Water-soluble fiber structure and water-soluble unit-dose article containing protease

Abstract

Described herein are household care compositions that deliver active agents onto fabrics or hard surfaces in the form of water-soluble unit dose articles that include a water-soluble fibrous structure and one or more particles, as well as methods for making the same.

Description

Technical Field

[0001] Described herein are household care compositions for delivering an active agent onto a fabric or a hard surface in the form of a water-soluble unit dose article comprising a water-soluble fibrous structure and one or more particles, and methods of making the same.

Background Art

[0002] Water-soluble unit dose articles are desired by consumers because they provide a convenient, efficient, and clean way to dispense fabric or hard surface treatment compositions. Water-soluble unit dose articles provide a consistent dosage of the treatment composition, thereby avoiding over-dosing or under-dosing. Consumer interest in fibrous water-soluble unit dose articles has been steadily increasing. The technology associated with such articles has continued to evolve in terms of providing the desired active agents along with articles that enable the consumer to perform the tasks they seek to accomplish. Consumers desire fibrous water-soluble unit dose articles that have a cleaning ability equal to or better than conventional forms of fabric treatment compositions such as unit dose articles composed of liquids, powders, and water-soluble films. Formulators of conventional fabric detergents understand that by incorporating alkyl alkoxylated sulfate surfactants into the detergent, they can improve the cleaning performance of the detergent, particularly with respect to stains under specific washing conditions and related to specific consumers. However, many different types of stains exhibit different reactions with different washing conditions and washing compositions. Thus, formulators may incorporate alkyl alkoxylated sulfates and alkoxylated fatty alcohol surfactants in combination with other anionic surfactants such as linear alkylbenzene sulfonates to treat a wider range of stains under a wider range of washing conditions. However, effectiveness can vary depending on the washing conditions and other components in the unit dose. One specific type of stain that can be difficult to remove is stain caused by body oils or sebum.

Summary of the Invention

Problems to be Solved by the Invention

[0003] Therefore, it is necessary to formulate a fibrous water-soluble unit dosage capable of removing body oil stains such as sebum. Furthermore, there is also a need for a washing method that removes sebum stains from clothing. Surprisingly, as described herein, a water-soluble unit dosage article containing a protease and a basic pH adjuster has been found to improve the removal of body soil stains.

Means for Solving the Problems

[0004] Water A water-soluble unit dosage article is disclosed. The water-soluble unit dosage article includes a water-soluble fibrous structure containing a basic pH adjuster and at least one protease enzyme.

[0005] A water-soluble unit dosage article is further disclosed. The water-soluble unit dosage article includes a water-soluble fibrous structure containing a plurality of fiber elements including from about 10 wt% to about 80% alkyl alkoxylated sulfate, one or more basic pH adjusters, and one or more protease enzymes.

Brief Description of the Drawings

[0006]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0007] Definitions The characteristics and advantages of the present invention will become apparent from the following description, which includes examples intended to give a broad representation of the present invention. Various modifications will be apparent to those skilled in the art from this description and the practice of the present invention. This scope is not intended to be limited to the specific forms disclosed, and the present invention encompasses all modifications, equivalents, and alternatives within the spirit and scope of the present invention as defined by the claims.

[0008] As used herein, articles such as "the", "a", and "an" are understood to mean one or more of what is claimed or described when used in the claims or the specification.

[0009] As used herein, the terms "include", "includes", and "including" are intended to be non-limiting.

[0010] The terms "substantially free of" or "substantially absent" as used herein, when referring to a component, mean either that the component is completely absent or that it is present only in trace amounts as an impurity or an unintended by-product of another component. A composition that is "substantially free of" a component means that the composition contains less than about 0.5 wt%, 0.25 wt%, 0.1 wt%, 0.05 wt%, or 0.01 wt% of the component, or even 0 wt% of the component.

[0011] It should be understood that the term "comprising" also includes embodiments where the term "comprising" means "consisting of" or "consisting essentially of".

[0012] As used herein, "sebum" refers to the oily secretion of the sebaceous gland and any artificial composition intended to reproduce the oily secretion of the sebaceous gland. Exemplary sebums include, but are not limited to, the artificial sebum described in European Patent No. 1482907, the artificial sebum described in European Patent No. 0142830 (B1), the artificial sebum according to D4265-14, and the artificial sebum sold as CFT PCS-132. CFT PCS-132 has an approximate composition of 18% free fatty acids, 32% tallow (stearic acid / oleic acid triglyceride), 4% fatty acid triglyceride, 12% hydrocarbon mixture, 18% lanolin (wax-like ester, C13-C24), 12% Cutina (wax and wax ester), and 4% cholesterol.

[0013] All of the patent documents and other documents cited are hereby incorporated by reference in their entirety as if fully set forth herein in relevant parts. The citation of any patent document or other document does not admit that the cited patent document or other document is prior art with respect to the present invention.

[0014] Unless otherwise indicated herein, all concentrations and ratios are based on the weight of the composition.

[0015] All maximum numerical limitations given throughout this specification are to be construed as including all lower numerical limitations as if such lower numerical limitations were expressly recited herein. All minimum numerical limitations given throughout this specification are to be construed as including all higher numerical limitations as if such higher numerical limitations were expressly recited herein. All numerical ranges given throughout this specification are to be construed as including all narrower numerical ranges within such broader numerical ranges as if such narrower numerical ranges were all expressly recited herein.

[0016] Fibrous water-soluble unit dose article As used herein, the terms "water-soluble unit dose article," "water-soluble fibrous structure," and "water-soluble fibrous element" mean that the unit dose article, fibrous structure, and fibrous element are miscible with water. In other words, the unit dose article, fibrous structure, or fibrous element can form a homogeneous solution with water under ambient conditions. As used herein, "ambient conditions" means 23°C ± 1.0°C and relative humidity 50% ± 2%. The water-soluble unit dose article may contain an insoluble substance that is dispersible at a suspended mean particle size of less than about 20 micrometers or less than about 50 micrometers under aqueous washing conditions.

[0017] The fibrous water-soluble unit dose articles may include any of the disclosures found in U.S. Patent Application Publication No. 15 / 880,594, filed on January 26, 2018, U.S. Patent Application Publication No. 15 / 880,599, filed on January 26, 2018, and U.S. Patent Application Publication No. 15 / 880,604, filed on January 26, 2018, which are incorporated herein by reference in their entirety.

[0018] These fibrous water-soluble unit dose articles can dissolve under various washing conditions, such as low temperature, low water volume and / or short washing cycles or cycles when the consumer overfills the washing machine, especially with items having a particularly high water absorption capacity, and at the same time deliver sufficient active agent to exert the intended effect on the target consumer substrate (with performance similar to today's liquid products). Further, the water-soluble unit dose articles described herein can be manufactured economically by spinning fibers containing the active agent. The water-soluble unit dose articles described herein also have improved washing performance.

[0019] The surface of the fibrous water-soluble unit dose article may include a printed area. The printed area may cover from about 10% to about 100% of the surface of the article. The printed area may include ink, pigment, dye, bluing agent, or a mixture thereof. The printed area may be opaque, translucent, or transparent. The printed area may include a single color or multiple colors. The printed area may be present on more than one side of the article and may include explanatory text and / or graphics. The surface of the water-soluble unit dose article may include an aversion agent, such as a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, sodium benzoate, or a mixture thereof. Any suitable concentration of the aversion agent may be used. Suitable concentrations include, but are not limited to, 1 to 5000 ppm, or further 100 to 2500 ppm, or further 250 to 2000 ppm.

[0020] The water-soluble unit-dose articles disclosed herein include a water-soluble fibrous structure and one or more particles. The water-soluble fibrous structure may include a plurality of fiber elements, such as a plurality of filaments. One or more particles, such as one or more active agent-containing particles, may be distributed throughout the structure. The water-soluble unit-dose article may include two or more and / or three or more fiber elements that are intertwined with each other or otherwise associated with each other to form a fibrous structure, and one or more particles that may be distributed throughout the fibrous structure.

[0021] The fibrous water-soluble unit-dose article may exhibit a thickness of more than 0.01 mm, and / or more than 0.05 mm, and / or more than 0.1 mm, and / or about 100 mm or less, and / or about 50 mm or less, and / or about 20 mm or less, and / or about 10 mm or less, and / or about 5 mm or less, and / or about 2 mm or less, and / or about 0.5 mm or less, and / or about 0.3 mm or less as measured by the thickness test method described herein.

[0022] The fibrous water-soluble unit-dose article, when measured according to the basis weight test method described herein, is about 500 grams / m 2 ~ about 5,000 grams / m 2 or about 1,000 grams / m 2 ~ about 4,000 grams / m 2 or about 1,500 grams / m 2 ~ about 3,500 grams / m 2 or about 2,000 grams / m 2 ~ about 3,000 grams / m 2 and may have a basis weight.

[0023] The fibrous water-soluble unit-dose article may comprise a water-soluble fibrous structure and a plurality of particles distributed throughout the structure, and the water-soluble fibrous structure may comprise a plurality of fibrous elements that are identical or substantially identical from a compositional perspective. The water-soluble fibrous structure may comprise two or more different fibrous elements. Non-limiting examples of differences between fibrous elements include physical differences such as differences in diameter, length, texture, shape, rigidity, and elasticity; chemical differences such as crosslinking level, solubility, melting point, Tg, active agent, filament-forming material, color, concentration of active agent, basis weight, concentration of filament-forming material, presence of any coating on the fibrous element, biodegradability, hydrophobicity, contact angle; differences in whether the fibrous element loses its physical structure when exposed to the intended use conditions; differences in whether the form of the fibrous element changes when exposed to the intended use conditions; and differences in the rate at which the fibrous element releases one or more of its active agents when exposed to the intended use conditions. Two or more fibrous elements within the fibrous structure may comprise different active agents. This may be the case when different active agents, such as an anionic surfactant and a cationic polymer, may be incompatible with each other. When using different fibrous elements, the resulting structure may exhibit different wetting, water absorption, and solubility characteristics.

[0024] The fibrous water-soluble unit-dose article may exhibit different regions, such as regions with different basis weights, densities, calipers, and / or wetting characteristics. The fibrous water-soluble unit-dose article may be compressed at the end-sealing points. The fibrous water-soluble unit-dose article may comprise a texture on one or more of its surfaces. The surface of the fibrous water-soluble unit-dose article may comprise a pattern, such as a non-random repeating pattern. The fibrous water-soluble unit-dose article may comprise openings. The fibrous water-soluble unit-dose article may comprise a fibrous structure having discrete regions of fibrous elements that are different from other regions of fibrous elements in the structure. The fibrous water-soluble unit-dose article may be used as is or may be coated with one or more active agents.

[0025] The fibrous water-soluble unit-dose article may include one or more plies. The fibrous water-soluble unit-dose article may include at least two, and / or at least three, and / or at least four, and / or at least five plies. The fibrous ply may be a fibrous structure. Each ply may include one or more layers, for example, one or more fibrous element layers, one or more particle layers, and / or one or more fibrous element / particle mixed layers. The layer may be sealed. In particular, the particle layer and the fibrous element / particle mixture layer may be sealed so that particles do not leak out. The water-soluble unit-dose article may include a plurality of plies, each ply including two layers where one layer is a fibrous element layer and one layer is a fibrous element / particle mixed layer, and the plurality of plies are sealed together (e.g., at the edges). The sealing may help the unit-dose article maintain its original structure in addition to preventing the leakage of particles. However, when the water-soluble unit-dose article is added to water, the unit-dose article dissolves and releases the particles into the cleaning liquid.

[0026] Figure 2 is a micro-CT scan image showing a cross-sectional view of an example of a water-soluble unit-dose article including three plies, where each ply is formed of two layers, a fibrous element layer and a fibrous element / particle mixture layer. Each of the three plies includes a plurality of fibrous elements 30, in this case filaments, and a plurality of particles 32. The multi-ply multi-layer article is sealed at the edge 200 so that particles do not leak out. The outer surface of the article 202 is a fibrous element layer.

[0027] The fibrous elements and / or particles may be arranged within the article, within a single ply, or within a plurality of plies to provide the water-soluble unit-dose article with two or more regions containing different active agents. For example, one region of the article may include a bleaching agent and / or a surfactant, and another region of the article may include a softening agent.

[0028] The fibrous water-soluble unit dose article can be hierarchically viewed as starting from the form in which the consumer interacts with the water-soluble article and acting in reverse towards the raw materials from which the water-soluble article is made, such as ply, fibrous structures, and particles. The fibrous ply can be a fibrous structure. For example, FIG. 1 shows a first ply 10 and a second ply 15 associated with the first ply 10, and the first ply 10 and the second ply 15 each include a plurality of fiber elements 30, in this case filaments, and a plurality of particles 32. In the second ply 15, the particles 32 are randomly dispersed along the x-axis, y-axis, and z-axis, and in the first ply, the particles 32 are within pockets.

[0029] Surprisingly, it has been found that fibrous water-soluble unit dose articles comprising a water-soluble fibrous structure and one or more rheology-modifying particles comprising an alkyl alkoxylated sulfate as described herein exhibit improved dissolution and cleaning. More specifically, the water-soluble unit dose articles described herein may comprise a water-soluble fibrous structure and one or more rheology-modifying particles comprising (a) from about 10% to about 80% by weight of an alkyl alkoxylated sulfate and (b) from about 0.5% to about 20% by weight of a rheology modifier. The particles described herein may comprise one or more additional active agents (in addition to the surfactants described above).

