USOO9334465B2

(12) United States Patent (10) Patent No.: US 9,334,465 B2 Fernandez Prieto et al. (45) Date of Patent: May 10, 2016

(54) STRUCTURING USING AN EXTERNAL USPC ...... 510/535, 353 STRUCTURANT AND A COSMOTROPE See application file for complete search history. (71) Applicant: The Procter & Gamble Company, (56) References Cited Cincinnati, OH (US) U.S. PATENT DOCUMENTS (72) Inventors: Susana Fernandez Prieto, Benicarlo 5,916,967 A * 6/1999 Jones ...... A61K 8,731 (BE); Johan Smets, Lubbeek (BE); 510/405 Vincent Josep Nebot Carda, Vila Real 8,222, 197 B2* 7/2012 Fernandez Prieto . C07C 237/22 510,303 (ES); Beatriu Escuder Gil, Sant Mateu 8,236,748 B2* 8/2012 Fernandez Prieto . C07C 237/22 (ES); Juan Felipe Miravet-Celades, 510,501 Castellon (ES) 2008/0057005 A1 3/2008 Lehn et al. 2008, 0087293 A1* 4, 2008 Glenn ...... A45D 19,0008 132/210 (73) Assignee: The Procter & Gamble Company, 2009, O124.533 A1 5, 2009 Kottke et al. Cincinnati, OH (US) 2011/0166291 A1 7, 2011 Turk et al. 2011 O220537 A1* 9, 2011 Fernandez-Prieto CO7C 237/22 (*) Notice: Subject to any disclaimer, the term of this 206,524.7 patent is extended or adjusted under 35 2011/0223125 A1* 9/2011 Hough ...... A61K 8,8152 424.70.12 U.S.C. 154(b) by 0 days. 2011/0224124 A1* 9, 2011 Fernandez Prieto ... CO7C 237/22 510/405 (21) Appl. No.: 14/106,891 2011/0243873 A1* 10/2011 Hough ...... A61K 8.91 424.70.16 (22) Filed: Dec. 16, 2013 2011/0256085 A1 * 10/2011 Talingting Pabalan A61 K8/042 424.70.13 (65) Prior PublicationO O Data 2013/0029894 A1 1/2013 Bettiol ...... C11D510,236 3/1266 US 2014/0179591 A1 Jun. 26, 2014 2014/0179591 A1* 6/2014 Fernandez Prieto ..... C11D 3/06 • 1-ys 510,535 (30) Foreign Application Priority Data OTHER PUBLICATIONS Dec. 20, 2012 (EP) ...... 121986O1 EP Search Report, EP 12198.601, dated May 16, 2013, containing 6 pageS. (51) Int. Cl. Suzuki M et al: “New 1-valine-based hydrogelators:formation of Supramolecular hydrogels'. Tetrahedron Letters, Elsevier, t t R Ansterdam, NL, vol. 45, No. 28, Jul. 5, 2004 pp. 5399-5402, ( .01) XP004.518889, ISSN: 0040-4039, DOI: 10.1016/J.TETLET2044. CID 7/00 (2006.01) 05.056 p. 5400, left-hand col., line 16—right-hand col., line 33*. CID 3/20 (2006.01) CID 3/32 (2006.01) * cited by examiner CID 3/37 (2006.01) CID 3/06 (2006.01) Primary Examiner — Nicole M Buie-Hatcher CID 3/30 (2006.01) Assistant Examiner — M. Reza Asdjodi CID 7/04 (2006.01) (74) Attorney, Agent, or Firm — Gregory S. (52) U.S. Cl. Darley-Emerson; Leonard W Lewis; Steve W Miller CPC CIID3/046 (2013.01); CIID3/06 (2013.01); CI ID3/2079 (2013.01); CI ID3/2086 (57) ABSTRACT (2013.01); CIID 3/30 (2013.01): CI ID 3/32 The structuring ability of fluid compositions comprising an (2013.01); CIID3/3726 (2013.01): CIID amido-gellant or HEUR polymeric structurant can be 17/003 (2013.01): CIID 17/043 (2013.01) improved with the addition of a cosmotrope. (58) Field of Classification Search CPC ...... C11D3/046; C11D 3/2079 14 Claims, 1 Drawing Sheet U.S. Patent May 10, 2016 US 9,334,465 B2

