阅读说明：本技术 减少织物上的恶臭的方法 (Method for reducing malodor on fabrics ) 是由 M·R·斯维克 索尔·梅丽莎·埃斯科巴尔 S·A·德莱尼 弗兰克·威廉·德诺姆 马克·威廉· 于 2020-03-19 设计创作，主要内容包括：本发明涉及使用酸递送组合物来减少织物上的恶臭的方法。(The present invention relates to a method of reducing malodor on fabrics using an acid delivery composition.)

1. A method of reducing malodor on a fabric, the method comprising the steps of;

a. mixing fabric with a wash liquor, wherein the fabric comprises at least one source of malodor, and wherein the wash liquor comprises a detergent and a concentrated acid delivery source in water-soluble unit dose form;

b. washing the fabrics in the wash liquor using an automatic wash operation, a manual wash operation, or a mixture thereof, preferably using an automatic wash operation; and

c. separating the fabric and the wash liquor from each other.

2. The method of any one of the preceding claims;

a. wherein the fabric is washed in the wash liquor at a temperature of between 10 ℃ and 60 ℃, preferably between 10 ℃ and 45 ℃, more preferably between 10 ℃ and 35 ℃;

b. wherein the washing operation in step b takes 5 to 60 minutes, preferably 5 to 45 minutes, more preferably 5 to 30 minutes;

c. or a mixture thereof.

3. The method of any preceding claim, wherein the laundry detergent comprises an ingredient selected from the list comprising: cationic polymers, polyester terephthalates, amphiphilic graft copolymers, carboxymethylcellulose, enzymes, perfumes, encapsulated perfumes, bleaching agents or mixtures thereof.

4. The method according to any preceding claims, wherein laundry detergent composition is a liquid, and wherein liquid laundry detergent composition has a pH of between 6 and 10, more preferably between 6.5 and 8.9, most preferably between 7 and 8, wherein the pH of the liquid laundry detergent composition is measured as neat pH.

5. The method according to any one of claims 1 to 4, wherein the laundry detergent composition is a liquid, and wherein the liquid laundry detergent composition has a pH of between 6 and 10, more preferably between 6.5 and 8.9, most preferably between 7 and 8, wherein the pH of the liquid laundry detergent composition is measured as neat pH.

6. The method according to any one of claims 1 to 4, wherein the laundry detergent composition is a liquid, and wherein the liquid laundry detergent composition has a pH of between 2 and 6, more preferably between 2 and 5, most preferably between 3 and 4, wherein the pH of the liquid laundry detergent composition is measured as neat pH.

7. The method of any preceding claim, wherein the water-soluble unit dose comprises an active agent acid selected from the group consisting of: acetic acid, adipic acid, aspartic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, citric acid, formic acid, glutaric acid, gluconic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid-disuccinic acid, tartaric acid-monosuccinic acid, salts thereof, or mixtures thereof.

8. The method of claim 7, wherein the active agent acids are citric acid and sodium citrate.

9. The method of any preceding claim, wherein the water-soluble unit dose comprises citric acid comprising a coating.

10. The method of any one of claims 7 to 9, wherein the citric acid is used as a bittering agent within the water-soluble unit dose article.

11. The method of any preceding claim, wherein the water-soluble fiber unit dose comprises a bittering agent on an outer surface.

12. The method of any one of the preceding claims, wherein the water-soluble unit dose comprises an active agent, wherein the active agent comprises about 50% to 70% by weight of the water-soluble unit dose.

13. The method of any preceding claim, wherein the water-soluble unit dose comprises a soluble fibrous structure, wherein the soluble fibrous structure forms a pouch that encapsulates an active agent.

14. The method of claim 13, wherein the active agent is mixed with the soluble fibrous structure to form a coform structure.

15. The method of any one of claims 13 to 14, wherein the soluble fibrous structure comprises a fibrous element having a surfactant therein.

16. The method of any one of the preceding claims, wherein the composition of the water-soluble unit dose comprises 50% or more biobased material.

17. The method of any one of claims 13 to 16, wherein the fibrous structure comprises a fibrous element comprising starch.

Technical Field

The present invention relates to a method of reducing malodor on fabrics using a combination of a detergent composition and an acid delivery system.

Background

Laundry washing processes are designed to remove soils from fabrics. Some soils can cause malodours on fabrics and in some cases these malodours can persist even after laundry washing operations.

Thus, there is a continuing need for methods of reducing malodor on fabrics.

It was surprisingly found that the method according to the invention reduces malodour on fabrics.

Without being bound by theory, it is believed that the addition of the concentrated acid delivery system in combination with the detergent during this wash cycle provides a reduced malodor benefit on the fabric through the wash.

Disclosure of Invention

A first aspect of the present invention is a method of reducing malodor on a fabric, the method comprising the steps of;

a. mixing the fabric with a wash liquor, wherein the fabric comprises at least one source of malodor, and wherein the wash liquor comprises a detergent and a concentrated acid delivery source;

b. washing the fabric in a wash liquor using an automatic wash operation, a manual wash operation or a mixture thereof, preferably an automatic wash operation; and

c. the fabric and the wash liquor are separated from each other.

A second aspect of the present invention is the use of a method of reducing malodour on fabrics in a wash liquor, the method comprising the steps of:

a. mixing the fabric with a wash liquor, wherein the fabric comprises at least one source of malodor, and wherein the wash liquor comprises a detergent having a pH of less than 6 and a concentrated acid delivery source;

b. washing the fabric in a wash liquor using an automatic wash operation, a manual wash operation or a mixture thereof, preferably an automatic wash operation; and

c. the fabric and the wash liquor are separated from each other.

Drawings

FIG. 1 is a schematic illustration of a cross-sectional view of an example of a multi-ply fibrous structure.

Fig. 2 is a perspective view of an example of a water-soluble unit dose article.

FIG. 3 is a micro CT scan image showing a cross-sectional view of an example of a water-soluble unit dose article taken along line 3-3.

Fig. 4 is an enlarged view of a portion of fig. 3.

Detailed Description

Method

The present invention relates to a method of reducing malodor on fabrics.

"malodour" in the context of the present invention is an undesirable or undesirable odour on fabrics. Those skilled in the art will recognize what is an undesirable odor as compared to a desirable odor.

The method comprises the step of mixing the fabric with a wash liquor, wherein the fabric comprises at least one source of malodour, and wherein the wash liquor is prepared by diluting a laundry detergent composition and a water-soluble fibre unit dose in water by a factor of 100 to 3000, preferably 300 to 900. The fabric may be any suitable fabric. By fabric is preferably meant a textile or cloth comprising a network of natural or synthetic fibres. Suitable fabrics will be known to those skilled in the art. The fabric may be selected from cotton, polyester, cotton/polyester blends, polyamide, lycra, rayon, or mixtures thereof.

The fabric comprises at least one source of malodor. One skilled in the art will know of suitable sources of malodor. The malodor source may include chemical breakdown products of the body scale. The malodor source may include 6-methyl-5-heptan-2-one, trans-2-heptanal, 3-methyl-2-butenal, or mixtures thereof.

The person skilled in the art will know how to prepare the washing liquid. Without being bound by theory, addition of the laundry detergent composition to water will cause the laundry detergent composition to dissolve and form a wash liquor.