[0030] The rheology-modifying particles are (a) from about 10% to about 80% by weight of an alkyl alkoxylated sulfate; and (b) from about 0.5% to about 20% by weight of an alkoxylated amine, preferably an alkoxylated polyamine, more preferably a quaternized or non-quaternized alkoxylated polyethylene im n( The alkoxylated polyalkyleneimine having one or more alkoxy side chains bonded to at least one nitrogen atom in the polyalkyleneimine core having) , an ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymer (Each of x1 and x2 is in the range of about 2 to about 140, and y is in the range of about 15 to about 70 ) , and mixtures thereof a rheology modifier selected from the group consisting of may be included.

[0031] As used herein, the term "rheology modifier" means a material that interacts with a concentrated surfactant, preferably a concentrated surfactant having an intermediate phase structure, so as to substantially reduce the viscosity and elasticity of the concentrated surfactant. Suitable rheology modifiers include sorbitol ethoxylate, glycerol ethoxylate, sorbitan esters, tallow alkyl ethoxylated alcohols, ethylene oxide - propylene oxide - ethylene oxide (EOx1POyEOx2) triblock copolymers wherein each of x1 and x2 is in the range of about 2 to about 140 and y is in the range of about 15 to about 70, alkoxylated amines, alkoxylated polyamines, polyethyleneimine (PEI), alkoxylated variants of PEI, preferably ethoxylated PEI, and mixtures thereof, but are not limited thereto. The rheology modifier may be combined with a polyethylene glycol (PEG) having a weight average molecular weight of about 2,000 daltons to about 8,000 daltons and include one of the above polymers, for example, ethoxylated PEI.

[0032] As used herein, the term "functional rheology modifier" means a rheology modifier having additional detergent functionality. In some cases, the dispersant polymers described herein below may also function as functional rheology modifiers. The functional rheology modifier may be present in the detergent particles of the present invention at a concentration of about 0.5 wt% to about 20 wt%, preferably about 1 wt% to about 15 wt%, more preferably about 2 wt% to about 10 wt% of the composition.

[0033] Although not bound by theory, the functional rheology modifier can interact with the molecular structure of intermediate surfactants, particularly alcohol-based anionic sulfate surfactants, and the intermediate phase is thought to have more water than the solid surfactant and less water than the micellar phase characteristic of the cleaning solution. In other words, the intermediate surfactant represents the transition state from solid to micellar phase that can be achieved in the successful use of fibrous water-soluble unit dose articles containing water-soluble fiber structures and particles, and if the rheology of this intermediate state is too viscous or sticky, undesirable residues may occur on the fabric under conditions of insufficient local dilution and / or insufficient shear. By substantially reducing the viscosity and elasticity of the intermediate phase, the rheology modifier aids dispersion, reducing the risk of residue formation on the fabric. Further, for any residues that may form, such as lumpy gels, the rheology modifier can reduce their persistence. The net effect is to reduce the generation of surfactant residues remaining on the fabric through washing.

[0034] Alkoxylated amines: Alkoxylated amines may be partially or fully protonated or unprotonated over the pH range of the concentrated surfactant mixture. Alternatively, the alkoxylated amines may be partially or fully quaternized. The alkoxylated amines may be unquaternized. The alkoxylated amines may contain ethoxylate (EO) groups.

[0035] The alkoxylated amines may be linear, branched, or a combination thereof, preferably branched.

[0036] The alkoxylated amines may contain two or more amine moieties such as N,N,N’,N’-tetrakis(2-hydroxyethyl)ethylenediamine (also described as a type of hydroxyalkylamine). N,N,N’,N’-tetrakis(2-hydroxyethyl)ethylenediamine also functions as a chelating agent.

[0037] The alkoxylated amine may (or may alternatively) contain an alkoxylated amine including an alkoxylated polyalkyleneimine. The alkoxylated polyalkyleneimine may be an alkoxylated polyethyleneimine (PEI).

[0038] Typically, the alkoxylated polyalkyleneimine polymer includes a polyalkyleneimine backbone chain. The polyalkylimine may include a C2 alkyl group, a C3 alkyl group, or a mixture thereof, preferably a C2 alkyl group. The alkoxylated polyalkyleneimine polymer may have a polyethyleneimine (「PEI」) backbone chain.

[0039] The alkoxylated PEI may include a polyethyleneimine backbone chain having a weight average molecular weight of about 400 to about 1000, or about 500 to about 750, or about 550 to about 650, or about 600 when measured before ethoxylation.

[0040] The PEI backbone chain of the polymers described herein, before alkoxylation, has the following general empirical formula:

[0041]

Chemical Formula

[0042] The alkoxylated polyalkyleneimine polymer includes an alkoxylated nitrogen group. The alkoxylated polyalkyleneimine polymer may independently contain, on average, per alkoxylated nitrogen, about 50 or less, or about 40 or less, or about 35 or less, or about 30 or less, or about 25 or less, or about 20 or less alkoxylate groups. The alkoxylated polyalkyleneimine polymer may independently contain, on average, per alkoxylated nitrogen, at least about 5, or at least about 10, or at least about 15, or at least about 20 alkoxylate groups.

[0043] An alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may contain ethoxylate (EO) groups, propoxylate (PO) groups, or a combination thereof. An alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may contain ethoxylate (EO) groups. An alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may not contain propoxylate (PO) groups.

[0044] An alkoxylated amine, preferably an alkoxylated polyalkyleneimine polymer, more preferably alkoxylated PEI, may contain, on average per alkoxylated nitrogen, about 1 to 50 ethoxylate (EO) groups and about 0 to 5 propoxylate (PO) groups. An alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may contain, on average per alkoxylated nitrogen, about 1 to 50 ethoxylate (EO) groups and may not contain propoxylate (PO) groups. An alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may contain, on average per alkoxylated nitrogen, about 10 to 30 ethoxylate (EO) groups, preferably about 15 to 25 ethoxylate (EO) groups.

[0045] Suitable polyamines include low molecular weight, water-soluble, and mildly alkoxylated ethoxylated / propoxylated polyalkyleneamine polymers. "Mildly alkoxylated" means that the polymers of the present invention produce about 0.5 to about 20, or 0.5 to about 10 alkoxylations per nitrogen on average. The polyamine may be "substantially uncharged", which means that there are about 2 or fewer positive charges per about 40 nitrogens present in the backbone of the polyalkyleneamine polymer at pH 10 or pH 7. However, it is recognized that the charge density of the polymer can vary with pH.

[0046] Suitable alkoxylated polyalkyleneimines such as PEI600 EO20 are available from BASF (Ludwigshafen, Germany).

[0047] Ethylene oxide - propylene oxide - ethylene oxide (EOx1POyEOx2) triblock copolymer: In the ethylene oxide - propylene oxide - ethylene oxide (EOx1POyEOx2) triblock copolymer, each of x1 and x2 is in the range of about 2 to about 140, and y is in the range of about 15 to about 70. The ethylene oxide - propylene oxide - ethylene oxide (EOx1POyEOx2) triblock copolymer preferably has an average propylene oxide chain length of 20 to 70, preferably 30 to 60, more preferably 45 to 55 propylene oxide units.

[0048] Preferably, the ethylene oxide - propylene oxide - ethylene oxide (EOx1POyEOx2) triblock copolymer has a weight average molecular weight of about 1000 to about 10,000 Daltons, preferably about 1500 to about 8000 Daltons, more preferably about 2000 to about 7000 Daltons, even more preferably about 2500 to about 5000 Daltons, and most preferably about 3500 to about 3800 Daltons.

[0049] Preferably, each ethylene oxide block or chain independently has an average chain length of 2 to 90, preferably 3 to 50, more preferably 4 to 20 ethylene oxide units.

[0050] Preferably, the copolymer comprises from 10 wt% to 90 wt%, preferably from 15 wt% to 50 wt%, most preferably from 15 wt% to 25 wt% of a composite ethylene-oxide block of the copolymer. Most preferably, the total ethylene oxide content is equally divided between the two ethylene oxide blocks. As used herein, equally divided means that each ethylene oxide block on average contains from 40% to 60%, preferably from 45% to 55%, even more preferably from 48% to 52%, most preferably 50% of the total number of ethylene oxide units, and the percentages of both ethylene oxide blocks total 100%. Some ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymers (wherein each of x1 and x2 ranges from about 2 to about 140 and y ranges from about 15 to about 70) improve detergency.

[0051] Preferably, the copolymer has a weight average molecular weight of from about 3500 to about 3800 Daltons, a propylene oxide content of 45 - 55 propylene oxide units, and an ethylene oxide content of 4 - 20 ethylene oxide units per ethylene oxide block.

[0052] Preferably, the ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymer has a weight average molecular weight of from 1000 to 10,000 Daltons, preferably from 1500 to 8000 Daltons, more preferably from 2000 to 7500 Daltons. Preferably, the copolymer comprises from 10 wt% to 95 wt%, preferably from 12 wt% to 90 wt%, most preferably from 15 wt% to 85 wt% of a composite ethylene-oxide block of the copolymer. Some ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymers, wherein each of x1 and x2 ranges from about 2 to about 140 and y ranges from about 15 to about 70, improve dissolution.

[0053] Suitable ethylene oxide-propylene oxide-ethylene oxide triblock copolymers are commercially available from BASF as the Pluronic PE series or from Dow Chemical as the Tergitol L series. A particularly suitable material is Pluronic PE 9200.

[0054] Alkyl alkoxylated sulfate: An alkyl alkoxylated sulfate (AAS) can be an alkyl ethoxylated sulfate (AES), preferably an ethoxylated C 12 ~C 18 alkyl sulfate.

[0055] Typically, the weight ratio of the alkyl alkoxylated sulfate to the rheology modifier ranges from 4:1 to 40:1. The weight ratio of the alkyl alkoxylated sulfate to the rheology modifier can depend on the molecular weight of the alcohol precursor of the alkyl alkoxylated sulfate, the degree of alkoxylation, and the blend ratio of LAS / AES in the blended surfactant system. For example, in the case of an AE1 alcohol precursor having a degree of ethoxylation of about 1.0 (e.g., NaAE1S), a NaLAS / NaAE1S blend ratio of about 1 / 3, and a carbon chain length blend of 12 to 15, the functional rheology modifier / NaAE1S mass ratio can be at least about 7% to improve dissolution, and in the case of a higher MW alcohol precursor having a carbon chain length blend of 14 to 15, the preferred functional rheology modifier / NaAE1S mass ratio can be at least about 9%. The concentration of the functional rheology modifier can be adjusted to maintain product dissolution over a wide range of possible anionic surfactant materials and their blend ratios.

[0056] The mass of the rheology modifier (RM) relative to the mass of the NaAES surfactant can follow the following relationship: RM / NaAES ≧ f(alc) / (a×(LAS / AES)+b), where f(alc) is a function of the structure and molecular weight of the alcohol used to produce the AES surfactant, (LAS / AES) is the blend ratio of LAS to AES in the surfactant paste, a is ~30, and b is ~2. For the reference blend of mainly C12 - C15 linear alcohol ethoxylate (C25AE1), f(alc) is ~1.0, and for the reference blend of mainly C14 - C15 linear alcohol ethoxylate (C45AE1), f(alc) is ~1.2. The above guidelines further depend on the degree of ethoxylation and any branched structure of the ethoxylated alcohol precursor into the AES surfactant. The above guidelines can be expressed as a guidance ratio, and a value ≧1 may indicate improved dissolution, while a value <1 may indicate worse dissolution. The guidance ratio is (RM / NaAES) / (f(alc) / (30×(LAS / AES)+2)).

[0057] The particles may contain from about 15 wt% to about 60 wt%, or 20 wt% to 40 wt% of an alkyl alkoxylated sulfate, or from 30 wt% to 80 wt%, or even 50 wt% to 70 wt% of an alkyl alkoxylated sulfate.

[0058] The particles may contain an alkylbenzene sulfonate, for example, a linear alkylbenzene sulfonate (LAS). The particles may contain from 1 wt% to 50 wt% of an alkylbenzene sulfonate, or from 5 wt% to 30 wt% of an alkylbenzene sulfonate.

[0059] The particles may have a particle size distribution such that D50 is greater than about 150 micrometers and less than about 1700 micrometers. The particles may have a particle size distribution such that D50 is greater than about 212 micrometers and less than about 1180 micrometers. The particles may have a particle size distribution such that D50 is greater than about 300 micrometers and less than about 850 micrometers. The particles may have a particle size distribution such that D50 is greater than about 350 micrometers and less than about 700 micrometers. The particles may have a particle size distribution such that D20 is greater than about 150 micrometers and D80 is less than about 1400 micrometers. The particles may have a particle size distribution such that D20 is greater than about 200 micrometers and D80 is less than about 1180 micrometers. The particles may have a particle size distribution such that D20 is greater than about 250 micrometers and D80 is less than about 1000 micrometers. The particles may have a particle size distribution such that D10 is greater than about 150 micrometers and D90 is less than about 1400 micrometers. The particles may have a particle size distribution such that D10 is greater than about 200 micrometers and D90 is less than about 1180 micrometers. The particles may have a particle size distribution such that D10 is greater than about 250 micrometers and D90 is less than about 1000 micrometers.

[0060] The particles may be used in bead-like detergents or derivatives thereof. The particles may have a particle size distribution such that D50 is greater than about 1 mm and less than about 4.75 mm. The particles may have a particle size distribution such that D50 is greater than about 1.7 mm and less than about 3.5 mm. The particles may have a particle size distribution such that D20 is greater than about 1 mm and D80 is less than about 4.75 mm. The particles may have a particle size distribution such that D20 is greater than about 1.7 mm and D80 is less than about 3.5 mm. The particles may have a particle size distribution such that D10 is greater than about 1 mm and D90 is less than about 4.75 mm. The particles may have a particle size distribution such that D10 is greater than about 1.7 mm and D90 is less than about 3.5 mm.