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|-N arm www.Y.A.N&MNNYNsawaxem meanNassassy --8 m akamerasaara US 9,334,465 B2 1. 2 STRUCTURING USING AN EXTERNAL chloride, tetramethylammonium acetate, tetramethylammo STRUCTURANT AND A COSMOTROPE nium bromide, tetramethylammonium fluoride, tetramethy lammonium formate, tetramethylammonium Sulphate, tet FIELD OF THE INVENTION ramethylammonium bisulphate, tetramethylammonium hydrogensulphate, tetramethylammonium citrate, tetram The present invention relates to the structuring of fluid ethylammonium phosphate, lithium fluoride, lithium chlo compositions using a combination of an external structurant ride, trilithium citrate, lithium acetate, lithium phosphate, and a cosmotrope. lithium formate, lithium Sulphate, caesium fluoride, Caesium chloride, Caesium acetate, caesium phosphate, caesium cit BACKGROUND OF THE INVENTION 10 rate, caesium Sulphate, rubidium acetate, rubidium chloride, rubidium fluoride, rubidium formate, rubidium sulphate, External structurants, useful for providing rheological ben rubidium bromide, and mixtures thereof. efits to fluid compositions, include those derived from poly The present invention also relates to a process of forming mers (both natural and synthetic), castor oil, fatty acids, fatty Such compositions, and the use of a cosmotrope for increasing esters, or fatty soap water-insoluble waxes. However, the 15 the Viscosity of a composition comprising an external struc required performance ingredients often complicate the addi turant selected from the group consisting of an amidogellant, tion of external structurants known in the art and may even be a hydrophobically modified ethoxylated urethane polymeric incompatible with them. For instance, many external struc structurant, and mixtures thereof. turants are degraded by performance ingredients, such as It has been discovered that the fluid compositions of the enzymes. They are also often incompatible with low pH and 20 present invention provide increased viscosity and structuring, peroxide bleaches. In addition, external structurants gener even at lower levels of the external structurant. In addition, ally require the use of structurant premixes incorporating since the cosmotrope can be readily mixed into fluid compo large amounts of water. Such structurant premixes are less sitions having a high viscosity, the compositions of the Suitable for compact detergents and for unit-dose applica present invention can be more easily made, by first combining tions. 25 the external structurant with the fluid composition, and only Amido-gellants and hydrophobically modified ethoxy increasing the Viscosity after adding the cosmotrope. lated urethane (HEUR) polymeric structurants provide struc turing for fluid compositions, while also being compatible BRIEF DESCRIPTION OF THE DRAWINGS with a broad range of potential ingredients, such as bleaches and/or enzymes. They also provide an aesthetically pleasing 30 FIG. 1 details G' and G" within the linear viscoelastic pour profile without negatively impacting the composition region and the oscillation stress at the point where G' and G" clarity. Moreover, they can be formulated into structurant cross over as a measure for gel strength. premixes that are low water, or even entirely water-free. It is desirable to reduce the amount of such external struc DETAILED DESCRIPTION OF THE INVENTION turants, while still providing the desired viscosity and level of 35 structuring. Also, amido gellants and HEUR polymers can be Suitable fluid compositions include, but are not limited to, difficult to mix into a fluid composition, particularly when consumer products such as: products for treating fabrics, such high viscosities are desired. as for laundry detergent compositions, as well as for laundry Therefore, a need remains for a means of achieving the and rinse additives; products for treating hard Surfaces in the desired viscosity, and level of structuring, while using less of 40 area of home care, including dishwashing compositions, floor the external structurant, and also simplifying the process of cleaning compositions, and toilet bowl cleaning composi mixing the external structurant into the fluid composition. tions; and personal care compositions such as shampoos, skin EP2365050 and EP2365052 disclose amido-gellants cleaners and exfolients, shaving liquids (including foams and which are suitable for use in fluid compositions. EP2365051 gels), and oral care (including toothpastes, gels and whitening and EP2365053 disclose fluid detergent compositions com- 45 compositions). prising amido gellants. WO 97/40133 discloses compositions A particularly preferred embodiment of the invention is a comprising HEUR polymers. “fluid detergent composition'. As used herein, “fluid deter gent composition” refers to any composition comprising a SUMMARY OF THE INVENTION fluid capable of wetting and cleaning a Substrate. Such as 50 fabric. Suitable fluid detergent compositions include “fluid The present invention relates to fluid compositions com laundry detergent compositions'. As used herein, “fluid laun prising: an external structurant selected from the group con dry detergent composition” refers to any laundry treatment sisting of an amido gellant, a hydrophobically modified composition comprising a fluid capable of wetting and clean ethoxylated urethane polymeric structurant, and mixtures ing fabric e.g., clothing, in a domestic washing machine. thereof, and a cosmotrope selected from the group consisting 55 The fluid composition can include solids or gases in Suit of calcium fluoride, calcium Sulphate, calcium citrate, cal ably subdivided form, but the overall composition excludes cium formate, calcium hydrogenphosphate, calcium dihydro product forms which are non-fluid overall, such as tablets or genphosphate, tricalcium diphosphate, calcium acetate, granules. The fluid compositions preferably have densities in Sodium fluoride, Sodium acetate, Sodium phosphate, sodium the range from of 0.9 to 1.3 grams per cubic centimeter, more hydrogenphosphate, sodium dihydrogenphosphate, potas- 60 preferably from 1.00 to 1.10 grams per cubic centimeter, sium formate, tripotassium citrate, potassium chloride, potas excluding any Solid additives but including any bubbles, if sium fluoride, potassium bromide, potassium acetate, potas present. sium Sulphate, monopotassium phosphate, dipotassium The fluid composition may be dilute or concentrated liq phosphate, tripotassium phosphate, ammonium chloride, uids. Preferably, the fluid composition comprises from 1% to ammonium fluoride, ammonium Sulphate, ammonium phos- 65 95% by weight of water and/or non-aminofunctional solvent. phate, ammonium acetate (ammonium ethanoate), ammo For concentrated fluid compositions, the composition prefer nium citrate, ammonium formate, tetramethylammonium ably comprises from 15% to 70%, more preferably from 20% US 9,334,465 B2 3 4 to 50%, most preferably from 25% to 45% by weight of water preferably from 0.05 wt % to 5 wt %, even more preferably and/or non-aminofunctional solvent. Alternatively, the fluid from 0.075 wt % to 2 wt %, most preferably from 0.1 wt % to composition may be almost entirely non-aqueous, and com 0.5 wt % of the fluid composition. prise a non-aminofunctional Solvent. Such fluid compositions may contain very little water. Such non-aqueous fluid com 1. Amido-Gellants: positions preferably comprise less than 15%, more preferably Amido gellants, of use in the present invention, preferably less than 10%, even more preferably less than 7% by weight comprise at least two nitrogen atoms, wherein at least two of of water. Most preferably, non-aqueous liquid compositions said nitrogen atoms form amido functional groups. The comprise no intentionally added water, beyond that added as amido gellant preferably has the following formula: part of another ingredient. 10 As used herein, “non-aminofunctional solvent refers to any organic solvent, of use in the fluid composition, which contains no amino functional groups. Preferred non-amino O O functional solvents are liquid at ambient temperature and pressure (i.e. 21°C. and 1 atmosphere), and comprise carbon, 15 hydrogen and oxygen. More preferred non-aminofunctional Solvents include monohydric alcohols, dihydric alcohols, wherein: R and R2 are aminofunctional end-groups which polyhydric alcohols, glycerol, glycols, polyalkylene glycols may be the same or different and L is a linking moiety of Such as polyethylene glycol, and mixtures thereof. Mixtures molecular weight from 14 to 500 g/mol. An aminofunctional of solvents are highly preferred, especially mixtures of two or end-group is one that comprises a nitrogenatom. The linking more of the following: lower aliphatic alcohols such as etha moiety, L, can be any Suitable group that connects the amido nol, propanol, butanol, isopropanol; diols such as 1,2-pro functional groups together. By Suitably selecting the linking panediol or 1,3-propanediol; and glycerol. moiety, L, the separation of the amido functional groups can All percentages, ratios and proportions used herein are by be adjusted. weight percent of the composition, unless otherwise speci 25 fied. All average values are calculated “by weight of the Preferably, the amido gellant has a molecular weight from composition or components thereof, unless otherwise 150 to 1500 g/mol, more preferably from 300 g/mol to 900 expressly indicated. g/mol, most preferably from 400 g/mol to 700 g/mol. External Structurant: In a preferred embodiment: R is R or The external structurant preferably imparts a shear thin 30 ning viscosity profile to the fluid composition, independently from, or extrinsic from, structuring effects of any surfactants AA of the composition. Preferred external structurants include those which provide a pouring viscosity from 50 cps to --. 20,000 cps, more preferably from 200 cps to 10,000 cps, most 35 Hor R preferably from 500 cps to 7,000 cps. The fluid composition preferably has a resting viscosity of at least 1,500 cps, pref erably at least 10,000 cps, more preferably at least 50,000 cps. and R is R. or This resting (low stress) viscosity represents the Viscosity of the fluid composition under gentle shaking in the package and 40 during transportation. Alternatively, the fluid composition AA may be a thixotropic gel. Such compositions may have a resting viscosity of from 10,000 cps to 500,000 cps, prefer --. ably from 100,000 cps to 400,000 cps, more preferably from Hor R 200,000 to 300,000. The preferred shear-thinning character 45 istics of the fluid detergent is defined as a ratio of low stress wherein AA is selected from the group consisting of Viscosity to pouring viscosity of at least 2, preferably at least 10, more preferably at least 100, up to 2000. The pouring viscosity is measured at a shear rate of 20 sec', which is a CH CH shear rate that the fluid composition is typically exposed to 50 during pouring. The resting (low stress) viscosity is deter mined under a constant stress of 0.1 Pa during a viscosity R", H, -CH3, CH3, —CH-(CH3, creep experiment over a 5 minute interval. Rheology mea OH surements over the 5 minute interval are made after the com position has rested at Zero shear rate for at least 10 minutes, 55 between loading the sample in the rheometer and running the -CH-OH, CH, -CH2-SH, test. The data over the last 3 minutes are used to fit a straight -CH2-CH2-S-CH3, line, and from the slope of this line, the low stress viscosity is t calculated. The viscosity is measured at 21°C. using a TAAR -CH2-CH2-CH2-NH-C-NH2, 2000 (or ARG2) rheometer with a 40 mm stainless steel cone 60 having an angle of 1. CH-CH The external structurant is selected from the group consist ing of an amido gellant, a hydrophobically modified ethoxy CH , -CH-CH-CH-CH-NH2, lated urethane (HEUR) polymeric structurant, and mixtures O thereof. 65 The fluid composition preferably comprises the external -CH-CH-C-NH2, —ch-ch-I-Ot structurant at a level of from 0.01 wt % to 10 wt %, more US 9,334,465 B2 5 6 -continued -continued H or R O -CH ( -cis-Il-oil NH 5

