JP7149035B2 - Water-soluble unit dose article comprising water-soluble fibrous structures and particles - Google Patents

Description

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

Water-soluble unit dose articles are desired by consumers because they provide a convenient, efficient, and clean method of dispensing fabric or hard surface treatment compositions. Water soluble unit dose articles avoid overdosing or underdosing by providing a metered dose of treatment composition. There is an increasing consumer interest in fibrous water-soluble unit dose articles. The technology associated with such articles continues to evolve in terms of delivering the desired active agents along with articles that enable the consumer to perform the task desired.

Many consumers use washing machines that use less water than previous generations. Accordingly, there is a need for fibrous water-soluble unit dose articles that incorporate fibrous water-soluble unit doses that can be rapidly dissolved in limited amounts of fluids. By dissolving faster in a confined fluid, the cleaning agents can be released so that they are readily available. Surprisingly, as described herein, water-soluble unit dose articles comprising low-density particles with desirable densities and particle size distributions deliver similar amounts of surfactant while delivering similar amounts of surfactant to other compositions. It was found to exhibit an improved dissolution profile for products.

Described herein are water-soluble unit doses comprising water-soluble fibrous structures comprising particles having a linear alkylbenzene sulfonate to alkyl ethoxylated sulfate ratio of greater than 1.

1 schematically depicts a cross-sectional view of an example multi-ply fibrous structure; 1 is a micro CT scan image showing a cross-sectional view of an example water-soluble unit dose article. The process of making plies of material. 1 is a perspective view of one embodiment of a single dose laundry detergent unit embodying the novel design; FIG. Figure 5 is a front view of the single dose laundry detergent unit of Figure 4; Fig. 5 is a right side view of the single dose laundry detergent unit of Fig. 4; Figure 5 is a rear view of the single dose laundry detergent unit of Figure 4; Figure 5 is a left side view of the single dose laundry detergent unit of Figure 4; Figure 5 is a bottom view of the single dose laundry detergent unit of Figure 4; Figure 5 is a top view of the single dose laundry detergent unit of Figure 4; 1 is a perspective view of one embodiment of a single dose laundry detergent unit embodying the novel design; FIG. Figure 12 is a front view of the single dose laundry detergent unit of Figure 11; Figure 12 is a right side view of the single dose laundry detergent unit of Figure 11; Figure 12 is a rear view of the single dose laundry detergent unit of Figure 11; Figure 12 is a left side view of the single dose laundry detergent unit of Figure 11; Figure 12 is a bottom view of the single dose laundry detergent unit of Figure 11; Figure 12 is a top view of the single dose laundry detergent unit of Figure 11; 1 is a perspective view of one embodiment of a single dose laundry detergent unit embodying the novel design; FIG. Figure 19 is a front view of the single dose laundry detergent unit of Figure 18; Figure 19 is a right side view of the single dose laundry detergent unit of Figure 18; Figure 19 is a rear view of the single dose laundry detergent unit of Figure 18; Figure 19 is a left side view of the single dose laundry detergent unit of Figure 18; Figure 19 is a bottom view of the single dose laundry detergent unit of Figure 18; Figure 19 is a top view of the single dose laundry detergent unit of Figure 18; 1 is a perspective view of one embodiment of a single dose laundry detergent unit embodying the novel design; FIG. Figure 26 is a front view of the single dose laundry detergent unit of Figure 25; Figure 26 is a right side view of the single dose laundry detergent unit of Figure 25; Figure 26 is a rear view of the single dose laundry detergent unit of Figure 25; Figure 26 is a left side view of the single dose laundry detergent unit of Figure 25; Figure 26 is a bottom view of the single dose laundry detergent unit of Figure 25; Figure 26 is a top view of the single dose laundry detergent unit of Figure 25; 1 is a perspective view of one embodiment of a single dose laundry detergent unit embodying the novel design; FIG. Figure 33 is a front view of the single dose laundry detergent unit of Figure 32; Figure 33 is a right side view of the single dose laundry detergent unit of Figure 32; Figure 33 is a rear view of the single dose laundry detergent unit of Figure 32; Figure 33 is a left side view of the single dose laundry detergent unit of Figure 32; Figure 33 is a bottom view of the single dose laundry detergent unit of Figure 32; Figure 33 is a top view of the single dose laundry detergent unit of Figure 32; 1 is a perspective view of one embodiment of a lidless container embodying the new design; FIG. Figure 40 is a right side view of the container of Figure 39; Figure 40 is a rear view of the container of Figure 39; Figure 40 is a left side view of the container of Figure 39; Figure 40 is a front view of the container of Figure 39; Figure 40 is a top view of the container of Figure 39; Figure 40 is a bottom view of the container of Figure 39; 1 is a perspective view of one embodiment of a container having a lid embodying the new design; FIG. Figure 47 is a right side view of the container of Figure 46; Figure 47 is a rear view of the container of Figure 46; Figure 47 is a left side view of the container of Figure 46; Figure 47 is a front view of the container of Figure 46; Figure 47 is a top view of the container of Figure 46; Figure 47 is a bottom view of the container of Figure 46;

DEFINITIONS Characteristics and advantages of the present invention will become apparent from the following description, including examples that are intended to give a broad representation of the invention. Various modifications will become apparent to those skilled in the art from this description and practice of the invention. The scope is not intended to be limited to the particular forms disclosed, and the invention covers all modifications, equivalents, and equivalents included within the spirit and scope of the invention as defined by the claims. , and alternatives.

As used herein, articles including "the," "a," and "an" refer to one or more of what is claimed or described when used in a claim or specification. is understood to mean

As used herein, the terms “include,” “includes,” and “including” are intended to be non-limiting.

The terms “substantially free” or “substantially free,” as used herein, refer to the complete absence of that component or its most It means either to be in small quantities. A composition that is "substantially free" of an ingredient means that the composition contains about 0.5%, 0.25%, 0.1%, 0.05%, or 0.5%, by weight of the composition. It means that it contains less than 01%, or even 0% by weight of that component.

It should be understood that the term "comprising" also includes embodiments in which the term "comprising" means "consisting of" or "consisting essentially of."

As used herein, "sebum" means the oily secretion of the sebaceous glands and any artificial composition intended to mimic the oily secretions of the sebaceous glands. Representative sebum include artificial sebum described in EP 1482907, artificial sebum described in EP 0142830B1, artificial sebum according to D4265-14, and artificial sebum sold as CFT PCS-132. include but are not limited to: CFT PCS-132 is 18% free fatty acids, 32% beef tallow (stearic/oleic triglycerides), 4% fatty acid triglycerides, 12% hydrocarbon mixtures, 18% lanolin (waxy esters, C13-C24 ), 12% cucina (waxes and wax esters), and 4% cholesterol.

All cited patent documents and other documents, in relevant part, are incorporated by reference as if fully restated herein. Citation of any patent or other document is not an admission that the cited patent or other document is prior art to the present invention.

All concentrations and ratios herein are by weight of the composition, unless otherwise indicated.

Every maximum numerical limitation given throughout this specification will include every lower numerical limitation, as if such lower numerical limitations were expressly written herein. should understand. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. All numerical ranges given throughout this specification should include all narrower numerical ranges subsumed within such broader numerical ranges, as if such narrower numerical ranges were all expressly written herein. contains as if it were

Fibrous Water-Soluble Unit Dose Article As used herein, the phrases "water-soluble unit dose article,""water-soluble fibrous structure," and "water-soluble fiber element" refer to the unit dose article, fibrous structure, and It means that the fibrous elements are miscible with water. In other words, the unit dose article, fibrous structure, or fibrous element can form a homogeneous solution with water at ambient conditions. As used herein, "ambient conditions" means 23°C ± 1.0°C and 50% ± 2% relative humidity. Water-soluble unit dose articles may contain insoluble materials that are dispersible under aqueous washing conditions with a suspended average particle size of less than about 20 microns, or less than about 50 microns.

Fibrous water-soluble unit dose articles are disclosed in U.S. Patent Application No. 15/880,594 (filed Jan. 26, 2018), U.S. Patent Application No. 15/880,599 (2018), which is incorporated by reference in its entirety. filed Jan. 26, 2018), and US Patent Application No. 15/880,604 (filed Jan. 26, 2018).

These fibrous water-soluble unit dose articles can be washed under a variety of washing conditions, e.g. It is capable of dissolving under high pressure while delivering sufficient active agent to the intended consumer substrate (with performance similar to today's liquid products) to exert its intended effect. Additionally, the water-soluble unit dose articles described herein can be economically manufactured by spinning fibers containing the active agent. The water-soluble unit dose articles described herein also have improved cleaning performance.

The surface of the fibrous water-soluble unit dose article may include printed areas. The printed area may cover from about 10% to about 100% of the surface of the article. The printed areas may include inks, pigments, dyes, bluing agents, or mixtures thereof. The printed area can be opaque, translucent, or transparent. The print area may include a single color or multiple colors. The printed area may be on more than one side of the article and may include descriptive text and/or graphics. The surface of the water-soluble unit dose article may contain an aversive agent, such as a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable concentration of aversive agent may be used. Suitable concentrations include, but are not limited to, 1-5000 ppm, alternatively 100-2500 ppm, alternatively 250-2000 ppm.

The water-soluble unit dose articles disclosed herein comprise a water-soluble fibrous structure and one or more particles. A water-soluble fibrous structure may comprise a plurality of fibrous 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 is distributed throughout the fibrous structure with a plurality of two or more and/or three or more fibrous elements intertwined or otherwise associated with each other to form the fibrous structure. may include one or more particles that may be

The fibrous water-soluble unit dose article has a thickness greater than 0.01 mm, and/or greater than 0.05 mm, and/or greater 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 It may exhibit a thickness of about 0.3 mm or less.

The fibrous water-soluble unit dose article is from about 500 grams/m ² to about 5,000 grams/m ² , or about 1,000 grams/m ² as measured according to the Basis Weight Test Method described herein. basis weight of from about 4,000 grams/m ² , or from about 1,500 grams/m ² to about 3,500 grams/m ² , or from about 2,000 grams/m ² to about 3,000 grams/m ² may have

The fibrous water-soluble unit dose article may comprise a water-soluble fibrous structure and a plurality of particles distributed throughout the structure, wherein the water-soluble fibrous structure is the same or substantially the same from a compositional standpoint. contains a plurality of fibrous elements of A water-soluble fibrous structure may comprise two or more different fibrous elements. Non-limiting examples of fiber element differences include physical differences such as differences in diameter, length, texture, shape, stiffness, elasticity, cross-linking levels, solubility, melting point, Tg, active agents, filament-forming materials. color, concentration of active agent, basis weight, concentration of filament-forming material, presence of any coatings on the fibrous elements, biodegradable or not, hydrophobic or not, contact angle, etc. whether the fibrous element loses its physical structure when the fibrous element is exposed to the intended conditions of use, and whether the fibrous element loses its physical structure when the fibrous element is exposed to the intended conditions of use. difference in whether the morphology of the element changes, and difference in the rate at which the fibrous element releases one or more of its active agents when the fibrous element is exposed to the conditions of intended use; obtain. Two or more fibrous elements within a fibrous structure may contain different active agents. This may be the case where different active agents, such as anionic surfactants and cationic polymers, may be incompatible with each other. When using different fibrous elements, the resulting structure may exhibit different wetting, water absorption, and solubility characteristics.