[0061] The particle size distribution is measured according to the particle size distribution test method of the present applicants.

[0062] The particles may contain from about 10% to about 80% by weight, preferably from about 20% to about 60% by weight, more preferably from about 30% to about 50% by weight of a detergent builder.

[0063] The particles may contain from about 2% to about 40% by weight, preferably from about 5% to about 30% by weight, more preferably from about 10% to about 20% by weight of a buffering agent.

[0064] The particles may contain from about 2% to about 20% by weight, preferably from about 5% to about 10% by weight of a chelating agent.

[0065] The particles may contain from about 2% to about 20% by weight, preferably from about 5% to about 10% by weight of a dispersant polymer.

[0066] The particles may contain from 0.5% to 15% by weight of a soluble film or fibrous structured polymer. Examples of soluble films or fibrous structured polymers include, but are not limited to, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, modified starch or cellulose polymers, and mixtures thereof. Such polymers may be present in the product recycle stream including unit dose products containing soluble fiber or film materials, e.g., pouch materials, and in this case, it is advantageous to incorporate the recycled material into the present particles.

[0067] The rheology-modified particles may be coated or at least partially coated with a layer composition, as disclosed, for example, in US Patent Application Publication No. 2007 / 0196502. Preferably, the layer composition comprises a non-surfactant active substance. More preferably, the non-surfactant active substance is selected from the group consisting of a builder, a buffer, and a dispersant polymer. Even more preferably, the non-surfactant active substance is selected from the group consisting of zeolite A, sodium carbonate, sodium bicarbonate, and a soluble polycarboxylate polymer. This is particularly advantageous when the active substance (non-limiting example: AES) is suitable for washing under cold water and / or high-hardness washing water conditions. The presence of the active substance in the layer promotes the initial dissolution of cold water and / or hardness-resistant chemicals. Without being bound by theory, it is assumed that if the cold water and hardness-resistant chemicals dissolve in a faster order, more conventional washing active substances (non-limiting example: LAS surfactant) can be protected, resulting in excellent overall washing performance.

[0068] Process for producing rheology-modified particles Rheology-modified detergent particles can be produced according to a paste agglomeration process using a concentrated aqueous paste comprising a mixture of an alkyl alkoxylated sulfate anionic cleaning surfactant and a rheology modifier, preferably a functional rheology modifier. The paste agglomeration process comprises: (a) adding powder raw materials into a mixing granulator, wherein the powder raw materials may include one or more dry builders, buffers, dispersant polymers or chelating agent components, necessary powder process aids, and fines recycled from the agglomeration process; (b) adding a paste comprising a premix of a concentrated surfactant and a functional rheology modifier; (c) operating the mixing granulator to disperse the powder into the paste and provide a mixing flow field suitable for forming aggregates; optionally, (d) adding additional powder components to at least partially coat the aggregates and reduce stickiness on their surfaces; (e) optionally, drying the obtained aggregates in a fluidized bed dryer to remove excess moisture; (f) optionally, cooling the aggregates in a fluidized bed cooler; (g) preferably, removing any excess fine particles from the particle size distribution of the aggregates by elutriation from the fluidized bed in step e and / or f and recycling the fines back to step a; (h) preferably, removing excess oversize particles from the particle size distribution of the aggregates by sieving classification; and (i) crushing the oversize particles and recycling the crushed particles to step a, e, or f. The paste agglomeration process may be a batch process or a continuous process.

[0069] Variations of the above preferred embodiments may include adding an additional LAS co-surfactant in a stream separate from the pre-mixed surfactant paste of step (b). Process options include adding pre-neutralized LAS as a solid powder in step (a), adding a neutralized or partially neutralized LAS paste as an auxiliary material in step (b), or adding a liquid acid precursor (HLAS) as an auxiliary material in step (b). In the latter case, sufficient free alkali must be present in the powder added in step (a) to effectively neutralize the HLAS during the agglomeration process. Alternatively, the neutralization of HLAS may be carried out in a separate pretreatment step by first premixing the HLAS with an alkali buffer powder component and any other optional solid carrier to form a neutralized premix of powdered LAS and alkali buffer powder, and then adding the premix in step (a) above.

[0070] Alternatively, a concentrated aqueous paste comprising a mixture of an alkyl alkoxylated sulfate anionic cleaning surfactant and a rheology modifier may be used with an extrusion process. Extrusion processes are well known in the art.

[0071] Alternatively, a rheology modifier may be used as a binder in the agglomeration process to produce rheology-modified detergent particles.

[0072] Surprisingly, the rheology-modified particles are finer and stronger compared to the same particles without the rheology modifier.

[0073] pH adjuster The single unit dosage may contain one or more basic pH adjusters that raise the pH of the cleaning solution above pH 8. Suitable basic pH adjusters include, but are not limited to, compounds containing sulfate ions, dihydrogen phosphate ions, fluoride ions, nitrite ions, acetate ions, bicarbonate ions, hydrogen sulfide ions, ammonia, carbonate ions, hydroxide ions, and combinations thereof. Including a basic pH adjuster does not exclude, for example, including an acidic pH adjuster such as citric acid. The single unit dosage may contain an acidic pH adjuster as long as the final pH of the cleaning solution is above 8, for example, 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6, 9.8, 10, 10.2, 10.4, 10.6, 10.8, 11, 11.2, 11.4, 11.6, 11.8, 12, 12.2, 12.4, 12.6, 12.8, or 13.

[0074] Concentrated surfactant paste The concentrated surfactant paste is an intermediate composition that can form rheology-modifying particles in combination with other components. The concentrated surfactant composition may include, consist essentially of, or consist of the following components: a surfactant system that may include an alkyl alkoxylated sulfate surfactant; a rheology modifier described herein; an organic solvent system, and water. These components are described in more detail below.

[0075] The concentrated surfactant composition includes a surfactant system that is about 70% to about 90% by weight of the composition and may include from about 50%, or from about 60%, or from about 70%, or from about 80% to about 100% of an alkyl alkoxylated sulfate surfactant, a rheology modifier that is about 0.1% to about 25% by weight of the composition, an organic solvent system that is less than about 5% by weight of the composition, and water. The surfactant system of the paste preferably includes a LAS co-surfactant. When LAS is included in the surfactant system, the LAS:AES ratio may be from about 0 to about 1, preferably from about 0.2 to about 0.7, more preferably from about 0.25 to about 0.35.

[0076] Solid carriers: Suitable solid carriers include inorganic salts such as sodium carbonate, sodium sulfate, and mixtures thereof. Other preferred solid carriers include aluminosilicates such as zeolites, dry dispersant polymers in fine powder form, and absorbent grade fumed or precipitated silica (e.g., precipitated hydrophilic silica commercially available under the trade name SN340 by Evonik Industries AG). Mixtures of solid carrier materials may be used.

[0077] Fiber structure The fibrous structure includes one or more fibrous elements. The fiber elements can be associated with each other to form a structure. The fibrous structure can include particles within and / or on the structure. The fibrous structure can be homogeneous, layered, single, zone-shaped, or otherwise as desired, with different active agents defining various aforementioned parts.

[0078] The fibrous structure may include one or more layers, and the layers together form a ply.

[0079] Fiber element The fiber element may be water-soluble. The fiber element may include one or more filament-forming materials and / or one or more active agents such as surfactants. The one or more active agents may be releasable from the fiber element, such as when the fiber element and / or the fibrous structure containing the fiber element are exposed to the intended use conditions.

[0080] The fiber elements of the present invention can be spun from a filament-forming composition, also referred to as a fiber element-forming composition, via suitable spinning process operations (such as meltblowing, spunbonding, electrospinning, and / or rotational spinning, etc.).

[0081] As used herein, "filament-forming composition" and / or "fiber element-forming composition" means a composition suitable for manufacturing the fiber elements of the present invention, such as melt blowing and / or spunbonding. The filament-forming composition includes one or more filament-forming materials that exhibit properties suitable for spinning the materials into fiber elements. The filament-forming materials can include polymers. In addition to the one or more filament-forming materials, the filament-forming composition may include one or more active agents, such as surfactants. Further, the filament-forming composition may include one or more polar solvents (such as water), in which one or more, for example all, of the filament-forming materials and / or one or more, for example all, of the active agents are dissolved and / or dispersed before spinning the fiber elements (such as filaments derived from the filament-forming composition).

[0082] The filament-forming composition may include two or more different filament-forming materials. Thus, the fiber element may be single-component (one type of filament-forming material) and / or multi-component such as bicomponent. Two or more different filament-forming materials may be randomly combined to form a fiber element. Two or more different filament-forming materials may be regularly combined to form a fiber element, such as a sheath-core type bicomponent fiber element, which is not considered a random mixture of different filament-forming materials for the purposes of this disclosure. The bicomponent fiber element may be in any form such as side-by-side, sheath-core, sea-island type, etc.

[0083] The fiber element may not substantially contain an alkyl alkoxylated sulfate. Each fiber element may contain, on a dry fiber element basis, from about 0 wt%, or about 0.1 wt%, or about 5 wt%, or about 10 wt%, or about 15 wt%, or about 20 wt%, or about 25 wt%, or about 30 wt%, or about 35 wt%, or about 40 wt% to about 0.2 wt%, or about 1 wt%, or about 5 wt%, or about 10 wt%, or about 15 wt%, or about 20 wt%, or about 25 wt%, or about 30 wt%, or about 35 wt%, or about 40 wt%, or about 50 wt% of an alkyl alkoxylated sulfate. The amount of alkyl alkoxylated sulfate in each of the fiber elements is sufficiently small so as not to affect its processing stability and film solubility. When dissolved in water, the alkyl alkoxylated sulfate may pass through a highly viscous hexagonal phase at a specific concentration range, for example 30 to 60 wt%, resulting in the formation of a gel-like substance. Thus, when incorporated in a significant amount into the fiber element, the alkyl alkoxylated sulfate can significantly slow down the dissolution of the water-soluble unit dose article in water, and even worse, undissolved solids may remain later. Correspondingly, most of such surfactants are incorporated into the particles.

[0084] Each fiber element may contain at least one filament-forming material and an activator, preferably a surfactant. The surfactant may have a relatively low hydrophilicity because such surfactants are less likely to form a viscous gel-like hexagonal phase when diluted. By using such a surfactant in filament formation, gel formation during washing can be effectively reduced, and thus, dissolution can be faster and residues in washing can be reduced or eliminated. The surfactant can be selected from the group consisting of, for example, non-alkoxylated C6-C20 linear or branched alkyl sulfates (AS), C6-C20 linear alkylbenzene sulfonates (LAS), and combinations thereof. The surfactant may be C6-C20 linear alkylbenzene sulfonate (LAS). LAS surfactants are well-known in the art and can be easily obtained by sulfonating commercially available linear alkylbenzenes. Exemplary C6-C 20 As the linear alkylbenzene sulfonate, C6-C 20 salts of alkali metals, alkaline earth metals, or ammonium of linear alkylbenzene sulfonic acid, for example, C 11 -C 18 or C 11 -C 14 include sodium, potassium, magnesium, and / or ammonium salts of linear alkylbenzene sulfonic acid. C 12 Sodium or potassium salts of linear alkylbenzene sulfonic acid, for example, C 12 The sodium salt of linear alkylbenzene sulfonic acid, i.e., sodium dodecylbenzenesulfonate, may be used as the first surfactant.

[0085] The fiber element may include a filament-forming material that is at least about 5 wt%, and / or at least about 10 wt%, and / or at least about 15 wt%, and / or at least about 20 wt%, and / or less than about 80 wt%, and / or less than about 75 wt%, and / or less than about 65 wt%, and / or less than about 60 wt%, and / or less than about 55 wt%, and / or less than about 50 wt%, and / or less than about 45 wt%, and / or less than about 40 wt%, and / or less than about 35 wt%, and / or less than about 30 wt%, and / or less than about 25 wt% based on the dry fiber element and / or the dry fiber structure, and an activator, preferably a surfactant, that is more than about 20 wt%, and / or at least about 35 wt%, and / or at least about 40 wt%, and / or at least about 45 wt%, and / or at least about 50 wt%, and / or at least about 55 wt%, and / or at least about 60 wt%, and / or at least about 65 wt%, and / or at least about 70 wt%, and / or less than about 95 wt%, and / or less than about 90 wt%, and / or less than about 85 wt%, and / or less than about 80 wt%, and / or less than about 75 wt% based on the dry fiber element and / or the dry fiber structure. The fiber element may include a surfactant that is more than about 80 wt% based on the dry fiber element and / or the dry fiber structure.

[0086] Preferably, each fiber element may be characterized by a sufficiently high total surfactant content, e.g., at least about 30 wt%, or at least about 40 wt%, or at least about 50 wt%, or at least about 60 wt%, or at least about 70 wt% of a first surfactant based on the dry fiber element and / or the dry fiber structure.

[0087] The total concentration of the filament-forming material present in the fiber element may be from about 5 wt% to less than about 80 wt% based on the dry fiber element and / or the dry fiber structure, and the total concentration of the surfactant present in the fiber element may be more than about 20 wt% to about 95 wt% based on the dry fiber element and / or the dry fiber structure.

[0088] One or more of the fiber elements may contain at least one additional surfactant selected from the group consisting of other anionic surfactants (i.e., other than AS and LAS), nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants, and combinations thereof.