R' ro H H or R', O

10 s NH s H or R O -CH OH -CH-C-NH2, O-H or R', R ro H 15 and R and R independently have the formula: Preferably, L', L" from formula III and A, B, C, D from formula III are independently selected from the group con (L)-(L") R, where (m+q) is from 1 to 10. II) sisting of: 2O However, for R, the combination of AA, R', and R must be selected Such that R is an aminofunctional end-group. H or R Similarly, for R, the combination of AA, R', and R must be selected Such that R is an aminofunctional end-group. -- R O 25 H O R s -N- s -- s Preferably, L has the formula: Hor R A-B. C-D, where (a+b+c+d) is from 1 to 20, III o --( R or H HOH R', wherein L', L" from formula II and A, B, C, D from formula O III are independently selected from the group consisting of 30 -I-y O

2,3,5,6 position*

35

s 2,3,5,6 position* 40 ( O s H or R -I-O- O 2,3,5,6 position*

-N ( N/ -NES/ V -O- s R', O O O

-o-I-O- --o-o- -o-l- s 2,3,5,6 position* 50 - O-H or R. O O s E s H or R 2,3,5,6 position* *the arrow indicates up to 4 substitutions in the positions 55 indicated, and Xananion and R. RandR" are independently selected from AA and the group consisting of: R' ro H s O O O R. -H, -CH3, -(CH2)-CH3, -OH, -SN, -O-S- O - - S- O - -S-N- 60 O O s O s O s -COOH, -(CH2),-COOCH, -I-Ns. 2,3,5,6 position* -OSOH, -SO3H, -(CH-COO.Y., O O

65 --o-o-c-ch. -- s -NH2, US 9,334,465 B2 7 8 -continued -continued O s -N O-H / C s e, O s 5 S O /M \, 2,3,4 position* 2,3,5,6 position* O

- --o-it-s-ch.C 3.5 position* 2,3,4 position* O CH3 N -- O-CH2-CH2-S -- - N s s 15 O 2,3,4 position* S / \ -N o-ch-ch-i-Citch.O s 2N. RN O 2,3,4 position* 1.2 position* 2O --o-cis-cis- SOH, O O XO1 O s C s N 25 O --( 2.34 position* --o-c-cc. | S s O -O -S NO2, O s 30 O-CH O O O CH NO --0 O CH 35 --o-ch, NO2, O-CH, O s O 1.2 position* --o-c-c=ch. 40 NO O 2.34 position* -I-O-ch, - O 45 O CH3

2,3,4 position* --o-ch,

NO s O s 50 O ON O CH s --o-ch, O O CH

s -I-O-(-ch. 55 NO s CH NO O CH3, - I -v-g-g-O-H-H-S NO22 60 -I-O-ch, c/

O-CH

O O MV 65 -O-CH -( ) --o-c-N. US 9,334,465 B2 10 -continued -continued O CH3 2,3,4 position* O

CH s O 2,3,5,6 position* 2.3 position*

O -N NH 10 NO s OH 2,3,5,6 position* 2,3,4 position* O OH , - cis-- OH, 15 HN HN

---|-ol.... i -(\l, –K(l 2.34 position* 2.3.6 position* 2,3,5,6 position* ( s Cl N 2.34 position* 2,3,4,6 position* 25

RN , -N NH, 30 3,4,5,6 position* N N , -SH, NH2. 35 In a more preferred embodiment, the amido gellant is char *the arrow indicates up to 4 substitutions in the positions acterized in that: indicated, r, m and n are integers from 1 to 20 and Y-- is a L is an aliphatic linking group with a backbone chain of from cation 40 2 to 20 carbon atoms, preferably —(CH), wherein n is Preferably, R. R' and R" are independently selected from selected from 2 to 20. Preferably, R and R both have the the group consisting of Structure:

-H, -CH3, -(CH2)-CH3, -OH, -NH2, 45 AA O

O s ----. -N

-(CH2)-COOH, -I-Ns. le s wherein: AA is selected from the group consisting of 2,3,4 position* 50 NS CH CH3 CH-CH 2N, s 2,3,5,6 position* —( -cis-( —( 55 CH3, CH3, CH3 s - -CH-CH2-S-CH, -CH s 3.5 position* N 60 -(N=/ X and R is selected from the group: 2.34 position* -- ) 65 OH, -( )- OH, -( ) s US 9,334,465 B2 11 12 -continued pH-sensitive groups, the pKa of the amido gellant can be tailored. Hence, the choice of the pH-sensitive groups can be used to select the pH at which the amido gellant builds vis / \ -o-c-( ) cosity. HC In one embodiment, L. R. R. and mixtures thereof, may comprise the pH tuneable group. In a preferred embodiment, 7 R and R2 comprise the pH-tuneable group. In another embodiment R. R' and R" are amino functional end-groups, preferably amido functional end-group, more preferably pH 10 tuneable amido functional groups. In a preferred embodi ment, the pH tuneable group comprises at least one pyridine In another embodiment R. R' and R" can independently be group. Preferably, amido gellant comprises a pH tuneable selected from the group consisting of an ethoxy group, an group, Such that the amido gellant has a pKa of from 0 to 30, epoxy group with 1 to 15 ethoxy or epoxy units. In another 15 more preferably from 1.5 to 14, even more preferably from 3 embodiment, one or more of R. R' and R" may comprise a to 9, even more preferably from 4 to 8. functional end group selected from the group consisting of The amido-gellants can also be used for improving the an aromatic, alicyclic, heteroaromatic, heterocyclic group structuring of the fluid composition and for Suspending ingre including mono-, di-, and oligo-polysaccharides. dients such as particulates in the fluid composition. Prefer In another embodiment, two or more of L, Land L" are the ably, the fluid composition comprising the amido-gellant has same group. The amido gellant molecule can be symmetric a resting viscosity (see Test Methods) of at least 1,000 cps, with respect to the L entity or can be asymmetric. Without more preferably at least 10,000 cps, most preferably at least intending to be bound by theory, it is believed that symmetric 50,000 cps. This resting (low stress) viscosity represents the amido gellant molecules allow for more orderly structured Viscosity of the fluid composition under gentle shaking. Such networks to form, and are hence more efficient at sequestering 25 as during transportation. water and providing structuring. In contrast, compositions To provide more robust structuring, the fluid detergent may comprising one or more asymmetric amido gellant molecules comprise a mixture of two or more amido gellants. Such a can create less ordered networks. mixture may include an amido gellant which has a higher In one embodiment, the AA comprises at least one of solubility in water, with an amido gellant with higher solu Alanine, B-Alanine and Substituted Alanines; Linear Amino 30 Alkyl Carboxylic Acid; Cyclic Amino-Alkyl Carboxylic bility in non-aminofunctional solvents. Without intending to Acid; Aminobenzoic Acid Derivatives: Aminobutyric Acid be bound by theory, it is believed that combining an amido Derivatives; Arginine and Homologues; Asparagine; Aspartic gellant that is more soluble in water with an amidogellant that Acid, p-Benzoyl-Phenylalanine; Biphenylalanine: Citrul is more soluble in non-aminofunctional Solvents provides line; Cyclopropylalanine; Cyclopentylalanine; Cyclohexyla 35 improved structuring and stability to the formula. A preferred lanine: Cysteine, Cystine and Derivatives; Diaminobutyric combination is: N,N'-(2S,2S)-1,1'-(dodecane-1,12-diylbis Acid Derivatives; Diaminopropionic Acid: Glutamic Acid (azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)disonicoti Derivatives; Glutamine; Glycine; Substituted Glycines; His namide with the more water-soluble N,N'-(2S,2S)-1,1'-(pro tidine: Homoserine; Indole Derivatives; Isoleucine; Leucine pane-1,3-diylbis(azanediyl)bis(3-methyl-1-oxobutane-2.1- and Derivatives: Lysine; Methionine; Naphthylalanine; Nor 40 diyl)diisonicotinamide. leucine; Norvaline: Ornithine; Phenylalanine: Ring-Substi The amido gellant molecules may also comprise protective tuted Phenylalanines; Phenylglycine; Pipecolic Acid, Nipe groups, preferably from 1 to 2 protective groups, most pref cotic Acid and Isonipecotic Acid; Proline; Hydroxyproline: erably two protective groups. Examples of suitable protective Thiazolidine: Pyridylalanine; Serine; Statine and Analogues: groups are provided in “Protecting Groups, P. J. Kocienski, Threonine; Tetrahydronorharman-3-carboxylic Acid; 1.2.3, 45 ISBN 313 1356014, Georg Thieme Verlag, Stuttgart; and 4-Tetrahydroisoquinoline; Tryptophane; Tyrosine; Valine; “Protective Groups in Organic Chemistry'. T. W. Greene, P. and combinations thereof. G. M. Wuts, ISBN 0-471-62301-6, John Wiley & Sons, Inc, In one embodiment, the amido gellant comprises a pH New York. tuneable group, to resultina pH-tuneable amidogellant. A pH The amido gellant preferably has a minimum gelling con tunable amido gellant can provide the fluid composition with 50 centration (MGC) of from 0.1 to 100 mg/mL in the fluid a viscosity profile that changes with the pH of the composi composition, preferably from 0.1 to 25 mg/mL, more pre tion. Hence, a pH tunable amido gellant can be added to a fluid composition at a pH at which the viscosity is sufficiently ferred from 0.5 to 10 mg/mL in accordance with the MGC low to allow easy mixing, before changing the pH such that Test Method. The MGC as used herein can be represented as the pH tunable amido gellant provides structuring. 55 mg/ml or as a wt %, where wt % is calculated as the MGC in The pH tunable amido gellants comprise at least one pH mg/ml divided by 10. In one embodiment, when measured in sensitive group, that is either protonated or deprotonated by a the fluid composition, the MGC is from 0.1 to 100 mg/mL, change in composition pH. When a pH tunable amido gellant preferably from 0.1 to 25 mg/mL of said amido gellant, more is added to a fluid composition comprising water, it is preferably from 0.5 to 10 mg/mL, or at least 0.1 mg/mL, at believed that the uncharged form of the amido gellant builds 60 least 0.3 mg/mL, at least 0.5 mg/mL, at least 1.0 mg/mL, at viscosity while the charged form is more soluble and less least 2.0 mg/mL, at least 5.0 mg/mL of amido gellant. While efficient at forming a viscosity building network. By increas the invention includes fluid compositions having an amido ing or decreasing the pH (depending on the selection of the gellant concentration either above or below the MGC, the pH-sensitive groups) the amido gellant is either protonated or amido gellants of the invention result in particularly useful deprotonated. Thus, by changing the pH of the solution, the 65 rheologies below the MGC.. solubility, and hence the viscosity building behaviour, of the Suitable amido gellants, and mixtures thereof, may be amido gellant can be controlled. By careful selection of the selected from table 1:

US 9,334,465 B2 29 30 wherein: selected from the group consisting of calcium fluoride, cal R is an alkyl chain, preferably a C6-C24 alkyl chain, more cium Sulphate, calcium citrate, calcium formate, calcium preferably a C12-C18 alkyl chain, n is preferably from 25 to hydrogenphosphate, Calcium dihydrogenphosphate, trical 400, preferably from 50 to 250, more preferably from 75 to cium diphosphate, calcium acetate, Sodium fluoride, sodium 180, X can be any suitable linking group. acetate, sodium phosphate, sodium hydrogenphosphate, Suitable HEUR polymeric structurants can have a molecu Sodium dihydrogenphosphate, potassium formate, tripotas lar weight of from 1,000 to 1,000,000, more preferably from sium citrate, potassium chloride, potassium fluoride, potas 15,000 to 50,000 g/mol. An example of a suitable HEUR sium bromide, potassium acetate, potassium Sulphate, mono polymeric structurant is ACUSOL 880, sold by ROHM and potassium phosphate, dipotassium phosphate, tripotassium HAAS. 10 phosphate, ammonium chloride, ammonium fluoride, ammo Cosmotrope: nium Sulphate, ammonium phosphate, ammonium acetate A cosmotrope is used in the compositions of the present (ammonium ethanoate), ammonium citrate, ammonium for invention, to improve the efficacy of an external structurant mate, tetramethylammonium chloride, tetramethylammo selected from the group consisting of an amido gellant, a nium acetate, tetramethylammonium bromide, tetramethy hydrophobically modified ethoxylated urethane polymeric 15 lammonium fluoride, tetramethylammonium formate, structurant, and mixtures thereof. tetramethylammonium Sulphate, tetramethylammonium Cosmotropes are salts which stabilize hydrophobic groups bisulphate, tetramethylammonium hydrogensulphate, tet or molecules in aqueous solution and reduce the Solubility of ramethylammonium citrate, tetramethylammonium phos hydrophobic groups or molecules. Without wishing to be phate, and mixtures thereof. Even more preferably, the cos bound by theory, it is believed that the cosmotrope lowers the motrope is selected from the group consisting of calcium solubility of hydrophobic groups in the external structurant, fluoride, calcium Sulphate, calcium citrate, calcium formate, including the aminofunctional end-groups of the amido-gel calcium acetate, Sodium fluoride, Sodium acetate, potassium lants, and the ethylene glycol or propylene glycol blocks of formate, tripotassium citrate, potassium chloride, potassium the HEUR polymer, thereby increasing the viscosity and acetate, potassium Sulphate, ammonium chloride, ammo structuring provided by the external structurant. By lowering 25 nium Sulphate, acetate (ammonium ethanoate), ammonium the concentration at which the external structurant self citrate, ammonium formate, tetramethylammonium chloride, assembles, the cosmotrope also lowers the concentration at tetramethylammonium acetate, tetramethylammonium for which the external structurant provides viscosity and struc mate, tetramethylammonium Sulphate, tetramethylammo turing. nium bisulphate, tetramethylammonium hydrogensulphate, In the context of the present invention, the cosmotrope is 30 tetramethylammonium citrate, and mixtures thereof. believed to strengthen the intermolecular interactions The cosmotrope is preferably present at a level of from between amido groups of the amido gellants or of the HEUR 0.1% to 10%, preferably from 0.2% to 5%, more preferably polymeric structurants, and hence improve the ability of Such from 0.3% to 3% by weight of the fluid composition. amido gellants and HEUR structurants to self-assemble. Adjunct Ingredients: Without wishing to be bound by theory, it is believed that the 35 The fluid composition may also include ingredients cosmotropes of the present invention, being ions with high selected from the group consisting of anionic Surfactant, Surface charge, low polarizability and strong hydration, are nonionic Surfactant, amphoteric Surfactant, Zwitterionic Sur able to partially “salt-out” the external structurant, and hence factant, cationic Surfactant, enzymes, enzyme stabilizers; reduce its solubility. It is believed that this salting-out process amphiphilic alkoxylated grease cleaning polymers; clay soil reduces the concentration of the external structurant, at which 40 cleaning polymers; soil release polymers; soil Suspending gelation starts to occur. polymers; bleaching systems; optical brighteners; hueing The cosmotropes of the present invention may be selected dyes; particulate material; perfume and other odour control from the group consisting of calcium fluoride, calcium Sul agents, including perfume delivery systems; hydrotropes; phate, calcium citrate, calcium formate, calcium hydrogen Suds Suppressors; fabric care benefit agents; pH adjusting phosphate, calcium dihydrogenphosphate, tricalcium diphos 45 agents; dye transfer inhibiting agents; preservatives; non phate, calcium acetate, Sodium fluoride, Sodium acetate, fabric substantive dyes; and mixtures thereof. Sodium phosphate, sodium hydrogenphosphate, sodium In a preferred embodiment, the fluid composition com dihydrogenphosphate, potassium formate, tripotassium cit prises a Surfactant. Such fluid detergent compositions of the rate, potassium chloride, potassium fluoride, potassium bro present invention typically comprise from 1% to 70%, pref mide, potassium acetate, potassium Sulphate, monopotas 50 erably from 5% to 60% by weight, more preferably from 10% sium phosphate, dipotassium phosphate, tripotassium to 50%, and most preferably from 15% to 45% by weight of phosphate, ammonium chloride, ammonium fluoride, ammo a surfactant. The surfactant is preferably selected from the nium Sulphate, ammonium phosphate, ammonium acetate group consisting of anionic, nonionic Surfactants and mix (ammonium ethanoate), ammonium citrate, ammonium for tures thereof. The preferred ratio of anionic to nonionic sur mate, tetramethylammonium chloride, tetramethylammo 55 factant is from 100:0 (i.e. no nonionic surfactant) to 5:95, nium acetate, tetramethylammonium bromide, tetramethy more preferably from 99:1 to 1:4, most preferably 5:1 to lammonium fluoride, tetramethylammonium formate, 1.5:1. tetramethylammonium Sulphate, tetramethylammonium The fluid detergent compositions of the present invention bisulphate, tetramethylammonium hydrogensulphate, tet preferably comprises from 1 to 50%, preferably from 5 to ramethylammonium citrate, tetramethylammonium phos 60 40%, more preferably from 10 to 30% by weight of one or phate, lithium fluoride, lithium chloride, trilithium citrate, more anionic Surfactants. Preferred anionic Surfactant are lithium acetate, lithium phosphate, lithium formate, lithium selected from the group consisting of C11-C18 alkylben Sulphate, caesium fluoride, Caesium chloride, Caesium Zene sulphonates, C10-C20 branched-chain and random acetate, caesium phosphate, caesium citrate, caesium Sul alkyl sulphates, C10-C18 alkyl ethoxy sulphates, mid-chain phate, rubidium acetate, rubidium chloride, rubidium fluo 65 branched alkyl Sulphates, mid-chain branched alkyl alkoxy ride, rubidium formate, rubidium sulphate, rubidium bro sulphates, C10-C18 alkyl alkoxy carboxylates comprising mide, and mixtures thereof. Preferably, the cosmotrope is 1-5 ethoxy units, modified alkylbenzene sulphonate, C12 US 9,334,465 B2 31 32 C20 methyl ester sulphonate, C10-C18 alpha-olefin sulpho C15 alcohols with from 5 to 20 moles of ethylene oxide per nate, C6-C20 sulphosuccinates, and mixtures thereof. How mole of alcohol, e.g., C12-C13 alcohol condensed with about ever, by nature, every anionic Surfactant known in the art of 6.5 moles of ethylene oxide per mole of alcohol. Additional detergent compositions may be used, such as those disclosed Suitable nonionic Surfactants include polyhydroxy fatty acid in “Surfactant Science Series”, Vol. 7, edited by W. M. Lin 5 amides of the formula: field, Marcel Dekker. However, the compositions of the present invention comprise preferably at least one Sulphonic acid Surfactant, such as a linear alkylbenzene Sulphonic acid, O R1 or the water-soluble salt forms. Anionic Sulphonate or Sulphonic acid surfactants Suitable 10 for use herein include the acid and salt forms of linear or branched C5-C20, more preferably C10-C16, most prefer wherein R is a C9-C17 alkyl or alkenyl, R is a methyl group ably C11-C13 alkylbenzene sulphonates, C5-C20 alkyl ester and Z is glycidyl derived from a reduced Sugar oralkoxylated Sulphonates, C6-C22 primary or secondary alkane Sulpho derivative thereof. Examples are N-methyl N-1-deoxygluci nates, C5-C20 Sulphonated polycarboxylic acids, and mix 15 tyl cocoamide and N-methyl N-1-deoxyglucityl oleamide. tures thereof. The aforementioned surfactants can vary The fluid compositions of the present invention may com widely in their 2-phenyl isomer content. prise a detersive enzyme, which