若しくはスルホン化したもの（variants）で、ＢＡＳＦからＬｕｔｅｎｚｉｔ Ｚ ９６（登録商標）として入手可能。
⁹ ＤＴＰＡは、ダウケミカル社（Ｍｉｄｌａｎｄ，Ｍｉｃｈｉｇａｎ，ＵＳＡ）から供給されているジエチレントリアミン五酢酸である。
¹⁰ 好適な蛍光白色剤は、例えば、Ｔｉｎｏｐａｌ（登録商標）ＡＭＳ、Ｔｉｎｏｐａｌ（登録商標）ＣＢＳ−Ｘ、スルホン化亜鉛フタロシアニン（Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ（Ｂａｓｅｌ，Ｓｗｉｔｚｅｒｌａｎｄ））である。０〜５％の範囲の量で提供され得る。
¹¹ 好適な防腐剤としては、０〜１％の範囲の量で提供され得るメチルイソシアゾリノン（ＭＩＴ）又はベンズイソシアゾリノン（ＢＩＴ）が挙げられる。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.
^{The three} proteases can be obtained from Genencor International (Palo Alto, California, USA) (eg, Purple Prime®, Excellase®), or from Novozymes (Bagsvaerd, Denmark) (eg, Liquanase®). Trademark)) Can be supplied.
⁴ Available from Novozymes (Bagsvaerd, Denmark) (eg, Natalase®, Mannaway®).
⁵ Available from Novozymes (eg, Whitezymes®).
Polyethyleneimine with 20 ethoxylate groups per ^6- NH (MW = 600).
⁷ Random 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, the weight ratio of polyethylene oxide to polyvinyl acetate is about 40:60, does not exceed one graft point per 50 ethylene oxide units, and BASF to Sokalan PG101®. It is available as.
^8th order general structure, screw ((C ₂ H ₅ O) (C ₂ H ₄ O) _n ) (CH ₃ ) −N ⁺ −C _x H _2x −N ⁺ − (CH ₃ ) − screw ((C ₂₎ A compound having H ₅ O) (C ₂ H ₄ O) _n ) (in the formula, n = 20 to 30, x = 3 to 8) or a sulfated or sulfonated compound thereof (variants) from BASF to Ethylenez. Available as 96 (registered trademark).
⁹ DTPA is diethylenetriamine pentaacetic acid supplied by Dow Chemical Company (Midland, Michigan, USA).
¹⁰ Suitable fluorescent whitening agents are, for example, Tinopal® AMS, Tinopal® CBS-X, Sulfated Zinc Phthalocyanine (Ciba Specialty Chemicals (Basel, Switzerland)). It may be provided in an amount in the range 0-5%.
¹¹ Suitable preservatives include methyl isocyanate (MIT) or benzisocyanazolinone (BIT), which may be provided in an amount ranging from 0 to 1%.

Example 12: An exemplary single dose formulation with a high concentration liquid detergent
The following high-concentration liquid laundry detergent compositions 12A-12E are prepared and each encapsulated in a multi-compartment pouch formed of a polyvinyl alcohol film.

¹Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
²ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。
^*限定されないが、プロパンジオール、グリセロール、エタノール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコールを挙げることができる。

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.
^* Not limited, but may include propanediol, glycerol, ethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol.

Example 13: An exemplary dishwashing detergent (having a high concentration liquid detergent)
Dishwashing detergent compositions 13A to 13F are blended according to the present invention by integrally mixing the components listed below.

¹Ｓａｓｏｌから市販されているＩｓａｌｃｈｅｍ（登録商標）１２３である。
²ＢＡＳＦから市販されているＥｍｕｌａｎ（登録商標）ＨＥ５０である。
^*微量成分としては、香料、染料、防腐剤が挙げられる。
ＶＰ：ビニルピロリドン
ＤＡＤＭＡＣ：Ｎ，Ｎ−ジメチルジアリルアンモニウム塩化物

¹ Isalchem® 123 commercially available from Sasol.
² Emulan® HE50 commercially available from BASF.
^* Trace components include fragrances, dyes, and preservatives.
VP: Vinylpyrrolidone DADMAC: N, N-dimethyldiallylammonium chloride

All percentages and ratios are calculated by weight unless otherwise specified. All percentages and ratios are calculated based on the total composition unless otherwise specified. All maximum numerical limits described throughout this specification shall include all smaller numerical limits as if such smaller numerical limits were expressly stated herein. Should be understood. All minimum numerical limits described throughout this specification include all higher numerical limits as if such higher numerical limits were explicitly stated herein. All numerical ranges given throughout the specification include all narrower numerical ranges that fall within such a wider numerical range, as if all such narrow numerical ranges were expressly described herein. ..

All documents cited in this application, such as cross-referenced or related patents or applications, are hereby incorporated by reference in their entirety, unless expressly excluded or otherwise limited. Citation of any document is not considered prior art for any invention disclosed or claimed herein, or it may be used alone or in combination with any other reference (s). At times, it is not considered to teach, suggest, or disclose any such invention. In addition, if any meaning or definition of a term in this document conflicts with the meaning or definition of the same term in the document incorporated by reference, the meaning or definition given to that term in this document applies. Shall be.

