Particulate composition

Abstract

A free-flowing particulate composition comprising at least 50% by weight of one or more amphoteric surfactants and at least 0.1% by weight of one or more chelating agents.

Description

[0001] The present invention relates to compositions useful in preparing cleanser formulations and personal care compositions. In particular, the present invention relates to solid compositions comprising amphoteric surfactants in the form of free-flowing particles.

[0002] It would be highly desirable to provide cleaning formulations and personal care compositions in solid form. Solid compositions are generally easier to handle than liquid compositions and have a reduced environmental impact compared to aqueous compositions due to the avoidance of unnecessary water transport.

[0003] However, difficulties arise during the preparation of solid compositions in that many of the component ingredients are usually only available in the form of aqueous solutions.

[0004] One ingredient commonly used in detergent formulations and personal care compositions is cocamidopropyl betaine (or CAPB).

[0005] CAPBs are highly effective surfactants and can enhance the performance of other surfactants present in the composition.

[0006] CAPB is typically available as an aqueous solution, typically containing about 30% by weight of active surfactant. CAPB is available in solid form, but the material is highly hygroscopic, meaning it forms a solid cake during storage. Consequently, the material is not available in a free-flowing form and can be difficult to incorporate into formulations.

[0007] Free-flowing particulate materials are easier to handle and add than gels or bulk solids and are highly desirable when forming pressed powder tablets and the like.

[0008] Surprisingly, the present inventors have found that the inclusion of small amounts of chelating agents can improve or maintain the flow properties of solid compositions comprising amphoteric surfactants, especially after prolonged storage.

[0009] According to a first aspect of the present invention there is provided a free-flowing granular composition comprising at least 50 wt% of one or more amphoteric surfactants and at least 0.1 wt% of one or more chelating agents.

[0010] According to a second aspect of the present invention there is provided the use of one or more chelating agents for improving the flowability of a granular composition comprising at least 50 wt% of one or more amphoteric surfactants.

[0011] Preferred features of the first and second aspects will now be described.

[0012] A free-flowing particulate composition is a solid composition, for example in the form of a powder, agglomerates, granules, needles, or a combination thereof.

[0013] A solid composition, formulation or component referred to herein refers to a composition, formulation or component that is in the solid state under normal atmospheric conditions (ie, at 1 atmosphere and 298 K).

[0014] The present invention relates to free-flowing granular compositions comprising one or more amphoteric surfactants.

[0015] Amphoteric surfactants are any surfactants that have the ability to exhibit both positive and negative sites. The one or more amphoteric surfactants can be selected from the class of surfactants known as betaines, sultaines or zwitterionic surfactants, or other amphoteric surfactants such as those based on aliphatic nitrogen derivatives or amine oxides.

[0016] Suitable amphoteric surfactants for use herein may be selected from betaines such as alkyl betaines, alkylamidopropyl betaines, alkylamidopropyl hydroxysulfobetaines, alkyl amphoacetates, alkyl amphodiacetates, alkyl amphopropionates, alkyl amphodipropionates, alkyliminodipropionates and alkyliminodiacetates.

[0017] Suitable amphoteric surfactants for use herein may include those having an alkyl or alkenyl group having from 7 to 22 carbon atoms and conforming to the following general formula: where R 1 is an alkyl or alkenyl group having 7 to 22 carbon atoms; R 2 and R 3 Each is independently an alkyl group, a hydroxyalkyl group or a carboxyalkyl group of 1 to 6 carbon atoms; m is 2 to 4; n is 0 or 1; X is an alkylene group of 1 to 6 carbon atoms optionally substituted with a hydroxy group; and Y is -CO2 or -SO3.

[0018] Suitable amphoteric surfactants for use herein may include simple betaines of the formula: and amido betaines of the formula: Where m is 2 or 3.

[0019] In both formulas, R 1 、R 2 and R 3 As previously defined. 1 Especially can be derived from coconut mixed C 12 and C 14 alkyl groups, such that at least half, preferably at least 60%, of the groups R 1 Has 10 to 14 carbon atoms.2 and R 3 Preferred is methyl.

[0020] In some embodiments, substantially all groups R 1 It has 12 carbon atoms.

[0021] In some embodiments, substantially all groups R 1 It has 14 carbon atoms.

[0022] In some embodiments, substantially all groups R 1 It has 16 carbon atoms.

[0023] In some embodiments, substantially all groups R 1 It has 18 carbon atoms.

[0024] The one or more amphoteric surfactants may include a sulfobetaine (or sulfobetaine) of the formula: wherein m is 2 or 3, or variations thereof, wherein, -(CH2)3SO3 - Replaced by Among these formulas, R 1 、R 2 and R 3 As previously defined.

[0025] The one or more amphoteric surfactants may include amphoacetates and amphodiacetates. Amphoacetates generally conform to the following formula: Amphodiacetates generally conform to the following formula: wherein R is an aliphatic group of 7 to 22 carbon atoms and M is a cation such as sodium, potassium, ammonium or substituted ammonium.

[0026] Suitable acetate-based amphoteric surfactants include lauroamphoacetate; alkyl amphoacetates; cocoamphodiacetate; cocoamphoacetate; disodium cocoamphodiacetate; sodium cocoamphoacetate; disodium cocoamphodiacetate; disodium capryloamphodiacetate; disodium lauroamphoacetate; sodium lauroamphoacetate and disodium wheatgermamphodiacetate.

[0027] Suitable betaine surfactants include alkyl amide betaines; alkyl betaines, C 12 / 14Alkyl dimethyl betaine; Cocamidopropyl betaine; Tallow bis(hydroxyethyl) betaine; Cetyl dimethyl betaine; Coco dimethyl betaine; Alkyl amidopropyl sulfobetaine; Alkyl dimethylamine betaine; Cocamidopropyl dimethyl betaine; Alkyl amidopropyl dimethylamine betaine; Cocamidopropyl betaine; Lauryl betaine; Lauryl amidopropyl betaine; Cocamidopropyl betaine; Lauryl betaine; Alkyl amido betaine; Coco betaine; Lauryl betaine; Dimethicone propyl PG-betaine; Oleyl betaine; N-alkyl dimethyl betaine; Coco-biguanide derivative, C 8 / 10 Amide betaine; C 10 Amide Betaine C 12 Amidobetaine; Lauryl dimethyl betaine; Alkyl amidopropyl betaine; Amidobetaine; Alkyl betaine; Cetyl betaine; Oleamidopropyl betaine; Isostearamidopropyl betaine; Lauramidopropyl betaine; 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine; 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine; Sodium 2-alkyl-N-carboxymethyl-N-carboxymethyloxyethyl imidazolinium betaine; N-alkyl Ammonium betaine; N-alkyl-N,N-dimethyl-N-(3-sulfopropyl)-ammonium betaine; Cocodimethyl betaine; Apricot amidopropyl betaine; Isostearamidopropyl betaine; Myristamidopropyl betaine; Palmitoyl amidopropyl betaine; Cocamidopropyl hydroxysultaine; Undecylenamidopropyl betaine; Cocamide sultaine; Alkyl amido betaine; C 12 / 18 Alkylamidopropyl dimethylamine betaine; lauryl dimethyl betaine; ricinoleamide betaine; tallow amino betaine.