are typically used to provide Anionic Sulphate salts suitable for use in compositions of improved cleaning performance and/or fabric care benefits. the invention include: primary and secondary alkyl Sulphates, The detersive enzyme may be present in an amount of from having a linear or branched alkyl or alkenyl moiety having 0.0001% to 8% by weight of the fluid composition. It has been from 9 to 22 carbon atoms, more preferably from 12 to 18 found that the external structurants, of use in the present carbon atoms; beta-branched alkyl Sulphate surfactants; and invention, are not degraded by enzyme action. Suitable mixtures thereof. enzymes can be selected from the group consisting of lipase, Mid-chain branched alkylsulphates or sulphonates are also protease, amylase, cellulase, pectate lyase, Xyloglucanase, Suitable anionic Surfactants for use in the compositions of the 25 and mixtures thereof. A preferred enzyme combination com invention. Preferred are the C5-C22, preferably C10-C20 prises lipase, protease, cellulase, amylase, and mixtures mid-chain branched alkyl primary sulphates. When mixtures thereof. The fluid composition preferably comprises a pro are used, the average number of carbon atoms for the alkyl teolytic enzyme. Such as protease. Detersive enzymes are moieties is preferably within the range of from 14.5 to 17.5. described in greater detail in U.S. Pat. No. 6,579,839. Preferred mono-methyl-branched primary alkylsulphates are 30 The combination of external structurant and cosmotrope selected from the group consisting of the 3-methyl to 13-me are particularly Suited for Suspending particulate material, in thyl pentadecanol sulphates, the corresponding hexadecanol fluid compositions of the present invention. Suitable particu sulphates, and mixtures thereof. Dimethyl derivatives or other late material may be selected from the group consisting of biodegradable alkyl Sulphates having light branching can clays, Suds Suppressors, encapsulated sensitive ingredients, similarly be used. 35 aesthetic adjuncts such as pearlescent agents including mica, Other suitable anionic surfactants for use herein include pigment particles, or the like. Preferred particulate materials fatty methyl ester Sulphonates and/or alkyl ethyoxy Sulphates are encapsulated sensitive ingredients selected from the (AES) and/or alkyl polyalkoxylated carboxylates (AEC). group consisting of perfume microcapsules, encapsulated Mixtures of anionic Surfactants can be used, for example bleaches, encapsulated enzymes, and mixtures thereof. Per mixtures of alkylbenzenesulphonates and AES. 40 fume microcapsules are particularly preferred. Perfume The anionic Surfactants are typically present in the form of microcapsules comprise a microcapsule core and a microcap their salts with alkanolamines or alkali metals such as sodium sule wall that surrounds the microcapsule core. The core and potassium. Preferably, the anionic Surfactants are neu comprises a perfume. Perfume microcapsules, and methods tralized with alkanolamines Such as monoethanolamine or of making them are disclosed in the following references: US triethanolamine, and are fully soluble in the liquid phase. 45 2003-215417A1; US 2003-216488 A1: US 2003-158344A1: The fluid detergent compositions of the present invention US 2003-165692 A1: US 2004-071742 A1: US 2004-071746 preferably comprise up to 30%, preferably from 1 to 15%, A1: US 2004-072719 A1: US 2004-072720 A1 EP 1393706 more preferably from 2 to 10% by weight of one or more A1: US 2003-203829 A1; US 2003-195133 A1; US 2004 nonionic Surfactants. Suitable nonionic Surfactants include, 087477 A1: US 2004-0106536A1; U.S. Pat. No. 6,645,479; but are not limited to C12-C 18 alkyl ethoxylates (AE) 50 U.S. Pat. No. 6,200,949; U.S. Pat. No. 4,882,220; U.S. Pat. including the so-called narrow peaked alkyl ethoxylates, No. 4,917,920; U.S. Pat. No. 4,514,461; U.S. RE 327 13: U.S. C6-C12 alkyl phenol alkoxylates (especially ethoxylates and Pat. No. 4,234.627. Suitable levels of particulate materials are mixed ethoxy/propoxy), block alkylene oxide condensate of from 0.0001% to 5%, or from 0.1% to 1% by weight of the C6-C12 alkylphenols, alkylene oxide condensates of C8-C22 fluid detergent composition. alkanols and ethylene oxide/propylene oxide block polymers 55 Water-Soluble Unit Dose Articles: (Pluronic R-BASF Corp.), as well as semi polar nonionics Since the external structurants and cosmotropes of the (e.g., amine oxides and phosphine oxides). An extensive dis present invention are also effective at structuring fluid com closure of suitable nonionic surfactants can be found in U.S. positions that are low in water, they are particularly suitable as Pat. No. 3,929,678. components of fluid compositions that are to be enclosed Alkylpolysaccharides such as disclosed in U.S. Pat. No. 60 within a water soluble film, to form a water-soluble unit dose 4.565,647 are also useful nonionic surfactants for composi article. tions of the invention. Also suitable are alkyl polyglucoside It has also been found that fluid compositions, of the Surfactants. In some embodiments, Suitable nonionic Surfac present invention, are able to sequester water and inhibit the tants include those of the formula R. (OCH), OH, wherein water, present in the fluid composition, from interacting with R is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, 65 the water Soluble film. As such, fluid compositions compris and n is from 3 to about 80. In some embodiments, the ing higher levels of water can be encapsulated into a water nonionic Surfactants may be condensation products of C12 soluble film to form unit-dose articles. Where the fluid com US 9,334,465 B2 33 34 position comprises less than 30%, preferably less than 25%, making fluid compositions that are Suitable for packaging more preferably less than 17% by weight of water, the fluid into water-soluble unit dose articles. The structurant premix composition can be enclosed in a water-soluble or dispersible may also be free or essentially free of added electrolytes. film, to form a water-soluble unit dose article, without dis Suitable organic solvents include those that are liquid at 21° solving the water soluble film. Fluid compositions of the C., and are preferably selected from the group consisting of present invention, which are non-aqueous fluid compositions, non-aminofunctional solvents, nonionic Surfactants, anionic can also be enclosed within a water soluble film, to form a Surfactants, and mixtures thereof. Non-aminofunctional Sol water-soluble unit dose article. vents are most preferred. Suitable water soluble films comprise polymers, copoly 10 The organic solvent is preferably selected from the group mers or derivatives thereof. Preferred polymers, copolymers consisting of an organic solvent, a nonionic Surfactant, an or derivatives thereof are selected from the group consisting anionic Surfactant, or mixtures thereof. of polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene In another embodiment, the process comprises the addi oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, tional step of cooling the resultant fluid composition, before a cellulose esters, cellulose amides, polyvinyl acetates, poly 15 further step of adding heat sensitive ingredients such as deter carboxylic acids and salts, polyaminoacids or peptides, sive enzymes, perfume microcapsules, and mixtures thereof. polyamides, polyacrylamide, copolymers of maleic/acrylic When cooling the fluid composition, the composition tem acids, polysaccharides including starch and gelatin, natural perature is brought below the temperature at which the heat gums such as Xanthum and carragum. More preferred poly sensitive ingredients are subject to decomposition. mers are selected from polyacrylates and water-soluble acry In another embodiment, the step of combining the struc late copolymers, methylcellulose, carboxymethylcellulose turant premix with the fluid premix is performed by adding sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, the structurant premix at a temperature of at least 80°C., to hydroxypropyl methylcellulose, maltodextrin, poly the fluid premix, heated up to a temperature of not more than methacrylates, and most preferably selected from polyvinyl 25 60° C., preferably not more than 50° C. Heat-sensitive ingre alcohols, polyvinyl alcohol derivatives or copolymers, dients, such as those selected from the group consisting of hydroxypropyl methyl cellulose (HPMC), hydroxypropyl enzymes, perfumes, perfume microcapsules, bleach cata methyl cellulose derivatives or copolymers, and combina lysts, photobleaches, bleaches, dyes, and mixtures thereof, tions thereof. 