[0089] Other suitable anionic surfactants include C6 - C 20 linear or branched alkyl sulfonates, C6 - C 20 linear or branched alkyl carboxylates, C6 - C 20 linear or branched alkyl phosphates, C6 - C 20 linear or branched alkyl phosphonates, C6 - C 20 alkyl N - methylglucamide, C6 - C 20 methyl ester sulfonate (MES), and combinations thereof.

[0090] Suitable nonionic surfactants include alkoxylated aliphatic alcohols. The nonionic surfactant can be selected from ethoxylated alcohols of the formula R(OC2H4) n OH and ethoxylated alkylphenols, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkylphenyl radicals having alkyl groups containing from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. Non - limiting examples of nonionic surfactants useful herein include C8 - C 18 alkyl ethoxylates, e.g., NEODOL® nonionic surfactants from Shell, C6 - C 12 alkylphenol alkoxylates, where the alkoxylate units can be ethylene oxide units, propylene oxide units, or mixtures thereof, C 12 - C 18 alcohols, and C6 - C 12 alkylphenol condensates with ethylene oxide / propylene oxide block polymers, e.g., Pluronic® from BASF, C 14 - C22 Medium-chain branched alcohols (branched alcohols, BA); C 14 ~C 22 Medium-chain branched alkyl alkoxylates (BAE x , where x is from 1 to 30), alkyl polysaccharides, specifically alkyl polyglycosides, polyhydroxy fatty acid amides, and ether-capped poly(oxyalkylated) alcohol surfactants. Suitable nonionic detergency surfactants also include alkyl polyglycosides and alkyl alkoxylated alcohols. Suitable nonionic surfactants also include those sold by BASF under the trade name Lutensol®.

[0091] Non-limiting examples of cationic surfactants include quaternary ammonium surfactants, which may have up to 26 carbon atoms, alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; cationic ester surfactants; and amino surfactants, such as amidopropyldimethylamine (APA). Suitable cationic detergency surfactants also include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

[0092] Suitable cationic detergency surfactants are quaternary ammonium compounds having the following general formula: (R)(R1)(R2)(R3)N + X - wherein R is a linear or branched, substituted or unsubstituted C 6~18an alkyl or alkenyl moiety, where R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or hydroxyethyl moiety, X is an anion that provides charge neutrality, and suitable anions include, for example, halides such as chloride, sulfates, and sulfonates. Suitable cationic detergency surfactants are mono-C 6~18 alkylmono-hydroxyethyldimethylquaternary ammonium chloride. Highly suitable cationic detergency surfactants are mono-C 8~10 alkylmono-hydroxyethyldimethylquaternary ammonium chloride, mono-C 10~12 alkylmono-hydroxyethyldimethylquaternary ammonium chloride, and mono-C 10 alkylmono-hydroxyethyldimethylquaternary ammonium chloride.

[0093] Suitable examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, including derivatives of heterocyclic secondary and tertiary amines; derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds; betaines including alkyldimethylbetaine, coco dimethylamidopropyl betaine, and sulfo and hydroxy betaines; C8 - C 18 (e.g., C 12 - C 18 ) amine oxides; N-alkyl-N,N-dimethylamino-1-propanesulfonate (the alkyl group may be C8 - C 18 ).

[0094] Suitable amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, where the aliphatic group may be straight-chain or branched-chain, and where at least one of the aliphatic substituents contains at least about 8 carbon atoms or from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-solubilizing group, such as carboxy, sulfonate, sulfate, aliphatic derivatives of heterocyclic secondary and tertiary amines. Suitable amphoteric surfactants also include sarcosinates, glycocinates, taurinates, and mixtures thereof.

[0095] The fiber element may include a surfactant system containing only an anionic surfactant, for example, either a single anionic surfactant or a combination of two or more different anionic surfactants. Alternatively, the fiber element may include, for example, a combination of one or more anionic surfactants and one or more nonionic surfactants, or a combination of one or more anionic surfactants and one or more zwitterionic surfactants, or a combination of one or more anionic surfactants and one or more amphoteric surfactants, or a combination of one or more anionic surfactants and one or more cationic surfactants, or a composite surfactant system containing a combination of all of the above types of surfactants (i.e., anionic, nonionic, amphoteric, and cationic).

[0096] Generally, the fiber element is an elongated microparticle whose length is much greater than the average diameter, for example, the ratio of the length to the average diameter is at least about 10. The fiber element can be a filament or a fiber. A filament is relatively longer than a fiber. A filament can have a length of about 5.08 cm (2 inches) or more, and / or about 7.62 cm (3 inches) or more, and / or about 10.16 cm (4 inches) or more, and / or about 15.24 cm (6 inches) or more. A fiber can have a length of less than about 5.08 cm (2 inches), and / or less than about 3.81 cm (1.5 inches), and / or less than about 2.54 cm (1 inch).

[0097] One or more filament-forming materials and an activator may be present in the fiber element at a weight ratio of the total concentration of the filament-forming material to the activator of about 2.0 or less, and / or about 1.85 or less, and / or less than about 1.7, and / or less than about 1.6, and / or less than about 1.5, and / or less than about 1.3, and / or less than about 1.2, and / or less than about 1, and / or less than about 0.7, and / or less than about 0.5, and / or less than about 0.4, and / or less than about 0.3, and / or greater than about 0.1, and / or greater than about 0.15, and / or greater than about 0.2. One or more filament-forming materials and an activator may be present in the fiber element at a weight ratio of the total concentration of the filament-forming material to the activator of about 0.2 to about 0.7.

[0098] The fiber element may include, based on the dry fiber element and / or based on the dry fiber structure, about 10 wt% to less than about 80 wt% of a filament-forming material, such as a polyvinyl alcohol polymer, a starch polymer, and / or a carboxymethyl cellulose polymer, and about more than 20 wt% to about 90 wt% of an activator, such as a surfactant, based on the dry fiber element and / or based on the dry fiber structure. The fiber element may further include a plasticizer (e.g., glycerin) and / or an additional pH adjuster (e.g., citric acid). The fiber element may have a weight ratio of the filament-forming material to the activator of about 2.0 or less. The filament-forming material may be selected from the group consisting of polyvinyl alcohol, starch, carboxymethyl cellulose, polyethylene oxide, and other suitable polymers, particularly hydroxyl-containing polymers and derivatives thereof. The filament-forming material may be in the range of a weight average molecular weight of about 100,000 g / mol to about 3,000,000 g / mol. In this range, it is considered that the filament-forming material can provide extensional rheology so that the fiber diameter reduction is not inhibited in the fiber production process.

[0099] One or more active agents may be releasable and / or released when the fibrous element and / or the fibrous structure containing the fibrous element is exposed to the intended use conditions. One or more active agents in the fibrous element may be selected from the group consisting of surfactants, organic polymer compounds, and mixtures thereof.

[0100] The fibrous element may exhibit a diameter of less than about 300 μm, and / or less than about 75 μm, and / or less than about 50 μm, and / or less than about 25 μm, and / or less than about 10 μm, and / or less than about 5 μm, and / or less than about 1 μm when measured according to the diameter test method described herein. The fibrous element may exhibit a diameter greater than about 1 μm when measured according to the diameter test method described herein. The diameter of the fibrous element can be used to control the release rate of one or more active agents present in the fibrous element and / or the rate of loss and / or change of the physical structure of the fibrous element.

[0101] The fibrous element may contain two or more different active agents that are compatible or incompatible with each other. The fibrous element may include active agents within the fibrous element and active agents on the outer surface of the fibrous element, such as an active agent coating on the fibrous element. The active agent on the outer surface of the fibrous element may be the same as or different from the active agent present within the fibrous element. If different, the active agents may be compatible or incompatible with each other. One or more active agents may be uniformly distributed or substantially uniformly distributed throughout the fibrous element. One or more active agents may be distributed as discrete regions within the fibrous element.

[0102] Active agent The water-soluble unit-dose articles described herein may contain one or more active agents. The active agent may be present as a premix in the fibrous elements (as described above), in the particles (as described above), or in the article. The premix may be, for example, a slurry of an active agent combined with an aqueous absorbent. The active agent may be selected from the group consisting of surfactants, structuring agents, builders, organic polymer compounds, enzymes, enzyme stabilizers, bleaching systems, optical brighteners, hue agents, chelating agents, antifoaming agents, conditioning agents, humectants, fragrances, fragrance microcapsules, fillers or carriers, alkaline systems, pH control systems, buffers, alkanolamines, and mixtures thereof.

[0103] Surfactant The surfactant may be selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. These surfactants are described in more detail above.

[0104] Enzyme Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, mannanase, pectate lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, mannanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof. A typical combination may be, for example, an enzyme cocktail that includes protease and one or more non-protease enzymes, such as amylase or lipase used in combination with any of those listed above.

[0105] When present in the detergent composition, the foregoing additional enzyme may be present at an enzyme protein concentration of about 0.00001 wt% to about 2 wt%, about 0.0001 wt% to about 1 wt%, or even about 0.001 wt% to about 0.5 wt% of the composition. The compositions disclosed herein may contain about 0.001 wt% to about 1 wt% of an enzyme (as an adjuvant) selected from the group consisting of lipase, amylase, protease, mannanase, cellulase, pectinase, and mixtures thereof.

[0106] Protease Preferably, the enzyme composition contains one or more proteases. Suitable proteases include metalloproteases and serine proteases, for example, neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62). Suitable proteases include those of animal, plant, or microbial origin. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the foregoing suitable proteases. In one aspect, suitable proteases may be alkaline microbial proteases or / and serine proteases such as trypsin-type proteases.

[0107] Surprisingly, under appropriate washing alkalinity, single unit doses containing protease have been found to exhibit improved washing against body soils such as sebum. Without being bound by theory, at a pH of 8 or higher, protease may be thought to hydrolyze esters in sebum stains, resulting in a surprising removal of sebum stains.

[0108] Examples of suitable neutral or alkaline proteases include the following. Subtilisin (EC 3.4.21.62) derived from Bacillus species, including those described in U.S. Patent Nos. 6,312,936 (B1), 5,679,630, 4,760,025, 7,262,042, and International Publication No. 09 / 021867, such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii. Trypsin-type or chymotrypsin-type proteases such as trypsin (e.g., of porcine or bovine origin), including Fusarium protease described in International Publication No. 89 / 06270 and chymotrypsin protease derived from Cellumonas described in International Publication Nos. 05 / 052161 and 05 / 052146. Metalloprotease derived from Bacillus amyloliquefaciens described in International Publication No. 07 / 044993 (A2).

[0109] The protease of the present invention may be a serine protease derived from the subtilisin family (EC 3.4.21.62). In one aspect, such a suitable protease may be of microbial origin. The protease may have an isoelectric point of about 6.5 to about 11.5, preferably about 8 to about 10.5, and most preferably about 9 to about 10. The protease having this isoelectric point exhibits a good balance between good activity in the cleaning solution and a favorable adhesion profile to the fabric substrate, particularly cotton, seen during cleaning. Without being bound by theory, if it has too much positive charge, it will be "too sticky" to the fabric and cannot move effectively on the surface (desorption and reattachment or "roll") of the enzyme, and thus cannot digest a sufficient amount to interact sufficiently with the protein on the surface to exert an effect. On the other hand, if it has too much negative charge, it will not adhere well enough, resulting in an enzyme that cannot reach a sufficient amount of dirt efficiently enough to digest the dirt on the surface of the fabric.

[0110] According to this nomenclature, for example, the one substituted with glutamic acid instead of glycine at position 195 is designated as G195E. The one with glycine deleted at the same position is designated as G195 * and the one with an additional amino acid residue, such as lysine inserted, is designated as G195GK. When a particular enzyme contains a "deletion" compared to other enzymes and an insertion is made at such a position, this is, for the insertion of aspartic acid at position 36 * shown as 36D. Multiple mutations are separated by a plus, i.e., S99G+V102N represents that the mutations at positions 99 and 102 are substitutions of glycine with serine and asparagine with valine, respectively. When the amino acid at a certain position (e.g., 102) can be substituted by another amino acid selected from a group of amino acids, such as the group consisting of N and I, this is shown as V102N, I or V102N / I.

[0111] In all cases, the generally recognized one-letter or three-letter amino acid abbreviations of IUPAC are used.

[0112] Protease amino acid number The numbers used in this patent are for the indicated sequences and are not BPN numbers.

[0113] Amino acid identity The relationship between two amino acid sequences is described by the parameter "identity". For the purposes of the present invention, the alignment of two amino acid sequences is determined by using the Needle program from the EMBOSS package (http: / / emboss.org) version 2.8.0. The Needle program implements the global alignment algorithm described by Needleman, S.B. and Wunsch, C.D. (1970) J. Mol. Biol. 48, 443-453. The substitution matrix used is BLOSUM62, the gap opening penalty is 10, and the gap extension penalty is 0.5.

[0114] The degree of identity between the amino acid sequence of the enzyme used in this specification ("this sequence") and a different amino acid sequence ("heterologous sequence") is calculated by dividing the number of exact matches in the alignment of the two sequences by the shorter of the length of "this sequence" or the length of the "heterologous sequence". This result is expressed as identity (%). An exact match occurs when the same amino acid residue is present at the same position in the overlapping part of "this sequence" and "heterologous sequence". The length of a sequence is the number of amino acid residues in the sequence.

[0115] As used herein, the term "isoelectric point" refers to the electrochemical properties of an enzyme such that the enzyme has a net charge of 0, calculated by the method described below.