The wash liquor may be formed automatically within the drum of an automatic washing machine, or may be made in a manual washing operation.

The laundry detergent composition may be contained in a water-soluble unit dose article, wherein the water-soluble unit dose article comprises a water-soluble film. The laundry detergent composition may be a liquid detergent or a powder detergent. The laundry detergent composition may be a fiber detergent or in the form of a sheet. The detergent will be mixed with water to form the main wash liquid. The wash liquor may be formed automatically within the drum of an automatic washing machine, or may be made in a manual washing operation. When made in the drum of an automatic washing machine, fabrics to be washed and water-soluble unit dose articles are conventionally added to the drum and the door of the washing machine is closed. The washing machine then automatically adds water to the drum to form a wash liquor.

Preferably, the wash liquor comprises between 1L and 64L, preferably between 2L and 32L, more preferably between 3L and 20L of water.

Laundry detergent compositions are described in more detail below.

The method further comprises washing the fabric in the wash liquor using an automatic wash operation, a manual wash operation or a combination thereof, preferably an automatic wash operation.

Those skilled in the art will know how to wash fabrics in an automatic washing operation, a manual washing operation, or a combination thereof.

Preferably, the temperature of the wash liquor is between 5 ℃ and 90 ℃, preferably between 10 ℃ and 60 ℃, more preferably between 12 ℃ and 45 ℃, most preferably between 15 ℃ and 40 ℃.

Preferably, washing the fabric in the wash liquor takes between 5 and 50 minutes, preferably between 5 and 40 minutes, more preferably between 5 and 30 minutes, even more preferably between 5 and 20 minutes, most preferably between 6 and 18 minutes to complete.

Preferably, the wash liquor comprises between 1kg and 20kg, preferably between 3kg and 15kg, most preferably between 5kg and 10kg of fabrics.

The wash liquor may comprise water of any hardness preferably varying between 0gpg and 40 gpg. The lower hardness water is referred to as soft water, and the higher hardness water is referred to as hard water.

The method further comprises separating the fabric and the wash liquor from each other.

After the fabric is washed, the fabric and the wash liquor are separated from each other. Such separation may involve removing the fabric from the wash liquor, or draining the wash liquor from the fabric. In automatic washing machine operation, it is preferred to drain wash liquid from the fabrics. For the avoidance of doubt, some of the wash liquor may remain saturated into the fabric after it has been separated from the main wash liquor, i.e. the fabric remains wet. For the purposes of the present invention, once the fabrics are separated from the main volume of wash liquor or the secondary volume of wash liquor has been drained, the fabrics and wash liquor are considered to be separated from one another, although some residual wash liquor may still be impregnated into the fabrics.

The method also includes drying the fabric.

One skilled in the art will know suitable methods to dry the fabric. The fabric may be dried in place at room temperature, dried in an automatic dryer, or a combination thereof. One skilled in the art will know when to consider a fabric as dry rather than wet.

Laundry detergent composition

The process according to the present invention comprises the step of diluting the laundry detergent composition. The laundry detergent composition may have a pH of greater than 6 or less than 6.

Laundry detergent compositions having a pH greater than 6 may be in the form of a powder, a liquid, a water-soluble unit dose article or a mixture thereof, preferably comprising a water-soluble unit dose of a liquid composition.

The solid laundry detergent composition may comprise solid particles or may be a single homogeneous solid. Preferably, the solid laundry detergent composition comprises a particulate. This means that the solid laundry detergent composition comprises separate solid particles, as opposed to a solid which is a single homogeneous solid. The particles may be free flowing or may be compacted, preferably free flowing.

The term "liquid laundry detergent composition" refers to any laundry detergent composition comprising a liquid capable of wetting and treating fabrics, and includes, but is not limited to, liquids, gels, pastes, dispersions, and the like. Liquid compositions may include solids or gases in suitably subdivided form, but liquid compositions do not include generally non-fluid forms such as powders, tablets or granules.

The water-soluble unit dose articles are described in more detail below.

The laundry detergent composition comprises between 0.01% and 5%, more preferably from 0.03% to 1%, most preferably from 0.05% to 0.5% by weight of the laundry detergent composition of an oligoamine or a salt thereof. Oligoamines or their salts are described in more detail below.

The laundry detergent composition preferably comprises a non-soap surfactant. More preferably, the non-soap surfactant is selected from non-soap anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, or mixtures thereof. The laundry detergent composition preferably comprises between 10% and 60%, more preferably between 20% and 55% by weight of the laundry detergent composition of a non-soap surfactant.

Preferably, the non-soap anionic surfactant comprises linear alkylbenzene sulphonate, alkoxylated alkyl sulphate, alkyl sulphate or a mixture thereof. Preferably, the alkyl sulfate is an ethoxylated alkyl sulfate.

Preferably, the laundry detergent composition comprises between 5% and 50%, preferably between 15% and 45%, more preferably between 25% and 40%, most preferably between 30% and 40% by weight of the detergent composition of non-soap anionic surfactant.

Preferably, the non-soap anionic surfactant comprises linear alkylbenzene sulphonate and alkoxylated alkyl sulphate, wherein the ratio of linear alkylbenzene sulphonate to alkoxylated alkyl sulphate, preferably the weight ratio of linear alkylbenzene sulphonate to ethoxylated alkyl sulphate, is from 1:2 to 20:1, preferably from 1.1:1 to 15:1, more preferably from 1.2:1 to 10:1, even more preferably from 1.3:1 to 5:1, most preferably from 1.4:1 to 3: 1.

Preferably, the laundry detergent composition comprises between 0% and 10%, preferably between 0.01% and 8%, more preferably between 0.1% and 6%, most preferably between 0.15% and 4% by weight of the laundry detergent composition of a nonionic surfactant. The nonionic surfactant is preferably selected from the group consisting of alcohol alkoxylates, oxo alcohol alkoxylates, guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates or mixtures thereof.

Preferably, the liquid laundry detergent composition comprises between 1.5% and 20%, more preferably between 2% and 15%, even more preferably between 3% and 10%, most preferably between 4% and 8% by weight of the laundry detergent composition of soap, preferably a fatty acid salt, more preferably an amine neutralised fatty acid salt, wherein preferably the amine is an alkanolamine, more preferably selected from monoethanolamine, diethanolamine, triethanolamine or mixtures thereof, more preferably monoethanolamine.

The laundry detergent composition comprises an ingredient selected from the list comprising: cationic polymers, polyester terephthalates, amphiphilic graft copolymers, carboxymethylcellulose, enzymes, perfumes, encapsulated perfumes, bleaching agents or mixtures thereof. Without being bound by theory, it is believed that further addition of these materials may further contribute to malodor reduction.

Laundry detergent compositions may comprise adjunct ingredients selected from non-aqueous solvents, water, hueing dyes, aesthetic dyes, enzymes, cleaning polymers, builders such as fatty acids, bleaches, dispersants, dye transfer inhibitor polymers, optical brighteners, opacifiers, antifoams or mixtures thereof.