Fibrous water-soluble unit dose articles may exhibit different regions, such as different regions of basis weight, density, caliper, and/or wettability characteristics. The fibrous water-soluble unit dose article may be compressed at the end sealing points. The fibrous water-soluble unit dose article may include texture on one or more of its surfaces. The surface of the fibrous water-soluble unit dose article may include patterns, such as non-random repeating patterns. The fibrous water-soluble unit dose article may contain an aperture. A fibrous water-soluble unit dose article may comprise a fibrous structure having discrete regions of fibrous elements that are distinct 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.

A fibrous water-soluble unit dose article may comprise one or more plies. The fibrous water-soluble unit dose article may comprise at least 2, and/or at least 3, and/or at least 4, and/or at least 5 plies. A fibrous ply can be a fibrous structure. Each ply may include one or more layers, such as one or more fibrous element layers, one or more particulate layers, and/or one or more mixed fibrous element/particle layers. The layer(s) may be encapsulated. In particular, the particle layer and the fibrous element/particle mixture layer may be sealed against particle leakage. The water-soluble unit dose article may comprise a plurality of plies, each ply comprising two layers, one layer being a fibrous element layer and one layer being a fibrous element/particle mixture layer, wherein the plurality of plies. are sealed together (eg, at the edges). In addition to preventing particle leakage, sealing can help the unit dose article maintain its original structure. However, when the water-soluble unit dose product is added to water, the unit dose product dissolves, releasing particles into the wash liquor.

FIG. 2 is a micro-CT scan image showing a cross-sectional view of an example water-soluble unit dose article comprising three plies, where each ply is made up of two layers: a fibrous element layer and a fibrous element/particle mixture layer. formed. 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 multilayer article is sealed at edges 200 to prevent particle leakage. The outer surface of article 202 is a layer of fibrous elements.

The fibrous elements and/or particles may be arranged within a water-soluble unit dose article, within a single ply, or within multiple plies so as to provide the water-soluble unit dose article with two or more regions containing different active agents. . For example, one area of the article may contain bleach and/or surfactant, and another area of the article may contain softener.

Fibrous water-soluble unit dose articles begin in the form in which the consumer interacts with the water-soluble article and work backwards toward the raw materials, e.g., plies, fibrous structures, and particles from which the water-soluble article is made. can be viewed hierarchically. A 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, the first ply 10 and the second ply 15 each having a plurality of fibrous elements 30, In this case, it contains a filament and a plurality of particles 32 . In the second ply 15 the particles 32 are randomly distributed in the x, y and z axes and in the first ply the particles 32 are in pockets.

The water-soluble unit dose articles described herein comprise a water-soluble fibrous structure, (a) from about 10% to about 80% by weight of an alkylalkoxylated sulfate, and (b) from about 0.5% to about and one or more rheology modifying particles comprising 20% by weight rheology modifying agent. The particles described herein may contain one or more additional active agents (in addition to the surfactants described above).

The rheology-modified particles are
(a) from about 10% to about 80% by weight of an alkylalkoxylated sulfate;
(b) from about 0.5% to about 20% by weight of a rheological modification selected from the group consisting of alkoxylated amines, preferably alkoxylated polyamines, more preferably quaternized or non-quaternized alkoxylated polyethyleneimines; A polyalkyleneimine core, ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymers, wherein each of x ₁ and x ₂ ranges from about 2 to about 140 and y ranges from about 15 to about 70, and mixtures thereof; and rheology modifiers.

As used herein, the term "rheology modifier" refers to a concentrated surfactant, preferably a concentrated interfacial agent having a mesostate phase structure, so as to substantially reduce the viscosity and elasticity of the concentrated surfactant. It means a material that interacts with the active agent. Suitable rheology modifiers include sorbitol ethoxylates, glycerol ethoxylates, sorbitan esters, tallowalkyl ethoxylated alcohols, ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymers with x ₁ and x ₂ Triblock copolymers, alkoxylated amines, alkoxylated polyamines, polyethyleneimine (PEI), alkoxylated variants of PEI, preferably each range from about 2 to about 140 and y ranges from about 15 to about 70. Examples include, but are not limited to, ethoxylated PEI, and mixtures thereof. The rheology modifier may include one of the above polymers, such as ethoxylated PEI, in combination with polyethylene glycol (PEG) having a weight average molecular weight of about 2,000 Daltons to about 8,000 Daltons. .

As used herein, the term "functional rheology modifier" means a rheology modifier with additional detergent functionality. In some cases, the dispersant polymers described herein below can also function as functional rheology modifiers. Functional rheology modifiers are present at concentrations of from about 0.5% to about 20%, preferably from about 1% to about 15%, more preferably from about 2% to about 10%, by weight of the composition. It may be present in the detergent granules of the invention.

Without wishing to be bound by theory, it is believed that functional rheology modifiers can interact with the molecular structure of mesophase surfactants, particularly alcoholic anionic sulfate surfactants, wherein the mesophase is a solid phase It is believed to have more water than surfactants and less water than the micellar phase typical of cleaning solutions. In other words, mesophase surfactants represent the solid-to-micellar phase transition state that can be achieved in the successful use of fibrous water-soluble unit dose articles, including water-soluble fibrous structures and particles. If the rheology is too viscous or tacky, under conditions of insufficient local dilution and/or insufficient shear, undesirable residue may be produced on the fabric. By substantially reducing the viscosity and elasticity of the mesophase, the rheology modifier aids dispersion and thus reduces the risk of residue formation on the fabric. Additionally, any residue that may form, such as clumpy gels, can be reduced by rheology modifiers. The net effect is to reduce the generation of surfactant residue that remains on the fabric through washing.

Alkoxylated Amines: Alkoxylated amines may be partially or fully protonated or unprotonated over the pH range of the concentrated surfactant mixture. Alternatively, the alkoxylated amine may be partially or fully quaternized. Alkoxylated amines may be non-quaternized. Alkoxylated amines may contain ethoxylate (EO) groups.

The alkoxylated amine may be linear, branched, or a combination thereof, preferably branched.

Alkoxylated amines may contain two or more amine moieties such as N,N,N',N'-tetra(2-hydroxyethyl)ethylenediamine (also described as a class of hydroxyalkylamines). N,N,N',N'-tetra(2-hydroxyethyl)ethylenediamine also functions as a chelating agent.

Alkoxylated amines may include alkoxylated amines, including alkoxylated polyalkyleneimines (or may be alkoxylated amines, including alkoxylated polyalkyleneimines). The alkoxylated polyalkyleneimine may be alkoxylated polyethyleneimine (PEI).

Typically, the alkoxylated polyalkyleneimine polymer contains a polyalkyleneimine backbone. The polyalkylimine may contain C2 alkyl groups, C3 alkyl groups, or mixtures thereof, preferably C2 alkyl groups. Alkoxylated polyalkyleneimine polymers may have a polyethyleneimine (“PEI”) backbone.

The alkoxylated PEI may comprise a polyethyleneimine backbone 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 prior to ethoxylation. good.

The PEI backbone of the polymers described herein has the following general empirical formula prior to alkoxylation:

（式中、Ｂは、分岐によるこの構造の連続を表す）を有してもよい。いくつかの態様では、ｎ＋ｍは、８、又は１０、又は１２、又は１４、又は１８、又は２２以上である。

(where B represents the continuation of this structure through branching). In some aspects, n+m is 8, or 10, or 12, or 14, or 18, or 22 or more.

Alkoxylated polyalkyleneimine polymers contain alkoxylated nitrogen groups. The alkoxylated polyalkyleneimine polymer independently averages 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 may contain alkoxylate groups of The alkoxylated polyalkyleneimine polymer may independently contain an average of at least about 5, or at least about 10, or at least about 15, or at least about 20 alkoxylate groups per alkoxylated nitrogen.

The alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may contain ethoxylate (EO) groups, propoxylate (PO) groups, or combinations thereof. The alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may contain ethoxylate (EO) groups. Alkoxylated polyalkyleneimine polymers, preferably alkoxylated PEI, may be free of propoxylate (PO) groups.

Alkoxylated amines, preferably alkoxylated polyalkyleneimine polymers, more preferably alkoxylated PEIs, average from about 1 to 50 ethoxylate (EO) groups and from about 0 to 5 propoxylate groups per alkoxylated nitrogen. (PO) group may be included. The alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, may contain an average of about 1 to 50 ethoxylate (EO) groups per alkoxylated nitrogen and contains no propoxylate (PO) groups. . The alkoxylated polyalkyleneimine polymer, preferably alkoxylated PEI, has an average of about 10 to 30 ethoxylate (EO) groups, preferably about 15 to 25 ethoxylate (EO) groups per alkoxylated nitrogen. may contain.

Suitable polyamines include low molecular weight, water-soluble, and lightly alkoxylated ethoxylated/propoxylated polyalkyleneamine polymers. By "lightly alkoxylated" is meant that the polymers of the present invention have an average of from about 0.5 to about 20, or from 0.5 to about 10 alkoxylations per nitrogen. The polyamine may be "substantially uncharged", which means that at pH 10 or pH 7 there are no more than about 2 positive charges for every about 40 nitrogens present in the backbone of the polyalkyleneamine polymer. means However, it is recognized that the charge density of a polymer can change with pH.

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

Ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymer: In the ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymer, each of x ₁ and x ₂ ranges from about 2 to about 140 and y is It ranges from about 15 to about 70. The ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymer preferably has an average propylene oxide chain length of 20-70, preferably 30-60, more preferably 45-55 propylene oxide units.

Preferably, the ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymer is about 1000 to about 10,000 daltons, preferably about 1500 to about 8000 daltons, more preferably about 2000 to about 7000 daltons, even more It preferably has a weight average molecular weight of from about 2500 to about 5000 Daltons, most preferably from about 3500 to about 3800 Daltons.

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.

Preferably, the copolymer comprises from 10% to 90%, preferably from 15% to 50%, most preferably from 15% to 25% by weight of the copolymer of composite ethylene-oxide blocks. Most preferably, the total ethylene oxide content is divided equally between the two ethylene oxide blocks. Equally divided herein means that each ethylene oxide block has an average of 40% to 60%, preferably 45% to 55%, even more preferably 48% to 52%, most preferably 50% of the total number of ethylene oxide units. %, meaning that the % of both ethylene oxide blocks add up to 100%. Certain ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymers wherein each of x ₁ and x ₂ ranges from about 2 to about 140 and y ranges from about 15 to about 70 Certain triblock copolymers improve washability.

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

Preferably, the ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymer has a weight average molecular weight of 1000-10,000 Daltons, preferably 1500-8000 Daltons, more preferably 2000-7500 Daltons. Preferably, the copolymer comprises from 10% to 95%, preferably from 12% to 90%, most preferably from 15% to 85% by weight of the copolymer of composite ethylene-oxide blocks. Certain ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymers wherein each of x ₁ and x ₂ ranges from about 2 to about 140 and y ranges from about 15 to about 70. Certain triblock copolymers improve dissolution.

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

Alkyl alkoxylated sulfates: Alkyl alkoxylated sulfates (AAS) are alkyl ethoxylated sulfates (AES), preferably ethoxylated C ₁₂ -C ₁₈ alkyl sulfates having an average degree of ethoxylation of from about 0.5 to about 3.0. It's okay.