30 are added to the resultant fluid composition after the struc Process of Making a Fluid Detergent Composition Compris turant premix has been added, and after the composition has ing the External Structurant and Cosmotrope: been cooled to below 45° C., preferably below 30°C. In such The present invention also provides for a preferred process processes, the cosmotrope can be added before or after the of making a fluid composition comprising the steps of pro resultant fluid composition has been cooled. viding a fluid premix comprising a solvent selected from: 35 Where the fluid composition comprises less than 30%, water, non-aminofunctional Solvent, and mixtures thereof. preferably less than 25%, more preferably less than 17% by combining an external structurant selected from the group weight of water, the fluid composition can be enclosed in a consisting of an amido gellant, a hydrophobically modified water-soluble or dispersible film, to forma water-soluble unit ethoxylated urethane polymeric structurant, and mixtures dose article. Most preferably, in processes for making a unit thereof, with the fluid premix; and combining a cosmotrope 40 dose article, the fluid composition is a non-aqueous fluid with the fluid premix. composition. It is preferred that the cosmotrope is combined with the Test Methods: fluid premix, in a step after combining the external structurant A) pH Measurement: with the fluid premix. Cosmotropes comprise small, readily 45 The pH is measured on the neat composition, at 25°C., dispersible ions, which can be easily distributed into the par using a Santarius PT-10P pH meter with gel-filled probe (such tially structured fluid premix, even as the Viscosity increases. as the Toledo probe, part number 52 000 100), calibrated However, the cosmotrope can be combined with the fluid according to the instructions manual. premix before the external structurant is added. B) Minimum Gelling Concentration (MGC) When making a fluid detergent composition, the fluid pre 50 MGC is calculated by a tube inversion method based on R. mix preferably comprises a Surfactant selected from an G. Weiss, P. Terech; “Molecular Gels: Materials with self anionic Surfactant, nonionic Surfactant, and mixtures thereof. assembled fibrillar structures' 2006 Springer, p 243. In order The surfactant is typically combined into the premix before to determine the MGC, three screenings are done: adding the external structurant. As such, the process may 55 First Screening: further comprise a step of adding a surfactant to the fluid prepare several vials increasing the external structurant premix before the external structurant is combined with the concentration from 0.5% to 5.0 weight % in 0.5% steps fluid premix. Determine in which interval the gel is formed (one inverted The external structurant may be combined with the fluid sample still flowing and the next one is already a strong gel). premix, as part of a structurant premix. It has been found that 60 In case no gel is formed at 5%, higher concentrations are used. such structurant premixes can be free or essentially free of Second Screening: water. For instance, in one embodiment, the structurant pre prepare several vials increasing the external structurant mix comprises a solvent, preferably an organic Solvent, to concentration in 0.1 weight% steps in the interval determined solubilise the amido gellant. This is a Substantial advantage 65 in the first screening. when structuring fluid compositions that are either highly Determine in which interval the gel is formed (one inverted concentrated or comprise very little water. For instance, when sample still flowing and the next one is already a strong gel) US 9,334,465 B2 35 36 Third Screening: The method of measuring the Minimum Gelling Concen in order to have a very precise percentage of the MGC, run tration provides a measure of the minimum concentration of a third screening in 0.025 weight % steps in the interval the external structurant at which gelling occurs. As can be determined in the second screening. seen by comparing Examples 2 and 3 with example 1 (no added salt), the cosmotrope reduces the concentration of the The Minimum Gelling Concentration (MGC) is the lowest external structurant, at which the external structurant gels the concentration which forms a gel in the third screening (does fluid composition. In contrast, the addition of sodium thiocy not flow on inversion of the sample). anate (NaSCN) results in an increase in the minimum gelling For each screening, samples are prepared and treated as concentration. follows: 8 mL vials (borosilacate glass with Teflon cap, ref. 10 Liquid detergent compositions were prepared as follows: Step 1: A structurant premix A was prepared by dissolving B7857D, Fisher Scientific Bioblock) are filled with 1.4% N,N'-(2R,2R)-1,1'-(dodecane-1,12-diylbis 2.0000+0.0005 g (KERN ALJ 120-4 analytical balance with (azanediyl))bis(3-methyl-1-ox-obutane-2,1-diyl)diisonicoti t0.1 mg precision) of the fluid (comprising the fluid compo namide in 9.8 grams of linear alkylbenzene Sulphonic acid at sition and external structurant) for which we want to deter 250 C. mine the MGC. The vial is sealed with the screw cap and left 15 Step 2: Detergent feeds B1 to B6 were prepared, having compositions as described in Table 1. B1 comprised no cos for 10 minutes in an ultrasound bath (Elma Transsonic T 710 motrope or additional other salt, and is thus a comparative DH, 40 kHz, 9.5 L, at 25°C. and operating at 100% power) in example. B2 to B5 comprise a cosmotrope, to form fluid order to disperse the solid in the fluid. Complete dissolution is compositions of the present invention. B6 comprises a salt then achieved by heating, using a heating gun (Bosch PHG that is not a cosmotrope, and is thus also a comparative 2), and gentle mechanical stirring of the vials. It is crucial to example. observe a completely clear solution. Handle vials with care. While they are manufactured to resist high temperatures, a TABLE 1 high solvent pressure may cause the vials to explode. Vials are Detergent Feed (grams cooled to 25°C., for 10 min in a thermostatic bath (Compat 25 ible Control Thermostats with controller CC2, D77656, Ingredient B1 B2 B3 B4 B5 Huber). Vials are inverted, left inverted for 1 minute, and then Linear Alkylbenzene Sulphonic acid 1.3 1.3 1.3 1.3 1.3 observed for which samples do not flow. After the third (LAS) C12-14 alkyl ethoxy 3 Sulphate 7.2 7.2 7.2 7.2 7.2 screening, the concentration of the sample that does not flow 30 Mono Ethanol Amine salt after this time is the MGC. For those skilled in the art, it is Citric acid 1.7 1.7 1.7 1.7 1.7 Grease Cleaning Alkoxylated O.3 O.3 O.3 O.3 O.3 obvious that during heating solvent vapours may be formed, Polyalkylenimine Polymer and upon cooling down the samples, these vapours can con SoilSuspending Alkoxylated O.9 O.9 O.9 dense on top of the gel. When the vial is inverted, this con Polyalkylenimine Polymer’ 35 Diethylene triamine penta acetate O.24 O.24 O.24 O.24 O.24 densed vapour will flow. This is discounted during the obser Boric acid 1.2 Vation period. If no gels are obtained in the concentration Glycerine 1.8 Calcium formate O.S interval, higher concentrations must be evaluated. Calcium Sulphate C) Gel Strength: Potassium chloride An AR-G2 rheometer from TA Instruments is used for Calcium nitrate 40 Minors: dyes, perfume, stabilizers, Up to 5 grams rheological measurements. antifoam ... Plate: 40 mm standard 1 steel cone plate. 600 gimol molecular weight polyethylenimine core with 24 ethoxylate groups per —NH The gel strength, as defined by the cross-over of the elastic and 16 propoxylate groups per —NH. modulus, G', and the viscous modulus, G", is measured using 2600 gimol molecular weight polyethylenimine core with 20 ethoxylate groups per —NH. a stress Sweep test whereby the oscillation stress is increased 45 from 0.001 Pa to 10 Pa, taking 10 points per decade at 20°C. Step 3: 10.7 grams of structurant premix A were slowly added to 88.3 grams of the above detergent feeds at 400 rpm, and at a frequency of 1 Hz. We use G' value within the linear at 35°C., and the resulting mixture was adjusted to pH 8 with Viscoelastic region as a measure for the gel strength, as shown sodium hydroxide. The resulting mixture was allowed to cool in FIG. 1. to 25°C., before the pH sensitive ingredient (1.0 gram pro 50 tease) was added under gentle stifling, at 400 rpm for 10 min. The gel strength was measured according test method C. A EXAMPLES higher gel strength corresponds to a greater degree of struc turing. The following fluid compositions were prepared according Comparative fluid composition, EX 6, comprised no addi 55 tional salt. Fluid compositions Ex 7 to Ex 9, of the present to the MGC test method, using N,N'-(2R,2R)-1,1'-(propane invention, comprise cosmotropes. Comparative fluid compo 1,3-diylbis(azanediyl)bis(3-methyl-1-ox-obutane-2,1-diyl) sition EX 10 comprised a salt that is not a cosmotrope (cal disonicotinamide as the external structurant: cium nitrate).