[0116] Isoelectric point As used herein, the isoelectric point of an enzyme (referred to as IEP or pI) refers to the theoretical isoelectric point measured according to the online pI tool available from the ExPASy server at the following web address. http: / / web.expasy.org / compute_pi /

[0117] The method used in this section is described in the following references: Gasteiger E., Hoogland C., Gattiker A., Duvaud S., Wilkins M.R., Appel R.D., Bairoch A.; Protein Identification and Analysis Tools on the ExPASy Server; (In) John M.Walker (ed): The Proteomics Protocols Handbook, Humana Press (2005).

[0118] The protease of the composition of the present invention is an endoprotease, and "endoprotease" is understood herein as a protease that degrades peptide bonds of non-terminal amino acids, in contrast to exoproteases that degrade peptide bonds from the ends.

[0119] Suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one embodiment, the suitable protease is an alkaline microbial protease. Examples of suitable alkaline proteases include subtilisin (EC 3.4.21.62) derived from Bacillus species such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus pumilus, and Bacillus gibsonii.

[0120] Preferred proteases include those derived from Bacillus gibsonii or Bacillus lentus.

[0121] In a preferred embodiment, the enzyme comprises one or more mutations and / or insertions. A mutant protease for use herein has mutations with respect to a protease having at least 70%, preferably at least 85%, preferably at least 90%, more preferably at least 95%, even more preferably at least 99%, particularly 100% identity to the amino acid sequence of SEQ ID NO: 1. The mutant protease has substitutions at one or more, preferably two or more, more preferably three or more of the following positions: 9, 15, 22, 24, 32, 33, 48 - 54, 58 - 62, 74, 94 - 107, 114, 116, 123 - 133, 150, 153, 157, 158 - 161, 164, 169, 175 - 186, 188, 197, 198, 199, 200, 203 - 216, 226, 231, 239, 242, 246, 255 and / or 265. Preferably, the protease has substitutions at one or more of the following positions: 9, 15, 22, 24, 32, 66, 74, 94, 97, 99, 101, 102, 114, 116, 126, 127, 128, 150, 152, 157, 161, 182, 183, 188, 200, 203, 211, 212, 216, 226, 239, 242, and / or 265.

[0122] Preferred substitutions and insertions include one or more, preferably two or more, more preferably three or more of the following positions: X3T, X4I, X9R, X15T, X22R / A, X24R, X66A, X74D, X85S, X97D, X97AD, X97A, S97SE, X99G, X99M, X101A, X102N / I, X114L, X116V, X116R, X126L, X127Q / E, X128A, X153D, X157D, X161A, X164S, X182D, X188P, X199I, X200L / D / E, X203W, X212D, X216S, X226V, X231H, X239R, X242D, X246K, X255D and / or X265F.

[0123] Preferred substitutions and insertions include one or more, preferably two or more, more preferably three or more, of the following positions: S3T, V4I, S9R, A15T, T22R / A, S24R, V66A, N74D, N85S, S97D, S97AD, S97A, S97SE, S99G, S99M, S101A, V102N / I, N114L, G116V, G116R, S126L, P127Q, S128A, G153D, G157D, Y161A, R164S, S182D, A188P, V199I, Q200L / D / E, Y203W, N212D, M216S, A226V, Q231H, Q239R, N242D, N246K, N255D and / or E265F.

[0124] Preferred proteases include those having mutations relative to a protease having at least 70%, preferably at least 90%, more preferably at least 95%, even more preferably at least 99%, and particularly 100% identity to the amino acid sequence of SEQ ID NO: 1 and containing the following mutations: S97SE; S97AD; N74D + S101A + V102I; S85N + S99G + V102N; V66A + S99G + V102N; G116V + S126L + P127Q + S128A; S3T + V4I + A188P + V193M + V199I + L211D; S3T + V4I + R99G + A188P + V193M + V199I + L211D; S3T + V4I + V193M + V199I + L211D; S9R + A15T + V66A + N212D + Q239R, optionally including one or more of Q200L / D / E and Y203W; S99N + G116V + S126L + P127Q + S128A; S99G + S101A + V102I, optionally including one or more, preferably two or more, of T22A, T22R, N144L, G157D, S182D, A226V, Q239R, and E265F.

[0125] Preferred proteases include those derived from Bacillus gibsonii or Bacillus lentus.

[0126] Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase®, and Esperase® by Novozymes A / S (Denmark), those sold under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, and Purafect OXP® by Genencor International, those sold under the trade names Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel / Kemira, namely BLAP (the sequence shown in FIG. 29 of U.S. Patent No. 5,352,604 having the following mutations: S99D + S101R + S103A + V104I + G159S, hereinafter referred to as BLAP), BLAP R (BLAP having S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP having S3T + V4I + V205I), and BLAP F49 (BLAP having S3T + V4I + A194P + V199M + V205I + L217D) (all manufactured by Henkel / Kemira), and KAP (subtilisin of Bacillus alkalophilus having the mutations A230V + S256G + S259N) manufactured by Kao.

[0127] Builder Suitable builders include aluminosilicates (such as zeolite builders like zeolite A, zeolite P, and zeolite MAP), silicates, phosphates, such as polyphosphates (e.g., sodium tripolyphosphate), specifically its sodium salts; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acids, sodium, potassium, or alkanolammonium salts, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types, and phytic acid. Additional suitable builders can be selected from citric acid, lactic acid, fatty acids, polycarboxylate builders, such as copolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and / or maleic acid, and other suitable ethylenic monomers having various additional functional groups. Alternatively, the composition may substantially contain no builder.

[0128] Polymer dispersant Suitable polymers include, but are not limited to, polyacrylates, poly(acrylic acid-maleic acid) copolymers, and sulfonated modifications thereof, such as polymer carboxylates like hydrophobically modified sulfonated acrylic acid copolymers. The polymer can be a cellulose-based polymer, polyester, polyterephthalate, polyethylene glycol, ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymer, where each of x1 and x2 is in the range of about 2 to about 140 and y is in the range of about 15 to about 70, polyethyleneimine, any modified variants thereof, such as polyethylene glycol having grafted vinyl and / or alcohol moieties, and any combination thereof. In some cases, the dispersant polymer can also function as a rheology modifier as described above.

[0129] Suitable polyethyleneimine polymers include propoxylated polyalkyleneimine (e.g., PEI) polymers. The propoxylated polyalkyleneimine (e.g., PEI) polymer may be ethoxylated. The propoxylated polyalkyleneimine (e.g., PEI) polymer may have an inner polyethylene oxide block and an outer polypropylene oxide block, and the degrees of ethoxylation and propoxylation do not exceed or fall below specific limit values. The ratio (n / p) of the polyethylene block to the polypropylene block may be from about 0.6, or from about 0.8, or from about 1, up to about 10, or up to about 5, or up to about 3. The n / p ratio can be about 2. The propoxylated polyalkyleneimine may have a PEI backbone chain with a weight average molecular weight (measured before alkoxylation) of about 200 g / mol to about 1200 g / mol, or about 400 g / mol to about 800 g / mol, or about 600 g / mol. The molecular weight of the propoxylated polyalkyleneimine may be about 8,000 to about 20,000 g / mol, or about 10,000 to about 15,000 g / mol, or about 12,000 g / mol.

[0130] Suitable propoxylated polyalkyleneimine polymers may include compounds having the following structure:

[0131] [Chemical formula] (wherein EO is an ethoxylate group and PO is a propoxylate group). The compound shown above is a PEI with a molar ratio of EO:PO of 10:5 (e.g., 2:1). Other similar suitable compounds may contain EO and PO groups present in a molar ratio of about 10:5 or about 24:16.

[0132] Soil release polymer Suitable soil release polymers have a structure defined by one of the following structures (I), (II), or (III): (I) -[(OCHR 1 -CHR 2 ) a-O-OC-Ar-CO-] d (II)-[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e (III)-[(OCHR 5 -CHR 6 ) c -OR 7 f (wherein a, b, and c are 1 to 200, d, e, and f are 1 to 50, Ar is 1,4-disubstituted phenylene, sAr is 1,3-disubstituted phenylene substituted at the 5-position with SO3Me, Me is Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetra-alkylammonium (wherein the alkyl group is C1-C 18 alkyl or C2-C 10 hydroxyalkyl), or a mixture thereof, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H or C1-C 18 n- or iso-alkyl, R 7 is linear or branched C1-C 18 alkyl, or linear or branched C2-C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C8-C 30 aryl group, or a C6-C 30 arylalkyl group).

[0133] ​Suitable soil release polymers include polyester soil release polymers such as the Repel-o-tex polymers supplied by Rhodia, including Repel-o-tex SF, SF-2 and SRP6. Other suitable soil release polymers include Texcare polymers supplied by Clariant, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325. Other suitable soil release polymers are Marloquest polymers (such as Marloquest SL supplied by Sasol).

[0134] Cellulosic polymers Suitable cellulosic polymers include those selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses. The cellulosic polymers can be selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. In one embodiment, the carboxymethyl cellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

[0135] Amine Non-limiting examples of amines can include, but are not limited to, polyetheramines, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylene pentamine, triethylene tetramine, diethylene triamine, or mixtures thereof.

[0136] Bleaching agent Suitable bleaching agents other than the bleaching catalyst include optical bleaching agents, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, and mixtures thereof. Generally, when using a bleaching agent, the detergent composition of the present invention may contain from about 0.1% to about 50% by weight, or even from about 0.1% to about 25% by weight, of the bleaching agent in the detergent composition.

[0137] Bleaching catalyst Suitable bleaching catalysts include, but are not limited to, iminium cations and polyions, iminium zwitterions, modified amines, modified amine oxides, N-sulfonylimines, N-phosphonylimines, N-acylimines, thiadiazole dioxide, perfluoroimines, cyclic sugar ketones, and mixtures thereof.

[0138] Brightening agent Commercially available fluorescent brightening agents suitable for the present disclosure can be classified into subgroups including, but not limited to, derivatives of stilbenes, pyrazolines, coumarins, benzoxazoles, carboxylic acids, methine cyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered heterocycles, and various other substances.

[0139] The fluorescent brightener may be selected from the group consisting of disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the trade name Tinopal AMS-GX by BASF), disodium 4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available under the trade name Tinopal UNPA-GX by BASF), and disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available under the trade name Tinopal 5 BM-GX by BASF). More preferably, the fluorescent brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate.

[0140] The brightener may be added in particulate form or as a premix with a suitable solvent, such as a nonionic surfactant, propanediol.

[0141] Fabric colorant Hue agents (sometimes also referred to as complementary color agents, blueing agents, or whitening agents) typically impart a blue or purple hue to the fabric. Hue agents can be used either alone or in combination to create a specific hue and / or to impart a hue to different types of fabrics. This can be achieved, for example, by mixing red and green - blue dyes to produce a blue or purple hue. Hue agents can be selected from any known chemical classification of dyes, including, but not limited to, acridine, anthraquinone (including polycyclic quinones), azine, azo including premetallized azo (e.g., monoazo, diazo, trisazo, tetrakisazo, polyazo), benzodifuran and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoid, methane, naphthalimide, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazole, stilbene, styryl, triarylmethane, triphenylmethane, xanthene, and mixtures thereof.

[0142] Suitable fabric colorants include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes also include small molecule dyes and polymer dyes. Suitable small molecule dyes are classified as blue, violet, red, green or black and provide the desired shade either alone or in combination, for example, small molecule dyes selected from the group consisting of dyes falling within the Color Index (C.I.) classification of direct dyes, basic dyes, reactive dyes or hydrolyzed reactive dyes, solvent dyes, or disperse dyes. Suitable polymer dyes include polymers containing covalently (sometimes referred to as bonded) chromophores (dye-polymer conjugates), for example, polymers having chromophores copolymerized into the main chain of the polymer, and polymer dyes selected from the group consisting of mixtures thereof. Suitable polymer dyes also include fabric direct colorants sold under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA), polymer dyes selected from the group consisting of polymers formed from at least one reactive dye and a polymer containing a moiety selected from the group consisting of hydroxyl moieties, primary amine moieties, secondary amine moieties, thiol moieties, and mixed moieties thereof, and polymer dyes selected from the group consisting of dye-polymer conjugates formed from Liquitint® Violet CT, carboxymethyl cellulose (CMC) conjugated with C.I. Reactive Blue 19 sold under the trade name AZO-CM-CELLULOSE, product code S-ACMC by Megazyme (Wicklow, Ireland), reactive blue, reactive violet, or reactive red dyes conjugated with CMC, alkoxylated triphenyl-methane polymer colorants, alkoxylated thiophene polymer colorants, and mixtures thereof.

[0143] The aforementioned fabric colorants may be used in combination (any mixture of fabric colorants may be used).

[0144] Encapsulating agent The encapsulated body may include a core and a shell having an inner surface and an outer surface, and the shell encapsulates the core. The core can contain any laundry care aid, but typically, the core is selected from the group consisting of perfume; brightening agent; color tone dye; insect repellent; silicone; wax; flavoring agent; vitamin; fabric softener; skin care agent, in one aspect, paraffin; enzyme; antibacterial agent; bleaching agent; sensory agent; and mixtures thereof. The shell may include materials selected from the group consisting of polyethylene; polyamide; polyvinyl alcohol optionally containing other co-monomers; polystyrene; polyisoprene; polycarbonate; polyester; polyacrylate; aminoplast (in one aspect, the aminoplast may include polyurea, polyurethane, and / or polyureaurethane, and in one aspect, the polyurea may include polyoxymethylene urea and / or melamine formaldehyde); polyolefin; polysaccharide (in one aspect, the polysaccharide may include alginate and / or chitosan); gelatin; shellac; epoxy resin; vinyl polymer; water-insoluble inorganic material; silicone; and mixtures thereof.