Typically, the weight ratio of alkylalkoxylated sulfate to rheology modifier ranges from 4:1 to 40:1. The weight ratio of alkylalkoxylated sulfate to rheology modifier can depend on the molecular weight of the alcohol precursor of the alkylalkoxylated sulfate, the degree of alkoxylation, and the blend ratio of LAS/AES in the blended surfactant system. For example, for an AE1 alcohol precursor with a degree of ethoxylation of about 1.0 (eg, NaAE ₁ S), a NaLAS/NaAE ₁ S blend ratio of about 1/3, and a carbon chain length blend of 12-15 , the functional rheology modifier/NaAE ₁ S mass ratio may be at least about 4%, such as 5% to 10%, to improve dissolution, and a blend of 14 to 15 carbon chain lengths For higher MW alcohol precursors having a preferred functional rheology modifier/NaAE1S weight ratio may be at least about 9%, such as 9% to 20%. The concentration of the functional rheology modifier can be adjusted to maintain product solubility over a wide range of possible anionic surfactant materials and blend ratios thereof.

The mass of rheology modifier (RM) to the mass of NaAES surfactant can obey the following relationship: RM/NaAES≧f(alc)/(ax(LAS/AES)+b), where f(alc) is a function of the structure and molecular weight of the alcohol used to make the AES surfactant. , (LAS/AES) is the blend ratio of LAS to AES in the surfactant paste, where a is ˜30 and b is ˜2). For the reference blend of C12-C15 linear alcohol ethoxylates (C25AE1), f(alc) is ˜1.0, and for the reference blend of C14-C15 linear alcohol ethoxylates (C45AE1): f(alc) is ~1.2. The above guidelines are further dependent on the degree of ethoxylation and any branching structure of the ethoxylated alcohol precursor to the AES surfactant. The guideline can be expressed as a guidance ratio, where a value of ≧1 may indicate improved dissolution and a value of <1 may indicate worse dissolution. The guidance ratio is (RM/NaAES)/(f(alc)/(30*(LAS/AES)+2)).

The particles are about 15% to about 60%, or 20% to 40% by weight alkylalkoxylated sulfate, or 30% to 80%, or even 50% to 70% by weight alkylalkoxylated May contain sulfate.

The particles may comprise an alkylbenzene sulfonate, such as linear alkylbenzene sulfonate (LAS). The particles may comprise 1% to 50% by weight alkylbenzene sulfonate, or 5% to 30% by weight alkylbenzene sulfonate.

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

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

The particle size distribution is measured according to Applicants' Particle Size Distribution Test Method.

The particles may comprise from about 10% to about 80%, preferably from about 20% to about 60%, preferably from about 30% to about 50% by weight detergent builder.

The particles may comprise from about 2% to about 40%, preferably from about 5% to about 30%, preferably from about 10% to about 20% by weight of buffering agent.

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

The particles may comprise from about 2% to about 20%, preferably from about 5% to about 10%, by weight of dispersant polymer.

The particles may contain from 0.5% to 15% by weight of soluble film or fiber structuring polymer. Examples of soluble film or fiber structuring polymers include, but are not limited to, polyvinyl alcohol, polyvinylpyridone, polyethylene oxide, modified starch or cellulose polymers, and mixtures thereof. Such polymers may be present in product recycle streams containing unit dose products containing soluble fiber or film materials, such as pouch materials, in which case it is advantageous to incorporate such recycled materials into the particles.

The particles may have a density of less than 500 g/L. The particles are, for example, 50 g/L to 450 g/L, 100 g/L to 400 g/L, 150 g/L to 350 g/L, 200 g/L to 400 g/L, 250 g/L to 400 g/L, or 300 g/L to It may have a density of less than 450 g/L, such as 400 g/L.

The particles may have a density of 250 g/L to 400 g/L while having a particle size distribution such that the D10 is greater than about 300 microns and the D90 is less than about 1100 microns. The particles may have a particle size distribution such that the D10 is between 300 and 500 microns.

Applicants have found that by using low density particles within a desired size distribution, the dissolution rate and availability of the surfactant is greatly increased while delivering similar levels of surfactant as high density particles. found that it can be done.

Additionally, the use of low density, high activity particles allows the use of increased particle amounts, thereby delivering higher levels of particle percentage as a function of the finished total pad weight percentage.

Furthermore, as shown in Table 5, using low density particles allows for a significant increase in LAS surfactant of greater than 20% (such as 20% to 40%) in total textiles.

The rheology-modified particles may be coated or at least partially coated with a layer composition, for example, as disclosed in US 2007/0196502. Preferably, the layer composition contains non-surfactant actives. More preferably, said non-surfactant actives are selected from the group consisting of builders, buffers and dispersant polymers. Even more preferably, the non-surfactant active material is selected from the group consisting of zeolite A, sodium carbonate, sodium bicarbonate, and soluble polycarboxylate polymers. This is particularly advantageous when the active (AES as a non-limiting example) is suitable for washing under cold water and/or hard wash water conditions. The presence of actives in the layer promotes initial dissolution of cold water and/or hardness resistant chemicals. Without wishing to be bound by theory, the earlier order cold water and hardness resistant chemicals dissolve, the more traditional cleaning actives (LAS surfactants as a non-limiting example) may be protected. It is hypothesized that this can result in superior overall cleaning performance.

Rheology Modified Particle Preparation Process A concentrated aqueous paste containing a mixture of an alkylalkoxylated sulfate anionic detersive surfactant and a rheology modifier, preferably a functional rheology modifier, is used to form rheology modified detergent particles according to a paste agglomeration process. can be made. The paste agglomeration process is the step of (a) adding powdered raw materials into a mixer granulator, wherein the powdered raw materials are combined with one or more dry builders, buffers, dispersant polymers or chelating agents, and any necessary powder processing aids. (b) adding a paste comprising a premix of concentrated surfactants and functional rheology modifiers; and (c) a mixing granulator. to provide a suitable mixing flow field for dispersing the powder in the paste and forming agglomerates; and optionally (d) adding additional powder ingredients to form the agglomerates. (e) optionally drying the resulting agglomerates in a fluid bed dryer to remove excess moisture; f) optionally cooling the agglomerate in a fluidized bed cooler and (g) preferably granulating the agglomerate by elutriation from the fluidized bed of steps e and/or f. removing any excess fines from the size distribution and recycling the fines back to step a; and (h) removing excess oversized particles from the size distribution of the agglomerates, preferably by sieving. and (i) crushing the oversized 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.

A variation of the above preferred embodiment may comprise adding additional LAS co-surfactant in a stream separate from the premixed surfactant paste of step (b). Process options include adding pre-neutralized LAS as a solid powder in step (a) and adding 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 the alkaline buffer powder component and any other solid carrier to obtain a HLAS in powder form and the alkaline buffer powder. Form a combined pre-mixture and then add the pre-mixture in step (a) above.

As shown in the table below, surprisingly, by adding LAS in particle form to a separate surfactant slurry during the particle agglomeration process, e.g. It was found possible to produce particles with LAS to AES ratios greater than 1, such as 2.5, 1.1-2.0, 1.2-1.8. These particles are capable of achieving lower densities while increasing the amount of readily available LAS. As shown in the table below, when combined with a web containing LAS, the LAS to AES ratio of the total product is, for example, from 1.01 to 3.0, from 1.05 to 2.5, from 1.1 to It can be greater than 1.0, such as 2.0, 1.2-1.8.

Alternatively, a concentrated aqueous paste containing a mixture of alkylalkoxylated sulfate anionic detersive surfactants and rheology modifiers, an extrusion process may be used. Extrusion processes are well known in the art.

Alternatively, rheology modifiers may be used as binders in the aggregation process to make rheology modified detergent particles.

Surprisingly, the rheology-modified particles are finer and stronger than the same particles without the rheology modifier.

pH Adjusting Agents A single unit dose may contain one or more basic pH adjusting agents to raise the pH of the wash solution to a pH above 8. Suitable basic pH adjusters include sulfate, dihydrogen phosphate, fluoride, nitrite, acetate, bicarbonate, hydrogen sulfide, ammonia, carbonate, hydroxide and their Compositions including combinations include, but are not limited to. The inclusion of a basic pH adjuster does not exclude the inclusion of an acidic pH adjuster such as citric acid. A single unit dose may be used when the final pH of the washing solution is .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, as long as it exceeds 8, it may contain an acidic pH adjuster.

Concentrated Surfactant Pastes Concentrated surfactant pastes are intermediate compositions that can be combined with other ingredients to form rheology-modified particles. A concentrated surfactant composition may comprise the following components: a surfactant system, which may include an alkylalkoxylated sulfate surfactant, a rheology modifier as described herein, an organic solvent system, and water; It may consist essentially of these or may consist of them. These ingredients are described in more detail below.

A concentrated surfactant composition is from about 70% to about 90% surfactant system, by weight of the composition, from about 50%, or from about 60%, or from about 70%, or from about 80% to about 100% of an alkylalkoxylated sulfate surfactant; from about 0.1% to about 25% by weight of the composition of a rheology modifier; and from about 5% by weight of the composition. less than the organic solvent system and water. The surfactant system of the paste preferably includes a LAS co-surfactant. When LAS is included in the surfactant system, the ratio of LAS to:AES is 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, Even more preferably, it may be from 0.3 to about 0.6.

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

Fibrous Structure A fibrous structure comprises one or more fibrous elements. The fibrous elements can be associated with each other to form a structure. The fibrous structure may include particles within and/or on the structure. The fibrous structure may be homogeneous, layered, unitary, zoned, or as otherwise desired, with different active agents defining the various aforementioned portions.

The fibrous structure may include one or more layers, the layers together forming a ply.

Fibrous Element The fibrous element may be water soluble. The fibrous element may comprise 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 fibrous element, such as when the fibrous element and/or the fibrous structure containing the fibrous element are exposed to the intended conditions of use.

The fiber elements of the present invention may be spun from filament-forming compositions, also referred to as fiber element-forming compositions, via suitable spinning process operations such as meltblowing, spunbonding, electrospinning and/or rotary spinning. good.

As used herein, "filament-forming composition" and/or "fibrous element-forming composition" refer to compositions suitable for producing the fibrous elements of the present invention, such as meltblowing and/or spunbonding. means. A filament-forming composition comprises one or more filament-forming materials that exhibit properties that make the material suitable for spinning into fibrous elements. The filament-forming material may comprise a polymer. In addition to one or more filament-forming materials, the filament-forming composition may include one or more active agents, such as surfactants. Additionally, the filament-forming composition may comprise one or more polar solvents (such as water) in which one or more, such as all filament-forming materials and/or one or more, such as all of active agents are dissolved and/or dispersed prior to spinning the fibrous elements (such as filaments derived from the filament-forming composition).

A filament-forming composition may comprise two or more different filament-forming materials. Thus, the fibrous element may be monocomponent (one filament-forming material) and/or multicomponent, such as bicomponent. Two or more different filament-forming materials may be randomly combined to form the fibrous elements. Two or more different filament-forming materials may be joined together in an orderly manner to form a fibrous element, such as a sheath-core bicomponent fibrous element, which for the purposes of this disclosure is defined as a random are not considered to be mixtures. The bicomponent fiber element may be of any form such as side-by-side, sheath-core, islands-in-the-sea.

The fibrous component may be substantially free of alkylalkoxylated sulfates. Each fibrous element contains, based on the dry fibrous element, 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%, or about 25%, or about 30%, or about 35%, or about 40%, or about 50% by weight of the alkylalkoxylated sulfate. The amount of alkylalkoxylated sulfate in each of the fibrous elements is small enough so as not to affect its processing stability and film solubility. Alkylalkoxylated sulfates, when dissolved in water, can undergo a highly viscous hexagonal phase in certain concentration ranges, eg, 30-60% by weight, resulting in a gel-like material. Thus, when incorporated in substantial amounts into the fibrous element, alkyl alkoxylated sulfates can significantly slow down the dissolution of water-soluble unit dose articles in water and, even worse, leave behind undissolved solids. . Correspondingly, the majority of such surfactants are incorporated into the particles.