Ex1 Ex2 Ex3 Ex4 ExS Comparative Of invention Of invention Comparative Comparative Salt No salt 0.8 wt % NaF. 2 wt % NaF. 2 wt % NaSCN2 4 wt % NaSCN2 MGC (%) 1075 O.885 O600 1.225 1.450 Cosmotrope of use in compositions of the present invention *Comparative salt US 9,334,465 B2

Fluid compositions

Ex 6 Ex 7 Ex8 Ex9 Ex1O comparative Inventive Inventive Inventive Comparative 88.3 g Detergent Feed B1 B2 B3 B4 B5 10.7 g structurant premix A. A. A. A. A. Sodium hydroxide to pH 8 to pH 8 to pH 8 to pH 8 to pH 8 Protease 1 g 1 g 1 g 1 g 1 g Gel strength (Pa) 13 50 25 17 13 (see test method C) Purafect Prime (R, 40.6 mg activeig,

The Gel Strength Method provides a measure of the degree 4. The fluid composition according to claim 1, wherein the of structuring provided to the fluid composition, with a higher 15 amido gellant has a minimum gelling concentration (MGC) value corresponding to an improvement in structuring. As can of from about 0.1 to about 100 mg/mL. be seen by comparing Examples 7 to 9 with example 6 (no 5. The fluid composition according to claim 1, wherein the added salt), the cosmotrope increased the amount of structur cosmotrope is selected from the group consisting of calcium ing provided by the external structurant, to the fluid compo fluoride, calcium Sulphate, sodium fluoride, potassium fluo sition. In contrast, the addition of a comparative salt, which is ride, potassium Sulphate, ammonium fluoride, ammonium not a cosmotrope, did not result in any increase instructuring. Sulphate, tetramethylammonium fluoride, tetramethylammo nium Sulphate, and mixtures thereof. The dimensions and values disclosed herein are not to be 6. The fluid composition according to claim 5, wherein the understood as being strictly limited to the exact numerical cosmotrope is selected from the group consisting of calcium values recited. Instead, unless otherwise specified, each Such fluoride, Sodium fluoride, potassium fluoride, ammonium dimension is intended to mean both the recited value and a 25 fluoride, tetramethylammonium fluoride, and mixtures functionally equivalent range Surrounding that value. For thereof. example, a dimension disclosed as “40 mm is intended to 7. The fluid composition according to claim 6, wherein the mean “about 40 mm. cosmotrope comprises sodium fluoride. What is claimed is: 8. The fluid composition according to claim 1, wherein the 1. A fluid composition, comprising: 30 cosmotrope is present at a level of from about 0.3% to about a. an external structurant which is an amido gellant, 3% by weight of the fluid composition. wherein said amido gellant having the following for 9. The fluid composition according to claim 1, wherein the mula: fluid composition further comprises a Surfactant. 10. The fluid composition according to claim 1, wherein 35 the fluid composition further comprises less than about 30% by weight of water. 11. The fluid composition according to claim 10, wherein the fluid composition is encapsulated by a water-soluble film material comprising a polymers, copolymer or derivatives 40 thereof selected from the group consisting of polyvinyl alco hols, polyvinyl alcohol derivatives or copolymers, hydrox wherein: R and R2 are aminofunctional end-groups ypropyl methyl cellulose (HPMC), hydroxypropyl methyl which may be the same or different, and L is a linking cellulose derivatives or copolymers, and combinations moiety of molecular weight from about 14 to about thereof. 500 g/mol; 45 b. a cosmotrope selected from the group consisting of: 12. A process for making a fluid composition according to calcium fluoride, calcium Sulphate, sodium fluoride, claim 1, comprising the steps of potassium fluoride, potassium bromide, potassium Sul a. providing a fluid premix comprising a solvent selected phate, ammonium fluoride, ammonium Sulphate, tet from: water, non-aminofunctional Solvent, and mixtures ramethylammonium bromide, tetramethylammonium thereof; 50 b. combining an external structurant selected from the fluoride, tetramethylammonium sulphate, lithium fluo group consisting of an amido gellant, a hydrophobic ride, lithium Sulphate, cesium fluoride, cesium Sulphate, ally modified ethoxylated urethane polymeric struc rubidium fluoride, rubidium sulphate, rubidium bro turant, and mixtures thereof, with the fluid premix; and mide, and mixtures thereof, c. combining a cosmotrope with the fluid premix. wherein the cosmotrope is present at a level of from 55 about 0.2% to about 5% by weight of the fluid com 13. A process according to claim 12, further comprising the position. step of adding a surfactant to the fluid premix before step (b). 2. The fluid composition according to claim 1, wherein the 14. A process for making a unit dose article, comprising the composition comprises from about 0.01 wt % to about 10 wt steps of claim 12, further comprising the step of encapsulat ing the fluid composition in a water-soluble film, wherein the % of the external structurant. 60 3. The fluid composition according to claim 1, wherein the fluid composition comprises less than about 30% by weight amido gellant has a molecular weight from about 150 to about of water. 1500 g/mol.