Having exemplified and described specific embodiments of the present invention, it will be apparent to those skilled in the art that various other modifications and modifications can be made without departing from the spirit and scope of the invention. Therefore, all such modifications and amendments included within the scope of the present invention are intended to be covered by the appended claims.

Claims (15)

(A) 5% by weight to 50% by weight of one or more branched dealkylated C _{6 to} C ₁₄ alkyl sulfate (AS) surfactants, wherein the one or more branched dealkylated C ₆ ~ C ₁₄ Alkyl sulfate (AS) surfactants containing branched alkyl moieties having a weight average carbon atom number in the range 9-14,
(B) One or more linear or branched C _{4 to} C ₁₁ alkyl or aryl alkoxylated alcohols having a weight average alkoxylation degree in the range of 1 to 10 from 0.05% to 10% by weight (AA). ) Containing surfactants and (c) one or more additional ingredients
The one or more branched non-alkoxylated C _{6 to} C ₁₄ alkyl sulfate (AS) surfactants are a mixture, and the mixture is a mixture.
(1) 20% to 80% by weight branched non-alkoxylated C ₁₂ AS surfactant of the mixture, and (2) 20% to 80% by weight branched non-alkoxylated C ₁₃ AS interface of the mixture. Contains activator
The branched non-alkoxylated C _{12 to} C ₁₃ AS surfactants are described in the general formula (I),

[In the formula, M is an alkali metal, alkaline earth metal, ammonium, amine or alkanolamine cation, x and y are independently selected from integers in the range 0-10, z is in the range 1-4. The sum of x + y is greater than or equal to z, and the sum of x + y + z is in the range 3-11. ], A cleaning composition. The cleaning according to claim 1, wherein the one or more branched non-alkoxylated C _{6 to} C ₁₄ AS surfactants are present in an amount in the range of 6% to 30% of the total weight of the cleaning composition. Composition. The cleaning composition according to claim 1 or 2, which contains 0.5% or less of either a linear or branched alkoxylated AS surfactant. One or more of the linear or branched C _{4 to} C ₁₁ AA surfactants include a linear or branched alkyl moiety having a weight average carbon atom number in the range of 4 to 10. Claims 1 to 1. The cleaning composition according to any one of 3. The cleaning according to any one of claims 1 to 4, wherein the one or more linear or branched C _{4 to} C ₁₁ AA surfactants have a weight average alkoxylation degree in the range of 2 to 8. Composition. The cleaning composition according to any one of claims 1 to 5, wherein one or more linear or branched C _{4 to} C ₁₁ AA surfactants are ethoxylated. Claims 1 to which one or more linear or branched C _{4 to} C ₁₁ AA surfactants are present in an amount in the range of 0.1% to 6% of the total weight of the cleaning composition. The cleaning composition according to any one of 6. The weight ratio of the one or more branched C _{6 to} C ₁₄ AS surfactants to the one or more linear or branched C _{4 to} C ₁₁ AA surfactants is 20: 1 to 1: 2. The cleaning composition according to any one of claims 1 to 7, which is in the range of. The cleaning composition is one selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and combinations thereof. The cleaning composition according to any one of claims 1 to 8, further comprising the above additional surfactant. The cleaning composition according to any one of claims 1 to 9, wherein the cleaning composition is a granular laundry detergent composition. Use of the cleaning composition according to any one of claims 1 to 10 for hand-washing tableware or fabrics. It ’s a method of treating dirty materials.
a) The step of preparing the cleaning composition according to any one of claims 1 to 11, and
b) A step of bringing the detergent composition into contact with at least a part of the dirty material.
c) The process of rinsing the dirty material and
Including methods. 12. The method of claim 12, wherein steps (b) and (c) are both performed by hand and the dirty material is a dirty fabric. (A) 1% to 30% by weight branched non-alkoxylated C ₁₂ AS surfactant,
(B) 1% to 30% by weight branched non-alkoxylated C ₁₃ AS surfactant,
(C) from 0.1% to 15%, including linear C ₆ AA surfactant and (d) 1 or more additional components having a weight average degree of ethoxylation ranging from 4-6,
The branched non-alkoxylated C _{12 to} C ₁₃ AS surfactants are of the general formula (I),

[In the formula, M is an alkali metal, alkaline earth metal, ammonium, amine or alkanolamine cation, x and y are independently selected from integers in the range 0-10, z is in the range 1-4. The sum of x + y is greater than or equal to z, and the sum of x + y + z is in the range 3-11. ], A laundry detergent composition. (A) 20% to 50% by weight branched non-alkoxylated C ₁₂ AS surfactant,
(B) 20% to 50% by weight branched non-alkoxylated C ₁₃ AS surfactant,
(C) 5% to 30% by weight, include the linear C ₆ AA surfactant and (d) 1 or more additional components having a weight average degree of ethoxylation ranging from 4-6,
The branched non-alkoxylated C _{12 to} C ₁₃ AS surfactants are of the general formula (I),

[In the formula, M is an alkali metal, alkaline earth metal, ammonium, amine or alkanolamine cation, x and y are independently selected from integers in the range 0-10, z is in the range 1-4. The sum of x + y is greater than or equal to z, and the sum of x + y + z is in the range 3-11. ], A concentrated laundry detergent composition.

Images