Each fibrous element may contain at least one filament-forming material and an active agent, preferably a surfactant. Surfactants may have relatively low hydrophilicity because such surfactants are less likely to form a viscous gel-like hexagonal phase when diluted. It's for. The use of such surfactants in filament formation can effectively reduce gel formation during washing, which in turn can result in faster dissolution and less or no residue in washing. Surfactants are selected, for example, from the group consisting of non-alkoxylated C6-C20 linear or branched alkyl sulfates (AS), C6-C20 linear alkylbenzene sulfonates (LAS), and combinations thereof. can be done. The surfactant may be a C6-C20 linear alkylbenzene sulfonate (LAS). LAS surfactants are well known in the art and readily available by sulfonating commercially available linear alkylbenzenes. Exemplary C ₆ -C ₂₀ linear alkylbenzene sulfonates that can be used include alkali metal, alkaline earth metal, or ammonium salts of C ₆ -C ₂₀ linear alkylbenzene sulfonic acids, such as C ₁₁ Sodium, potassium, magnesium, and/or ammonium salts of ˜C ₁₈ or C ₁₁ -C ₁₄ linear alkylbenzene sulfonic acids. A sodium or potassium salt of a _C12 linear _alkylbenzene sulfonic acid, for example a sodium salt of a C12 linear alkylbenzene sulfonic acid, ie sodium dodecylbenzene sulfonate, may be used as the first surfactant.

The fibrous component comprises 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%, based on the dry fibrous component and/or the dry fibrous structure; and/or less than about 80% by weight, and/or less than about 75% by weight, and/or less than about 65% by weight, and/or less than about 60% by weight, and/or less than about 55% by weight, and/or about 50% by weight less than about 45% by weight and/or less than about 40% by weight and/or less than about 35% by weight and/or less than about 30% by weight and/or less than about 25% by weight filaments forming material and greater than about 20% by weight, and/or at least about 35% by weight, and/or at least about 40% by weight, and/or at least about 45% by weight, based on the dry fibrous element and/or the dry fibrous structure; 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 about 95 wt% less than about 90%, and/or less than about 85%, and/or less than about 80%, and/or less than about 75% by weight of an active agent, preferably a surfactant; may include The fibrous element may comprise greater than about 80% surfactant by weight on a dry fibrous element and/or dry fibrous structure basis.

Preferably, each fibrous element has 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%, or at least about 70% by weight of the first surfactant.

The total concentration of filament-forming materials present in the fibrous element may be from about 5% to less than about 80% by weight, based on the dry fibrous element and/or on the dry fibrous structure, and the interface present in the fibrous element The total concentration of active agents may be from greater than about 20% to about 95% by weight based on the dry fibrous element and/or the dry fibrous structure.

One or more of the fibrous components may include other anionic surfactants (i.e. other than AS and LAS), nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants, and combinations thereof.

Other suitable anionic surfactants include C ₆ -C ₂₀ linear or branched alkyl sulfonates, C ₆ -C ₂₀ linear or branched alkyl carboxylates, C ₆ -C ₂₀ Linear or branched alkyl phosphates, C ₆ -C ₂₀ linear or branched alkyl phosphonates, C ₆ -C ₂₀ alkyl N-methylglucose amides, C ₆ -C ₂₀ methyl ester sulfonates (MES) , and combinations thereof.

Suitable nonionic surfactants include alkoxylated fatty alcohols. Nonionic surfactants may be selected from ethoxylated alcohols and ethoxylated alkylphenols of formula R(OC ₂ H ₄ ) _n OH, where R contains from about 8 to about 15 carbon atoms. The alkyl groups are selected from the group consisting of aliphatic hydrocarbon radicals and alkylphenyl radicals in which the alkyl group contains 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 _{- C18} alkyl ethoxylates, such as NEODOL® nonionic surfactants from Shell, alkoxylate units C ₆ -C ₁₂ alkylphenol alkoxylates, C ₁₂ -C ₁₈ alcohols, and C ₆ -C ₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymers, wherein can be ethyleneoxy units, propyleneoxy units, or mixtures thereof , for example, Pluronic® from BASF, C ₁₄ -C ₂₂ medium chain branched alcohols, BA, C ₁₄ -C ₂₂ medium chain branched alkyl alkoxylates (BAEx, where x is 1-30 ), alkyl polysaccharides, specifically alkyl polyglycosides, polyhydroxy fatty acid amides, and ether-capped poly(oxyalkylated) alcohol surfactants. Suitable nonionic detersive surfactants also include alkylpolyglucosides and alkylalkoxylated alcohols. Suitable nonionic surfactants also include those sold by BASF under the trade name Lutensol®.

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, dimethylhydroxyethyllaurylammonium chloride, polyamine cationic surfactants, cationic ester surfactants, and amino surfactants such as amidopropyldimethylamine (APA). Suitable cationic detersive surfactants also include alkylpyridinium compounds, alkylquaternary ammonium compounds, alkylquaternary phosphonium compounds, alkyltertiary sulfonium compounds, and mixtures thereof.

Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula:
(R) (R ₁ ) (R ₂ ) (R ₃ ) N ⁺ X ⁻
wherein R is a linear or branched, substituted or unsubstituted C _6-18 alkyl or alkenyl moiety, R ₁ and R ₂ are independently selected from methyl or ethyl moieties, R3 is a hydroxyl _, hydroxymethyl or hydroxyethyl moiety and X is an anion that provides charge neutrality, suitable anions include halides such as chloride, sulfate, and sulfonate . A preferred cationic detersive surfactant is mono-C _6-18 alkyl mono-hydroxyethyldimethyl quaternary ammonium chloride. Highly preferred cationic detersive surfactants are mono-C _8-10 alkyl mono-hydroxyethyldimethyl quaternary ammonium chloride, mono-C _10-12 alkyl mono-hydroxyethyldimethyl quaternary ammonium chloride, and mono- C ₁₀ alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride.

Suitable examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, including derivatives of heterocyclic secondary and tertiary amines, quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds derivatives of, alkyldimethylbetaines, cocodimethylamidopropylbetaines, and betaines including sulfo and hydroxybetaines, C ₈ -C ₁₈ (eg C ₁₂ -C1 ₈ )amine oxides, N-alkyl-N,N-dimethylamino- 1-propanesulfonate (where the alkyl group can be C ₈ -C ₁₈ ).

Suitable amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or where the aliphatic group may be linear or branched and one of the aliphatic substituents has at least about 8 1 carbon atom 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 secondary and tertiary amines are included. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof.

The fibrous element may comprise a surfactant system containing only anionic surfactants, for example either a single anionic surfactant or a combination of two or more different anionic surfactants. Alternatively, the fibrous component may comprise, for example, a combination of one or more anionic surfactants and one or more nonionic surfactants, or one or more anionic surfactants and one or more zwitterionic surfactants. or one or more anionic surfactants and one or more amphoteric surfactants, or one or more anionic surfactants and one or more cationic surfactants agents, or complex surfactant systems containing combinations of all of the above types of surfactants (ie, anionic, nonionic, amphoteric, and cationic).

Generally, fibrous elements are elongated particulates having a length that greatly exceeds the average diameter, eg, a ratio of length to average diameter of at least about 10. The fibrous elements may be filaments or fibers. Filaments are relatively longer than fibers. The filament is about 2 inches or greater, and/or about 7.62 cm (3 inches) or greater, and/or about 10.16 cm (4 inches) or greater, and/or about 15.24 cm (6 inches) or longer. The fibers may have a length of less than about 5.08 cm (2 inches) and/or about 3.81 cm (1.5 inches) and/or about 2.54 cm (1 inch).

The one or more filament-forming materials and active agents are about 2.0 or less, and/or about 1.85 or less, and/or about 1.7 or less, and/or about 1.6 or less, and/or about 1 less than .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 of filament-forming material to active agent of 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 It may be present in the fibrous element in a weight ratio of the total concentration. The one or more filament-forming materials and active agent may be present in the fibrous element in a weight ratio of total concentration of filament-forming material to active agent of from about 0.2 to about 0.7.

The fibrous element comprises from about 10% to less than about 80% by weight filament-forming material, such as polyvinyl alcohol polymer, starch polymer, and/or carboxymethylcellulose polymer, based on dry fibrous element and/or dry fibrous structure, and dry fiber. It may also contain from greater than about 20% to about 90% by weight of active agents, such as surfactants, on an element basis and/or a dry fibrous structure basis. The fibrous element may further comprise a plasticizer (eg glycerin) and/or an additional pH adjuster (eg citric acid). The fibrous elements may have a weight ratio of filament-forming material to active agent of less than or equal to about 2.0. Filament-forming materials may be selected from the group consisting of polyvinyl alcohol, starch, carboxymethylcellulose, polyethylene oxide, and other suitable polymers, especially hydroxyl-containing polymers and derivatives thereof. The filament-forming material may range in weight average molecular weight from about 100,000 g/mole to about 3,000,000 g/mole. In this range, it is believed that the filament-forming material may provide extensional rheology such that it is not so elastic as to impede fiber thinning in the fiber-making process.

The one or more active agents may be releasable and/or may be released upon exposure of the fibrous element and/or fibrous structure comprising the fibrous element to intended conditions of use. The one or more active agents in the fibrous element may be selected from the group consisting of surfactants, organic polymeric compounds, and mixtures thereof.

The fiber element is 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 when measured according to the Diameter Test Method described herein , and/or may exhibit a diameter of less than about 5 μm, and/or less than about 1 μm. The fibrous elements 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 rate of release of one or more active agents present in the fibrous element and/or the rate of degradation and/or change of the physical structure of the fibrous element.

The fibrous element may contain two or more different active agents that are compatible or incompatible with each other. The fibrous element may include an active agent within the fibrous element and an active agent 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. When different, the active agents may be compatible with each other or may be incompatible. The one or more active agents may be uniformly distributed or substantially uniformly distributed throughout the fibrous element. The one or more active agents may be distributed as discrete regions within the fibrous element.

Active Agents 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 element (as described above), in the particles (as described above), or in the article. A premix can be, for example, a slurry of the active agent combined with the aqueous absorbent. Active agents include surfactants, structuring agents, builders, organic polymer compounds, enzymes, enzyme stabilizers, bleaching agents, brightening agents, toning agents, chelating agents, antifoaming agents, conditioning agents, moisturizing agents, fragrances, and fragrances. It may be selected from the group consisting of microcapsules, fillers or carriers, alkaline systems, pH control systems, buffers, alkanolamines, and mixtures thereof.

Surfactants Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof may be selected from the group consisting of These surfactants are described in more detail above.

Enzymes Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases. , tannases, pentosanases, maranases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail, which may include, for example, a protease and one or more non-protease enzymes such as, for example, an amylase or a lipase combined with any of those listed above.

When present in the detergent composition, the additional enzymes are from about 0.00001% to about 2%, from about 0.0001% to about 1%, or even from about 0.001%, by weight of the composition. Enzyme protein concentrations from weight percent to about 0.5 weight percent may be present. The compositions disclosed herein contain from about 0.001% to about 1% by weight of an enzyme (auxiliary as an agent).