[0028] Suitable glycine-based amphoteric surfactants include cocoyl amphocarboxyglycinate; tallow amphocarboxyglycinate; capryloyl amphocarboxyglycinate, oleoyl amphocarboxyglycinate, bis-2-hydroxyethyl tallow glycinate; lauroyl amphocarboxyglycinate; tallow polyamphoglycinate; cocoyl amphocarboxyglycinate; oleyl polyamphoglycinate; NC 10 / 12 Fatty acid amide ethyl-N-(2-hydroxyethyl)-glycine salt; NC 12 / 18 - fatty acid amide ethyl-N-(2-hydroxyethyl)-glycinate; dihydroxyethyl tallow glycinate.

[0029] Suitable amine oxide surfactants for use herein include those of formula R 1 R 2 R 3 N + O - Alkylamine oxide and formula R 1CO(CH2) n NR 2 R 3 N + O - Acylamine oxide, wherein R 1 、R 2 and R 3 As previously defined, and n is 1 to 6. Preferably n is 3, R 2 and R 3 are all methyl, and R 1 It is an alkyl or alkenyl group having 10 to 18, preferably 12 to 16 carbon atoms.

[0030] Preferably, the acetate-based amphoteric surfactants used herein include sodium lauroamphoacetate, disodium lauroamphoacetate, and mixtures thereof.

[0031] Preferably, the betaine surfactant used herein is an amido betaine. Preferred amido betaines include lauramidopropyl betaine and cocamidopropyl betaine. Particularly preferred compounds include cocamidopropyl betaine.

[0032] Preferably, the sultaine surfactants for use herein include amidoalkylhydroxysultaines, such as cocamidopropylhydroxysultaine.

[0033] Preferably, the amine oxide surfactants for use herein include lauramidopropylamine oxide and alkyldimethylamine oxide containing mixed C12-C16 alkyl groups.

[0034] Preferably, the one or more amphoteric surfactants are selected from the group consisting of sulfobetaines, betaines, amphoacetates, glycine-based amphoteric surfactants, amine oxides, and mixtures thereof.

[0035] Preferably, the one or more amphoteric surfactants are selected from sulfobetaines, betaines, amphoacetates, glycine-based amphoteric surfactants and mixtures thereof.

[0036] Preferably, the one or more amphoteric surfactants are selected from sulfobetaines, betaines, amphoacetates, glycine-based amphoteric surfactants and mixtures thereof.

[0037] The one or more amphoteric surfactants are preferably selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants, amine oxides and mixtures thereof.

[0038] The one or more amphoteric surfactants are preferably selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants and mixtures thereof.

[0039] The one or more amphoteric surfactants are preferably selected from betaine surfactants.

[0040] Most preferably, the one or more amphoteric surfactants include cocamidopropyl betaine (CAPB).

[0041] CAPB can be prepared from fatty acids, fatty acid esters and / or oils (glycerides). Suitable raw materials that can be used to prepare CAPB surfactants include coconut fatty acids; coconut oil; coconut oil methyl esters; virgin coconut oil; refined, bleached and deodorized coconut oil; palm oil; palm kernel oil; C12-C18 fatty acids derived from hydrogenated palm kernel oil (hardened and distilled fatty acids) and their methyl esters; and "distilled and distilled" hardened coconut fatty acids and their methyl esters.

[0042] The fatty acid distribution of some preferred raw materials is as follows: fatty acid Mode Coconut oil (weight %) Palm kernel oil (weight %) Hexanoic acid <![CDATA[C6H 12 O2]]> 0.2-0.8 0-1 bitter <![CDATA[C8H 16 O2]]> 6-9 3-5 Decanoic acid <![CDATA[C 10 H 20 O2]]> 6-10 3-5 Lauric acid <![CDATA[C 12 H 24 O2]]> 46-50 44-51 Myristic acid <![CDATA[C 14 H4 182 O2]]> 17-19 15-17 Palmitic acid <![CDATA[C 16 H 32 O2]]> 8-10 7-10 stearic acid <![CDATA[C 18 H 36 O2]]> 2-3 2-3 Oleic acid <![CDATA[C 18 H 34 O2]]> 5-7 12-19 Linoleic acid <![CDATA[C 18 H 32 O2]]> 1-2.5 1-2 The free-flowing granular compositions of the present invention comprise one or more amphoteric surfactants.

[0043] In some embodiments, the composition may include an amphoteric surfactant.

[0044] In some embodiments, the composition may include a mixture of two or more amphoteric surfactants.

[0045] The skilled artisan will appreciate that commercial sources of amphoteric surfactants typically contain mixtures of surfactant compounds, such as mixtures of homologs and / or isomers.

[0046] Commercial sources of amphoteric surfactants may also contain impurities, by-products, and / or unreacted starting materials.

[0047] One or more amphoteric surfactants are present in the free-flowing granular composition in an amount of at least 50% by weight.

[0048] The one or more amphoteric surfactants may be present in the free-flowing granular composition in an amount of at least 55 wt%, preferably at least 60 wt%, suitably at least 65 wt%, for example at least 70 wt%.

[0049] The one or more amphoteric surfactants may be present in the free-flowing granular composition in an amount of up to 99 wt%, preferably up to 95 wt%, suitably up to 90 wt%, preferably up to 85 wt%.

[0050] Preferably, the one or more amphoteric surfactants may be present in the free-flowing granular composition in an amount of 50 to 97 wt%, preferably 60 to 90 wt%, more preferably 70 to 85 wt%.

[0051] The above amounts refer to the total amount of all amphoteric surfactants present in the composition.

[0052] For the avoidance of doubt, the above amounts refer to the total amount of active amphoteric surfactant compound present in the composition, excluding any impurities, unreacted starting materials and the like.

[0053] The free-flowing granular compositions of the present invention also comprise one or more chelating agents.

[0054] Any suitable chelating agent may be used.

