Detergent composition containing ultra-low molecular weight polysaccharides

Abstract

Detergent compositions are provided that include a polysaccharide selected from a carboxymethyl cellulose component, an anionic cellulose derivative, or a mixture thereof, and a surfactant system, wherein the polysaccharide has a molecular weight of from about 1,000 daltons to no more than 80,000 daltons.

Description

[Background technology]

[0001] Carboxymethylcellulose (CMC) with molecular weight greater than 80,000 Daltons (i.e., conventional carboxymethylcellulose) is incorporated into laundry detergent products to improve soil suspension profile, as well as to promote other benefits such as anti-redeposition, anti-scaling, and water softening. Conventional carboxymethylcellulose is also incorporated into other detergent systems for rheology and foam control. Unfortunately, these conventional carboxymethylcelluloses have significant limitations in terms of surfactant compatibility. As a result, given that detergent products are usually surfactant-based, these conventional carboxymethylcelluloses may cause loss of transparency and / or stability due to clouding, gelation, and / or phase separation, thereby limiting their use in liquid detergent products. To minimize these effects, structuring agents such as microfibrous cellulose have been added and / or conventional carboxymethyl cellulose has been subjected to ultrafine grinding, both of which increase manufacturing cost, time and complexity, see, e.g., U.S. Pat. No. 7,842,658, WO 2014 / 052317, U.S. Pat. Pub. No. 2008 / 0108541, and U.S. Pat. No. 8,642,529. Summary of the Invention [Problem to be solved by the invention]

[0002] Thus, there remains a need for improved detergent compositions having carboxymethyl cellulose or a cellulose derivative thereof that is more compatible with surfactant systems, thereby ameliorating some or all of the aforementioned undesirable effects on the overall composition. [Means for solving the problem]

[0003] Provided is a detergent composition comprising a polysaccharide selected from a carboxymethylcellulose component, an anionic cellulose derivative, or a mixture thereof, and a surfactant system; the polysaccharide has a molecular weight of about 1,000 Daltons (Da) to 80,000 Da. Provided is a laundry detergent composition comprising a carboxymethylcellulose component at a concentration of about 0.005% to about 10% by weight of the detergent composition and a surfactant system at a concentration of about 0.01% to about 70% by weight of the detergent composition; the carboxymethylcellulose component has a weight average molecular weight of about 1,000 Da to 80,000 Da, any molecular weight peak of the carboxymethylcellulose component is about 80,000 Da or less, and the laundry detergent composition is in liquid form. Provided is a use in a detergent of a polysaccharide selected from the group consisting of a carboxymethylcellulose component, an anionic cellulose derivative, and a mixture thereof; the polysaccharide has an average molecular weight of about 1,000 Da to 80,000 Da. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0004] Improved detergent compositions, particularly those comprising a carboxymethyl cellulose component, an anionic cellulose derivative, or a mixture thereof, having a weight average molecular weight (M) of about 1,000 Da to 80,000 Da or less. w In the present invention, a detergent composition has been developed that includes a specific polysaccharide having a carboxyl group and a surfactant system.

[0005] As used herein, detergent compositions include powder or liquid laundry detergents, powder or liquid dishwashing detergents, liquid hand soaps, and powder or liquid industrial detergents.

[0006] As used herein, unless the context indicates otherwise, molecular weight (M w ) is the weight average molecular weight.

[0007] As used herein, "ultra-low molecular weight" refers to a molecular weight (M) of about 1,000 Daltons (Da) to 80,000 Daltons (Da) or less. w )

[0008] As used herein, "conventional" refers to a molecule having a molecular weight (M) of greater than 80,000 Da. w )

[0009] Values ​​or ranges may be expressed herein as "about," from "about" one particular value, and / or to "about" another particular value. When such values ​​or ranges are expressed, other disclosed embodiments include the recited particular value, from the one particular value, and / or to the other particular value. Similarly, when a value is expressed as an approximation, using the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that a number of values ​​have been disclosed herein, and that each value, in addition to the value itself, is also herein disclosed as "about" that particular value. In embodiments, "about" can be used to mean, for example, within 10% of the recited value, within 5% of the recited value, or within 2% of the recited value.

[0010] Several aspects of detergent compositions and methods of manufacture are described herein.The parameters of different steps, components and features of the aspects are described separately, but may be combined consistently with the description of this claim to allow other aspects to be understood by those skilled in the art.Various terms used herein are defined in the following description in the same manner.Concentrations and percentages are by weight unless otherwise indicated by the context.

[0011] Without being bound to a single theory, it is believed that lowering the molecular weight of certain polysaccharides, such as carboxymethyl cellulose components, anionic cellulose derivatives, or mixtures thereof, alters their compatibility with other ingredients, such as organic solvents, salts, and surfactants. By using ultra-low molecular weight polysaccharides in detergents rather than traditional polysaccharides, the inventors have discovered the ability to formulate liquid detergent compositions with properties such as improved clarity and stability.

[0012] Furthermore, when the detergent composition is in liquid form, the very low molecular weight polysaccharide may be partially or completely dissolved in the composition and thus be in an active state within the composition. This is advantageous because when the wash cycle begins, the very low molecular weight polysaccharide can begin to provide anti-redeposition without first having to degrade to its active state. That is, the very low molecular weight polysaccharide may be capable of becoming functional at the beginning of the wash cycle, independent of the wash temperature.