Proteases Preferably, the enzyme composition comprises one or more proteases. Suitable proteases include metalloproteases and serine proteases, including 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 aforementioned preferred proteases. In one aspect, suitable proteases may be alkaline microbial proteases or/and serine proteases such as tryptic proteases.

Builders Suitable builders include aluminosilicates (e.g. zeolite builders such as Zeolite A, Zeolite P and Zeolite MAP), silicates, phosphates such as polyphosphates (e.g. sodium tri-polyphosphate), Specifically sodium salts thereof, 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 acid, sodium, potassium, or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic species, and phytic acid. . Additional suitable builders are 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 various types of Other suitable ethylenic monomers with additional functional groups may be selected. Alternatively, the composition may be substantially free of builders.

Polymeric Dispersants Suitable polymers include polymeric carboxylates such as polyacrylates, polyacrylic acid-maleic acid copolymers, and sulfonated modifications thereof, such as hydrophobically modified sulfonated acrylic acid copolymers. Not limited. The polymers are cellulosic polymers, polyesters, polyterephthalates, polyethylene glycols, ethylene oxide-propylene oxide-ethylene oxide (EOx ₁ POyEOx ₂ ) triblock copolymers, where each of x ₁ and x ₂ ranges from about 2 to about 140. and y ranges from about 15 to about 70. Any combination may be used. Optionally, the dispersant polymer can also function as a rheology modifier as described above.

Suitable polyethyleneimine polymers include propoxylated polyalkyleneimine (eg, PEI) polymers. Propoxylated polyalkyleneimine (eg, PEI) polymers may be ethoxylated. Propoxylated polyalkyleneimine (eg, PEI) polymers may have inner polyethylene oxide blocks and outer polypropylene oxide blocks, with a degree of ethoxylation and propoxylation that is neither above nor below specified limits. The ratio (n/p) of polyethylene blocks to polypropylene blocks 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 may be about two. The propoxylated polyalkyleneimine is a PEI having a weight average molecular weight (measured before alkoxylation) of from about 200 g/mole to about 1200 g/mole, or from about 400 g/mole to about 800 g/mole, or from about 600 g/mole. It may have a backbone chain. The molecular weight of the propoxylated polyalkyleneimine may be from about 8,000 to about 20,000 g/mole, or from about 10,000 to about 15,000 g/mole, or about 12,000 g/mole.

Suitable propoxylated polyalkyleneimine polymers may include compounds of the following structures.

（式中、ＥＯは、エトキシレート基であり、ＰＯは、プロポキシレート基である）。上に示す化合物は、ＥＯ：ＰＯのモル比が１０：５（例えば、２：１）であるＰＥＩである。その他の同様の好適な化合物は、約１０：５又は約２４：１６のモル比で存在するＥＯ及びＰＯ基を含んでもよい。

(where EO is an ethoxylate group and PO is a propoxylate group). The compound shown above is a PEI with an EO:PO molar ratio of 10:5 (eg, 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.

Soil Release Polymers Suitable soil release polymers have structures defined by one of structures (I), (II), or (III) below.
(I)-[(OCHR ¹ -CHR ² ) _a -O-OC-Ar-CO-] _d
(II)-[(OCHR ³ -CHR ⁴ ) _b -O-OC-sAr-CO-] _e
(III)-[( ^{OCHR5 - CHR6} ) _c -OR7] _f
During the ceremony,
a, b and c are 1 to 200;
d, e and f are 1 to 50;
Ar is 1,4-substituted phenylene;
sAr is a 1,3-substituted phenylene substituted with SO ₃ Me at the 5-position;
Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetra-alkylammonium (wherein the alkyl group is C ₁ -C ₁₈ alkyl or C ₂ - is a _C10 hydroxyalkyl), or mixtures thereof,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from H or C ₁ -C ₁₈ n- or iso-alkyl;
R ⁷ is a linear or branched C ₁ -C ₁₈ alkyl, or a linear or branched C ₂ -C ₃₀ alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or It is a C ₈ -C ₃₀ aryl group or a C ₆ -C ₃₀ arylalkyl group.

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

Cellulosic Polymers Suitable cellulosic polymers include those selected from alkylcelluloses, alkylalkoxyalkylcelluloses, carboxyalkylcelluloses, alkylcarboxyalkylcelluloses. Cellulosic polymers may be selected from the group consisting of carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof. In one aspect, the carboxymethylcellulose has a degree of carboxymethyl substitution of 0.5-0.9 and a molecular weight of 100,000 Da to 300,000 Da.

Amines 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 tetraethylenepentamine, triethylenetetramine, diethylenetriamine, or mixtures thereof.

Bleaching Agents Suitable bleaching agents other than bleaching catalysts include photobleaching agents, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, and mixtures thereof. Generally, when bleaching agents are used, the detergent compositions of the present invention contain from about 0.1% to about 50%, or even from about 0.1% to about 25%, by weight of the detergent composition, of bleaching agents. may contain.

Bleaching Catalysts Suitable bleaching catalysts include iminium cations and polyions, iminium zwitterions, modified amines, modified amine oxides, N-sulfonylimines, N-phosphonylimines, N-acylimines, thiadiazole dioxides, perfluoroimines, cyclic sugar ketones , and mixtures thereof.

Brighteners Commercially available optical brighteners suitable for the present disclosure include stilbenes, pyrazolines, coumarins, benzoxazoles, carboxylic acids, methinecyanines, dibenzothiophene-5,5-dioxides, azoles, 5- and 6-membered heterocycles , as well as derivatives of a variety of other substances, including but not limited to subgroups.

The optical brightener is disodium 4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbene disulfonate (brightener 15, marketed under the trade name Tinopal AMS-GX by BASF), 4,4′-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino }-2,2′-disodium stilbene disulfonate (marketed by BASF under the trade name Tinopal UNPA-GX), 4,4′-bis{[4-anilino-6-(N-2-hydroxyethyl- N-methylamino)-s-triazin-2-yl]-amino}-2,2′-stilbene disulfonate disodium (marketed by BASF under the trade name Tinopal 5 BM-GX); may More preferably, the optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate .

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

Fabric Hueing Agents Fabric hueing agents (sometimes also referred to as complementing agents, bluing agents, or whitening agents) typically impart a blue or purple tint to fabrics. Hueing agents can be used either alone or in combination to create shades of specific hues and/or to tint different types of fabrics. This can be brought about, for example, by mixing red and green-blue dyes to produce blue or violet shades. Toning agents include acridines, anthraquinones (including polycyclic quinones), azines, azos including premetallized azos (e.g. monoazo, diazo, trisazo, tetrakisazo, polyazo), benzodifurans and benzodifuranones, carotenoids, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoid, methane, naphthalimide, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazole, stilbene, styryl, triarylmethane, triphenylmethane, xanthene, and these may be selected from any known chemical class of dyes, including, but not limited to, mixtures of

Suitable fabric toning agents include dyes, dye-clay combinations, and organic and inorganic pigments. Suitable dyes also include small molecule dyes and polymeric dyes. Suitable small molecule dyes include, for example, direct dyes, basic dyes, reactive dyes or hydrolytic small molecule dyes selected from the group consisting of dyes falling within the Color Index (C.I.) classification of reactive dyes, solvent dyes, or disperse dyes. Suitable polymeric dyes include polymers containing covalently attached (sometimes referred to as attached) chromogens (dye-polymer conjugates), e.g. Polymer dyes selected from the group consisting of polymers with chromogens and mixtures thereof. Suitable polymeric dyes also include fabric substantive colorants sold under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA), at least one reactive dye, a hydroxyl moiety, a primary amine moiety, a dye-polymer conjugate formed from a polymer selected from the group consisting of a polymer comprising a moiety selected from the group consisting of a secondary amine moiety, a thiol moiety, and a mixture thereof. Also included are polymeric dyes. Suitable polymeric dyes include Liquitint® Violet CT, C.I. I. Carboxymethylcellulose (CMC) conjugated with reactive blue, reactive violet, or reactive red dyes such as CMC conjugated with reactive blue 19, alkoxylated triphenyl-methane polymer colorant, alkoxylated Also included are polymeric dyes selected from the group consisting of thiophene polymeric colorants, and mixtures thereof.

The foregoing fabric toning agents may be used in combination (any mixture of fabric toning agents may be used).

Encapsulation Body An inclusion body may comprise a core and a shell having an interior surface and an exterior surface, the shell enclosing the core. The core can contain any laundry care aid, but typically the core contains fragrances, brighteners, tinting dyes, insect repellents, silicones, waxes, fragrances, vitamins, fabric softeners, A skin care agent and, in one aspect, a material selected from the group consisting of paraffin, enzymes, antimicrobial agents, bleaching agents, sensates, and mixtures thereof, wherein the shell is made of polyethylene, polyamide, optionally other Polyvinyl alcohols, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyacrylates, aminoplasts containing co-monomers (in one aspect, the aminoplasts may comprise polyureas, polyurethanes, and/or polyureaurethanes; In aspects, the polyurea may include polyoxymethylene urea and/or melamine formaldehyde), polyolefins, polysaccharides (in one aspect, the polysaccharide may include alginate and/or chitosan), Laundry care aids selected from the group consisting of gelatin, shellac, epoxies, vinyl polymers, water-insoluble inorganic materials, silicones, and mixtures thereof may be included.

A preferred encapsulating agent contains a perfume. A preferred encapsulation comprises a shell which may comprise melamine formaldehyde and/or cross-linked melamine formaldehyde. Other preferred capsules include polyacrylate-based shells. A preferred encapsulant is disclosed comprising 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 has a breaking strength of 0.2 MPa to 10 MPa and 0% to 20%, or even 10% relative to the initial total amount of encapsulated benefit agent. or may have a benefit agent leakage rate of less than 5%. at least 75%, 85%, or even 90% of the inclusions are (i) 1 micrometer to 80 micrometers, 5 micrometers to 60 micrometers, 10 micrometers to 50 micrometers, or even 15 micrometers; and/or (ii) at least 75%, 85%, or even 90% of the inclusion bodies are between 30 nm and 250 nm, between 80 nm and 180 nm, or even between 100 nm and Those that can have a particle wall thickness of 160 nm are preferred. A formaldehyde scavenger may be used with the encapsulating agent, eg, in the capsule slurry, and/or may be added to the composition before, during, or after the encapsulating agent is added to the composition.

Suitable capsules can be made using well-known processes. Alternatively, suitable capsules can be purchased from Encapsys LLC (Appleton, Wisconsin USA). In preferred embodiments, the composition may comprise an adhesion aid, preferably in addition to the encapsulating agent. Preferred deposition 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 optionally one or more selected from the group comprising acrylic acid and acrylamide. Polymers containing dimethylaminoethyl methacrylate with monomers are included.

Perfume Non-limiting examples of perfumes and perfume ingredients include, but are not limited to, aldehydes, ketones, esters, and the like. Other examples include various natural extracts and natural extracts, including ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam extract, sandalwood oil, pine oil, cedar. can contain complex mixtures of The final perfume can contain very complex mixtures of such ingredients. A finished perfume may be included at a concentration ranging from about 0.01% to about 2% by weight of the detergent composition.

Anti-Transfer Agents Anti-transfer agents are effective in inhibiting the transfer of dye from one fabric to another during the wash process. Generally, such dye transfer inhibitors can include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, and mixtures thereof. When used, these agents comprise from about 0.0001% to about 10% by weight of the composition, in some examples from about 0.01% to about 5% by weight of the composition, and in other examples, Concentrations from about 0.05% to about 2% by weight of the composition may be used.