[0055] Preferably, the chelating agents used herein include aminocarboxylic acid chelating agents and aminophosphonic acid chelating agents. The active species provided in solution by such chelating agents are generally present in solution as anionic aminocarboxylates or aminophosphonates. Acid chelating agents derived from polycarboxylic acids are also suitable for use herein.

[0056] Suitable aminophosphonic acid-containing chelating agents with amino functionality include organic aminophosphonic acids, such as aminoalkylene poly(alkylene phosphonic) acids. Preferred chelating agents of this type include ethylenediaminetetramethylenephosphonic acid, and preferably diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetri(methylenephosphonic acid) and hexamethylenediaminetetra(methylenephosphonic acid). Such phosphonic acid chelating agents are commercially available under the trade name Dequest®, typically as their sodium salt. Suitable chelating agents can be aminotri(methylenephosphonic acid).

[0057] Suitable aminocarboxylic acid-containing chelating agents having amino functionality for use in the present invention include polyaminocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), ethylenetriaminepentaacetic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid, diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, ethanol-diglycine, propylenediaminetetraacetic acid (PDTA) and methylglycine diacetic acid (MGDA). Suitable aminocarboxylic acids for use herein are diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid (PDTA) and methylglycine diacetic acid (MGDA).

[0058] Further suitable chelating agents for use herein are iminodiacetic acid derivatives, for example 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid as described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agents described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid chelating agents described in EP-A-509,382 are also suitable.

[0059] EP-A-476,257 describes suitable amino-based chelating agents. EP-A-510,331 describes suitable chelating agents derived from collagen, keratin or casein. EP-A-528,859 describes suitable alkyliminodiacetic acid chelating agents. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N,N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N,N'-disuccinic acid (HPDDS) are also suitable.

[0060] Preferably, the one or more chelating agents are selected from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), ethylenediamine disuccinic acid (EDDS), methylglycine diacetic acid (MGDA), glutamic acid, N,N-diacetic acid (GLDA), iminodisuccinic acid (IDS); ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), aspartic acid diethoxysuccinic acid (AES), aspartic acid-N,N-diacetic acid (ASDA), ethylenediaminetetramethylenephosphonic acid (EDTMP), iminodifumaric acid (IDF), iminodiatartrate (IDT), iminodiamaleic acid (IDMAL), iminodiamalic acid (IDM), Ethylenediamine difumaric acid (EDDF), ethylenediamine dimalic acid (EDDM), ethylenediamine ditartaric acid (EDDT), ethylenediamine dimaleic acid and (EDDMAL), aminotri(methylenephosphonic acid) (ATMP); diethylenetriamine pentamethylenephosphonic acid (DETPMP), hydroxyethyliminodiacetic acid (HEIDA), aspartic acid diethoxysuccinic acid (AES), aspartic acid-N,N-diacetic acid (ASDA), diethylenetriamine pentamethylenephosphonic acid (DTPMPA), hydroxyethylenediaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), glucoheptonic acid, citric acid, poly(acrylic acid-co-phosphorous acid), tripolyphosphoric acid, polyacrylic acid and salts thereof and mixtures thereof. The sodium salts of the acids are preferred.

[0061] In some embodiments, the one or more chelating agents include tripolyphosphate or a salt thereof, such as sodium tripolyphosphate (STPP).

[0062] In some embodiments, the one or more chelating agents include polyacrylic acid or a salt thereof.

[0063] Preferably, the chelating agents used in the present invention are derivatives of polycarboxylic acids. This means that the chelating agent includes two or more carboxylic acid moieties or salts thereof. Suitable chelating agents for use herein may include 3, 4 or 5 carboxylic acid moieties.

[0064] Preferably, the one or more chelating agents are selected from iminodisuccinic acid (IDS), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), iminodisfumaric acid (IDF), iminodiatartrate (IDT), iminodimaleic acid (IDMAL), iminodiamalic acid (IDM), ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid (EDDM), ethylenediamineditartrate (EDDT), ethylenediaminedimaleic acid (EDDMAL) and aminotris(methylenephosphonic acid) (ATMP), citric acid, ethylenediaminedisuccinic acid (EDDS) and salts and mixtures thereof, especially the sodium salts thereof.

[0065] Suitably, the one or more chelating agents may be selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, NTA, AES, ASDA, DTPMPA, STPP and HEDTA.

[0066] Suitably, the one or more chelating agents may be selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, NTA, AES, ASDA, DTPMPA and HEDTA.

[0067] Preferably, the one or more chelating agents are selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, EDDS, citric acid, and salts and mixtures thereof.

[0068] Preferably, the one or more chelating agents are selected from MGDA, GLDA, EDTA, EDDS, STPP, citric acid, and salts and mixtures thereof.

[0069] Preferably, the one or more chelating agents are selected from MGDA, GLDA, EDTA, EDDS, citric acid, and salts and mixtures thereof.

[0070] Methylglycine diacetic acid (MGDA) has the structure shown in Figure 1: In the compositions of the present invention, MGDA may be present in a form having the structure shown in FIG1 and / or in a form in which multiple acidic protons have been replaced, i.e., in which 1, 2, or 3 acid groups have been neutralized or partially neutralized. It may be present as the free acid or as a salt or complex thereof.

[0071] MGDA may exist as an enantiomer or a mixture thereof. Preferably, it exists as a racemic mixture.

[0072] Preferably, MGDA is provided as the trisodium salt.

[0073] MGDA is commercially available as a solution containing 40% by weight of the trisodium salt and is sold under the trademark Trilon M.

[0074] Glutamic acid N,N-diacetic acid (GLDA) has the structure shown in Figure 2: In the composition of the present invention, GLDA may be present in a form having the structure shown in Figure 2 and / or in a form having the same structure in which several acidic protons have been replaced, i.e., in which 1, 2, 3 or 4 acid groups have been neutralized or partially neutralized. It may be present as the free acid or as a salt or complex thereof.

[0075] GLDA can exist as an enantiomer or a mixture thereof. Preferably, at least 50% exists as [S]-GLDA, preferably at least 70%, more preferably at least 90%, most preferably at least 95% by weight, for example about 98% by weight. In some preferred embodiments, GLDA consists essentially of the S enantiomer.

[0076] GLDA is commercially available as a solution comprising 38% by weight of the tetrasodium salt and is sold under the trademark Dissolvine GL-38.

[0077] DTPA has the structure shown in Figure 3: DTPA can be provided in a form having the structure shown in Figure 3, or in a form having the same structure in which multiple hydrogen atoms have been replaced, i.e., in which 1, 2, 3, 4, or 5 acid groups have been neutralized or partially neutralized.