[0145] Preferred encapsulants contain a fragrance. Preferred encapsulates include a shell that may contain melamine formaldehyde and / or crosslinked melamine formaldehyde. Other preferred capsules include a polyacrylate-based shell. Preferred encapsulants are disclosed as including a core material and a shell, the shell at least partially surrounding the core material. At least 75%, 85%, or even 90% of the encapsulant may have a breaking strength of 0.2 MPa to 10 MPa and a beneficial agent leakage rate of 0% to 20%, or even 10% or less than 5% based on the initial total amount of the encapsulated beneficial agent. It is preferred that at least 75%, 85%, or even 90% of the encapsulates have (i) a particle size of 1 micrometer to 80 micrometers, 5 micrometers to 60 micrometers, 10 micrometers to 50 micrometers, or even 15 micrometers to 40 micrometers, and / or (ii) at least 75%, 85%, or even 90% of the encapsulates may have a particle wall thickness of 30 nm to 250 nm, 80 nm to 180 nm, or even 100 nm to 160 nm. The formaldehyde scavenger may be used with the encapsulant, for example, in a capsule slurry, and / or may be added to the composition before, during, or after adding the encapsulant to the composition.

[0146] Suitable capsules can be made using known processes. Alternatively, suitable capsules can be purchased from Encapsys LLC (Appleton, Wisconsin USA). In a preferred embodiment, the composition may preferably contain an adhesion aid in addition to the encapsulant. Preferred adhesion aids are selected from the group consisting of cationic and nonionic polymers. Suitable polymers include cationic starch, cationic hydroxyethyl cellulose, polyvinyl formaldehyde, locust bean gum, mannan, xyloglucan, tamarind gum, polyethylene terephthalate, and polymers containing dimethylaminoethyl methacrylate with one or more monomers selected from the group optionally including acrylic acid and acrylamide.

[0147] Fragrance Non-limiting examples of fragrances and fragrance components include, but are not limited to, aldehydes, ketones, esters, etc. Other examples include various natural extracts and natural extracts, which can include complex mixtures of components such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam extract, frankincense oil, pine oil, cedar, etc. The finished fragrance can include very complex mixtures of such components. The finished fragrance can be included at a concentration in the range of about 0.01% to about 2% by weight of the detergent composition.

[0148] Dye transfer inhibitor Dye transfer inhibitors are effective in inhibiting the transfer of dyes from one fabric to another during the washing process. Generally, such dye transfer inhibitors can include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. When used, these agents can be used at a concentration of about 0.0001% to about 10% by weight of the composition, in some examples about 0.01% to about 5% by weight of the composition, and in other examples about 0.05% to about 2% by weight of the composition.

[0149] Chelating agent Suitable chelating agents include copper, iron, and / or manganese chelating agents, and mixtures thereof. Such chelating agents can be selected from the group consisting of phosphonates, aminocarboxylates, aminophosphonates, succinates, polyfunctionally substituted aromatic chelating agents, 2-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethyl inulin, and mixtures thereof. The chelating agent can exist in the acid form, or in the form of salts, including alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof. Other chelating agents suitable for use herein are commercially available DEQUEST series, as well as chelating agents manufactured by Monsanto, Akzo-Nobel, DuPont, Dow, BASF's Trilon® series, and Nalco.

[0150] Antifoaming agent Compounds for reducing or suppressing foam formation may be incorporated into water-soluble unit-dose articles. Antifoaming properties may be particularly important in so-called "high-concentration washing processes" and in front-loading washing machines. Examples of antifoaming agents include monocarboxylic fatty acids and soluble salts thereof, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C 18 ~C 40 ketones (e.g., stearone), N-alkylated aminotriazines, preferably waxy hydrocarbons having a melting point of less than about 100°C, silicone antifoaming agents, and secondary alcohols.

[0151] Further suitable defoaming agents are those derived from phenylpropylmethyl-substituted polysiloxanes.

[0152] The detergent composition may include an antifoaming agent selected from organomodified silicone polymers with aryl or alkylaryl substituents combined with a primary filler that is a silicone resin and modified silica. The detergent composition may contain from about 0.001 wt% to about 4.0 wt% of such an antifoaming agent of the composition.

[0153] The detergent composition contains an antifoaming agent selected from a) a mixture of about 80 to about 92% ethylmethyl, methyl(2-phenylpropyl)siloxane; about 5 to about 14% MQ resin in octyl stearate, and about 3 to about 7% modified silica; b) a mixture of about 78 to about 92% ethylmethyl, methyl(2-phenylpropyl)siloxane; about 3 to about 10% MQ resin in octyl stearate; about 4 to about 12% modified silica; or c) a mixture thereof, the percentages being based on the weight of the antifoaming agent.

[0154] Foam booster When high foaming is desired, C 10 ~C 16 A foam booster such as alkanolamide may be used. Some examples include C 10 ~C 14 monoethanol and diethanolamide. If desired, water-soluble magnesium and / or calcium salts such as MgCl2, MgSO4, CaCl2, CaSO4 can be added at a concentration of about 0.1 wt% to about 2 wt% of the detergent composition to provide additional foam and enhance the fat removal performance.

[0155] Conditioning agent Suitable conditioning agents include high melting point aliphatic compounds. High melting point aliphatic compounds useful herein have a melting point of 25°C or higher and are selected from the group consisting of aliphatic alcohols, fatty acids, aliphatic alcohol derivatives, fatty acid derivatives, and mixtures thereof. Suitable conditioning agents also include nonionic polymers and conditioning oils, such as hydrocarbon oils, polyolefins, and fatty acid esters.

[0156] Suitable conditioning agents generally include silicones (e.g., silicone oils, polyols, cationic silicones, silicone gums, high refractive index silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty acid esters), or conditioning agents characterized by combinations thereof, or conditioning agents that form liquid dispersed particles in the aqueous surfactant matrix herein by other means.

[0157] Fabric strengthening polymer Suitable fabric strengthening polymers are typically cationically charged and / or have a high molecular weight. The fabric strengthening polymer may be a homopolymer or may be formed from two or more types of monomers. The monomer weight of the polymer generally ranges from 5,000 to 10,000,000, typically at least 10,000, preferably 100,000 to 2,000,000. Preferred fabric strengthening polymers have a cationic charge density of at least about 0.2 meq / gm, preferably at least 0.25 meq / gm, more preferably at least 0.3 meq / gm at the pH of the intended use of the composition (this pH generally ranges from pH 3 to pH 9, preferably pH 4 to pH 8), but also preferably less than 5 meq / gm, more preferably less than 3 meq / gm, most preferably less than 2 meq / gm. The fabric strengthening polymer may be of natural origin or of synthetic origin.

[0158] Pearlescent agent Non-limiting examples of pearlescent agents include the following: mica, mica coated with titanium dioxide, bismuth oxychloride, fish scales, monoesters and diesters of alkylene glycols. The pearlescent agent may be ethylene glycol distearate (EGDS).

[0159] Hygiene and malodor Suitable hygiene and malodor active agents include zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac®, polyethyleneimine (such as Lupasol® manufactured by BASF) and its zinc complexes, silver and silver compounds, especially, Ag + Or those designed to slowly release a silver nano-dispersion.

[0160] Buffer system The water-soluble unit-dose articles described herein can be formulated to have a pH of the wash water of about 7.0 to about 12, in some examples about 7.0 to about 11, while being used in an aqueous cleaning operation. Techniques for controlling the pH at the recommended use concentration include the use of buffers, alkalis, or acids, which are known to those skilled in the art. These techniques include the use of sodium carbonate, citric acid or sodium citrate, lactic acid or lactate, monoethanolamine or other amines, boric acid or borate, and other pH-adjusting compounds known in the art, but are not limited thereto.

[0161] The detergent compositions herein may include a dynamic in-wash pH profile. In such detergent compositions, (i) the pH of the wash liquor exceeds 10 after about 3 minutes of contact with water, (ii) the pH of the wash liquor is less than 9.5 after about 10 minutes of contact with water, (iii) the pH of the wash liquor is less than 9.0 after about 20 minutes of contact with water, and (iv) optionally, wax-coated citric acid particles may be used together with other pH control agents such that the equilibrium pH of the wash liquor is in the range of about 7.0 to about 8.5.

[0162] Production method As illustrated in FIG. 3, a solution of the filament-forming composition 35 is provided. The filament-forming composition may include one or more filament-forming materials and, optionally, one or more active agents. The filament-forming composition 35 passes through one or more die block assemblies 40 including a plurality of spinnerets 45 to form a plurality of fiber elements 30 including one or more filament-forming materials and, optionally, one or more active agents. Using the plurality of die block assemblies 40, different layers of the fiber elements 30 can be spun, and the fiber elements 30 of different layers may have different compositions from each other or be the same as each other. To form three, four, or any other integer number of layers at a given ply, more than two die block assemblies connected in series can be provided. The fiber elements 30 can be deposited on a belt 50 moving in the machine direction MD to form a first ply 10.

[0163] Particles can be introduced into the flow of the fiber elements 30 between the die block assembly 40 and the belt 50. The particles can be supplied from a particle receiver to a belt feeder 41 or, optionally, a screw feeder. The belt feeder 41 can be set and controlled to deliver a desired particle mass to the process. The belt feeder can supply an air knife 42 that suspends and directs the particles in an air stream into the fiber elements 30 to form a particle-fiber layer in which the fiber elements 30 and the particles deposited on the belt 50 are mixed.

[0164] A first ply 10 can be provided to form a water-soluble product. A second ply 15 can be provided separately from the first ply 10. The first ply 10 and the second ply 15 can be superimposed on each other. By superimposed is meant that one is placed on top of or under the other, provided that an additional ply or other material, such as an active agent, may be disposed between the superimposed plies. A part of the first ply 10 can be joined to a part of the second ply 15 to form a water-soluble product 5. Each ply may include one or more layers.

[0165] particle-fiber layer The particle-fiber layer can be arranged in several ways. Clusters of particles can be distributed within pockets distributed within the layer, such pockets can be formed between layers of fiber elements, and the contact network and porosity within each cluster of particles are governed by the physics of conventional particle packing, but the clusters are substantially extended within the layer. The particles may be distributed relatively homogeneously throughout the fibrous structure, substantially without local particle clusters, the packing is substantially extended at the scale of the individual particles, there is less particle-to-particle contact, and the inter-particle pores are larger. Without being bound by theory, a water-soluble unit-dose article comprising a layer containing fiber elements and particles, when an adhesive surfactant such as AES is sequestered in the particles having an extended structure, is thought to improve the dispersion and dissolution of the unit-dose article by both the rapid water absorption into the extended structure of the water and the reduction of contact between the particles having the adhesive surfactant.

[0166] Washing method The present invention also encompasses a washing method of using an article according to the present invention, the washing method comprising the steps of putting at least one article according to the present invention into a washing machine together with the laundry to be washed, and performing a washing or cleaning operation.

[0167] Any suitable washing machine can be used.

[0168] One skilled in the art will recognize the machinery suitable for the relevant washing operations. The articles of the present invention can be used together with other compositions such as fabric additives, fabric softeners, and rinse aids.

[0169] The washing temperature can be, for example, 30 °C or lower. The washing process can include at least one washing cycle having a duration of 5 to 20 minutes. An automatic washing machine can include a rotating drum, and during at least one washing cycle, the drum has a rotational speed of 15 to 40 rpm, preferably 20 to 35 rpm.

[0170] A water-soluble single-dose article comprising a water-soluble fiber structure and one or more rheology-modifying particles distributed throughout the structure can remove one or more types of stains, such as, for example, butter, beef, grass, tea, spaghetti, sebum, wine, and any other type of stain that can be imparted to a fabric.

[0171] Surprisingly, a water-soluble single-dose article comprising a water-soluble fiber structure and one or more rheology-modifying particles distributed throughout the structure has been found to exhibit sebum stain removal properties that are unique to other types of single-dose articles, such as, for example, single-dose articles constructed of water-soluble films. As shown in the table below, when compared to a single-dose containing a liquid, a single dose of the water-soluble fiber structure has a significantly higher ability to remove artificial sebum stains, but the overall enzyme content of the single-dose does not increase.

[0172] The following samples were prepared according to the following compositions in Table 1.

[0173]

Table 1

[0174] A dyed fabric sample was prepared. Before the washing test, the visibility of the test stains was measured using a colorimeter. Each stain was measured individually. These starting values were recorded, and the percentage of removal of each individual test stain after washing was calculated. The dyed fabric (2 pieces per stain / cycle) and a 2.5 kg mixed ballast load (cotton and polycotton) were washed in formulations A&B enclosed in a PVA film (multi-compartment) (Kenmore washing machine, normal / regular cycle, 32 °C, water hardness: 1.5 mmol / L). After the washing cycle, the dyed fabric was dried in a tumble dryer. This washing process was repeated 4 times using a new stain each time, for a total of 8 pieces / stain. Within 24 hours after the washing test, the visibility of the remaining stains on the fabric was measured.

[0175] The percentage of stain removal index for each stain was calculated using the following formula. %SRI = (color 新しい染み - color 洗浄後の染み ) / (color 新しい染み ) × 100% To calculate the difference in stain removal between A, B, and C, %SRI C - %SRI A and %SRI C - %SRI B were calculated. A positive value indicates that the stain removal performance of C is better.