Chelating Agents Suitable chelating agents include copper, iron, and/or manganese chelating agents, and mixtures thereof. Such chelating agents include phosphonates, aminocarboxylates, aminophosphonates, succinates, polyfunctionally substituted aromatic chelating agents, 2-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethylinulin, and mixtures thereof. can be selected from the group consisting of The chelating agent can be present in the acid form or in the salt form, including alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof. Other chelating agents suitable for use herein are the commercially available DEQUEST series and chelating agents from Monsanto, Akzo-Nobel, DuPont, Dow, the Trilon® series from BASF and Nalco, BASF, DOW. , and a copolymer of maleic acid and acrylic acid available from Nippon Shokubai.

Suds Suppressors Compounds for reducing or inhibiting the formation of suds may be incorporated into water-soluble unit dose articles. Suds control can be particularly important in so-called "high concentration wash processes" and in front loading washing machines. Examples of foam inhibitors include monocarboxylic fatty acids and soluble salts therein, high molecular weight hydrocarbons such as paraffins, fatty acid esters (eg fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones. (eg, stearones), N-alkylated aminotriazines, waxy hydrocarbons preferably with melting points below about 100° C., silicone suds suppressors, and secondary alcohols.

Further suitable antifoam agents are derived from phenylpropylmethyl-substituted polysiloxanes.

The detergent composition may comprise a suds suppressor selected from organomodified silicone polymers with aryl or alkylaryl substituents in combination with primary fillers that are silicone resins and modified silicas. Detergent compositions may contain from about 0.001% to about 4.0% by weight of the composition of such suds suppressors.

The detergent composition comprises a) from about 80 to about 92% ethylmethyl, methyl(2-phenylpropyl)siloxane, from about 5 to about 14% MQ resin, and from about 3 to about 7% modified mixture with silica, b) about 78 to about 92% ethylmethyl, methyl(2-phenylpropyl)siloxane and about 3 to about 10% MQ resin and about 4 to about 12% modified in octyl stearate It may contain an inhibitor selected from mixtures with silica or c) mixtures thereof, the percentages being based on the weight of the defoamer.

Foam Boosters Foam boosters such as C ₁₀ -C ₁₆ alkanolamides may be used when high foaming is desired. Some examples include _{C10 -} C14 monoethanol and diethanolamide. optionally adding a water soluble magnesium and/or calcium salt such as MgCl ₂ , MgSO ₄ , CaCl ₂ , CaSO ₄ at a concentration of about 0.1% to about 2% by weight of the detergent composition; Additional foam may be provided to enhance grease removal performance.

Conditioning Agents Suitable conditioning agents include high melting point fatty compounds. High melting point fatty compounds useful herein have a melting point of 25° C. or higher and are selected from the group consisting of fatty alcohols, fatty acids, fatty 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.

Suitable conditioning agents generally include silicones (e.g., silicone oils, polyoils, cationic silicones, silicone gums, high refractive index silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty acid esters). ), or combinations thereof, or otherwise form dispersed particles of liquid in the aqueous surfactant matrix herein.

Fabric Reinforcing Polymers Suitable fabric reinforcing polymers are typically cationically charged and/or have high molecular weights. The fabric reinforcing 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 and preferably from 100,000 to 2,000,000. Preferred fabric reinforcing polymers have a pH of at least about 0.2 meq/gm, preferably at least 0.25 meq, at the pH of the composition's intended use, which generally ranges from pH 3 to pH 9, preferably pH 4 to pH 8. /gm, more preferably at least 0.3 meq/gm, but also preferably less than 5 meq/gm, more preferably less than 3 meq/gm, and most preferably less than 2 meq/gm. The fabric reinforcing polymer may be of natural or synthetic origin.

Pearlescent Agents Non-limiting examples of pearlescent agents include mica, titanium dioxide coated mica, bismuth oxychloride, fish scales, mono- and diesters of alkylene glycol. The pearlescent agent may be ethylene glycol distearate (EGDS).

Hygiene and odors Suitable hygiene and odor active agents include zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac®, polyethylenimine (such as Lupasol® from BASF) and its zinc complexes, silver and silver compounds, particularly those designed to slowly release Ag ⁺ or nanosilver dispersions.

Buffer System The water-soluble unit dose articles described herein, during use in aqueous cleaning operations, will have a pH of about 7.0 to about 12, in some instances about 7.0 to about 11, in the wash water. may be formulated to have Techniques for controlling pH at recommended working concentrations include the use of buffers, alkalis, or acids, which are well known to those skilled in the art. These techniques include the use of sodium carbonate, citric acid or sodium citrate, lactic acid or lactate salts, monoethanolamine or other amines, boric acid or borates, and other pH adjusting compounds well known in the art. include, but are not limited to.

The detergent compositions herein may comprise a dynamic in-wash pH profile. In such detergent compositions, (i) the pH of the wash liquor is greater than 10 after about 3 minutes of contact with water, and (ii) the pH of the wash liquor is less than 9.5 after about 10 minutes of contact with water; (iii) after about 20 minutes of contact with water, the pH of the wash solution is less than 9.0, and (iv) optionally, the equilibrium pH of the wash solution is in the range of about 7.0 to about 8.5; Wax-coated citric acid particles may be used along with other pH control agents.

Method of Making As illustrated in FIG. 3, a solution of filament-forming composition 35 is provided. The filament-forming composition may comprise one or more filament-forming materials and optionally one or more active agents. The filament-forming composition 35 is passed through one or more die block assemblies 40 with a plurality of spinnerets 45 to form a plurality of fiber elements including one or more filament-forming materials and optionally one or more active agents. form 30; Multiple die block assemblies 40 can be used to spin different layers of fibrous elements 30, the fibrous elements 30 of different layers having different compositions from each other or being the same as each other. Three or more die block assemblies arranged in series can be provided to form three, four, or any other integer number of layers in a given ply. The fibrous elements 30 can be deposited on a belt 50 moving in the machine direction MD to form the first ply 10 .

Particles can be introduced into the flow of fibrous elements 30 between die block assembly 40 and belt 50 . Particles can be fed from the particle receiver to a belt feeder 41 or optionally to a screw feeder. The belt feeder 41 can be set and controlled to deliver the desired particle mass to the process. The belt feeder feeds an air knife 42 that suspends and directs particles in the airflow within the fibrous elements 30 to form a particle-fiber layer of mixed fibrous elements 30 and particles that are subsequently deposited on the belt 50. can do.

A first ply 10 can be provided to form a water-soluble product. Second ply 15 may be provided separately from first ply 10 . The first ply 10 and the second ply 15 are superimposed on each other. Superimposed means positioned one above or below the other, with the proviso that additional plies or other materials, such as active agents, may be positioned between the superimposed plies. do. A portion of first ply 10 may be joined to a portion of second ply 15 to form water soluble product 5 . Each ply may include one or more layers.

Particle-Fiber Layer The particle-fiber layer may be arranged in several ways. The clusters of particles may be distributed in pockets distributed within the layers, such pockets may be formed between layers of fibrous elements, and the contact network and porosity within each cluster of particles may be , governed by the physics of conventional particle packing, but the clusters are substantially expanded within the layers. The particles may be distributed relatively homogeneously throughout the fibrous structure, substantially free of localized particle clusters, and the packing is substantially extended on the scale of individual particles, with more interparticle contact. less and the interparticle pores become larger. Without wishing to be bound by theory, it is believed that a water-soluble unit dose article comprising a layer comprising fibrous elements and particles can expand water when a sticky surfactant such as AES is sequestered in particles having an expanded structure. It is believed that both rapid water absorption into the structure and reduced contact between particles with sticky surfactant improve dispersion and dissolution of the unit dose article.

pouch. A single unit dose may be in the form of a pouch. The compositions are in unit dose form, in tablet form, or preferably in liquid/solid (optionally granulated)/gel/paste form retained within a water-soluble film (also known as a pouch or pod). may be provided by either The compositions may be enclosed in single-compartment pouches or multi-compartment pouches. Multi-compartment pouches are described in more detail in EP-A-2133410(A). Shading or non-shading dyes or pigments or other aesthetic agents may also be used in one or more compartments.

Suitable films for forming the pouches are soluble or dispersible in water, as measured by the method presented herein after using a glass filter having a maximum pore size of 20 micrometers. , preferably having a water solubility/dispersibility of at least 50%, preferably at least 75%, or even at least 95%:
To a pre-weighed 400 mL beaker, add 50 grams ± 0.1 grams of pouch material and add 245 mL ± 1 mL of distilled water. This is vigorously stirred for 30 minutes with a magnetic stirrer set at 600 rpm. The mixture is then filtered through a folded qualitative sintered glass filter with the pore size defined above (maximum 20 micrometers). Dry the water from the collected filtrate by any conventional method and determine the weight of the remaining material (this is the dissolved or dispersed fraction). Solubility or dispersibility can then be calculated. Preferred film materials are polymeric materials. Film materials can be obtained, for example, by casting, blow molding, extruding or blow extruding polymeric materials, as is known in the art. Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material include polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polycarboxylic acid. Acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, copolymers of maleic/acrylic acid, polysaccharides including starch and gelatin, natural gums such as xanthan and cara gum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrins, polymethacrylates, most preferably polyvinyl alcohol, polyvinyl alcohol copolymers and Hydroxypropyl methylcellulose (HPMC), and combinations thereof. Preferably, the concentration of polymer, eg PVA polymer, in the pouch material is at least 60%. The polymer may have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000, even more preferably from about 20,000 to 150,000. Mixtures of polymers may also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartment or pouch depending on its application and required needs. Suitable mixtures include, for example, mixtures in which one polymer has a higher water solubility than another polymer and/or one polymer has a higher mechanical strength than another polymer. Also, mixtures of polymers having different weight average molecular weights, such as PVA or copolymers thereof with a weight average molecular weight of about 10,000 to 40,000, preferably around 20,000, and about 100,000 to 300,000, preferably Also suitable are mixtures with PVA of weight average molecular weight around 150,000 or copolymers thereof. Also polymer blend compositions, for example, hydrolytically degradable water-soluble polymer blends (obtained by mixing polylactide and polyvinyl alcohol, typically about 1 to 35% by weight of polylactide and about 65 to Also suitable herein are polymer blend compositions, including polymer blends of polylactide and polyvinyl alcohol, including 99% by weight polyvinyl alcohol. Preferred for use herein are polymers that are about 60% to about 98% hydrolyzed, preferably about 80% to about 90% hydrolyzed, to improve the dissolution properties of the material.

Of course, different film materials and/or films of different thickness may be used to make the compartments of the present invention. An advantage of choosing different films is that the resulting compartments may exhibit different solubility or release characteristics.

The most preferred film materials are the PVA films known as MonoSol reference numbers M8630, M8900, H8779 (described in Applicants' co-pending application reference numbers 44528 and 11599), U.S. Patent Nos. 6,166,117 and 6, 787,512 and PVA films with corresponding solubility and deformation properties.

The film materials herein may also contain one or more additive-containing ingredients. For example, it may be beneficial to add plasticizers such as glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol and mixtures thereof. Other additives include functional detergent additives that are delivered to the wash water, such as organic polymeric dispersants.

The bittering agent may be incorporated into the pouch or pod either by incorporating it into the composition inside the pouch and/or by coating it onto a film.