[0078] When a salt of DTPA is included, this may be a salt of an alkali metal, alkaline earth metal, ammonia or a suitable amine.

[0079] When a monovalent counterion is used, the salt may be a mono-, di-, tri-, tetra-, or penta-salt. For divalent cations, a mono- or di-salt may be present. Mixed salts may also be present, for example, a disodium magnesium salt or a sodium magnesium salt may be present. Preferably, the counterion(s) for the DTPA residue are selected from one or more of sodium, magnesium, calcium, potassium, lithium, ammonium, and quaternary ammonium ions.

[0080] Preferably, when present, DPTA is included as the pentasodium salt.

[0081] EDTA has the structure shown in Figure 4: EDTA may be provided in a form having the structure shown in Figure 4, or in a form having the same structure wherein several hydrogen atoms have been replaced, ie wherein 1, 2, 3 or 4 acid groups have been neutralized or partially neutralized.

[0082] When a salt of EDTA is included, this may be a salt of an alkali metal, alkaline earth metal, ammonia or a suitable amine.

[0083] When a monovalent counterion is used, the salt can be a mono-, di-, tri-, or tetra-salt. For divalent cations, a mono- or di-salt can be present. Mixed salts can also be present, for example, a disodium magnesium salt or a sodium magnesium salt can be present. Preferably, the counterion(s) of the EDTA residue is selected from one or more of sodium, magnesium, calcium, potassium, lithium, ammonium, and quaternary ammonium ions. Preferably, when present, EDTA is present as a tetrasodium salt, a trisodium salt, or a disodium salt.

[0084] DETPMP has the structure shown in Figure 5: This compound may also be referred to as DETPMP or DTPMP. It may exist as the free acid or as a salt or complex thereof. DTPMPA is commercially available as a heptasodium salt and is sold under the trademark Dequest 2060 series.

[0085] Iminodisuccinic acid (IDS) has the structure shown in Figure 6: In this specification, IDS is used to refer to the structure shown in Figure 6 and identical structures wherein a number of the acidic protons have been replaced, ie wherein 1, 2, 3 or 4 acid groups have been neutralized or partially neutralized.

[0086] IDS or its salt may exist as enantiomers or mixtures thereof. Preferably, it exists as a racemic mixture.

[0087] IDS is commercially available as a solution containing 34% by weight of the tetrasodium salt or as a solid containing at least 75% by weight of the free acid active substance and is sold under the trademark Baypure CX100.

[0088] Hydroxyethyliminodiacetic acid (HEIDA) has the structure shown in Figure 7: In this specification, the term HEIDA is used to refer to the structure shown in Figure 7 and to the same structure wherein multiple acidic protons have been replaced, ie wherein one or two acid groups have been neutralized or partially neutralized.

[0089] ASDA is a structural isomer of IDS and has the structure shown in Figure 8: In the composition of the present invention, ASDA may be present in a form having the structure shown in Figure 4 and / or the same structure in which multiple acidic protons have been replaced, i.e., in which 1, 2, 3 or 4 acid groups have been neutralized or partially neutralized. It may be present as the free acid or as a salt or complex thereof.

[0090] Ethylenediamine disuccinic acid (EDDS), which has the structure shown in Figure 9: EDDS contains two stereogenic centers and there are three possible stereoisomers. A particularly preferred configuration is [S,S]-ethylenediamine disuccinic acid, which is readily biodegradable.

[0091] In the compositions of the present invention, EDDS may be present in a form having the structure shown in FIG9 and / or the same structure in which multiple hydrogen atoms have been replaced. Thus, EDDS may also contain succinates in which 1, 2, 3, or 4 acid groups have been neutralized or partially neutralized. It may be present as the free acid or as a salt or complex thereof.

[0092] One commercially available material is trisodium ethylenediamine disuccinate. The commercial products (Natrlquest E30 (RTM) or Enviomet C140 (RTM)) are provided as aqueous solutions containing 30% by weight EDDS (expressed as the free acid) or 37% by weight of the trisodium salt (including counterions).

[0093] Another commercially available form of EDDS is the tetrabasic acid sold under the trademarks Naturalquest E80 (RTM), Enviomet C265 (RTM) or Enviomet 280 (RTM). This is supplied in powder form containing 80% by weight of solid [S,S]EDDS as the acid and water of crystallization.

[0094] Hydroxyethylethylenediaminetriacetic acid (referred to as HEEDTA or HEDTA) has the structure shown in Figure 10: In the composition of the present invention, HEDTA may be present as a structure having the structure shown in Figure 10 and / or the same structure in which multiple acidic protons have been replaced, i.e., in which 1, 2 or 3 acid groups have been neutralized or partially neutralized. It may be present as the free acid or as a salt or complex thereof.

[0095] HEDTA is commercially available as the trisodium salt under the trade name Dissolvine H40.

[0096] In some cases, glucoheptonic acid may be used to describe a number of isomers. However, the glucoheptonic acid used in the present invention suitably has the structure β-glucoheptonic acid shown in Figure 11: This compound can exist in many stereoisomeric forms, and any of its enantiomers and diastereomers can be used in the present invention. Two common commercially available forms are α-glucoheptonic acid and β-glucoheptonic acid. In the compositions of the present invention, glucoheptonic acid is preferably present as β-glucoheptonic acid, i.e., a compound having the structure shown in Figure 11. Alternatively, it can be present as a salt in which the acid group has been neutralized or as a complex in which the acid group is complexed with another species.

[0097] The sodium salt of glucoheptonic acid is commercially available as the sodium salt or the boron complex and is sold under the trademark Crodaquest.

[0098] In some embodiments, the composition comprises poly(acrylic acid-co-hypophosphite) or a salt or complex thereof.

[0099] Poly(acrylic acid-co-phosphite) has the general structure shown in Figure 12: Typically, the molecular weight of the poly(acrylic acid-co-phosphinate) is less than 10,000, preferably less than 5,000, preferably less than 3,000. Preferably, m is at least 1, and n may be 0, but is preferably at least 1. Preferably, the sum of [m+n] is at most 135, and most preferably at most 40.

[0100] The poly(acrylic acid-co-phosphinate) may be present in the form shown, or as a sodium or potassium salt or as a complex.

[0101] Suitable polymers are available under the trade name Belsperse.

[0102] In the composition of the present invention, the poly(acrylic acid-co-phosphinate) may be present in the form shown in FIG12 , or it may be present as a salt or a complex.

[0103] Poly(acrylic acid-co-phosphinate) is commercially available and sold under the trademark Belsperse.