[0013] The ability of the ultra-low molecular weight polysaccharide to dissolve partially or completely in the liquid detergent composition is further advantageous because it can improve the transparency of the composition. The solid polysaccharide particles present in the composition, which are known to cause haze when using conventional polysaccharides, are little or completely eliminated when the ultra-low molecular weight polysaccharide is dissolved in the liquid detergent composition. Furthermore, the solubility of the ultra-low molecular weight polysaccharide advantageously provides stability to the liquid detergent composition without the need for structuring agents and / or the need to grind the ultra-low molecular weight polysaccharide into a superfine powder.

[0014] In some cases, the very low molecular weight polysaccharide is a carboxymethylcellulose component, such as sodium carboxymethylcellulose or modified carboxymethylcellulose, such as but not limited to hydrophobically modified CMC, cationically modified CMC, or sulfate or sulfonate modified CMC.The interchangeability of the use of carboxymethylcellulose and its modified forms in detergent applications is well known in the art, as described in EP2302025B1 and US6600033, both of which are incorporated herein by reference.Any reference herein to a carboxymethylcellulose (CMC) component is also meant to include modifications thereof.

[0015] The detergent composition may include anionic cellulose derivatives such as, but not limited to, carboxymethyl hydroxyethyl cellulose, and carboxymethyl hydroxypropyl cellulose (HPC).

[0016] Further reference to very low molecular weight polysaccharides is to include the aforementioned polysaccharides selected from carboxymethyl cellulose components, anionic cellulose derivatives, or mixtures thereof.

[0017] Detergent compositions have been developed that maintain clarity and stability while improving anti-redeposition properties. The detergent compositions may be in liquid or particulate form.

[0018] The ultra-low molecular weight polysaccharide may have a molecular weight of about 1,000 Da to 80,000 Da. For example, the ultra-low molecular weight polysaccharide may have a molecular weight of about 1,000 Da to about 40,000 Da. Alternatively, the ultra-low molecular weight polysaccharide may have a molecular weight of about 1,000 Da to about 30,000 Da. Alternatively, the ultra-low molecular weight polysaccharide may have a molecular weight of about 1,000 Da to about 15,000 Da. For example, ultra-low molecular weight polysaccharides are available in the following sizes: 1,000 Da, 2,000 Da, 3,000 Da, 4,000 Da, 5,000 Da, 6,000 Da, 7,000 Da, 8,000 Da, 9,000 Da, 10,000 Da, 11,000 Da, 12,000 Da, 13,000 Da, 14,000 Da, 15,000 Da, 16,000 Da, 17,000 Da, 18,000 Da, 19,000 Da, 20,000 Da, 21,000Da, 22,000Da, 23,000Da, 24,000Da, 25,000Da, 26,000Da, 27,000Da, 28,000Da, 29,000Da, 30,000Da, 31 ,000Da, 32,000Da, 33,000Da, 34,000Da, 35,000Da, 36,000Da, 37,000Da, 38,000Da, 39,000Da, 40,000Da, 41,0 00Da, 42,000Da, 43,000Da, 44,000Da, 45,000Da, 46,000Da, 47,000Da, 48,000Da, 49,000Da, 50,000Da, 51,000 Da, 52,000Da, 53,000Da, 54,000Da, 55,000Da, 56,000Da, 57,000Da, 58,000Da, 59,000Da, 60,000Da, 61,000Da , 62,000 Da, 63,000 Da, 64,000 Da, 65,000 Da, 66,000 Da, 67,000 Da, 68,000 Da, 69,000 Da, 70,000 Da, 71,000 Da, 72,000 Da, 73,000 Da, 74,000 Da, 75,000 Da, 76,000 Da, 77,000 Da, 78,000 Da, 79,000 Da, or 80,000 Da. The very low molecular weight polysaccharides of the present disclosure can also have a molecular weight between any of these recited molecular weights.

[0019] Very low molecular weight polysaccharides, in particular very low molecular weight CMC components, may have a monomodal, bimodal or multimodal molecular weight distribution, in each case having a molecular weight peak (M P ) is 80,000 Da or less. For example, the molecular weight peak may be about 750 to 60,000 Da.

[0020] In some cases, the very low molecular weight polysaccharide and in particular the very low molecular weight CMC component is present in the detergent composition at a concentration of about 0.005% to about 10% by weight of the detergent composition. For example, the very low molecular weight polysaccharide is present in the detergent composition at a concentration of about 0.01% to about 5% by weight of the detergent composition. Alternatively, the very low molecular weight polysaccharide may be present in the detergent composition at a concentration of about 0.05% to about 2% by weight of the detergent composition. For example, the very low molecular weight polysaccharides may be present in the detergent composition at about 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 1.10%, 1.20%, 1.35%, 1.4%, 1.50%, 1.65%, 1.80%, 1.85%, 1.86%, 1.87%, 1.88%, 1.89%, 1.90%, 1.95%, 1.96%, 1.97%, 1.98%, 1.99%, 2.00%, 2.01%, 2.02%, 2.03%, 2.04%, 2.05%, 2.06%, 2.07%, 2.08%, 2.09%, 2.1%, 2.17%, 2.19%, 2.20%, 2.25%, 2.26%, 2.27%, 2.28%, 2.30%, 2.31%, 2.32%, 2.33%, 2.34%, 2.35%, 2.36%, 2.37%, 2.38%, 2.39%, 2.40%, 2.41%, 2.42%, 2.43%, 2.44%, 2.45%, 2.46%, 2.47%, 2.48%, 2.49%, 2. 4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.1% by weight, 2.2% by weight, 2.3% by weight, 2.4% by weight, 2.5% by weight, 2.6% by weight, 2.7% by weight, 2.8% by weight , 2.9% by weight, 3% by weight, 3.1% by weight, 3.2% by weight, 3.3% by weight, 3.4% by weight, 3.5% by weight, 3.6% by weight, 3.7% by weight, 3.8% by weight, 3.9% by weight, 4% by weight, 4.1% by weight, 4.2% by weight, 4.3% by weight %, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, 4.9 wt%, 5 wt%, 5.1 wt%, 5.2 wt%, 5.3 wt%, 5.4 wt%, 5.5 wt%, 5.6 wt%, 5.7 wt%, 5. 8% by weight, 5.9% by weight, 6% by weight, 6.1% by weight, 6.2% by weight, 6.3% by weight, 6.4% by weight, 6.5% by weight, 6.6% by weight, 6.7% by weight, 6.8% by weight, 6.9% by weight, 7% by weight, 7.1% by weight, 7.2% by weight, 7 0.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, or 10% by weight.The very low molecular weight polysaccharides can also be present in the detergent composition at a concentration between any of these recited percentages.