[0176]

Table 2

[0177] Sample A represents a single unit dose article constructed of a water-soluble film with a preferred enzyme package, which is a Tide Pod. Sample B represents a single dose of a fibrous structure without a preferred enzyme package. Sample C represents a single dose of a fibrous structure with a preferred enzyme package. As shown in the above table, the single unit dose of the fibrous structure with a preferred enzyme package (Sample C) demonstrated significantly better performance than the single unit dose article constructed of a water-soluble film with a preferred enzyme package (Sample A) for stains of Black Todd Clay, grass, Lipton tea, sebum, and sebum dust. When compared with Sample B, Sample C demonstrated significantly better performance for sebum stains. The preferred enzyme package may be a combination of V42CWP, FN3, V445XWA, Termamyl Ultra, and mannanase.

[0178] As shown in the above table, the composition according to the present invention provided better stain removal of sebum stains, even though the total weight of the enzymes used in Sample C was 11.3% less than that in Sample A. Without being bound by theory, it is considered that a single dose of a fibrous structure can increase the alkalinity of the washing solution (Samples B and C). The resulting washing solution can reach a pH of 8 or higher, such as 8 - 14, 9 - 12, 9 - 11, or 10 - 12. At a pH above 8, the above enzymes can show increased effectiveness against sebum stains, and as a result, it is considered that stain removal increases by 20 - 30% as indicated by the Stain Removal Index (SRI). Specifically, as shown in the above table, Sample C showed an increase in SRI for the removal of artificial sebum compared to the other samples and the unit dose article constructed of a water-soluble film with the same mg / g enzyme concentration (Sample A).

[0179] Test Method Basis Weight Test Method Using an upper pan chemical balance with a sensitivity limit of ±0.001 g, stack 12 usable units and measure the basis weight of the fibrous structure. Use a wind guard to protect the balance from air currents and other disturbances. Prepare all samples using a precision cutting die measured to be 3.500 inches ±0.0035 inches × 3.500 inches ±0.0035 inches.

[0180] Using a precision cutting mold, cut the samples into squares. Gather the cut squares and stack them to the thickness of 12 samples. Measure the mass of the stacked samples and record the results in 0.001 g increments.

[0181] As follows, lbs / 3000ft 2 or g / m 2 Calculate the basis weight. Basis weight = (mass of stacked samples) / [(area of one square in the stacked samples) × (number of squares in the stacked samples)] For example, Basis weight (lbs / 3000ft 2 ) = [(mass of stacked samples (g) / 453.6 (g / lbs)] / [12.25 (in 2 ) / 144 (in 2 / ft 2 ) × 12]] × 3000 or, Basis weight (g / m 2 ) = mass of stacked samples (g) / [79.032 (cm 2 ) / 10,000 (cm 2 / m 2 ) × 12]

[0182] Report the results in 0.1 lbs / 3000ft 2 or 0.1 g / m 2 units. The sample dimensions may be changed or varied using a precision cutter similar to the above so that the area of the stacked samples is at least 100 square inches.

[0183] Thickness test method Five samples are cut from the fibrous structure sample such that each cut sample is larger in size than the load foot mounting surface of a VIR Electronic Thickness Tester Model II (available from Thwing-Albert Instrument Company, Philadelphia, PA). The thickness of the fibrous structure is measured by fixing the sample between a horizontal plane and the load foot mounting surface. Typically, the load foot mounting surface has a circular surface area of about 3.14 in 2 . The sample is fixed between a horizontal plane and the load foot mounting surface. The load foot mounting surface applies a restraint pressure of 15.5 g / cm 2 to the sample. The thickness of each sample is the gap that occurs between the plane and the load foot mounting surface. The thickness is calculated as the average thickness of the five samples. The results are reported in millimeters (mm).

[0184] Particle Size Distribution Test Method A particle size distribution test is performed to determine the characteristic size of the particles. This is carried out using ASTM D 502-89, "Standard Test Method for Particle Size of Soaps and Other Detergents," approved on May 26, 1989, along with additional specifications for the sieve sizes and sieve times used in the analysis. In accordance with Chapter 7, "Procedure using machine-sieving method," clean, dry nested sieves including U.S. Standard (ASTM E 11) sieves #4 (4.75 mm), #6 (3.35 mm), #8 (2.36 mm), #12 (1.7 mm), #16 (1.18 mm), #20 (850 um), #30 (600 um), #40 (425 um), #50 (300 um), #70 (212 um), #100 (150 um) are required to cover the range of particle sizes referred to herein. The specified mechanical sieving method is used with the above nested sieves. A suitable sieve shaker can be obtained from the W.S.Tyler Company (Ohio, U.S.A.). The sieve shaking test sample is approximately 100 grams and is shaken for 5 minutes.

[0185] Plot the micrometer-sized openings of each sieve against a logarithmic horizontal axis and plot the cumulative mass percentage (Q3) against a linear vertical axis. Plot the data on a semi-logarithmic plot. An example of this data representation is shown in Figure A.4 of ISO 92761:1998, "Representation of results of particle size analysis - Part 1: Graphical Representation". The characteristic particle size (Dx) is defined, for the purposes of this invention, as the horizontal axis value at the point where the cumulative mass percentage is equal to x percent, and is calculated by linear interpolation between the data points immediately above (a) and below (b) the x% value using the following equation. Dx = 10^[Log(Da) - (Log(Da) - Log(Db)) × (Qa - x%) / (Qa - Qb)] (where Log is the logarithm to the base 10, Qa and Qb are the cumulative mass percentages of the measured data immediately above and below the x percentile respectively, and Da and Db are the micrometer sieve size values corresponding to these data.)

[0186] Example data and calculations:

[0187]

Table 3

[0188] For D10 (x = 10%), the micron sieve size (Da) where the CMPF is immediately above 10% is 300 μm, and the screen (Db) immediately below is 212 μm. The cumulative mass (Qa) immediately above 10% is 15.2%, and immediately below (Qb) is 6.8%. D10 = 10^[Log(300) - (Log(300) - Log(212)) × (15.2% - 10%) / (15.2% - 6.8%)] = 242um

[0189] When D50 (x = 50%), the micron screen size (Da) where CMPF is directly above 50% is 1180 μm, and the screen (Db) directly below is 850 μm. The cumulative mass (Qa) directly above 90% is 99.3%, and the one directly below (Qb) is 89.0%. D50 = 10^[Log(600) - (Log(600) - Log(425)) × (60.3% - 50%) / (60.3% - 32.4%)] = 528 um

[0190] When D90 (x = 90%), the micron screen size (Da) where CMPF is directly above 90% is 600 μm, and the screen (Db) directly below is 425 μm. The cumulative mass (Qa) directly above 50% is 60.3%, and the one directly below (Qb) is 32.4%. D90 = 10^[Log(1180) - (Log(1180) - Log(850)) × (99.3% - 90%) / (99.3% - 89.0%)] = 878 um

[0191] Diameter test method Using a scanning electron microscope (SEM) or an optical microscope, and image analysis software, the diameter of discrete fiber elements or fiber elements within a fiber structure is determined. A magnification of 200 to 10,000 times is selected so that the fiber elements are appropriately magnified for measurement. When using an SEM, the sample is sputter-coated with gold or a palladium compound to avoid charging and vibration of the fiber elements in the electron beam. To measure the diameter of the fiber elements from the image (on the monitor screen) obtained using an SEM or an optical microscope, a manual procedure is used. Using a mouse and cursor tools, the edge of a randomly selected fiber element is located, and then the measurement is made across its width (i.e., perpendicular to the direction of the fiber element at that point) to the other edge of the fiber element. A calibrated image analysis tool with a scale provides a scale for obtaining the actual reading in μm units. For the fiber elements within a fiber structure, using an SEM or an optical microscope, several fiber elements are randomly selected from the entire sample of the fiber structure. At least two portions of the fiber structure are cut out and tested in this way. For statistical analysis, such measurements are performed at least 100 times in total, and then all the data are recorded. Using the recorded data, the average value (mean) of the diameter of the fiber elements, the standard deviation of the diameter of the fiber elements, and the median value of the diameter of the fiber elements are calculated.

[0192] Another useful statistic is the calculation of the amount of the set of fiber elements that are smaller than a specific upper limit. To determine this statistic, the software is programmed to count how many of the results of the diameter of the fiber elements are smaller than the upper limit, and that count (divided by the total number of data and multiplied by 100%) is recorded as a percentage as the percentage of those smaller than the upper limit (e.g., the percentage of those with a diameter less than 1 micrometer or the sub-micron percentage). The inventors represent the diameter (in μm) measured for an individual circular fiber element as di.

[0193] When the fiber element has a non-circular cross-section, the measured value of the diameter of the fiber element is determined as the hydraulic diameter and is set to be equal to the hydraulic diameter. The hydraulic diameter is obtained by multiplying the cross-sectional area of the fiber element by 4 and dividing it by the perimeter of the cross-section of the fiber element (the outer perimeter in the case of a hollow fiber element). The number-average diameter, or the average diameter, is calculated as follows:

[0194]

Number

[0195] Micro-CT method for QB02625 Using a micro-CT X-ray scanning device capable of acquiring a dataset with an isotropic spatial resolution of 7 μm, image the sample to be tested. An example of a suitable device is the SCANCO system model 50 micro-CT scanner (Scanco Medical AG, Bruttisellen, Switzerland) operating with the following settings: energy level: 45 kVp at 133 μA; projections: 3000; field of view: 35 mm; integration time: 750 ms; 4 times averaging; and voxel size: 7 μm.

[0196] Prepare the test sample to be analyzed by cutting a line from one sealed edge to the other end to form a triangle with a tip where the two complete sealed edges meet and a drop of about 20 mm. The resulting cut surface is about 28 mm in length. Stack the prepared samples alternately flat between the rings of the low-attenuation sample preparation mounting foam and place them in a plastic cylindrical tube with a diameter of 35 mm for scanning. Acquire the scan of the samples so that the entire volume of all the mounted cut samples is included in the dataset.

[0197] To reliably and repeatedly measure the volume percentages of fibers, particles, and void space within a sample, a small subvolume of the sample is extracted from a cross-section of the product that creates 3D slab data that can qualitatively evaluate the particles, fibers, and void space. A mask is created that encompasses this volume of data. The mask must not contain void elements outside of the product that would bias the void volume measurement. Further, the region of the product selected for analysis is based on a fixed distance from a physical landmark on the product.

[0198] To divide the interior of the volume into three regions: 1) particles, 2) fibers, and 3) void space, an automatic thresholding algorithm that optimally separates these three regions is utilized. Since particles are denser than fibers, an additional step of slight dilation of the segmented particles should also be performed. This allows for consideration of the expected partial volume average at the surface of the particles. The dilated segmented particles can then have a calculated total volume. Next, a lower threshold is used to separate the fibers from the air. The fiber volume is the common intersection of voxels above the lower threshold and is not part of the particle region. Finally, the void volume is then obtained by subtracting the combined volume of the fibers and particles from the overall mask volume.

[0199] This one implementation is done through the use of two software platforms: Avizo 9.2.0 and Matlab R2016b (both run on a Windows 64bit workstation). In this case, data was collected from a Scanco mCT50 3D X-ray micro-CT scanner, collecting data at a resolution of 7 micrometer voxels. After scanning and image reconstruction were complete, the scanner created a 16-bit dataset called an ISQ file, where the gray levels reflect changes in X-ray attenuation and thus are related to material density. In this case, the ISQ is quite large, with dimensions of 5038×5038×1326.

[0200] Load the ISQ file into Avizo 9.2.0. Convert it to 8 bits using a scaling factor of 0.15. Select a subvolume that is diagonal to one corner offset by 11 mm. Select a slab with a thickness of 3.5 mm for analysis.

[0201] To apply a robust automatic thresholding scheme, load the cross-sectional slices from each of the three samples into Matlab R2016B. Then, use a function called "multithresh()" to divide the segments into N different regions (in this example, N = 2). This function is based on a well-known algorithm called "Otsu's method" that provides optimal segmentation based on the distribution of the image histogram. Then, the average value of these thresholds for the three samples was selected. In this example, the threshold for separating particles from fibers was 124, and the threshold for separating fibers from air was 48. A further dilation using a spherical structuring element of radius 1 was used in the segmented particle data to compensate for partial volume averaging. Then, the histogram function in Avizo enables the calculation of the total volume related to the fiber, particle, and total mask volume. Then, the void volume is obtained by subtracting the fiber and particle volumes from the total mask volume. These results may then be transferred to Excel for further analysis or visualization.

[0202] Washing Residue Test Method The washing residue test qualitatively measures the detergent residue on the fabric. Each test includes four comparative product samples, and each product sample is repeated four times. For the test, a Whirlpool Duet washing machine (model number WFW 9200 SQO2) connected to a water temperature control system set at 50°F + / - 1°F is used.

[0203] The black billiard port is supplied by Equest U.K. (phone number (01207) 529920). 1. Material supply source: Denholme Velvets, Halifax Road, Denholme, Bradford, West Yorkshire, England BD13 4EZ (phone number (01274) 832646). 2. Type of material: 150 cm C.R. Cotton Pile Velvet, quality 8897, black, 72% cotton, 28% modal. 3. Equest sewing instructions: Cut out a 23.5 cm × 47 cm rectangle of black broadcloth. Fold the rectangle of black broadcloth to form a square with the broadcloth on the inside. Use an overlock stitch to sew the square along two sides, leaving one open edge. Sew a blank identification label (3 × 3 cm flat cotton) on one side.