[0104] 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP) has the structure shown in Figure 13: Commercially available HEDP is sold as a viscous yellow liquid containing about 60% by weight of active substance and is highly acidic. It can be present in the composition of the present invention as the free acid or as a salt or complex thereof. Preferably, it is added as the free acid.

[0105] Aminotri(methylenephosphonic acid) (ATMP) has the structure shown in Figure 14: It may be present in the composition of the invention as the free acid or as a salt or complex thereof. ATMP is commercially available as the free acid or sodium salt. It is sold under the trademark Dequest 2000 series.

[0106] Ethylenediaminetetramethylenephosphonic acid (EDTMP) has the structure shown in Figure 15: It may be present in the compositions of the present invention as the free acid or as a salt or complex thereof. It is commercially available as the sodium salt and under the trademark Dequest 2040 series.

[0107] Citric acid has the structure shown in Figure 16: Citric acid may be included as the free acid or as an alkali metal or optionally substituted ammonium salt. For example, citric acid may be present as a sodium salt, a potassium salt or a triethanolamine salt.

[0108] Preferably, the one or more chelating agents are present in the free-flowing granular composition of the invention in an amount of at least 0.2 wt%, preferably at least 0.5 wt%, suitably at least 0.75 wt%, for example at least 1 wt%.

[0109] Preferably, the one or more chelating agents are present in the free-flowing granular composition of the invention in an amount of at most 20 wt%, preferably at most 15 wt%, suitably at most 12 wt%, for example at most 10 wt%.

[0110] Preferably, the one or more chelating agents are present in the free-flowing granular composition of the present invention in an amount of 0.1-20 wt%, preferably 0.5-20 wt%, suitably 0.5-15 wt%, preferably 1-10 wt%.

[0111] In addition to the one or more amphoteric surfactants and the one or more chelating agents, the free-flowing granular composition of the present invention may optionally comprise one or more additional components.

[0112] In some embodiments, the free-flowing granular composition further comprises sodium chloride.

[0113] Preferably, sodium chloride is present in the free-flowing granular composition in an amount of from 0.1 to 40 wt%, preferably from 1 to 30 wt%, suitably from 5 to 25 wt%, preferably from 10 to 20 wt%.

[0114] Preferably, the free-flowing granular composition comprises less than 20 wt% water, preferably less than 15 wt%, more preferably less than 10 wt%, for example less than 5 wt% or less than 3 wt%.

[0115] Preferably, the free-flowing particulate composition comprises less than 1 wt% magnesium oxide, preferably less than 0.5 wt%, more preferably less than 0.1 wt%, for example less than 0.05 wt% or less than 0.01 wt%.

[0116] Preferably, the free-flowing composition of the present invention comprises from 50 to 97 wt% of one or more amphoteric surfactants and from 0.1 to 30 wt% of one or more chelating agents.

[0117] Preferably, the free-flowing composition of the present invention comprises 50 to 97 wt% of one or more amphoteric surfactants; 0.1 to 20 wt% of one or more chelating agents; 0.1 to 40 wt% of sodium chloride and up to 15 wt% of water.

[0118] Suitably, the free-flowing composition of the present invention comprises 60-85 wt% of one or more amphoteric surfactants; 0.1-10 wt% of one or more chelating agents; 5-25 wt% of sodium chloride and up to 10 wt% of water.

[0119] Preferably, the free-flowing composition of the present invention comprises 50-97 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants, amine oxides and mixtures thereof; and 0.1-30 wt% of one or more chelating agents.

[0120] Preferably, the free-flowing composition of the present invention comprises 50-97 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants, amine oxides and mixtures thereof; and 0.5-20 wt%, preferably 0.5-15 wt% of one or more chelating agents.

[0121] Suitably, the free-flowing composition of the present invention comprises 60-85 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants, amine oxides and mixtures thereof; 0.1-10 wt% of one or more chelating agents; 5-25 wt% of sodium chloride and up to 10 wt% of water.

[0122] Preferably, the free-flowing composition of the present invention comprises 50-97 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants, amine oxides and mixtures thereof; and 0.1-30 wt% of one or more chelating agents selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, EDDS, STPP, citric acid and salts and mixtures thereof.

[0123] Suitably, the free-flowing composition of the present invention comprises 60-85 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants, amine oxides and mixtures thereof; 0.1-10 wt% of one or more chelating agents selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, EDDS, STPP, citric acid and salts and mixtures thereof; 5-25 wt% of sodium chloride and up to 10 wt% of water.

[0124] Preferably, the free-flowing composition of the present invention comprises 50-97 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants and mixtures thereof; and 0.1-30 wt% of one or more chelating agents.

[0125] Suitably, the free-flowing composition of the present invention comprises 60-85 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants and mixtures thereof; 0.1-10 wt% of one or more chelating agents; 5-25 wt% of sodium chloride and up to 10 wt% of water.

[0126] Preferably, the free-flowing composition of the present invention comprises 50-97 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants and mixtures thereof; and 0.1-30 wt% of one or more chelating agents selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, EDDS, citric acid and salts and mixtures thereof.

[0127] Suitably, the free-flowing composition of the present invention comprises 60 to 85 wt% of one or more amphoteric surfactants selected from betaine surfactants, sultaine surfactants, amphoacetate surfactants and mixtures thereof; 0.1 to 10 wt% of one or more chelating agents selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, EDDS, citric acid and salts and mixtures thereof; 5 to 25 wt% of sodium chloride and up to 10 wt% of water.

[0128] Preferably, the free-flowing composition of the present invention comprises 50-97 wt% of one or more betaine surfactants; and 0.1-30 wt% of one or more chelating agents selected from MGDA, GLDA, EDTA, EDDS, citric acid, salts thereof and mixtures thereof.

[0129] Suitably, the free-flowing composition of the present invention comprises 60-85 wt% of cocamidopropyl betaine and mixtures thereof; 0.1-10 wt% of one or more chelating agents selected from MGDA, GLDA, EDTA, EDDS, citric acid and salts and mixtures thereof; 5-25 wt% of sodium chloride and up to 10 wt% of water.

[0130] Preferably, the free-flowing composition of the present invention comprises 50-97 wt% of one or more betaine surfactants; and 0.1-30 wt% of one or more chelating agents selected from MGDA, GLDA, EDTA, EDDS, citric acid, salts thereof and mixtures thereof.

[0131] Suitably, the free-flowing composition of the present invention comprises 60-85 wt% of cocamidopropyl betaine and mixtures thereof; 0.1-10 wt% of one or more chelating agents selected from MGDA, GLDA, EDTA, EDDS, citric acid and salts and mixtures thereof; 5-25 wt% of sodium chloride and up to 10 wt% of water.