Preferably, the laundry detergent composition comprises a chelant, wherein the chelant is preferably selected from the group consisting of phosphonates, amino carboxylates, amino phosphonates, polyfunctional substituted aromatic chelants or mixtures thereof, more preferably from DTPA (diethylenetriamine pentaacetic acid), HEDP (hydroxyethane diphosphonic acid), EDDS (ethylenediamine disuccinate (EDDS)), DTPMP (diethylenetriamine penta (methylenephosphonic acid)), EDTMP (ethylenediamine tetra (methylenephosphonic acid)), and mixtures thereof,(1, 2-dihydroxybenzene-3, 5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycinediacetic acid), GLDA (glutamic-N, N-diacetic acid), any suitable derivative thereof, a salt thereof, and mixtures thereof.

The laundry detergent composition may comprise an antioxidant. Without being bound by theory, it is believed that antioxidants can help improve malodor control and/or cleaning performance of the compositions, particularly in combination with the oligomeric amines of the present disclosure. Antioxidants can also help reduce yellowing that can be associated with amines, allowing amines to be formulated at relatively high levels.

The laundry detergent composition may comprise the hindered phenol antioxidant in an amount of from 0.001% to 2%, preferably from 0.01% to 0.5% by weight of the laundry detergent composition.

Suitable antioxidants may include alkylated phenols having the general formula:

wherein R is C₁-C₂₂Straight chain alkyl or C₃-C₂₂Branched alkyl groups, each (1) optionally having one or more esters (-CO) therein₂-) or an ether (-O-) linkage, and (2) is optionally substituted with an organic group comprising an alkyleneoxy or polyalkyleneoxy group selected from EO (ethoxy), PO (propoxy), BO (butoxy), and mixtures thereofMore preferably EO alone or a mixture of EO/PO; r may preferably be methyl, branched C₃-C₆Alkyl, or C₁-C₆Alkoxy, preferably methoxy; r¹Is C₃-C₆A branched alkyl group, preferably a tert-butyl group; x is 1 or 2.

Preferred types of alkylated phenols having this general formula may include hindered phenol compounds. As used herein, the term "hindered phenol" is used to refer to a compound comprising a phenolic group having (a) at least one C attached at an ortho position to at least one phenol-OH group₃Or higher branched alkyl, preferably C₃-C₆A branched alkyl group, preferably a tertiary butyl group, or (b) a substituent independently selected from the group consisting of: c₁-C₆Alkoxy, preferably methoxy; c₁-C₂₂Straight chain alkyl or C₃-C₂₂Branched alkyl, preferably methyl or branched C₃-C₆An alkyl group; or mixtures thereof. If the phenyl ring contains more than one-OH group, the compound is a hindered phenol, provided that at least one such-OH group is substituted as described immediately above. When any R group in the above structure comprises three or more contiguous monomers, the antioxidant is defined herein as a "polymeric hindered phenol antioxidant. Compositions according to the present disclosure may comprise a hindered phenol antioxidant. Preferred hindered phenol antioxidants include 3, 5-di-tert-butyl-4-hydroxytoluene (BHT).

Another class of hindered phenolic antioxidants that may be useful in the composition are benzofuran or benzopyran derivatives having the formula:

wherein R is₁And R₂Each independently is alkyl, or R₁And R₂Can be taken together to form C₅-C₆A cyclic hydrocarbyl moiety; b is absent or CH₂；R₄Is C₁-C₆An alkyl group; r₅Is hydrogen or-C (O) R₃Wherein R is₃Is hydrogen or C₁-C₁₉An alkyl group; r₆Is C₁-C₆An alkyl group; r₇Is hydrogen or C₁-C₆An alkyl group; x is-CH₂OH or-CH₂A, wherein A is a nitrogen-containing unit, a phenyl group, or a substituted phenyl group. Preferred nitrogen-containing a units include amino, pyrrole, piperidine, morpholine, piperazine, and mixtures thereof.

Suitable hindered phenol antioxidants may include: 2, 6-bis (1, 1-dimethylethyl) -4-methyl-phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylpropionic acid methyl ester; octadecyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate; or mixtures thereof.

Commercially available antioxidants that may be suitable include BHT, RALOX 35^TMAnd/or TINOGARD TS^TM。

Additional antioxidants may be employed. Examples of suitable antioxidants for use in the compositions include, but are not limited to, alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, ethoxyquin, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and its salts, and mixtures thereof. Notably, ethoxyquinoline (1, 2-dihydro-6-ethoxy-2, 2, 4-trimethylquinoline)^TMUnder the trade name Raschig^TMCommercially available from the company Raschig. Another type of antioxidant that may be used in the composition is 6-hydroxy-2, 5,7, 8-tetramethylchroman-2-carboxylic acid (Trolox)^TM) And 1, 2-benzisothiazolin-3-one (Proxel GXL)^TM). Antioxidants such as tocopherol sorbate, butylated hydroxybenzoic acid and salts thereof, gallic acid and alkyl esters thereof, uric acid and salts thereof, sorbic acid and salts thereof, and dihydroxy fumaric acid and salts thereof may also be useful.

Non-yellowing antioxidants, such as non-yellowing hindered phenolic antioxidants, may preferably be used. The use of antioxidants that form such yellow byproducts can be avoided if they result in a negative attribute in the consumer experience that is perceptible (such as, for example, the deposition of the yellow byproduct on the fabric). The skilled person is able to make informed decisions about the choice of antioxidant to be employed.

The above liquid laundry detergent composition preferably has a pH of between 6 and 10, more preferably between 6.5 and 8.9, most preferably between 7 and 8, wherein the pH of the liquid laundry detergent composition is measured as neat pH. To evaluate the liquid laundry detergent pH, wash liquor pH, or rinse liquor pH, a 50mL aliquot may be sampled from a north american top-loading washing machine having a volume of about 64 liters. Alternatively, if the detergent is a solid laundry detergent, the solid laundry washing machine preferably has a pH of between 6 and 10, more preferably between 6.5 and 8.9, most preferably between 7 and 8, wherein the pH of the solid laundry detergent composition is measured as 10 times diluted in demineralized water at 20 ℃.

Laundry detergent with pH below 6：

The detergent composition may be a low pH detergent composition comprising a sulfated surfactant, an organic acid, and an alkoxylated polyamine compound. Sulfated surfactants provide, for example, cleaning benefits in compositions suitable for cleaning hard surfaces and/or laundry. In order to provide effective cleaning, especially for laundry, it is desirable that the sulfated surfactant has an alkyl group of a specific chain length, for example at least 10 carbons, or at least 12 carbons, or at least 14 carbons. However, it is believed that longer alkyl chains tend to result in more interfaces being formed between the sulfated surfactants. This can present stability challenges because sulfated surfactants tend to hydrolyze in low pH systems, which is believed to be due in part to the interface between the surfactants. It has surprisingly been found that certain alkoxylated polyamine compounds can reduce the rate of hydrolysis. It is believed that the polyamine passes through the interruption H⁺Into the interface and/or by interrupting the interaction between the sulfated surfactants to provide a stabilizing effect.

Organic acids

Detergent compositions having a pH below 6 comprise one or more organic acids selected from acetic acid, lactic acid and citric acid.

The detergent compositions of the present invention may comprise additional organic acids. The additional organic acid may be in the form of an organic carboxylic acid or a polycarboxylic acid. Examples of organic acids that can be used include: acetic acid, adipic acid, aspartic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, citric acid, formic acid, glutaric acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiaacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid-disuccinic acid, tartaric acid-monosuccinic acid, or mixtures thereof. In some aspects, the compositions comprise an organic acid, such as citric acid, which can also be used as a detergent builder.