[0021] It has been found that ultra-low molecular weight polysaccharides, particularly ultra-low molecular weight CMC components, have surprisingly high solubility in liquid detergent compositions.Incorporating ultra-low molecular weight polysaccharides that have the ability to dissolve partially or completely into liquid detergent compositions allows ultra-low molecular weight polysaccharides to become functional soon after use, and therefore this increased solubility is advantageous because it allows ultra-low molecular weight polysaccharides to function earlier in the washing cycle compared to conventional polysaccharides.Therefore, by incorporating ultra-low molecular weight polysaccharides into liquid detergent compositions, washing cycle time can be advantageously shortened.

[0022] Furthermore, the surprisingly increased solubility of the ultra low molecular weight polysaccharides also results in a shorter activation time when incorporated into powder detergent compositions, thereby advantageously providing the detergent composition with the ability to begin functioning earlier in the wash cycle. By incorporating ultra low molecular weight polysaccharides that have the ability to become active in a shorter time compared to conventional polysaccharides, the resulting powder detergent composition may therefore also shorten the wash cycle time.

[0023] Without being bound to a single theory, it is also believed that the solubility of the ultra-low molecular weight CMC component can be improved by increasing its degree of substitution. The ultra-low molecular weight CMC component can have a degree of substitution of about 0.2 to about 1.5. For example, the ultra-low molecular weight CMC component can have a degree of substitution of about 0.4 to about 1.2. Alternatively, the ultra-low molecular weight CMC component can have a degree of substitution of about 0.6 to about 1. For example, the ultra-low molecular weight CMC component can also have a degree of substitution of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5. The ultra-low molecular weight CMC component can also have a degree of substitution within a range between any of these listed degrees of substitution.

[0024] Generally, the degree of substitution can be measured by any technique known in the art. For example, the degree of substitution, including that disclosed herein, can be measured by the following analytical method: a sample of CMC of known weight is burned to ash, i.e., heated at 650°C for 45 minutes, and then cooled to 25°C; the cooled sample is then dissolved in distilled water at a temperature of 80°C to form a sample mixture; the sample mixture is then cooled to 70°C, and then titrated with 0.1N sulfuric acid using methyl red as an indicator. The degree of substitution (DS) is calculated by the following formula, where b is the acid consumption (mL) and G is the weight of the sample (grams):

number

[0025] Furthermore, without being bound by a single theory, it is believed that increasing the degree of substitution of the ultra-low molecular weight CMC component can also minimize the degradation of the ultra-low molecular weight CMC component by enzymes that are typically present in laundry detergents.In addition to, or instead of, the ultra-low molecular weight CMC component can be further derivatized, for example, hydrophobically modified, to help minimize this degradation of the ultra-low molecular weight CMC component.A multi-component liquid detergent dosing system can be provided in which the enzyme is in one compartment of the system and is therefore separated from the ultra-low molecular weight CMC component until the use of the liquid detergent.

[0026] Furthermore, without being bound to a single theory, it is also believed that the incorporation of soluble very low molecular weight polysaccharides into liquid detergent compositions beneficially and surprisingly improves the clarity of the resulting compositions because the soluble very low molecular weight polysaccharides minimize, if not eliminate, the presence of solid polysaccharide particles in the liquid detergent, which would otherwise cause haze and thus adversely affect the overall clarity of the liquid detergent composition. For example, the detergent composition may have a high degree of transparency represented by a high transmittance value of 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100% at 0.1, 0.2, 0.3, 0.4 or 0.5% by weight of the detergent of CMC or anionic cellulose, e.g., a transmittance value of 96-100% at 0.1, 0.2, 0.3, 0.4 or 0.5% by weight of the detergent of CMC or anionic cellulose.

[0027] Generally, the clarity of the detergent compositions disclosed herein can be measured by any technique known in the art. For example, clarity can be determined by measuring the transmittance of the detergent composition.

[0028] Liquid detergent compositions containing conventional polysaccharides are generally known to be unstable due to the resulting phase separation of the conventional polysaccharides. Phase separation is undesirable, among other reasons, because it adversely affects the overall clarity of the liquid detergent composition. As a result, structuring agents added to such detergents and / or conventional polysaccharides undergo micronization.