[0132] In some embodiments, the free-flowing compositions of the present invention may comprise one or more additional components. Such components will be known to those skilled in the art and include, for example, fillers and binders.

[0133] The particles of the free-flowing granular composition of the present invention preferably have an average particle size of 10-5000 μm, preferably 50-2000 μm, more preferably 100-1500 μm, suitably 150-1000 μm.

[0134] The average particle size is preferably measured by sieving techniques. A suitable method for determining the average particle size is described in Example 4.

[0135] Surprisingly, the present inventors have found that the addition of small amounts of one or more chelating agents can improve the flow properties of granular compositions comprising amphoteric surfactants. In some cases, a composition comprising an amphoteric surfactant may be hygroscopic, but when a chelating agent is present, it maintains its free-flowing form during storage, despite being hygroscopic.

[0136] Preferably, the present invention provides a granular composition which retains its free-flowing form when stored under ambient conditions for at least one month.

[0137] Ambient conditions refer to storage at atmospheric pressure and a temperature between 15 and 25°C.

[0138] Preferably, the granular composition retains its free-flowing form when stored under ambient conditions for at least 3 months, preferably at least 6 months, for example at least 12 months.

[0139] Advantageously, it has been found that the granular composition of the present invention retains its free-flowing form when stored for more than 12 months under conditions of varying temperature and humidity. For example, the granular composition of the present invention retains its free-flowing form when stored for more than 12 months at temperatures of 5 to 40°C and humidity of up to 65%.

[0140] This is particularly advantageous since the granular composition can be stored and transported without requiring any special conditions.

[0141] Preferably, the granular composition of the present invention does not form a cake of material during storage.

[0142] The flowability of a granular composition can be measured by evaluating the degree of caking. A suitable method is described in Example 2. According to this method, the degree of caking is the amount of powder that appears as lumps and does not pass through a 2 mm sieve after being held under pressure for 1 hour under a 25 kg weight.

[0143] Preferably, the composition of the present invention has a degree of caking as measured by the method of Example 2 of less than 20%, preferably less than 10%, more preferably less than 5%, suitably less than 2% or less than 1%.

[0144] The flowability of the granular composition can be measured according to the procedure described in Example 3.

[0145] Preferably, the composition of the present invention has a flowability as measured by the method of Example 3 of at least 5 g / s, preferably at least 10 g / s, preferably at least 15 g / s, more preferably at least 20 g / s.

[0146] Preferably, the composition of the present invention retains a flowability of at least 5 g / s, preferably at least 10 g / s, preferably at least 15 g / s, more preferably at least 20 g / s as measured by the method of Example 3 after storage for 6 months.

[0147] Preferably, the composition of the present invention retains a flowability of at least 5 g / s, preferably at least 10 g / s, as measured by the method of Example 3, after storage for 24 months.

[0148] According to a third aspect of the present invention, there is provided a method for preparing the free-flowing granular composition of the first aspect, the method comprising: (i) providing an aqueous composition comprising one or more amphoteric surfactants and one or more chelating agents; and (ii) drying the composition obtained in step (i).

[0149] Preferred features of the third aspect are as defined in relation to the first and second aspects.

[0150] Step (i) involves providing an aqueous composition comprising one or more amphoteric surfactants and one or more chelating agents. The one or more amphoteric surfactants and one or more chelating agents are suitably provided in the composition in relative proportions to provide the desired ratio in the solid free-flowing particulate composition. Suitable ratios are as defined in relation to the first and second aspects.

[0151] In some embodiments, step (i) may comprise mixing an aqueous solution of one or more amphoteric surfactants with an aqueous solution of one or more chelating agents.

[0152] In some embodiments, step (i) may comprise mixing an aqueous solution of one or more amphoteric surfactants with one or more chelating agents in solid form.

[0153] In some embodiments, step (i) may comprise mixing one or more amphoteric surfactants in solid form with an aqueous solution of one or more chelating agents.

[0154] In some embodiments, step (i) may comprise adding water to the one or more amphoteric surfactants in solid form and the one or more chelating agents in solid form.

[0155] The aqueous solution used in step (i) is preferably highly concentrated and may be saturated.

[0156] The method may comprise, between step (i) and step (ii), the step of stirring the composition obtained in step (i) and / or heating the composition obtained in step (i).

[0157] Step (ii) involves drying the composition obtained in step (i).

[0158] Any suitable drying apparatus may be used in step (ii) and such apparatus are known to those skilled in the art.

[0159] In a preferred embodiment, step (ii) involves spray drying the composition obtained in step (i).

[0160] The free-flowing granular composition of the present invention is particularly useful in preparing cleaning formulations and personal care compositions. Because the composition is free-flowing, it can be easily added to and mixed with other ingredients.

[0161] Including components in the form of free-flowing particles can be particularly useful in compositions where rapid dissolution is desired.

[0162] According to a fourth aspect of the present invention there is provided a detergent formulation comprising a free-flowing granular composition comprising at least 50 wt% of one or more amphoteric surfactants and at least 0.1 wt% of one or more chelating agents.

[0163] Preferred features of the fourth aspect are as defined in relation to the first and second aspects.

[0164] The detergent formulations of the fourth aspect of the invention can be used in household cleaning, automatic dishwashing, hand dishwashing, laundry, fabric care, kitchen care, carpet cleaning, air fresheners, vehicle care, polishing products, machine cleaning and maintenance, pesticides, insecticides, fungicides, herbicides, oilfield chemical applications, marine applications, personal care and institutional / industrial cleaning.

[0165] In some preferred embodiments, the detergent formulation of the fourth aspect is a personal care composition, preferably a solid personal care composition. For example, the detergent formulation can be a solid shampoo bar, body wash, pre-shave care product (formulation), soap, synthetic detergent or conditioner.

[0166] In some embodiments, the personal care composition can be multifunctional.Solid personal care compositions advantageously avoid the transportation of unnecessarily large amounts of water and can be packaged in a more environmentally friendly manner.

[0167] Additional components suitable for inclusion in such compositions will be known to those skilled in the art.

[0168] The detergent formulation of the fourth aspect of the present invention may be particularly useful in household cleaning applications, especially toilet care.The detergent formulation may be particularly useful for cleaning toilets, in particular toilet bowls.

[0169] The detergent formulation of the fourth aspect of the present invention can be in solid form, i.e., can be a solid detergent formulation. The solid detergent formulation itself can be free-flowing, but this is not required. The solid detergent formulation can be in any suitable form, such as a solid stick, tablet, block, disc, rod or ball. The solid detergent formulation can be prepared in a manner known to those skilled in the art, such as by compacting, pouring and molding or extrusion.