[0204] Test preparation: 1. Turn the pouch inside out at one open edge so that the broadcloth is on the outside. 2. Write the product code and internal / external replication on the identification label in magic ink. 3. Place the recommended dosage of the water-soluble unit-dose product for normal / moderate soil and normal / moderate water hardness in the right rear corner of the black broadcloth pouch. 4. Fold the open end of the black pouch at a 2 cm seam and sew it closed at the center of the 2 cm-wide seam along the full length of the opening. 5. Repeat these steps so that there are a total of 4 replications per test product. 6. Place the black pouch in the washing machine and wash as follows.

[0205] Washing of the black pouch: Place 4 black broadcloth pouches on top of each other, alternating them so that all the water-soluble unit-dose products are adjacent to each other as shown in Figure 6. Place the arranged pouches at the back of the drum.

[0206] Turn on the washing machine, set it to the delicate wash program, use mixed water at 50°F + / - 1°F (via the water temperature control system) and a hardness of 6 gpg, and do not add any additional ballast load. Run the entire wash cycle in the washing machine. At the end of the wash cycle, remove the pouch from the washing machine and open it along three sides (all except the folded side) making sure not to spill any residue at all.

[0207] Grade the pouch immediately after opening. Record the grades of two independent scorers. Analyze the data as a Latin square design, incorporating the washing machine and product position into the statistical model. Construct least squares means and 95% confidence upper limit intervals. A water-soluble unit dose product is considered to have passed the test if the upper 95% one-sided confidence limit around the mean scale unit is less than 1.

[0208] Grade by visual observation of the residue remaining in / on the bag after washing. Grade the black pouch according to the following qualitative scale: 0 = No residue 0.5 = Very small spots with a maximum diameter of 1 cm 1 = Up to three small diffused spots each with a maximum diameter of 2 cm, the spots are flat (i.e., film-like) and translucent. 2 = More than three small diffused spots each with a diameter of 2 cm, the entire black pouch is covered with a flat translucent residue up to the maximum. 2.5 = Small opaque residue (i.e., gel-like) with a diameter of less than 1 cm. 3 = Opaque residue (e.g., gel-like) with a diameter of 1 cm - 2 cm. 4 = Opaque residue (e.g., gel-like) with a diameter of 3 cm - 4 cm. 5 = Thick gel-like residue with a diameter of 4 - 6 cm. 6 = Thick gel-like residue with a diameter > 6 cm. 7 = The product does not substantially dissolve and the residue is soft and gel-like. 8 = The product does not substantially dissolve and the residue is hard and elastic (feel like silicone), grade 8 is special as it may indicate that the product was contaminated.

Example

[0209] 1. A water-soluble unit-dose article comprising a water-soluble fiber structure containing a base pH adjuster and at least one protease enzyme. 2. The water-soluble unit-dose article according to paragraph A, wherein the at least one protease has an isoelectric point of about 6.5 to about 11.5. 3. The water-soluble unit-dose article according to paragraph B, wherein the at least one protease has an isoelectric effect of about 9 to 10. 4. The water-soluble unit-dose article according to any one of paragraphs A to C, wherein the base pH adjuster is selected from the group consisting of sulfate ion, dihydrogen phosphate ion, fluoride ion, nitrite ion, acetate ion, bicarbonate ion, hydrogen sulfide ion, ammonia, carbonate ion, hydroxide ion, and combinations thereof. 5. The water-soluble unit-dose article according to any one of paragraphs A to D, wherein the base pH adjuster contains hydroxide ion. 6. The water-soluble unit-dose article according to any one of paragraphs A to E, wherein the one or more protease enzymes are selected from the group consisting of metalloprotease, neutral protease, alkaline protease, serine protease, and combinations thereof. 7. The water-soluble unit-dose article according to paragraph F, wherein the protease is of animal, plant, or microbial origin. 8. The water-soluble unit-dose according to any one of paragraphs A to G, wherein the protease is a genetically modified variant of metalloprotease or serine protease. 9. The water-soluble unit-dose article according to any one of paragraphs A to H, wherein the water-soluble unit-dose further comprises one or more non-protease enzymes, and the one or more non-protease enzymes are selected from the group consisting of lipase, amylase, cellulase, xyloglucanase, and combinations thereof. 10. The water-soluble unit-dose article according to any one of paragraphs A to I, wherein the water-soluble unit-dose contains about 10 wt% to about 80% of an alkyl alkoxylated sulfate. 11. Each fiber element contains, based on the dry fiber element, about 10% to about 90% by weight of an active agent selected from the group consisting of a surfactant, builder, polymer dispersant, enzyme, enzyme stabilizer, bleaching system, brightening agent, hue agent, chelating agent, antifoaming agent, conditioning agent, humectant, fragrance, fragrance microcapsule, filler or carrier, alkaline system, pH control system, buffer, alkanolamine, mosquito repellent, and mixtures thereof, preferably a surfactant, the water-soluble unit dose article described in paragraph J. 12. The alkyl alkoxylated sulfate surfactant is preferably an alkyl ethoxylated surfactant having an average degree of ethoxylation of about 1 to about 3.5, more preferably about 1 to about 3, and even more preferably about 1 to about 2, the water-soluble unit dose article described in any one of paragraphs I - J. 13. The alkyl alkoxylated sulfate has an average alkyl chain length of about 10 to about 16 carbon atoms, preferably about 12 to about 15 carbon atoms, and even more preferably about 14 to about 15 carbon atoms, the water-soluble unit dose article described in any one of paragraphs I - L. 14. The alkyl alkoxylated sulfate is an ethoxylated C12 - C18 alkyl sulfate having an average degree of ethoxylation of about 0.5 to about 3.0, the water-soluble unit dose article described in any one of paragraphs I - M. 15. The one or more protease enzymes and the one or more other enzymes are incorporated into the article as granules, spray into a slurry, or a combination thereof, the water-soluble unit dose article described in any one of paragraphs A - N.

[0210] (Example 1) As shown in FIG. 3, a first layer of fiber elements is spun using a first spinning beam and collected on a forming belt. The forming belt having the first layer of fibers is then passed under a second spinning beam modified with a particle addition system. The particle addition system can substantially inject particles from the second spinning beam toward a landing zone on the forming belt directly below the fiber elements. A suitable particle addition system can be assembled from a particle feeder such as a vibratory, belt or screw feeder, and an injection system such as an air knife or other fluidization conveying system. To assist in a consistent distribution of particles in the cross - direction, preferably, the particles are supplied over a width substantially the same as the spinneret die to ensure that the particles are delivered across the full width of the composite structure. Preferably, the particle feeder is completely enclosed except for the outlet to minimize breakage of the particle feed material. By the co - collision of the particles and the fiber elements on the forming belt under the second spinning beam, particle packing is extended and a composite structure is created in which the fibers substantially penetrate the inter - particle pores.

[0211] Table 3 below lists non - limiting examples of the dried fiber compositions of the present invention used to make the fiber elements. To make the fiber elements, an aqueous solution preferably having a solids content of about 45% - 60% is processed through one or more spinning beams as shown in FIG. 3. Suitable spinning beams include a capillary die having an elongating air flow and a drying air flow suitable for substantially drying the elongated fibers before they collide on the forming belt.

[0212]

Table 4

[0213] Table 4 below lists non - limiting examples of the particle compositions of the present invention. The particles can be made by a variety of suitable processes including grinding, spray drying, agglomeration, extrusion, granulation, encapsulation, tableting, and any combination thereof. One or more particles may be mixed together prior to addition.

[0214]

Table 5

[0215] The resulting products are illustrated in Table 5, and using the undiluted chassis composition for the products, details of the structure of the product chassis by the fiber and particle components (from Tables 3 and 4 respectively) are provided. Note that other product auxiliary materials such as fragrances, enzymes, antifoaming agents, bleaching agents, etc. may be added to the chassis.

[0216] The cleaning residue test grades for each chassis are shown. The chassis exemplify various detergent products having a significant proportion of ethoxylated anionic surfactant (AES).

[0217]

Table 6

[0218] Raw materials of Example 1 LAS is a linear alkylbenzene sulfonate having an average aliphatic carbon chain length C 11 ~C 12 supplied by Stepan (Northfield, Illinois, USA) or Huntsman Corp. HLAS is in acid form.

[0219] AES is C 12~14 alkyl ethoxy(3)sulfate, C 14~15 alkyl ethoxy(2.5)sulfate, or C 12~15 alkyl ethoxy(1.8)sulfate supplied by Stepan (Northfield, Illinois, USA) or Shell Chemicals (Houston, TX, USA).

[0220] AS is C 12~14 sulfate and / or medium-chain branched alkyl sulfate supplied by Stepan (Northfield, Illinois, USA).

[0221] The dispersant polymer (Disp. polymer) has a molecular weight of 70,000 and an acrylate:maleate ratio of 70:30, and is supplied by BASF (Ludwigshafen, Germany).

[0222] The PEG-PVAc polymer is a polyvinyl acetate-grafted polyethylene oxide copolymer having a polyethylene oxide backbone chain and a plurality of polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone chain is about 6000, the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 - 60, and there is 1 or less grafting point per 50 ethylene oxide units. It is available from BASF (Ludwigshafen, Germany).

[0223] Ethoxylated polyethyleneimine (PE20) is a polyethyleneimine core with a molecular weight of 600 g / mol and having 20 ethoxylate groups per -NH, and is available from BASF (Ludwigshafen, Germany).

[0224] The dimensions and values disclosed herein should not be understood to be strictly limited to the exact numerical values recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and the functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0225] For clarity purposes, the total "weight %" values do not exceed 100 weight %.

[0226] All documents cited in this specification, including any documents incorporated by reference, related patents or applications, are hereby incorporated by reference in their entirety, unless expressly excluded or otherwise limited. The citation of any document shall not be construed as an admission that such document is prior art with respect to any invention disclosed or claimed in this specification, nor shall it be construed as teaching, suggesting or disclosing any such invention, either alone or in combination with any other reference(s). Further, if any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition given to the term in this document shall apply.

[0227] Although specific embodiments and / or forms of the invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended that all such changes and modifications within the scope of the invention be covered by the appended claims.

Claims

**Claim 1** A water-soluble unit-dose article comprising a water-soluble fiber structure containing a base pH adjuster and at least one protease enzyme, The water-soluble unit-dose article further comprises a rheology-modifying particle comprising a rheology modifier selected from the group consisting of an alkyl alkoxylated sulfate, an alkoxylated amine, an ethylene oxide-propylene oxide-ethylene oxide (EOx １ POyEOx ２ ) triblock copolymer (wherein each of x １ and x ２ is in the range of 2 to 140 and y is in the range of 15 to 70) and mixtures thereof). **Claim 2** The water-soluble unit-dose article according to claim 1, wherein the at least one protease enzyme has an isoelectric point of 6.5 to 11.

5. **Claim 3** The water-soluble unit-dose article according to claim 1 or 2, wherein the at least one protease enzyme has an isoelectric effect of 9 to 10. **Claim 4** The water-soluble unit-dose article according to any one of claims 1 to 3, wherein the base pH adjuster is selected from the group consisting of sulfate ion, dihydrogen phosphate ion, fluoride ion, nitrite ion, acetate ion, hydrogen carbonate ion, hydrogen sulfide ion, ammonia, carbonate ion, hydroxide ion, and combinations thereof. **Claim 5** The water-soluble unit-dose article according to any one of claims 1 to 4, wherein the base pH adjuster contains hydroxide ion. **Claim 6** The water-soluble unit-dose article according to any one of claims 1 to 5, wherein the at least one protease enzyme is selected from the group consisting of metalloprotease, neutral protease, alkaline protease, serine protease, and combinations thereof. **Claim 7** The water-soluble unit-dose article according to any one of claims 1 to 6, wherein the at least one protease enzyme is of animal, plant, or microbial origin. **Claim 8** The water-soluble unit-dose according to any one of claims 1 to 7, wherein the at least one protease enzyme is a genetically modified variant of metalloprotease or serine protease. **Claim 9** The water-soluble unit-dose article according to any one of claims 1 to 8, wherein the water-soluble unit-dose article further comprises one or more non-protease enzymes, and the one or more non-protease enzymes are selected from the group consisting of lipase, amylase, cellulase, xyloglucanase, and combinations thereof. **Claim 10** The water-soluble unit-dose article according to any one of claims 1 to 9, wherein the rheology-modifying particles contain 10% to 80% by weight of the alkyl alkoxylated sulfate and 0.5% to 20% by weight of the rheology modifier. **Claim 11** Each fiber element contains an active agent selected from the group consisting of a surfactant, a builder, a polymer dispersant, an enzyme, an enzyme stabilizer, a bleaching system, a brightening agent, a hue agent, a chelating agent, an antifoaming agent, a conditioning agent, a humectant, a fragrance, a fragrance microcapsule, a filler or carrier, an alkaline system, a pH control system, a buffer, an alkanolamine, a mosquito repellent, and mixtures thereof, in an amount of 10% to 90% by weight based on the dry fiber element. The water-soluble unit dose article according to any one of claims 1 to 10.

12. The water-soluble unit dose article according to any one of claims 1 to 11, wherein the alkyl alkoxylated sulfate has an average ethoxylation degree of 1 to 3.

5.

13. The water-soluble unit dose article according to any one of claims 1 to 12, wherein the alkyl alkoxylated sulfate has an average alkyl chain length of 10 to 16 carbon atoms.

14. The water-soluble unit dose article according to any one of claims 1 to 11, wherein the alkyl alkoxylated sulfate is an ethoxylated C12 - C18 alkyl sulfate having an average ethoxylation degree of 0.5 to 3.

0.

15. The water-soluble unit dose article according to any one of claims 1 to 14, wherein the at least one protease enzyme and one or more other enzymes are incorporated into the article as granules, spray into a slurry, or a combination thereof.

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