[0029] However, it has been discovered that minimal, if any, phase separation occurs in liquid detergent compositions containing ultra-low molecular weight polysaccharides. Without being bound to a single theory, this is believed to be due to the ability of ultra-low molecular weight polysaccharides to be partially or completely solubilized in liquid detergents. As a result, unlike conventional detergent compositions containing conventional polysaccharides, no structuring agent is required to minimize or prevent phase separation and therefore maintain the clarity of the detergent composition and / or ultra-fine grinding of the ultra-low molecular weight polysaccharides is not required. For example, the detergent composition may not include a cellulose fiber structuring agent such as microfiber cellulose, nanofiber cellulose or bacterial cellulose. For example, the detergent composition may have good stability represented by phase separation of 0 to 3, 4, 5, 6, 7, 8, or 9 mm at 0.1, 0.2, 0.3, 0.4, or 0.5% CMC or anionic cellulose by weight of the detergent.

[0030] In some cases, the surfactant system is present in the detergent composition at a concentration of about 0.01% to about 70% by weight of the detergent composition. For example, the surfactant system may be present in the detergent composition at a concentration of about 1% to about 40% by weight of the detergent composition. Alternatively, the surfactant system may be present in the detergent composition at a concentration of about 10% to about 40% by weight of the detergent composition. For example, the surfactant system may be present in the detergent composition at 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, or at least about 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, The surfactant system of the present disclosure may be present in a concentration of 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70% by weight. The surfactant system of the present disclosure may also be present in the detergent composition in a concentration between any of these recited percentages.

[0031] The surfactant system may include anionic surfactants, nonionic surfactants, or a combination of anionic and nonionic surfactants.

[0032] Further, when the surfactant system includes a combination of anionic and nonionic surfactants, the weight ratio of anionic surfactant to nonionic surfactant in the surfactant system can be from about 2 to about 1.

[0033] Non-limiting examples of suitable anionic surfactants include aliphatic sulfates, aliphatic sulfonates (e.g., C8-C22 sulfonates or disulfonates), aromatic sulfonates (e.g., alkyl benzene sulfonates), alkyl sulfosuccinates, alkyl and acyltaurates, alkyl and acylsarcosinates, sulfoacetates, alkyl phosphates, carboxylates, isethionates, and the like, as well as any combination thereof.

[0034] Non-limiting examples of suitable nonionic surfactants include alkylphenols with fatty alcohols, acids, amides, or alkylene oxides, sugar amides, alkyl polysaccharides, and the like, and combinations thereof.

[0035] The surfactant system may also include cationic surfactants, amphoteric surfactants, or a combination thereof. Alternatively, the surfactant system may not include cationic surfactants. The surfactant system may include anionic, nonionic, and amphoteric surfactants. It is also conceivable that the surfactant system does not include any other surfactants other than anionic and / or nonionic surfactants.

[0036] The detergent compositions may also contain anti-incrustation agents, fragrances, bleaches, corrosion inhibitors, antifoam agents, optical brighteners, enzymes, and the like, or combinations thereof. It is also contemplated that any of these additives may be omitted from the detergent composition.

[0037] Incorporating very low molecular weight polysaccharides into a liquid detergent composition can also increase the viscosity of the overall detergent composition, which is beneficial in that the very low molecular weight polysaccharides can therefore provide the detergent composition with a desired viscosity profile for dispensed use for appearance and / or rheology purposes.

[0038] Conventional detergents are generally known to include blends of anionic and nonionic surfactants to optimize performance and cost-effectiveness. However, surfactants themselves are known to have poor anti-redeposition properties, and therefore the use of these conventional detergents can lead to graying of textiles such as fabrics. As a result, anti-redeposition agents such as CMC are used in combination with these surfactants. CMC functions as an anti-redeposition agent by being selectively absorbed by textiles such as cotton-based textiles through hydrogen bonding. The anti-redeposition property of CMC is due to electrostatic repulsion between negatively charged soil particles and the negative charge of the carboxymethyl group. Thus, CMC functions as a soil carrier, among other things, in the detergent, preventing secondary deposition on textiles.

[0039] The liquid detergent composition comprising ultra-low molecular weight polysaccharides also has improved anti-redeposition properties compared to conventional detergent compositions (i.e., detergent compositions comprising conventional polysaccharides) and detergent compositions comprising structurants. It is also believed that the powder detergent composition may also have improved anti-redeposition properties compared to conventional detergent compositions. Without being bound to a single theory, it is believed that ultra-low molecular weight polysaccharides can penetrate more easily into the cavities on the surface of fabrics compared to conventional polysaccharides, and can also penetrate into areas that conventional polysaccharides cannot penetrate, and therefore the detergent composition, at least the liquid detergent composition, has improved anti-redeposition properties. For example, the anti-redeposition properties may be higher as reflected by an average measured reflectance of more than 7 units when compared to a control that does not contain CMC. For example, at 0.1, 0.2, 0.3, 0.4 or 0.5% CMC or anionic cellulose by weight of the detergent, the average measured reflectance may be greater than 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25. The composition may have excellent transmittance as described in paragraph 26, phase separation as described in paragraph 29, and / or anti-redeposition as described above.