[0170] The cleaner formulation of the fourth aspect of the invention may be a solid toilet block, such as a rim block or a tank block.

[0171] In a preferred embodiment, the present invention provides a solid toilet block (e.g., a rim block or a tank block) comprising a free-flowing granular composition comprising at least 50% by weight of one or more amphoteric surfactants and at least 0.1% by weight of one or more chelating agents.

[0172] The free-flowing particulate composition may be present in the cleaner formulation (e.g., solid toilet block) in any suitable amount, for example in an amount of 10 to 50 wt%, e.g., 15 to 40 wt%, or 17 to 35 wt%, based on the total weight of the cleaner formulation.

[0173] The free-flowing granular composition may be present in the detergent formulation in an amount to provide 5 to 90 wt%, eg, 8 to 40 wt%, or 13 to 30 wt% of the amphoteric surfactant, based on the total weight of the detergent formulation.

[0174] The free-flowing particulate composition may be present in the cleaner formulation (e.g., solid toilet block) in any suitable amount, for example in an amount of 0.1 to 20 wt%, such as 0.5 to 10 wt%, or 1 to 10 wt%, based on the total weight of the cleaner formulation.

[0175] The free-flowing granular composition may be present in the detergent formulation in an amount to provide 0.1 to 25 wt%, eg, 0.25 to 15 wt% or 0.5 to 10 wt% of amphoteric surfactant, based on the total weight of the detergent formulation.

[0176] The cleaner formulation (eg solid toilet block) of the fourth aspect may further comprise one or more additional components. Suitable such components will be known to those skilled in the art.

[0177] Suitable additional ingredients include additional surfactants, preservatives, pH adjusters, fillers, fragrances and hydrotropes.

[0178] The nature of the additional components that may be present in the cleaner formulation (eg solid toilet block) of the fourth aspect of the invention will depend on the intended use of the cleaner formulation.

[0179] In a preferred embodiment, the present invention provides a solid cleaner formulation (e.g., a solid toilet block) comprising a free-flowing granular composition comprising at least 50% by weight of one or more amphoteric surfactants and at least 0.1% by weight of one or more chelating agents.

[0180] Preferably, the detergent formulation comprises less than 10%, less than 5% or less than 1% by weight of alkylbenzene sulfonates (linear and branched). Preferably, the detergent formulation comprises less than 10%, less than 5% or less than 1% by weight of linear alkylbenzene sulfonates, and preferably is free of branched alkylbenzene sulfonates. Preferably, the detergent formulation may be substantially free of or completely free of alkylbenzene sulfonates. Suitably, the detergent formulation is free of linear alkylbenzene sulfonates and branched alkylbenzene sulfonates.

[0181] The cleaner formulation (eg solid toilet block) may comprise one or more additional surfactants, for example one or more amphoteric, anionic and / or nonionic surfactants, which may or may not be free-flowing, preferably one or more anionic surfactants.

[0182] In some preferred embodiments, the solid cleaner formulations (eg, solid toilet blocks) further comprise a hydrocarbyl sulfate surfactant.

[0183] The hydrocarbyl sulfate may comprise an alkyl sulfate, an alkenyl sulfate or a combination thereof. The hydrocarbyl sulfate may comprise a fatty alcohol sulfate. Suitably, the hydrocarbyl sulfate may comprise a C5-C 30 Alkyl or C5-C 30 Alkenyl sulfates, such as C 10 -C 20 Alkyl or C 10 -C 20 Alkenyl sulfate. Alkyl sulfate may include C5-C 30 Alkyl sulfate, preferably C 10 -C 20 Alkyl sulfate. The alkyl and / or alkenyl group(s) may be unsubstituted.

[0184] Hydrocarbyl sulfates may include metal hydrocarbyl sulfates and / or amine derivatives of hydrocarbyl sulfates. Metal hydrocarbyl sulfates refer to hydrocarbyl sulfates containing metal cations. Typically, hydrocarbyl sulfates include metal hydrocarbyl sulfates. Metal hydrocarbyl sulfates may include hydrocarbyl sulfates in which the cation is an alkali metal, such as sodium or potassium, or an alkaline earth metal, such as magnesium. Preferably, the metal hydrocarbyl sulfate comprises sodium hydrocarbyl sulfate. Amine derivatives of hydrocarbyl sulfates may include ammonium hydrocarbyl sulfates, alkylamine hydrocarbyl sulfates, alkanolamine hydrocarbyl sulfates, or combinations thereof.

[0185] Examples of suitable alkyl sulfates include C 12 -C 16 Sodium alkyl sulfate (such as EMPICOL ® LX series), C 12 -C 18 Sodium alkyl sulfate (such as EMPICOL ® LZ, CZ series), ammonium lauryl sulfate (such as EMPICOL ® AL series), monoethanolamine lauryl sulfate (such as EMPICOL ® LQ series), diethanolamine lauryl sulfate, triethanolamine lauryl sulfate (such as EMPICOL ®TL series), monoisopropanolamine lauryl sulfate, diisopropanolamine lauryl sulfate, triisopropanolamine lauryl sulfate, magnesium lauryl sulfate, potassium lauryl sulfate, ammonium myristyl sulfate, monoethanolamine myristyl sulfate, diethanolamine myristyl sulfate, triethanolamine myristyl sulfate, sodium myristyl sulfate, ammonium cetyl sulfate, diethanolamine cetyl sulfate, sodium cetyl sulfate, sodium cetearyl sulfate, ammonium cocosulfate, sodium tallow sulfate, sodium oleyl sulfate, diethanolamine oleyl sulfate, sodium 2-ethylhexyl sulfate (e.g., EMPICOL ® 0585 series), sodium decyl sulfate (such as EMPICOL ® 0758 series), C 10 -C 12 Sodium fatty alcohol sulfate (such as EMPICOL ® 0335 series), C8-C 10 Sodium fatty alcohol sulfate or a combination thereof. The name is EMPICOL ® Surfactants of FLEX(R) are commercially available from Innospec.

[0186] Suitably, the hydrocarbyl sulfate may include C 12 -C 16 Sodium alkyl sulfate (such as EMPICOL ® LX series), C 12 -C 18 Sodium alkyl sulfate (such as EMPICOL ® LZ, CZ series), magnesium lauryl sulfate, potassium lauryl sulfate, sodium myristyl sulfate, sodium cetyl sulfate, sodium cetearyl sulfate, sodium tallow sulfate, sodium oleyl sulfate, sodium decyl sulfate (such as EMPICOL ® 0758 series), C 10 -C 12 Sodium fatty alcohol sulfate (such as EMPICOL ® 0335 series), C8-C 10 Fatty alcohol sodium sulfate or a combination thereof. Preferably, the alkyl sulfate may include C 12 -C 16 Sodium alkyl sulfate (such as EMPICOL ® LX series), C 12 -C 18 Sodium alkyl sulfate (such as EMPICOL ® LZ, CZ series) or their combination.