Laundry Method The invention is also a laundry method using articles according to the invention, comprising the steps of placing at least one article according to the invention together with the laundry to be washed into a washing machine and performing a washing or cleaning operation. and a method of laundering. Specifically, the method includes obtaining a fabric having sebum deposited thereon, and treating the fabric with a washing step, the washing step comprising contacting the fabric with a cleaning solution. include. The wash liquor is prepared by diluting the water-soluble unit volume 300-800 times, preferably 400-700 times, in water, the wash liquor being of pH 8 or greater.

Any suitable washing machine may be used. Examples include automatic washing machines, hand washing operations, or a mixture thereof, preferably automatic washing machines.

Those skilled in the art will recognize suitable machines for the relevant cleaning operations. The articles of the present invention may be used with other compositions such as fabric additives, fabric softeners, rinse aids, and the like.

The wash temperature may be from 5°C to 90°C, such as 30°C or less. The washing process may include at least one washing cycle having a duration of 5-50 minutes. An automatic washing machine may comprise a rotating drum, the drum having a rotational speed of 15-40 rpm, preferably 20-35 rpm during at least one washing cycle.

The fabric may be cotton, polyester, cotton/polyester blends, or mixtures thereof, preferably cotton.

Water-soluble unit dose articles comprising a water-soluble fibrous structure and one or more rheology-modified particles distributed throughout the structure can be used, for example, in butter, beef, grasses, tea, spaghetti, sebum, wine, and fabrics. It may remove one or more types of stains, such as any other type of stain that may be imparted.

TEST METHODS Basis Weight Test Method A precision analytical balance with a sensitivity limit of ±0.001 g is used to measure the basis weight of the fibrous structure by stacking 12 usable units. Use a draft shield to protect the balance from air currents and other disturbances. All samples are prepared using a precision cutting die measuring 3.500 inches ± 0.0035 inches x 3.500 inches ± 0.0035 inches.

A precision cutting die is used to cut the sample into squares. The cut squares are grouped together and stacked to a thickness of 12 samples. Measure the mass of the stacked sample and record the result to the nearest 0.001 g.

Calculate basis weight in lbs/3000 ft ² or g/m ² as follows:
Basis weight = (mass of stacked sample) / [(area of one square in stacked sample) x (number of squares in stacked sample)]
for example,
Basis weight (lbs/3000 ft ² ) = [[stacked sample mass (g)/453.6 (g/lbs)]/[12.25 (in ² )/144 (in ² /ft ² ) x 12] ]×3000
or
Basis weight (g/m ² ) = weight of stacked sample (g)/[79.032 (cm ² )/10,000 (cm ² /m ² ) x 12]

Report results in units of 0.1 lbs/3000 ft ² or 0.1 g/m ² . A precision cutter similar to that described above may be used to vary or vary the sample dimensions so that the stacked sample area is at least 100 square inches.

Thickness Test Method 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 cutting five samples. Typically, the load foot mounting surface has a circular surface area of about 3.14 square inches. Fix the specimen between a horizontal plane and the load foot mounting surface. The load foot mounting surface applies a confining pressure of 15.5 g/cm ² to the sample. The thickness of each sample is the gap created between the plane and the load foot mounting surface. Thickness is calculated as the average thickness of five samples. Results are reported in millimeters (mm).

Granule Particle Size Distribution Test Method A granule size distribution test is performed to determine the characteristic size of the particles. This follows ASTM D 502-89, "Standard Test Method for Particle Size of Soaps and Other Detergents," approved May 26, 1989, along with further specifications for sieve size and sieving time used in the analysis. carried out using To cover the range of particle sizes referred to herein, according to Section 7, "Procedure using machine-sieving method," US Standard (ASTM E 11) sieves #4 (4.75 mm), #6 (3 .35mm), #8 (2.36mm), #12 (1.7mm), #16 (1.18mm), #20 (850um), #30 (600um), #40 (425um), #50 (300um) ), #70 (212 um), #100 (150 um), and a clean, dry sieve nest. A defined mechanical sieving method is used with the nested sieves described above. A suitable sieve shaker is available from W.W. S. available from Tyler Company (Ohio, USA). A sieve shake test sample is approximately 100 grams and is shaken for 5 minutes.

The data is plotted on a semi-logarithmic plot that plots the micrometer-sized openings of each sieve against the logarithmic horizontal axis and the cumulative mass percent (Q ₃ ) against the linear vertical axis. Examples of such data representations are found in ISO 9276-1:1998, "Representation of results of particle size analysis--Part 1: Graphical Representation", Figure A.1. 4. Characteristic particle size (Dx) is defined for the purposes of this invention as the abscissa value at the point where the cumulative mass percent equals x percent, just above (a) and just below the x% value using the following formula: Calculated by linear interpolation between the data points in (b).
Dx = 10 ^ [Log (Da) - (Log (Da) - Log (Db)) x (Qa - x%) / (Qa - Qb)]
(Wherein, Log is the base 10 logarithm, Qa and Qb are the cumulative mass percentiles of the measured data immediately above and below the x-th percentile, respectively, and Da and Db are , are the sieve size values (μm) corresponding to these data).

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

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

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

Diameter Test Method A Scanning Electron Microscope (SEM) or optical microscope and image analysis software are used to determine the diameter of discrete fiber elements or fiber elements within a fiber structure. A magnification of 200 to 10,000 times is selected to properly magnify the fiber element for measurement. When using SEM, gold or palladium compounds are sputtered onto the sample to avoid charging and vibration of the fiber elements in the electron beam. A manual procedure is used to measure the fiber element diameter from images (on a monitor screen) obtained using an SEM or optical microscope. Using the mouse and cursor tools, find the edge of a randomly selected fiber element and then the other edge of the fiber element across its width (i.e. perpendicular to the direction of the fiber element at that point). Measure up to A calibrated image analysis tool provides the scale to get the actual reading in microns. For the fiber elements within the fiber structure, SEM or optical microscopy is used to randomly select some fiber elements from the entire sample of the fiber structure. At least two portions of the fibrous structure are cut and tested in this manner. For statistical analysis, a total of at least 100 such measurements are performed and all data are then recorded. The recorded data are used to calculate the mean fiber element diameter (mean), the standard deviation of the fiber element diameter, and the median fiber element diameter.

Another useful statistic is the calculation of the amount of fibrous element population that is below a specified upper limit. To determine this statistic, the software was programmed to count the number of fiber element diameter results that were less than the upper limit, and that count (divided by the total number of data and multiplied by 100%) was , as percent less than the upper limit (eg, percent less than 1 micrometer in diameter or submicron percent). We denote the measured diameter (μm) for an individual circular fiber element as di.

If the fiber element has a non-circular cross-section, the measurement of the diameter of the fiber element is taken as the hydraulic diameter and set equal to the hydraulic diameter. The hydraulic diameter is the cross-sectional area of the fibrous element times four divided by the perimeter of the cross-section of the fibrous element (perimeter in the case of hollow fibrous elements). Number-average diameter, or mean diameter, is calculated as follows:

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

Analyze by cutting a line from one sealed edge to the other end to form a triangle approximately 20 mm below the tip where the two complete sealed edges meet A test sample is prepared to obtain a section approximately 28 mm in length. Prepared samples are laid flat in alternating layers between rings of low-attenuation sample preparation mounting foam and mounted within a 35 mm diameter plastic cylindrical tube for scanning. A scan of the sample is acquired such that the entire volume of all mounted cut samples is included in the data set.

To reliably and repeatably measure the volume percentage of fibers, particles, and void space within a sample, create 3D slab data from which the particles, fibers, and void space can be qualitatively evaluated from a cross-section of the product. Extract a small sub-volume of the sample. Create a mask that contains the data for this volume. The mask must not contain void elements outside the product that would bias the void volume measurement. Additionally, the area of the product selected for analysis is based on a fixed distance from physical landmarks on the product.

To divide the interior of the volume into three regions: 1) particles, 2) fibers, and 3) void space, we utilize an auto-thresholding algorithm that optimally separates these three regions. Since the particles are denser than the fibers, an additional step of slight expansion of the segmented particles should also be performed. This allows for the expected partial volume mean at the surface of the particles to be taken into account. The expanded segmented particles can then have a calculated total volume. A lower threshold is then used to separate the fibers from the air. The fiber volume is the intersection of voxels above the lower threshold and is not part of the particle area. Finally, the void volume is then obtained by subtracting the overall mask volume from the union of the fiber and particle volumes.

This single implementation is done through the use of two software platforms: Avizo 9.2.0 and Matlab R2016b, both running on Windows 64bit workstations. In this case, data were collected from a Scancom mCT503D X-ray micro-CT scanner and collected at a resolution of 7 micrometer voxels. After scanning and image reconstruction are complete, the scanner creates a 16-bit data set called an ISQ file, where gray levels reflect changes in x-ray attenuation and are, in turn, related to material density. . In this case, the ISQ is fairly large, with dimensions of 5038×5038×1326.

Load the ISQ file into Avizo 9.2.0. Convert to 8 bits using a scaling factor of 0.15. Select a subvolume that is oblique to one corner offset by 11 mm. A 3.5 mm thick slab is selected for analysis.

To apply a robust autothresholding scheme, cross-sectional slices from each of the three samples are read into Matlab R2016B. A function called "multithresh( )" is then used to divide the segment into N different regions (N=2 in this example). 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. The average value of these thresholds for 3 samples was then chosen. In this example, the threshold for separating particles from fibers was 124 and the threshold for separating fibers from air was 48. A further extension using a spherical structuring element of radius 1 is used in the segmented particle data to compensate for partial volume averaging. A histogram function in Avizo then allows the calculation of the total volume associated with the fibers and particles and the total mask volume. The void volume is then obtained from subtracting the volume of fibers and particles from the total mask volume. These results may then be transferred to Excel for further analysis or visualization.

Particle size density:
A particle size density test is used to measure the density of synthetic granular detergents.

The preparation of grams of sample per liter of cup density is measured on the product at room temperature. More than one carton may be required to conduct testing for small packing. The table below shows a preferred sampling of different size cartons.

To run the test, one should be a liter cup. The bottom opening of the funnel is then plugged and the room temperature sample is poured into the funnel (approximately 3/4 full). Enough sample should be used to fill and overflow the cup. The cup is then placed on the positioning stand, directly below the center of the funnel. Remove the plug and make sure the sample flows freely into the cup. Scrape the cup to make it full and level. Be very careful not to shake or tap the cup prior to scrubbing.

Finally, weigh the cup and contents. Density (grams per liter) equals the net weight in the cup (g).

Wash Residue Test Method The wash residue test qualitatively measures detergent residue on fabrics. Each test includes 4 comparative product samples, with 4 replicates for each product sample. The test uses a Whirlpool Duet washing machine (model number WFW 9200 SQO2) connected to a water temperature control system set at 50°F +/- 1°F.

A black velvet pouch is available from Equest U.S.A. K. (phone number (01207) 529920).
1. Material Source: Denholme Velvets, Halifax Road, Denholme, Bradford, West Yorkshire, England BD134EZ (phone number (01274) 832646).
2. Material type: 150 cm C.I. R. Cotton Pile Velvet, quality 8897, black, 72% cotton, 28% modal.
3. Equest suture instructions: Cut out a 23.5 cm x 47 cm black velvet rectangle. Fold the black velvet rectangle to create a velvet square on the inside. Using an overlock stitch, sew the square along two sides, leaving one open edge. A blank identification label (3 x 3 cm flat cotton) is sewn to one side.