The organic acid may be a water-soluble or water-miscible acid. In some aspects, the organic acid has an aqueous solubility at 20 ℃ of at least about 10g acid/100 ml water or at least about 30g acid/100 ml water or at least about 50g acid/100 ml water or at least about 70g acid/100 ml water or at least about 85g/100ml water. In some aspects, the composition is substantially free of fatty acids.

The organic acid may be a low molecular weight acid, for example an acid having a molecular weight of less than 210 g/mol. In some aspects, the organic acid has no more than nine carbon atoms, alternatively no more than six carbon atoms. The organic acid in the detergent composition may have no more than four carbon atoms or no more than three carbon atoms or less than three carbon atoms. Specific examples of the organic acid having less than three carbon atoms include formic acid and acetic acid.

In some aspects, the compositions of the present disclosure comprise from about 6% to about 30%, or from about 8% to about 25%, or from about 10% to about 15%, or from about 12% to about 17% (such as 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%) of an organic acid, by weight of the composition.

Unless otherwise specified herein, the pH of a composition is defined as the neat pH of the composition at 20 ± 2 ℃. Any meter capable of measuring a pH to ± 0.01pH units is suitable. Oliglon instruments (Thermo Scientific, Clintinpark-Keppekouter, Ninovesenweg 198, 9320 Eremodegem-Aalst, Belgium) or equivalents are acceptable instruments. The pH meter should be equipped with a suitable glass electrode for calomel or silver/silver chloride reference. Examples include Mettler DB 115. The electrodes should be stored in electrolyte solutions recommended by the manufacturer. The pH was measured according to standard procedures of the pH meter manufacturer. In addition, the manufacturer's instructions for setting up and calibrating the pH assembly should be followed.

Concentrated acid delivery source：

The concentrated acid delivery source comprises a fibrous water-soluble unit dose containing an active agent as described below. As used herein, the phrases "water-soluble unit dose article", "water-soluble fibrous structure" and "water-soluble fibrous element" refer to unit dose articles, fibrous structures and fibrous elements that are miscible with water. In other words, the unit dose article, fibrous structure or fibrous element is capable of forming a homogeneous solution with water at ambient conditions. As used herein, "ambient conditions" means 23 ℃ ± 1.0 ℃ and a relative humidity of 50% ± 2%. The water soluble unit dose article may contain an insoluble material which is dispersible to a suspension under aqueous washing conditions and has an average particle size of less than about 20 microns, or less than about 50 microns.

Fibrous water-soluble unit dose articles may include those found in U.S. patent application 15/880,594 filed on 26.1.2018; us patent application 15/880,599 filed on 26.1.2018; and us patent application 15/880,604 filed on 26.1.2018; these patent applications are incorporated by reference in their entirety.

These fibrous water-soluble unit dose articles can dissolve under a variety of wash conditions, such as low temperature, low water and/or one or more short wash cycles, where the consumer has overloaded the machine, particularly articles with high water absorption capacity, while providing sufficient active agent to achieve the desired effect on the target consumer substrate (with similar performance as today's liquid products). Furthermore, the water-soluble unit dose articles described herein can be produced in an economical manner by spinning fibers comprising 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 comprise a printed area. The printed area may cover from about 10% to about 100% of the surface of the article. The printed area may include inks, pigments, dyes, bluing agents, or mixtures thereof. The printed area may be opaque, translucent or transparent. The printed area may comprise a single colour or a plurality of colours. The printed area may be on more than one side of the article and contain instructional text and/or graphics. The surface of the water-soluble unit dose article may comprise an aversive agent, such as a bittering agent. Suitable bitterants include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable amount of aversive agent may be used. Suitable levels include, but are not limited to, 1ppm to 5000ppm, or even 100ppm to 2500ppm, or even 250ppm to 2000 ppm.

The water soluble unit dose may utilize an acid as the bittering agent, preferably citric acid and its salts. Citric acid may be mixed with any of the aforementioned bitterants. Citric acid may be used as a bittering agent within the article, while a different bittering agent is used on the surface of the article.

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

The fibrous water-soluble unit dose article may have about 500 grams/m as measured according to the basis weight test method described herein²To about 5,000 g/m²Or about 1,000 g/m²To about 4,000 g/m²Or about 1,500 g/m²To about 3,500 g/m²Or about 2,000 g/m²To about 3,000 g/m²Basis weight of (c).

The fibrous water-soluble unit dose article may exhibit different regions, for example different regions of basis weight, density, thickness and/or wetting characteristics. The fibrous water-soluble unit dose article may be compressed at the edge seal. The fibrous water-soluble unit dose article may comprise a texture on one or more surfaces thereof. The surface of the fibrous water-soluble unit dose article may comprise a pattern, for example a non-random repeating pattern. The fibrous water-soluble unit dose article may comprise an aperture. Fibrous water-soluble unit dose articles 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.

The fibrous water-soluble unit dose article may comprise one or more plies. The fibrous water-soluble unit dose article may comprise at least two and/or at least three and/or at least four and/or at least five plies. The fiber plies may be a fiber structure. Each ply may include one or more layers, such as one or more layers of fibrous elements, one or more layers of particles, and/or one or more layers of a fibrous element/particle mixture. The layer may be sealed. In particular, the particle layer and the fibrous element/particle mixture layer may be sealed such that the particles do not leak out. The water-soluble unit dose article may comprise a plurality of plies, wherein each ply comprises two layers, wherein one layer is a layer of fibrous elements, one layer is a layer of fibrous element/particle mixture, and the plurality of plies are sealed (e.g., at the edges) together. The seal inhibits leakage of the particles and helps the unit dose article retain its original structure. However, upon addition of the water-soluble unit dose article to water, the unit dose article dissolves and releases the particles into the wash liquor.

The fibrous water-soluble unit dose can be in the form of any three-dimensional structure. The fibrous water-soluble unit dose article may be apertured. The article may also be cut or formed into various sizes for different intended uses. For example, the water-soluble unit dose can be square, rounded square, kite, rectangular, triangular, circular, oval, and mixtures thereof.

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

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 comprises, from a compositional standpoint, a plurality of identical or substantially identical fibrous elements. The water-soluble fibrous structure may comprise two or more different fibrous elements. Non-limiting examples of differences in the fibrous elements may be physical differences, such as differences in diameter, length, texture, shape, rigidity, elasticity, and the like; chemical differences such as level of crosslinking, solubility, melting point, Tg, active agent, filament-forming material, color, active agent content, basis weight, filament-forming material content, presence or absence of any coating on the fibrous element, biodegradability or not, hydrophobicity or contact angle, and the like; whether the difference in the physical structure of the fibrous element is lost when exposed to conditions of intended use; a difference in whether the fibrous element changes morphology when exposed to conditions of intended use; and the difference in the rate at which the fibrous element releases one or more of its active agents when exposed to conditions of intended use. Two or more of the fibrous elements in the fibrous structure may comprise different active agents. This may be the case where different active agents may be incompatible with each other, for example anionic surfactants and cationic polymers. When different fibrous elements are used, the resulting structure may exhibit different wetting, absorption, and dissolution characteristics.