[0040] The properties of the ultra-low molecular weight polysaccharide affect the concentration used in the detergent composition and the properties of the detergent composition. At the lower end of the molecular weight range, a high concentration of the ultra-low molecular weight polysaccharide may be used to achieve a particular property. At the higher end of the molecular weight range, a low concentration of the ultra-low molecular weight polysaccharide may be used to achieve a particular property. Additionally, the properties of the ultra-low molecular weight polysaccharide may affect the surfactant concentration used in the detergent composition. One skilled in the art would be able to vary these parameters and test detergents using the provided protocols for advantageous phase separation, permeability or anti-redeposition characteristics. The detergent composition may comprise an ultra-low molecular weight polysaccharide at a concentration of about 0.05% to about 2% by weight of the detergent composition, and a surfactant system at a concentration of about 10% to about 40% by weight of the detergent composition, where the ultra-low molecular weight polysaccharide has a molecular weight of about 1,000 Da to about 30,000 Da. For example, the detergent composition may comprise an ultra-low molecular weight polysaccharide at a concentration of about 0.05% to about 2% by weight of the detergent composition, and a surfactant system at a concentration of about 1% to about 35% by weight of the detergent composition, where the ultra-low molecular weight polysaccharide has a molecular weight of about 30,000 Da to 80,000 Da. In another example, the detergent composition may comprise an ultra-low molecular weight polysaccharide at a concentration of about 0.1% to about 0.3% by weight of the detergent composition, and a surfactant system at a concentration of about 0.01% to about 30% by weight of the detergent composition, where the ultra-low molecular weight polysaccharide has a molecular weight of about 50,000 Da to 80,000 Da.

[0041] The detergent compositions described herein can be made using any known method.

[0042] For example, the method can include adding an ultra-low molecular weight polysaccharide to a surfactant system to form a detergent mixture, where the surfactant system includes an anionic surfactant and a nonionic surfactant and is present in the mixture at a concentration of from about 0.01% to about 70% by weight of the mixture.

[0043] The method may further include providing a very low molecular weight polysaccharide. For example, providing a very low molecular weight polysaccharide may include depolymerizing a polysaccharide starting material having a conventional molecular weight to form a very low molecular weight polysaccharide.

[0044] In general, the starting material can be depolymerized by any technique known in the art, such as those disclosed in EP 382577, GB 2,281,073, EP 708113, WO 2005 / 012540, U.S. Patent Publication No. 2005 / 020944, U.S. Patent Publication No. 2010 / 0063269, U.S. Patent No. 6,054,511, all of which are incorporated herein by reference. For example, the starting material can be depolymerized with hydrogen peroxide in water, or the starting cellulosic material is depolymerized with enzymes or acids.

[0045] The very low molecular weight polysaccharide may be in liquid form when added to the surfactant system. Alternatively, the very low molecular weight polysaccharide may be in particulate form when added to the surfactant system.

[0046] In some cases, the surfactant system is in liquid form. When the surfactant system is in liquid form, the very low molecular weight polysaccharide may be in liquid form when added to the surfactant system. Alternatively, when the surfactant system is in liquid form, the very low molecular weight polysaccharide may be in particulate form when added to the surfactant system.

[0047] In a further example, the surfactant system may be in particulate form. When the surfactant system is in particulate form, the very low molecular weight polysaccharide may be in liquid form when added to the surfactant system. Alternatively, when the surfactant system is in particulate form, the very low molecular weight polysaccharide may be in particulate form when added to the surfactant system.

[0048] The detergent compositions can be further understood by the following non-limiting examples. EXAMPLES

[0049] (Protocol 1: Measurement of molecular weight (Mw, Mp)) The molecular weight of CMC was measured using a GPCmax VE GPC solvent / sample module (Viscotek), column oven, 270 Dual Detector and Shodex RI-71. Prior to the measurement, the system was calibrated using narrow standard pullulan. 10 mg of CMC was dissolved in 0.1 M NaNO3 + 10% MeOH eluent at a concentration of 1 mg / ml and mixed for 16 hours to form the test sample. The sample was filtered through a 0.2 μm filter and 100 microliters of the filtered sample was injected onto two Viscotek A600M General Mixed 300 × 8.0 mm columns at a flow rate of 0.8 ml / min. The sample was then analyzed using right angle light scattering, viscosity and refractive index detectors (Viscotek). OmniSec (Viscotek) software converted the detector signals to molecular weight values ​​and gave weight average molecular weight (M w ) and peak molecular weight (M p ) was calculated.

[0050] (Protocol 2: Transmittance Measurement) The clarity of the solution was determined by measuring the transmittance of the sample by UV-VIS (Genesys 6, ThermoSpectronic) at 600 nm. The sample of CMC was added to the liquid detergent and mixed with a propeller mixer at 400 rpm for 1 hour at 25°C to form a test sample. For the 0.1% CMC concentration sample, 1 gram (dry weight) CMC / 999 gram liquid detergent was used, and for the 0.5% CMC concentration, 5 gram (dry weight) CMC / 995 gram liquid detergent was used. The test sample was then stored in a water bath at 37°C for 40 days. If any phase separation was observed, the premixed sample was mixed with a spatula before analysis. For each test sample, there was a reference sample of liquid detergent without CMC, whose transmittance was also measured and used as a reference. The higher the transmittance (%), the clearer the sample.