Exam preparation:
1. At one open edge, flip the pouch over so that the velvet is on the outside.
2. Write the product code and internal/external copy on the identification label with magic ink.
3. Place the recommended dose of water soluble unit dose product for normal/medium soil and normal/medium water hardness in the right rear corner of the black velvet pouch.
4. The open end of the black pouch is folded over at the 2 cm seam and closed with a seam at the center of the 2 cm wide seam along the entire length of the opening.
5. These steps are repeated for a total of 4 replicates per test product.
6. Place the black pouch in the washing machine and wash as follows.

Cleaning the black pouch:
Alternately, the four black velvet pouches are placed on top of each other such that the water soluble unit dose product is all adjacent to each other as shown in FIG. Place the placed pouch on the rear of the drum.

The washing machine is turned on, set to the delicate wash program, using a water mix of 50°F +/- 1°F (via water temperature control system) and 6 gpg hardness, with no additional ballast load. In the washing machine, go through the entire wash cycle. At the end of the wash cycle, the pouch is removed from the washing machine and opened along three sides (all but the folded side) to ensure no residue spills.

Grade the pouches immediately after opening. Record the grades of two independent graders. Data are analyzed as a Latin square, and the analysis incorporates washing machines and product locations into the statistical model. Least squares means and 95% upper confidence intervals are constructed. A water-soluble unit dose product is considered to have passed the test if the 95% one-sided upper confidence interval around the mean scale unit is less than one.

The grading is done by visual observation of the residue left in/on the bag after washing.

Grade the black pouches according to the following qualitative scale:
0 = no residue 0.5 = very small spots with maximum diameter of 1 cm 1 = up to 3 small diffuse spots with maximum diameter of 2 cm each, spots are flat (ie film-like) and translucent.
2 = More than 3 small diffuse spots, each 2 cm in diameter, up to the entire black pouch covered with a flat translucent residue.
2.5 = Small opaque residue less than 1 cm in diameter (ie gel-like).
3 = Opaque residue (eg, gel-like) 1-2 cm in diameter.
4 = Opaque residue (eg, gel-like) 3 cm to 4 cm in diameter.
5 = Thick gel-like residue with a diameter of 4-6 cm.
6 = Thick gel-like residue with diameter >6 cm.
7 = Product does not dissolve substantially, residue is soft and gel-like.
8 = Product did not dissolve substantially, residue was hard and elastic (feels like silicone), Grade 8 is special as it indicates that the product may have been contaminated.

(Example 1)
As shown in FIG. 3, a first spin beam is used to spin a first layer of fibrous elements and collect them on a forming belt. The forming belt with the first layer of fibers is then passed under a second spin beam modified with a particle addition system. The particle addition system can substantially inject particles from the second spin beam toward a landing zone on the forming belt immediately below the fiber elements. Suitable particle addition systems may be assembled from particle feeders such as vibratory, belt or screw feeders, and injection systems such as air knives or other fluidized conveying systems. To aid consistent distribution of the particles in the transverse direction, the particles are preferably fed over approximately the same width as the spinning die to ensure that the particles are delivered across the entire width of the composite structure. Preferably, the particle feeder is completely enclosed except for the outlet to minimize disruption of the particle feed material. Co-collision of the particles and fiber elements on the forming belt under the second spin beam expands the particle packings and creates a composite structure in which the fibers substantially penetrate the inter-particle pores.

Table 3 below lists non-limiting examples of dry fibrous compositions of the present invention used to make fibrous elements. To make the fibrous element, an aqueous solution, preferably having a solids content of about 45% to 60%, is processed through one or more spinning beams as shown in FIG. A suitable spin beam includes a capillary die having an attenuating air stream and a drying air stream suitable for substantially drying the attenuated fibers prior to impingement on the forming belt.

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

The resulting products are illustrated in Table 5, which provides details of the construction of the product chassis by fiber and particle components (from Tables 3 and 4, respectively) using the undiluted chassis composition for the product. Note that other product adjunct materials such as fragrances, enzymes, suds suppressors, bleaches, etc. may be added to the chassis.

The wash residue test grade for each chassis is shown. Chassis exemplifies a variety of detergent products with a significant proportion of ethoxylated anionic surfactants (AES).

As shown in Tables 5 and 6 and described above, C11 and C12 include both F2 and P12, while C13 includes F7 and P13. P12 and P13 differ from other particles by having a density of 250 g/L to 400 g/L and a particle size distribution such that D10 is greater than about 300 microns and D90 is less than about 1100 microns. has surprising advantages over Moreover, as shown in Table 4, both P12 and P13 achieve LAS:AES ratios greater than 1.0.

While not wishing to be bound by theory, particles with a LAS:AES ratio greater than 1 produced by introducing LAS into separate slurries or agglomerations are similar to introducing LAS through the fibrous web. A better fibrous detergent unit dose can be produced for a fibrous detergent unit dose having more than the amount of LAS. LAS particles introduced by agglomeration are believed to produce low density particles that can more easily wash out the active surfactant. As shown in Table 5, the use of particles exhibiting low density and a LAS:AES ratio greater than 1 results in a residual test pass rate with an average grade and a standard deviation of 0.0. This is particularly beneficial in that the composition does not require significant amounts of inorganic solubilizers, in contrast to Chassis C8. In comparison, other chassis with LAS:AES ratios greater than 1 introduced LAS via a web system and did not utilize particles with LAS:AES ratios greater than 1 (C1 used F1 and P1; C2 uses F2 and P1, C4 uses F2 and P3, C6 uses F2 and P4, C8 uses F2 and P6, C10 uses F2 and P8), FAIL OR or pass with a higher standard deviation, yielding less clean results. As previously mentioned, C8 requires an inorganic solubilizer (zeolite). Moreover, it is a chassis that can provide the majority of the LAS through the web, as shown by C10, which has a total LAS:AES ratio of 1:1.

As shown in Table 4, the particles contain less than 5% by weight of inorganic solubilizer, preferably 0% to 5% by weight of inorganic solubilizer, more preferably 0.01% to 3% by weight of inorganic solubilizer. Auxiliaries, even more preferably 0.001% to 1% by weight of inorganic solubilizers may be included.

As shown in Table 5, the water-soluble unit dose article contains less than 5 wt% inorganic solubilizer, preferably 0 wt% to 5 wt% inorganic solubilizer, more preferably 0.01 wt% to 3 wt%. % inorganic solubilizer, and even more preferably 0.001 wt % to 1 wt % inorganic solubilizer.

This effect of using low density particles with a LAS:AES ratio greater than 1 is further exemplified by C6, which utilizes higher density particles, P4 (shown in Table 6), as shown in Table 5, P4. , F2 does not pass the residue test because it contains a total product LAS:AES ratio greater than 1. As mentioned above, and not wishing to be bound by theory, lower density particles allow for increased dissolution rates and thus more readily available surfactants, increasing the availability of surfactants. It is believed to reduce the likelihood of residue while increasing.

Raw Materials for Example 1 LAS is a linear alkyl benzene sulfonate with an average aliphatic carbon chain length of C ₁₁ -C ₁₂ supplied by Stepan (Northfield, Illinois, USA) or Huntsman Corp. HLAS is in acid form.

AES is C ₁₂ -C ₁₄ alkylethoxy (3) sulfate, C ₁₄ -C ₁₅ alkylethoxy (2.5) supplied by Stepan (Northfield, Illinois, USA) or Shell Chemicals (Houston, TX, USA). ) sulfates, or C ₁₂ -C ₁₅ alkylethoxy (1.8) sulfates.

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

The dispersant polymer (Disp. polymer) is a 70,000 molecular weight acrylate with a maleate ratio of 70:30 (supplied by BASF, Ludwigshafen, Germany).

PEG-PVAc polymers are polyvinyl acetate grafted polyethylene oxide copolymers having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40-60 with no more than 1 graft point per 50 ethylene oxide units. It is sold by BASF (Ludwigshafenm, Germany).

Ethoxylated polyethyleneimine (PE20) is a 600 g/mole molecular weight polyethyleneimine core with 20 ethoxylate groups per -NH. It is sold by BASF (Ludwigshafenm, Germany).

Figures 4-10 show one embodiment of a single dose laundry detergent unit embodying the novel design.

Figures 11-18 show one embodiment of a single dose laundry detergent unit embodying the novel design.

Figures 18-24 show one embodiment of a single dose laundry detergent unit embodying the novel design.

Figures 25-31 show one embodiment of a single dose laundry detergent unit embodying the novel design.

Figures 32-38 show one embodiment of a single dose laundry detergent unit embodying the novel design.

Figures 39-45 show one embodiment of a lidless container embodying the new design.

Figures 46-52 show one embodiment of a container with a lid embodying the new design.

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

For purposes of clarity, total "% by weight" values do not exceed 100% by weight.

All documents cited herein, including cross-referenced documents or related patents or applications, are hereby incorporated by reference in their entirety unless expressly excluded or otherwise limited. . Citation of any document is not considered prior art to any invention disclosed or claimed herein, or taken alone or in combination with any other reference(s) At times, it is not considered to teach, suggest or disclose any such invention. 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 that term in this document shall control. shall be

While specific examples and/or embodiments 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. . It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (17)

A water-soluble unit dose article comprising a water-soluble fibrous structure comprising particles comprising a ratio of linear alkylbenzene sulfonate to alkyl ethoxylated sulfate of greater than 1. 2. The water-soluble unit dose article of Claim 1, wherein said water-soluble unit dose article comprises less than 5% by weight of an inorganic solubilizer . 3. A water-soluble unit dose article according to claim 1 or 2, wherein said particles comprise less than 5% by weight of an inorganic solubilizer . 4. The water-soluble unit dose article of claim 2 or 3, wherein said inorganic solubilizer comprises a zeolite. The alkyl ethoxylated sulfate is about 1 to about 3. A water-soluble unit dose article according to any one of claims 1 to 4, having an average degree of ethoxylation of 5 . A water-soluble unit dose article according to any preceding claim, wherein said particles exhibit a density of less than 500 grams per liter (g/L). A water-soluble unit dose article according to any preceding claim, wherein said water-soluble unit dose article comprises a rheology modifier, said rheology modifier being selected from the group consisting of alkoxylated amines . . 8. The water-soluble unit dose article of Claim 7, wherein the alkoxylated amine comprises ethoxylate (EO) groups, propoxylate (PO) groups, or combinations thereof . A water-soluble unit dose article according to any preceding claim, wherein the particles exhibit a particle size distribution such that the D10 is greater than about 300 microns and the D90 is less than about 1100 microns. A water-soluble unit dose article according to any preceding claim, wherein the particles exhibit a particle size distribution such that the D10 is between 300 micrometers and 500 micrometers. A water-soluble unit dose article according to any preceding claim, wherein said water-soluble unit dose article comprises perfume microcapsules. A water-soluble unit dose article according to any one of claims 1 to 11, wherein said water-soluble unit dose article comprises a toning agent. The water-soluble unit dose article of any one of claims 1-12, wherein the water-soluble unit dose article comprises a bleaching agent. The water-soluble unit dose article of any one of claims 1-13, wherein the water-soluble unit dose article comprises an enzyme. The water-soluble unit dose article of any one of claims 1-14, wherein the water-soluble unit dose article comprises a printed area. The water-soluble unit dose article of any one of claims 1-15, wherein the water-soluble unit dose article comprises an aversive agent. The water-soluble unit dose article of any one of claims 1-16, wherein the water-soluble unit dose article comprises a nonionic surfactant.

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