Fiber structure

The fibrous structure comprises one or more fibrous elements. The fiber elements may be associated with one another to form a structure. The fibrous structure may comprise particles within and/or on the structure. The fibrous structure may be uniform, layered, monolithic, zoned, or, if desired, have different active agents defining the various portions described above.

The fibrous structure may comprise one or more layers which together form a ply.

Fiber 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. One or more active agents may be released from the fibrous element, for example, when the fibrous element and/or fibrous structure comprising the fibrous element is exposed to conditions of intended use.

The fibrous elements of the present invention can be spun from a filament-forming composition (also referred to as a fibrous element-forming composition) via suitable spinning process operations, such as melt blowing, spunbonding, electrospinning and/or rotary spinning.

As used herein, "filament-forming composition" and/or "fibrous element-forming composition" means a composition suitable for use in making the fibrous elements of the present invention, such as by meltblowing and/or spunbonding. The filament-forming composition comprises one or more filament-forming materials that exhibit properties that make them suitable for spinning into fibrous elements. The filament-forming material may comprise a polymer. The filament-forming composition may further comprise one or more active agents, such as surfactants, in addition to the one or more filament-forming materials. In addition, the filament-forming composition may comprise one or more polar solvents, such as water, in which one or more, e.g., all, of the filament-forming materials and/or one or more, e.g., all, of the active agents are dissolved and/or dispersed prior to spinning the fibrous element, such as spinning the filaments from the filament-forming composition.

The filament-forming composition may comprise two or more different filament-forming materials. Thus, the fibrous element may be monocomponent (a filament-forming material) and/or multicomponent, such as bicomponent. Two or more different filament-forming materials are randomly combined to form a fibrous element. For purposes of this disclosure, two or more different filament-forming materials may be mixed in order to form a fibrous element, such as a core-shell bicomponent fibrous element, which is not considered to be a random mixture of different filament-forming materials. The bicomponent fiber elements can be in any form, such as side-by-side, core-shell, islands-in-the-sea, and the like.

The fibrous element may be substantially free of alkyl alkoxylated sulfates. Each fibrous element may comprise from about 0%, or from about 0.1%, or from about 5%, or from about 10%, or from about 15%, or from about 20%, or from about 25%, or from about 30%, or from about 35%, or from about 40% to about 0.2%, or to about 1%, or to about 5%, or to about 10%, or to about 15%, or to about 20%, or to about 25%, or to about 30%, or to about 35%, or to about 40%, or to about 50%, by weight based on the dry fibrous element, of alkyl alkoxylated sulfate. The amount of alkyl alkoxylated sulfate in each of the fibrous elements is sufficiently small so as not to affect its processing stability and film dissolution. Alkyl alkoxylated sulfates, when dissolved in water, can undergo a highly viscous hexagonal phase at a range of concentrations (e.g., 30% to 60% by weight) to produce a gelatinous mass. Thus, alkyl alkoxylated sulfates, if incorporated in significant amounts into the fibrous element, can significantly slow the dissolution of the water soluble unit dose article in water, and worse, thereafter result in undissolved solids. Accordingly, most of such surfactants are formulated as granules.

The fibrous elements may each comprise at least one filament-forming material and an active agent, preferably a surfactant. Surfactants may have a relatively low hydrophilicity because such surfactants are less likely to form a viscous, gelatinous hexagonal phase upon dilution. By using such surfactants in forming the filaments, gel formation during washing can be effectively reduced, which in turn can lead to faster dissolution and low or no residue in the wash. The surfactant may be selected, for example, from un-alkoxylated C₆-C₂₀Straight-chain or branched Alkyl Sulfates (AS), C₆-C₂₀Linear alkyl benzene sulfonate (LAS), and combinations thereof. The surfactant may be C₆-C₂₀Linear alkyl benzene sulphonate (LAS). LAS surfactants are well known in the art and are readily available by sulphonation of commercially available linear alkylbenzenes. Exemplary C that can be used₆-C₂₀The linear alkyl benzene sulfonate comprises alkali metal, alkaline earth metal or C₆-C₂₀Ammonium salts of linear alkyl benzene sulphonic acids, such as C₁₁-C₁₈Or C₁₁-C₁₄Sodium, potassium, magnesium and/or ammonium linear alkyl benzene sulphonic acid salts. C₁₂Process for preparing linear alkyl benzene sulfonic acidSodium or potassium salts, e.g. C₁₂The sodium salt of linear alkyl benzene sulphonic acid, sodium dodecyl benzene sulphonate, may be used as the first surfactant.

The fibrous element may comprise at least about 5%, and/or at least about 10%, and/or at least about 15%, and/or at least about 20%, and/or less than about 80%, and/or less than about 75%, and/or less than about 65%, and/or less than about 60%, and/or less than about 55%, and/or less than about 50%, and/or less than about 45%, and/or less than about 40%, and/or less than about 35%, and/or less than about 30%, and/or less than about 25%, by weight based on the dry fibrous element and/or dry fibrous structure, of the filament-forming material and greater than about 20%, and/or at least about 35%, and/or at least about 40%, and/or at least about 45%, and/or at least about 50%, and/or at least about 55%, and/or at least about 60%, and/or at least about 65%, and/or at least about 70%, and/or less than about 95%, and/or less than about 90%, and/or less than about 85%, and/or less than about 80%, and/or less than about 75% of an active agent, preferably a surfactant. The fibrous element may comprise greater than about 80% surfactant by weight based on the weight of the dry fibrous element and/or dry fibrous structure.

Preferably, each fibrous element can be characterized by a sufficiently high total surfactant content, such as at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70% of the first surfactant by weight based on the dry fibrous element and/or dry fibrous structure.

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

The one or more fibrous elements may comprise at least one additional surfactant selected from the group consisting of additional 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 C₆-C₂₀Straight or branched chain alkylsulfonic acid salts, C₆-C₂₀Straight or branched chain alkyl carboxylates, C₆-C₂₀Linear or branched alkyl phosphates, C₆-C₂₀Linear or branched alkylphosphonates, C₆-C₂₀Alkyl N-methylglucamides, C₆-C₂₀Methyl Ester Sulfonates (MES), and combinations thereof.

Suitable nonionic surfactants include alkoxylated fatty alcohols. The nonionic surfactant can be selected from the group consisting of formula R (OC)₂H₄)_nOH, wherein R is selected from the group consisting of aliphatic hydrocarbon groups containing from about 8 to about 15 carbon atoms and alkylphenyl groups wherein the alkyl group contains from about 8 to about 12 carbon atoms, and n has an average value of from about 5 to about 15. Non-limiting examples of nonionic surfactants useful herein include: c₈-C₁₈Alkyl ethoxylates, e.g. from ShellA nonionic surfactant; c₆-C₁₂An alkylphenol alkoxylate, wherein the alkoxylate unit may be an ethyleneoxy unit, a propyleneoxy unit, or mixtures thereof; c₁₂-C₁₈Alcohol and C₆-C₁₂Condensates of alkylphenols with ethylene oxide/propylene oxide block polymers, such as from BASFC₁₄-C₂₂Mid-chain branched alcohols, BA; c₁₄-C₂₂Mid-chain branched alkyl alkoxylates, BAE_xWherein x is 1 to 30; an alkyl polysaccharide; in particular alkyl polyglycosides; polyhydroxy fatty acid amides; and ether-terminated poly (alkoxylated) alcohol surfactants. Suitable nonionic detersive surfactants also include alkyl polyglucosides and alkyl alkoxylatedAn alcohol. Suitable nonionic surfactants also include BASF under the trade name BASFThose that are sold.

Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants, which may have up to 26 carbon atoms, include: alkoxylated Quaternary Ammonium (AQA) surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride; a polyamine cationic surfactant; an ester cationic surfactant; and amino surfactants such as amidopropyl dimethylamine (APA). Suitable cationic detersive surfactants also include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulfonium compounds, and mixtures thereof.

Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula:

(R)(R₁)(R₂)(R₃)N⁺X^-

wherein R is a linear or branched, substituted or unsubstituted C_6-18Alkyl or alkenyl moieties, R₁And R₂Independently selected from methyl or ethyl moieties, R₃Is a hydroxyl, hydroxymethyl, or hydroxyethyl moiety, X is an anion that provides electrical neutrality, and suitable anions include: halide ions (e.g., chloride); sulfate radical; and a sulfonate group. Suitable cationic detersive surfactants are mono-C_6-18Alkyl monohydroxyethyl dimethyl quaternary ammonium chloride. Highly suitable cationic detersive surfactants are mono-C_8-10Alkyl mono-hydroxyethyl bis-methyl quaternary ammonium chloride, mono C_10-12Alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides and mono-C₁₀Alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.

Suitable examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, including derivatives of heterocyclic secondary and tertiary amines; derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds; betaines, including alkyldimethyl betaines, coco dimethyl aminopropyl betaines, sulfo-and hydroxybetainesA cauliflower base; c₈To C₁₈(e.g., C)₁₂To C₁₈) An amine oxide; N-alkyl-N, N-dimethylamino-1-propanesulfonic acid salts, wherein the alkyl group may be C₈To C₁₈。

Suitable amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains at least about 8 carbon atoms, alternatively from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains a water-solubilizing anionic group, e.g., carboxy, sulfonate, sulfate. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurates, and mixtures thereof.

The fibrous element can include a surfactant system comprising only anionic surfactant, such as a single anionic surfactant or a combination of two or more different anionic surfactants. Alternatively, the fibrous element may comprise a complex surfactant system, e.g., comprising one or more anionic surfactants in combination with one or more nonionic surfactants, or one or more anionic surfactants in combination with one or more zwitterionic surfactants, or one or more anionic surfactants in combination with one or more amphoteric surfactants, or one or more anionic surfactants in combination with one or more cationic surfactants, or a combination of all of the above types of surfactants (i.e., anionic, nonionic, amphoteric and cationic surfactants).

Typically, the fibrous elements are elongated particles having a length that substantially exceeds the average diameter, e.g., a ratio of length to average diameter of at least about 10. The fibrous elements may be filaments or fibers. The filaments are relatively longer than the fibers. The filaments can have a length of greater than or equal to about 5.08cm (2 inches), and/or greater than or equal to about 7.62cm (3 inches), and/or greater than or equal to about 10.16cm (4 inches, and/or greater than or equal to about 15.24cm (6 inches.) the fibers can have a length of less than about 5.08cm (2 inches), and/or less than about 3.81cm (1.5 inches), and/or less than about 2.54cm (1 inch).

The one or more filament-forming materials and active agent may be present in the fibrous element in a weight ratio of filament-forming material to total content of active agent of about 2.0 or less, and/or about 1.85 or less, and/or less than about 1.7, and/or less than about 1.6, and/or less than about 1.5, and/or less than about 1.3, and/or less than about 1.2, and/or less than about 1, and/or less than about 0.7, and/or less than about 0.5, and/or less than about 0.4, and/or less than about 0.3, and/or greater than about 0.1, and/or greater than about 0.15, and/or greater than about 0.2. The one or more filament-forming materials and the active agent may be present in the fibrous element in a weight ratio of filament-forming material to total content of active agent of from about 0.2 to about 0.7.

The fibrous element may comprise from about 10% to less than about 80% of a filament-forming material, such as a polyvinyl alcohol polymer, a starch polymer, and/or a carboxymethyl cellulose polymer, by weight of the dry fibrous element and/or the dry fibrous structure, and from greater than about 20% to about 90% of an active agent, such as a surfactant, by weight of the dry fibrous element and/or the dry fibrous structure. The fibrous element may also contain a plasticizer such as glycerin and/or an additional pH adjusting agent such as citric acid. The fibrous element can have a weight ratio of filament-forming material to active agent of about 2.0 or less. The filament-forming material may be selected from polyvinyl alcohol, starch, carboxymethyl cellulose, polyethylene oxide and other suitable polymers, especially hydroxyl-containing polymers and derivatives thereof. The weight average molecular weight of the filament-forming material can range from about 100,000g/mol to about 3,000,000 g/mol. It is believed that within this range, the filament-forming material can provide stretch rheology without elasticity, thereby inhibiting fiber attenuation during fiber manufacturing.

The one or more active agents may be releasable and/or released when the fibrous element and/or fibrous structure comprising the fibrous element is exposed to conditions of intended 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 fibrous element may exhibit a diameter of less than about 300 μm, and/or less than about 75 μm, and/or less than about 50 μm, and/or less than about 25 μm, and/or less than about 10 μm, and/or less than about 5 μm, and/or less than about 1 μm, as measured according to the diameter test method described herein. The fibrous element can exhibit a diameter of greater than about 1 μm as measured according to the diameter test method described herein. The diameter of the fibrous element may be used to control the release rate and/or loss rate of one or more active agents present in the fibrous element and/or to alter the physical structure of the fibrous element.

The fibrous element may comprise two or more different active agents, which may or may not be compatible with each other. The fibrous element may comprise 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 in the fibrous element. If different, the active agents may or may not be compatible with each other. 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 agent

The water-soluble unit dose articles described herein may contain one or more active agents. The active agent may be present in the fibrous element in the form of different particles, in the form of particles or integrated into particles, or as a premix in the article. For example, the premix can be an active agent slurry combined with an aqueous absorbent.

The active agent may be an acid. Examples of acids suitable for use include, but are not limited to, organic acids selected from the group consisting of: acetic acid, adipic acid, aspartic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, citric acid, benzoic acid, formic acid, glutaric acid, gluconic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid-disuccinic acid, tartaric acid-monosuccinic acid, salts thereof, or mixtures thereof. Preferably, the acid is citric acid, lactic acid, acetic acid and/or tartaric acid, and more preferably citric acid.

In certain aspects, the acid comprises a coating. The coating can help prevent premature dissolution of the active agent. The preferred acid is citric acid and the preferred coating comprises maltodextrin, wax, citrate, sulfate, zeolite, anti-caking agents such as silica or other drying agents. Preferred combinations include Citric Acid coated with maltodextrin (available under the trade name Citric Acid DC), Citric Acid coated with citrate (available under the trade name citrateN) or Citric Acid coated with silica (obtained under the trade name Citric Acid S40).

The active agent may be incorporated into the water-soluble unit dosage composition at a level of from about 5% to about 90%, preferably from about 10% to about 80%, preferably from about 15% to about 75%, preferably from about 40% to about 70%, preferably from about 60% to about 70%, by weight of the article. The active agent may be incorporated as distinct particles, encapsulated particles, as particles in a slurry, as part of the fiber, or as a mixture thereof.