[0051] (Protocol 3: Measurement of anti-reattachment properties) The anti-adhesion properties of the samples were measured using a Tergotometer (Copley Scientific, Nottingham, UK). Four commercial liquid detergents and one standard liquid detergent AATCC 2003 were used. AATCC 2003 liquid reference detergent WOB (available from Testgewebe GmbH, Bruggen, Germany) was used with the following composition: 12.0% linear alkylbenzene sulfonate sodium salt, 8.0% non-ionic surfactant, 1.2% citric acid (as sodium citrate), 4.0% fatty acid (C24 sodium salt), 2.7% sodium hydroxide, 0.3% chelating agent (DTPA), 8.0% stabilizer (propanediol), 1.0% preservative (borax) and water to balance the formulation. For each different liquid detergent, a control test sample was prepared containing the detergent itself and no CMC. The use levels of each liquid detergent are listed in the table below: [Table 1]

[0052] For each test sample, a pot was filled with 800 mL of water with a water hardness of 18° dH and a temperature of 25°C. CMC was then added to the pot at either 0.1% based on the liquid detergent or 0.5% based on the liquid detergent. Eight 5cm*5cm white cotton swatches (Warwick Equest, Stanley, Durham, UK), 0.16g of carbon black, and the amount of liquid detergent based on Table 1 were added to the pot.

[0053] For each control sample, a pot was filled with 800 mL of water with a water hardness of 18° dH and a temperature of 25° C. Eight 5 cm*5 cm white cotton swatches (Warwick Equest, Stanley, Durham, UK), 0.16 g of carbon black, and the amount of liquid detergent according to Table 1 were added to the pot. No CMC was added to the control samples.

[0054] For each sample, the swatches were washed at a temperature of 25° C. with agitation at 200 rpm, after which the swatches were rinsed in water with a water hardness of 18° dH and a temperature of 25° C. The total wash time was 60 minutes and the total rinse time was 15 minutes. The swatches were then dried overnight at 25° C. before being ironed.

[0055] The reflectance of each swatch was then measured by a Minolta CM-3600d instrument (Konica). Prior to the measurement, the Minolta CM-3600d was calibrated by primary reference paper (CIE Whiteness D65 / 10° and ISO Brightness) from Inventia AB, Sweden. A secondary calibration was performed by reference fabric (CIE Whiteness D65 / 10° and Ganz Griesser) from Hohenstein Laboratories GmbH&Co.KG, Germany. The reflectance of each swatch of the test sample and each swatch of the control sample was measured and then averaged. The difference in the average measured reflectance of the test sample and the control sample was then calculated. The greater the difference, the whiter (less gray) the fabric swatch was, and consequently the more effective the anti-redeposition properties of the test sample were compared to the control sample. A test sample having an average measured reflectance of less than 7 units compared to its control sample was considered undesirable.

[0056] (Protocol 4: Measurement of the effect of anti-redeposition properties after storage on CMC premixed in liquid detergent) CMC was premixed with AATCC2003 liquid reference detergent WOB to a concentration of 0.5 wt% CMC, then split into two sets, one set left at room temperature for 1 day ("new") and the other set stored at 37°C for 40 days ("old"). Both new and old premixed samples were tested for anti-redeposition properties, and the results are shown in Table 3. If any phase separation was observed, the premixed samples were mixed before being placed in the pot. The pot was filled with 800mL of water with a water hardness of 18°dH and a temperature of 25°C. Eight 5cm*5cm white cotton swatches (Warwick Equest, Stanley, Durham, UK), 0.16g of carbon black, and the premixed samples were added to the pot. Otherwise, the test protocol followed protocol 3.

[0057] (Protocol 5: Stability Measurement) The CMC samples were added to the liquid detergent and mixed with a propeller mixer at 400 rpm for 1 hour at 25°C to form test samples. For 0.1% CMC concentration samples, 1 gram (dry weight) CMC / 999 gram liquid detergent was used, and for 0.5% CMC concentration, 5 gram (dry weight) CMC / 995 gram liquid detergent was used. The mixed samples were stored in sealed glass bottles in a water bath at 37°C for 40 days. After storage, the samples were cooled to room temperature and mixed with a spatula. 10 mL of the mixed sample was then placed in a 15 mL centrifuge tube (Duran Assistent, Germany). The samples were then centrifuged (Centrifuge 5804, Eppendorf) at 5000 rpm for 30 minutes to separate the phases (solid and liquid) of the sample. The solid phase was measured from the bottom of the centrifuge tube. The amount of solid phase of the sample measured in millimeters indicated the stability of the sample. Above 3 mm was considered an undesirable level in this test.

[0058] Example 1: Preparation of ultra-low molecular weight CMC with a molecular weight of less than 30,000 Da 1507 grams of tap water was added to a vessel equipped with a mixer. The temperature was then adjusted to 70°C, after which 100 grams of hydrogen peroxide solution (hydrogen peroxide aqueous solution, 50% active) was added to the vessel to form a mixture. 974.66 grams of CMC powder (ultra-low molecular weight CMC, 7.7% moisture content, 40,000 Da molecular weight, manufactured by CP Kelco Oy, Anekoski, Finland) and an additional 300 grams of hydrogen peroxide solution were then added stepwise to the mixture, which was simultaneously mixed using the mixer. Released oxygen was also removed from the top of the vessel by nitrogen flushing. 97.0 grams of caustic agent (sodium hydroxide aqueous solution, 50% active) was then added to the mixture, which was added to promote the hydrogen peroxide reaction, and the pH of the mixture was adjusted to 7.0. After confirming that 300 grams of hydrogen peroxide had reacted by using an indicator slip to detect residual peroxide, the mixture was cooled to 25° C. to form ultra-low molecular weight CMC with a molecular weight of 4,000 Da.