The water-soluble unit dose may contain one or more additional organic acids. The additional organic acid may be in the form of an organic carboxylic acid or a polycarboxylic acid. Examples of organic acids that can be used include: acetic acid, adipic acid, aspartic acid, benzoic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, citric acid, formic acid, glycolic acid, benzoic acid, gluconic acid, glutaric acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid-disuccinic acid, tartaric acid-monosuccinic acid, salts thereof, or mixtures thereof. In some aspects, the compositions comprise an organic acid, such as citric acid, which can also be used as a detergent builder.

The water-soluble unit dose may further comprise an acid having a pKa of about 1.0 to about 5.0. Suitable acids in this pKa range can be found in, but are not limited to, the handbook of CRC chemistry and Physics, 99 th edition, Taylor and Francis(CRC Handbook of Chemistry and Physics,99^th edition,Taylor&Francis).

The organic acid may be a water-soluble or water-miscible acid. In some aspects, the organic acid has an aqueous solubility at 20 ℃ of at least about 10g acid/100 ml water or at least about 30g acid/100 ml water or at least about 50g acid/100 ml water or at least about 70g acid/100 ml water or at least about 85g/100ml water. In some aspects, the composition is substantially free of fatty acids.

The organic acid may be a low molecular weight acid, for example an acid having a molecular weight of less than 210 g/mol. In some aspects, the organic acid has no more than nine carbon atoms, alternatively no more than six carbon atoms. The organic acid in the detergent composition may have no more than four carbon atoms or no more than three carbon atoms or less than three carbon atoms. Specific examples of the organic acid having less than three carbon atoms include formic acid and acetic acid.

Fig. 1 shows a first ply 10 and a second ply 15 associated with the first ply 10, wherein the first ply 10 and the second ply 15 each comprise a plurality of fibrous elements 30, in this case filaments, and a plurality of particles 32. In the second ply 15, the particles 32 are randomly dispersed in the x, y and z axes, and in the first ply, the particles 32 are in pockets.

Fig. 2 is a perspective view of a water-soluble unit dose article 60.

Fig. 3 is a micro-CT scan image showing a cross-sectional view of the example water-soluble unit dose article of fig. 2 taken along line 3-3. The water-soluble unit dose has a layer of fibrous element and a layer of fibrous element/particle mixture. The water-soluble unit dose comprises a plurality of fibrous elements 30, in this case filaments, and a plurality of particles 32. The multi-ply, multi-layer article is sealed at the edge 64 so that the particles do not leak out. The outer surface of the article is a layer of fibrous elements. As shown in fig. 3, particles 32 do not agglomerate between fibers and may be considered as individual particles.

Fig. 4 is an enlarged view 62 of a portion of fig. 3. As shown in fig. 4, the sealed edge 64 of the water-soluble unit dose 60 contains one or more citric acid particles 32.

Test compositions for the examples：

The following tests compare various detergents, rinse solutions and concentrated acid delivery sources described herein, alone and in combination. Specifically, when using both the acid rinse of the present invention (9Elements rinse) and the concentrated acid delivery system, 9Elements low pH formulated detergents, medium pH (pH 8.5) formulated detergents, and Platinum Advanced Shirt and Laundry detergents (Platinum Advanced shine & laundrory Detergent) were used.

Table 1: detergent composition

The 9Elements detergent composition is further described in us patent application 62/756,855 (first inventor Delaney, Sarah Ann) filed on 7.11.2018; this patent application is incorporated herein by reference.

All free and clear liquid detergents are north american liquid detergent compositions owned by Henkel AG & Company, KGaA, which contain AES, LAS and nonionic surfactants as well as a range of enzymes.

The Persil ProClean PRO10 original liquid detergent was a north american liquid detergent composition owned by Henkel AG & Company, KGaA, comprising AES, LAS and nonionic surfactants as well as a range of proteases, amylases and cellulases.

A 9Elements rinse comprising the following composition: citric acid, vinegar (6% acetic acid), sodium hydroxide, 1, 2-propanediol, perfume and deionized water. The 9Elements rinse is described in us patent application 62/756,672 (first inventor Delaney, Sarah Ann) filed on 11, 7, 2018; this patent application is incorporated herein by reference.

The above concentrated acid delivery system is exemplified by the following table with compositions according to the present disclosure. The concentrated acid delivery system is also described as Power Tab in the malodor data below.

Table 2: concentrated acid delivery source composition

LAS is a peptide having C supplied by Stepan, Northfield, Illinois, USA or Huntsman Corp₁₁-C₁₂Linear alkylbenzene sulfonates of average aliphatic carbon chain length. HLAS is in acid form.

AS is C supplied by Stepan, Northfield, Illinois, USA_12-14Sulfates and/or moderately branched alkyl sulfates.

The PEG-PVAc polymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and a plurality of 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 to 60 with no more than 1 graft point per 50 ethylene oxide units. From BASF (Ludwigshafen, Germany).

Ethoxylated polyethyleneimine (PE20) is a polyethyleneimine core of 600g/mol molecular weight with 20 ethoxylated groups per NH. From BASF (Ludwigshafen, Germany).

Citrocoat (NF5000) was purchased from Jungbunzlauer (Basel, Switzerland).

PVOH andfrom Sekisui Specialty Chemicals America, LLC, located in Dallas Texas.

Determination of pH

Unless otherwise specified herein, the pH of a composition is defined as the neat pH of the composition at 20 ± 2 ℃. Any meter capable of measuring a pH to ± 0.01pH units is suitable. Oliglon instruments (Thermo Scientific, Clintinpark-Keppekouter, Ninovesenweg 198, 9320 Eremodegem-Aalst, Belgium) or equivalents are acceptable instruments. The pH meter should be equipped with a suitable glass electrode for calomel or silver/silver chloride reference. Examples include Mettler DB 115. The electrodes should be stored in electrolyte solutions recommended by the manufacturer. The pH was measured according to standard procedures of the pH meter manufacturer. In addition, the manufacturer's instructions for setting up and calibrating the pH assembly should be followed.

Malodor removal Wash test

The purpose of the malodor removal wash test was to cross-compare the ability of different wash methods to reduce malodor on fabrics. The malodorous mixture is applied to articles on laundry to be washed in a subsequent full-scale wash scale, after which the amount of malodorous active remaining on the dried fabric is analytically determined by GC-MS headspace SPME analysis. Each product was tested on 8 different washing machines, each containing 16 malodor tracers (so that 64 total replicates were measured), and the individual results were averaged and reported.

1) A washing step:

● washing machine: efficient front loading type washing machine (Duet9200)

● washing cycle: normal cycle, 19.6L wash cycle water, 7gpg, 25 deg.C, 3.9kg mixed cotton/polyester cotton press load (50X 50cm knit sample: 17 cotton/12 polyester cotton), 16 malodor tracers (2X 5 inch polyester cotton (50/50) sample)

● washing product: one soluble unit dose containing 25.4g of the detergent tested

2) And (3) drying:

● dryer: maytag Double Stack

● drying cycle: 35 minutes at 60 ℃ -65 ℃ (setting: LOW)

● storing: the dried samples were placed in Mylar bags (used to store fabric up to rated polyester resin coated aluminum bags) which were sealed with a heat sealer for storage prior to analytical testing.

3) Analysis of malodor characterization:

the principle behind analytical malodor characterization techniques is that the physical characteristics of the malodor components require components with low vapor pressures and/or low odor detection thresholds. With these properties allows the malodours to partition into the headspace. Thus, a headspace measurement above the fabric can be made to determine the amount of malodor on the fabric sample.

The analysis was performed with a gas chromatograph 7890B equipped with a Mass Selective Detector (MSD) (5977B) and a Chemstation quantification pack connected to a Gerstel multifunction sampler equipped with a Solid Phase Micro Extraction (SPME) probe and DB-FFAP column Agilent part number 122-3232. divinylbenzene/Carboxen/polydimethylsiloxane SPME fibers (or similar fibers) available from heliceco part number 57298-U were used.

The malodor tracer was cut into 2 "x 2.5" pieces and placed in a 10mL headspace crimp vial (Restek-part No. 21165-221). The tracer was allowed to equilibrate in the vial for 12 hours prior to GC-MS headspace SPME analysis.

GC-MS parameters:

gerstel autosampler parameters

● SPME: from incubators

● incubation temperature: 80 deg.C

● incubation time: 90.00min

● sample tray type: VT32-10

● vial permeability: 22.00mm

● extraction time: 20.00min

● injection infiltration: 54.00mm

● desorption time: 300s

GC oven parameters

● front SS inlet He

■ mode splitting

■ heater: 250 deg.C

■ pressure: 11.962psi

■ Total flow Rate: 79.5mL/min

■ diaphragm purge flow: 3mL/min

■ split ratio 50:1

■ GC run time: 22.5min

● baking oven

■ initial temperature: 40 deg.C

■ retention time: 0min

■ heating procedure

● rate: 12 ℃/min

● temperature: 250 deg.C

● retention time: 5min

MSD parameters

The detection runs in a minimum range of 40 to 350m/z in scan mode. The quantitative characteristic ion as well as a minimum of 1 qualitative characteristic ion, preferably 2 qualitative characteristic ions, of each malodor component is determined. The defined quantitative characteristic ion and the qualitative characteristic ion for each component must be based on the MSD compound library or standard.

For each malodorous material, a calibration curve was generated from standards in mineral oil. Using the calibrated headspace response, the integral of Extracted Ions (EICs) for each malodorous component in the test sample was plotted or recorded and the replicates were averaged.

The artificial scale (ABS) -squalene oxidation marker has been specifically analyzed and summarized for the data shown below. More specifically, the ABS-squalene oxidase markers used are 3-methylbutenal, 2-heptenal and 6-methyl-5-hepten-2-one.

Material：

1) Preparation of malodor tracers：

Malodor tracers are prepared by applying the just-prepared malodor mixture to a sample of polyester cotton cloth (PC) (50/50), wherein the textile finishes applied to the fabrics by textile mills, which may cause interference, are removed. The malodorous mixture was applied to a 2 x 5 inch sample of polyester cotton cloth 50/50 on the same morning as the full scale run. PC 50/50 samples were supplied by APD (Accurate Product Development, global material supplier, located in Cincinnati, Ohio).

The malodorous mixture was applied to a PC 50/50 sample using an Integra Viaflo automatic pipette. 96-channel heads (8 rows of 12 tips each) and 300. mu.l pipette tips were used. For this test, 5 rows of 12 tips per row were used to apply the malodor mixture on the fabric tracer. Each tip applied 15 μ l on the fabric tracer. 16 malodor mixtures containing fabric tracer were prepared and wrapped together in aluminum foil for storage until the wash test began.

2) Malodor mixture composition:

by mixing the individual compounds, the following malodour mixtures were prepared:

table 3: malodorous mixtures

Malodorous mixtures	Order of addition	Weight (g)
			ABS from APD	2	27
Squalene (CAS: 111-02-4)	3	27

Test results：

The data shown in the table below show that the oxidation by-products of ABS and squalene are significantly reduced for all example formulations. The formulation of the embodiment comprises:

the significant reduction in the oxidation by-products of ABS and squalene indicate a significant improvement in the malodor reduction characteristics of the examples relative to the reference formulation.

Table 4: malodor test design and results

As shown in the above table, the addition of power Tab allowed a greater reduction in malodor at 95% significance (37.52 versus 127.32) and an even greater reduction when combined with additional acid rinse softener at 95% significance (22.39 versus 127.32) relative to 9-Elements detergent alone. Furthermore, the addition of power Tab to detergents such as 9-Elements can achieve malodor reduction at 95% confidence even higher than premium liquid detergents such as Persil Proclean PRO10 (37.52 vs 66.36). This occurs even if PowerTab is used in the wash liquor during the wash cycle.

Decontamination

Soil release testing was conducted in a front loading HE machine according to the guidelines provided by the standard guidelines for evaluating household laundry soil release performance in ASTM 4265-14. Technical stain samples of cotton CW120 containing 22 stains were purchased. Using each respective detergent composition listed in the following Table, in a conventional North American washing machineThe machine used 7 grains per gallon hardness, and the normal cycle at 86F was selected. Image analysis was used to compare each stain to an unstained fabric control. The software converts the captured images into standard colorimetric values and compares these with standards based on the commonly used Macbeth color reduction chart, assigning a colorimetric value (stain content) for each stain. Eight replicates of each were prepared. The stain removal index was then calculated according to the formula shown below.

The stain removal effect of the samples was measured as follows:

ΔE_initialStain content before washing

ΔE_{Washing machine}Stain content after washing

Examples

The embodiments provided below are intended to be illustrative in nature and not limiting.

Example 1: exemplary compositions

Table 1 shows compositions according to the present disclosure. Sarah is to be added:

● all free and transparent detergents (market products)

●9Elements PowerTab

Decontamination

Example (b): effect of citric acid base PowerTab synergist on inhibiting pH of aqueous solution during washing

This example demonstrates the cleaning of a detergent by the traditional marketFree&Improved stain removal efficacy was obtained by adding a 9-Elements PowerTab citric acid formulation to the wash on Clear Liquid. The ability of citric acid to act as a builder in the wash to remove metals enables metal sensitive stains to be removed due to the addition of acid in the wash step of the laundry wash cycle, whereas conventional detergents do not effectively remove these stains due to their formulated pH (typically in the pH range of 7-9).

To evaluate the effect of adding a 9Elements PowerTab citric acid accelerator on a conventional (median pH) detergent in the wash, a soil release test was performed. The results are provided in table 5.

Table 5: stain removal effect in front loading HE machines and cotton fabrics

As shown in table 5, the addition of the 9Elements citric acid PowerTab formulation to the wash enabled increased stain removal on a large number of stains (i.e., those that migrate by chelation such as tea and coffee). Thus, a wash process that is not effective in removing these types of low pH-responsive stains due to the pH range of the detergent formulation employed can now have this effect by adding the 9Elements PowerTab formulation.

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

Each document cited herein, including any cross referenced or related patent or patent application and any patent application or patent to which this application claims priority or its benefits, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with any disclosure of the invention or the claims herein or that it alone, or in combination with any one or more of the references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.