[0059] (Example 2: Performance test) Sample 1, ultra-low molecular weight CMC of Example 1 having a molecular weight of 4,000 Da, a molecular weight peak of 2,500 Da, and a unimodal molecular weight distribution.

[0060] Sample 2, a commercial CMC from CP Kelco with an ultra-low molecular weight CMC of 40,000 Da, a molecular weight peak at 20,000 Da, and a unimodal molecular weight distribution.

[0061] Sample 3, Finnfix® 30, conventional molecular weight CMC, molecular weight peaks at 90,000 Da, 80,000 and 20,000 Da, and a bimodal molecular weight distribution.

[0062] Sample 4, Finnfix® 300, conventional molecular weight CMC, molecular weight of 150,000 Da, molecular weight peaks at 140,000 and 20,000 Da, and a bimodal molecular weight distribution.

[0063] [Table 2-1] [Table 2-2] *Study conducted according to Protocol 2 **Study performed according to Protocol 5 ***Study performed according to Protocol 3

[0064] [Table 3]

[0065] As can be seen from the 0.5% CMC dosage level in Table 2, Sample 1 provides high clarity (high transmittance values, 96-100%) and good stability (low phase separation, 0-3 mm) in the liquid detergent. At the 0.5% CMC use level, Sample 2 provides a clearly more dangerous liquid detergent after 40 days stability testing compared to Sample 1. However, the stability of Sample 2 at 0.5% use level is better after 40 days compared to the stability of Samples 3 and 4 at 0.5%. Additionally, Samples 1 and 2 provide similar, and in some cases superior, anti-redeposition results at 0.5% use level in liquid detergent compared to Samples 3 and 4.

[0066] Additionally, as can be seen from the 0.1% CMC dosage levels in Table 2, the 0.1% usage level of Sample 1 provides the highest clarity and stability when compared to the other samples. The 0.1% usage level of Sample 2 exhibits little phase separation (1-3 mm) and high clarity and stability (60% higher transmittance) compared to the 0.5% usage level. Additionally, the 0.1% usage levels of Samples 1 and 2 typically have similar, and in most cases superior, anti-redeposition effectiveness compared to the 0.1% usage levels of Samples 3 and 4.

[0067] The results in Table 3 show that the anti-redeposition performance is slightly lower after storage time compared to the liquid detergent and CMC tested in the fresh state, but the anti-redeposition performance is still at a very high level even after 40 days of storage at 37° C. (whiteness increase is more than 7 units). Therefore, based on the results shown in Tables 2 and 3, it can be concluded that ultra-low molecular weight CMC is compatible with various liquid detergents, which gives very good anti-redeposition properties overall, and the anti-redeposition performance remains high even after storage of the liquid detergent.

[0068] Based on these results, rather than using conventional CMC, which typically requires a structurant or micronization to have adequate clarity and stability, incorporating ultra-low molecular weight CMC into commercial liquid detergents would be beneficial in providing desired liquid detergents with adequate clarity, stability and anti-redeposition properties.

[0069] Wherever context and technical reasons permit, the following numbered embodiments, aspects, and features of the disclosure are provided to emphasize the ability of various features that may be disclosed only in certain embodiments to be combined with other disclosed embodiments.

[0070] (Aspect:) Item 1: A detergent composition comprising a polysaccharide selected from the group consisting of a carboxymethyl cellulose component, an anionic cellulose derivative, and a mixture thereof, and a surfactant system; the polysaccharide has a weight average molecular weight of about 1,000 Daltons to 80,000 Daltons or less. Item 2. The detergent composition according to Item 1, wherein the polysaccharide has a molecular weight of about 1,000 Da to about 40,000 Da. Item 3. The detergent composition according to Item 1, wherein the polysaccharide has a molecular weight of about 1,000 Da to about 30,000 Da. Item 4. The detergent composition according to Item 1, wherein the polysaccharide has a molecular weight of about 1,000 Da to about 15,000 Da. Item 5. The detergent composition according to any one of Items 1 to 4, wherein the polysaccharide has a molecular weight peak of about 80,000 Da or less. Item 6. The detergent composition according to any one of Items 1 to 4, wherein the polysaccharide has a molecular weight peak of about 750 Da to about 80,000 Da. Item 7. The detergent composition according to any one of Items 1 to 6, wherein the polysaccharide is a carboxymethyl cellulose component. Item 8. The detergent composition according to item 7, wherein the carboxymethylcellulose component is sodium carboxymethylcellulose. Item 9. The detergent composition according to item 7, wherein the carboxymethylcellulose component is a modified carboxymethylcellulose. Item 10. The detergent composition according to item 7, wherein the carboxymethylcellulose component is a hydrophobically modified carboxymethylcellulose. Item 11. The detergent composition according to item 7, wherein the carboxymethylcellulose component is a cationically modified carboxymethylcellulose. Item 12. The detergent composition of item 7, wherein the carboxymethylcellulose component is a sulfate- or sulfonate-modified carboxymethylcellulose. Item 13. The detergent composition according to any one of Items 7 to 12, wherein the carboxymethyl cellulose component has a degree of substitution of about 0.2 to about 1.5. Item 14. The detergent composition according to Item 13, wherein the carboxymethyl cellulose component has a degree of substitution of about 0.4 to about 1.2. Item 15. The detergent composition according to Item 13, wherein the carboxymethyl cellulose component has a degree of substitution of about 0.6 to about 1. Item 16. The detergent composition according to any one of Items 1 to 15, wherein the carboxymethyl cellulose component is present in the detergent composition at a concentration of about 0.005% to about 10% by weight of the detergent composition. Item 17. The detergent composition according to any one of Items 1 to 15, wherein the carboxymethyl cellulose component is present in the detergent composition at a concentration of about 0.01% to about 5% by weight of the detergent composition. Item 18. The detergent composition according to any one of items 1 to 15, wherein the carboxymethyl cellulose component is present in the detergent composition at a concentration of about 0.05% to about 2% by weight of the detergent composition. Item 19. The detergent composition according to any one of items 1 to 18, wherein the surfactant system is present in the detergent composition at a concentration of from about 0.01% to about 70% by weight of the detergent composition. Item 20. The detergent composition according to any one of items 1 to 18, wherein the surfactant system is present in the detergent composition at a concentration of from about 1% to about 40% by weight of the detergent composition. Item 21. The detergent composition according to any one of items 1 to 18, wherein the surfactant system is present in the detergent composition at a concentration of from about 10% to about 40% by weight of the detergent composition. Item 22. The detergent composition according to any one of items 1 to 21, wherein the surfactant system comprises an anionic surfactant, a nonionic surfactant, or a combination of an anionic surfactant and a nonionic surfactant. Item 23. The detergent composition according to Item 22, wherein the weight ratio of anionic surfactant to nonionic surfactant in the surfactant system is from about 2 to about 1. Item 24. The detergent composition according to any one of items 1 to 23, wherein the detergent composition does not contain a cellulose fiber structuring agent. Item 25. The detergent composition according to any one of items 1 to 24, wherein the detergent composition is in a liquid form. Item 26. The detergent composition according to any one of Items 1 to 24, wherein the detergent composition is in a particulate form. Item 27. A laundry detergent composition comprising a carboxymethylcellulose component at a concentration of about 0.005% to about 10% by weight of the detergent composition and a surfactant system at a concentration of about 0.01% to about 70% by weight of the detergent composition; the carboxymethylcellulose component has a weight average molecular weight of about 1,000 Da to 80,000 Da or less, any molecular weight peak of the carboxymethylcellulose component is about 80,000 Da or less, and the laundry detergent composition is in a liquid form. Item 28. The laundry detergent composition according to Item 27, wherein the carboxymethyl cellulose component has an arbitrary molecular weight peak of about 750 Da to about 60,000 Da.

[0071] It will be appreciated that various of the above-disclosed features and functions, or alternatives thereof, may be desirably combined into many other different products or applications. Those skilled in the art may subsequently make various presently unforeseen or unexpected substitutions, modifications, variations, or improvements therein, which are intended to be included within the scope of the following claims.

Claims

1. 1. A detergent composition comprising:

1. A detergent composition comprising a polysaccharide and 5% to 70% by weight of a surfactant system, based on the total weight of the composition; the polysaccharide is selected from the group consisting of a carboxymethyl cellulose component, an anionic cellulose derivative, and mixtures thereof; the polysaccharide has a weight average molecular weight in the range of 1,000 to 40,000 daltons; and the detergent composition does not contain any polysaccharide having a molecular weight peak greater than 80,000 daltons.

2. 2. The detergent composition of claim 1, wherein the polysaccharide has a weight average molecular weight of from 1,000 Da to 30,000 Da.

3. 2. The detergent composition of claim 1, wherein the polysaccharide is a carboxymethyl cellulose component.

4. 4. The detergent composition of claim 3, wherein the carboxymethyl cellulose component is: a) sodium carboxymethylcellulose; or b) modified carboxymethylcellulose; or c) hydrophobically modified carboxymethylcellulose; or d) cationic modified carboxymethylcellulose; or e) Sulfate- or sulfonate-modified carboxymethylcellulose.

5. 4. The detergent composition of claim 3, wherein the carboxymethyl cellulose component has a degree of substitution of from about 0.2 to about 1.

5.

6. 10. The detergent composition of claim 1, wherein the polysaccharide is present in the detergent composition at a concentration of from about 0.005% to about 10% by weight of the cleaning composition.

7. 10. The detergent composition of claim 1, wherein the surfactant system is present in the detergent composition at a level of from about 10% to about 40% by weight of the detergent composition.

8. 10. The detergent composition of claim 1, wherein the surfactant system comprises an anionic surfactant, a nonionic surfactant, or a combination of anionic and nonionic surfactants.

9. 9. A detergent composition according to claim 8, wherein the weight ratio of anionic surfactant to nonionic surfactant in the surfactant system is from 2 to 1.

10. 10. The detergent composition of claim 1, wherein the detergent composition is free of a cellulosic fiber structurant.

11. The detergent composition of claim 1 , wherein the detergent composition is in liquid or particulate form.

12. 1. A laundry detergent composition comprising:

1. A laundry detergent composition comprising a carboxymethylcellulose component at a concentration of 0.005% to 10% by weight of said detergent composition and a surfactant system at a concentration of 5% to 70% by weight of said detergent composition; said carboxymethylcellulose component having a weight average molecular weight in the range of about 1,000 Da to 40,000 Da, said laundry detergent composition does not contain any polysaccharides having a molecular weight peak greater than about 80,000 Da, and said laundry detergent composition is in liquid form.

13. 13. The laundry detergent composition of claim 12, wherein the polysaccharide has a weight average molecular weight of from 1,000 Da to 30,000 Da.

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