[0187] When present, the hydrocarbyl sulfate may be present in the cleaner formulation (e.g., solid toilet block) in any suitable amount, for example in an amount of 5 to 50 wt%, such as 10 to 40 wt%, or even 12 to 35 wt%, based on the total weight of the cleaner formulation.

[0188] In some preferred embodiments, the cleaner formulation (eg, solid toilet block) may be substantially free or completely free of hydrocarbyl sulfates.

[0189] In some preferred embodiments, the cleaner formulation (eg, solid toilet block) may be substantially free or completely free of alkylbenzene sulfonates.

[0190] In some preferred embodiments, the cleaner formulations (eg, solid toilet blocks) may be substantially free or completely free of hydrocarbyl sulfates and alkylbenzene sulfonates.

[0191] As used herein, the term "substantially free" means that the material in question is present in the formulation (if any) as an incidental impurity. In other words, the material does not affect the properties of the formulation. As used herein, the term "completely free" means that the material in question is not present in the formulation at all.

[0192] In some preferred embodiments, the cleaner formulation (eg, solid toilet blocks) further comprises a taurate surfactant.

[0193] The cleaning formulation may comprise an alkyl acyl taurate of formula (A): where R 4 It is C5-C 30 Alkyl groups, such as C 10 -C 20 Alkyl, and R 5 It is a C1-C6 alkyl group, for example a C1-C4 alkyl group.

[0194] R 4 and R 5 Each may be an unsubstituted alkyl group.

[0195] R 4 Suitable are residues of fatty acids. Fatty acids obtained from natural oils typically include mixtures of fatty acids. For example, fatty acids obtained from coconut oil contain a mixture of fatty acids including C 12 Lauric acid, C 14 Myristic acid, C 16 Palmitic acid, C8 octanoic acid, C 10 Decanoic acid and C 18 Stearic acid and oleic acid.

[0196] R 4 The residues of one or more naturally occurring fatty acids and / or one or more synthetic fatty acids may be included. 4 May consist essentially of the residue of a single fatty acid.

[0197] Can derive R4 Examples of carboxylic acids include cocoic acid, hexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, gadoleic acid, arachidonic acid, eicosapentaenoic acid, behenic acid, erucic acid, docosahexaenoic acid, lignoceric acid, naturally occurring fatty acids such as those obtained from rice bran oil, oat oil, wheat germ oil, hempseed oil, coconut oil, tallow, palm kernel oil, milk fat, palm oil, olive oil, corn oil, linseed oil, peanut oil, fish oil, and rapeseed oil; synthetic fatty acids made as a single chain length or a selected chain length distribution; and mixtures thereof.

[0198] Preferably, the compound of formula (A) comprises methylacyl taurate. Examples of suitable alkyl acyl taurates include sodium lauroyl methyl taurate, sodium methyl myristoyl taurate, sodium methyl palmitoyl taurate, sodium methyl stearoyl taurate, sodium methyl cocoyl taurate, sodium methyl oleoyl taurate, and combinations thereof.

[0199] Preferred taurate surfactants of formula (A) include sodium methyl oleoyl taurate, sodium methyl cocoyl taurate or mixtures thereof.

[0200] Alternatively and / or additionally, the detergent formulation may comprise an alkyl acyl taurate of formula (B): in: R 6 and R 7 Each independently selected from H or C 1-4 alkyl, provided that R 6 and R 7 One of them is H, and R 6 and R 7 The other one is C 1-4 alkyl; R 9 It is C 1-6 Alkyl, C 2-6 Alkenyl or C substituted by aryl 1-6 alkyl; and R 8 It is C 4-25 Alkyl or C 4-25 Alkenyl, where C 4-25 Alkyl or C 4-25 The alkenyl group is optionally substituted with a hydroxy group.

[0201] Preferably, R 6 and R 7 One of them is C 1-4alkyl, and the other is H. More preferably, R 6 and R 7 One of them is a methyl group and the other is an H.

[0202] Preferred R 9 It is C 1-6 Alkyl or C 2-6 Alkenyl, preferably C 1-6 Alkyl groups, such as C 1-2 More preferably, R 9 It's methyl.

[0203] R 8 Preferably C 8-18 Alkyl or C 8-18 Alkenyl, where C 8-18 Alkyl or C 8-18 The alkenyl group is optionally substituted with a hydroxyl group. 8 is unsubstituted C 8-18 Alkyl or unsubstituted C 8-18 Alkenyl.

[0204] R 8 Suitable are residues of fatty acids. Fatty acids obtained from natural oils typically include mixtures of fatty acids. For example, fatty acids obtained from coconut oil contain a mixture of fatty acids including C 12 Lauric acid, C 14 Myristic acid, C 16 Palmitic acid, C8 octanoic acid, C 10 Decanoic acid and C 18 Stearic acid and oleic acid.

[0205] R 8 The residues of one or more naturally occurring fatty acids and / or one or more synthetic fatty acids may be included. 8 May consist essentially of the residue of a single fatty acid.

[0206] Can derive R 8 Examples of carboxylic acids include coconut, hexanoic, caproic, capric, lauric, myristic, palmitic, palmitoleic, stearic, oleic, linoleic, arachidic, gadoleic, arachidonic, eicosapentaenoic, behenic, erucic, docosahexaenoic, lignoceric, naturally occurring fatty acids such as those obtained from rice bran oil, oat oil, wheat germ oil, hempseed oil, coconut oil, tallow, palm kernel oil, milk fat, palm oil, olive oil, corn oil, linseed oil, peanut oil, fish oil, and rapeseed oil; synthetic fatty acids made as a single chain length or a selected chain length distribution; and mixtures thereof.

[0207] Preferred R 8is unsubstituted C 4-25 Alkyl groups, such as unsubstituted C 8-18 alkyl.

[0208] When present, the taurate (e.g., alkylacyl taurate) can be present in the cleaner formulation (e.g., solid toilet block) in any suitable amount, for example, in an amount of 1 to 30 wt %, such as 2 to 30 wt %, or even 10 to 20 wt %, based on the total weight of the cleaner formulation.

[0209] In some preferred embodiments, the detergent formulation (e.g., solid toilet block) further comprises a filler. The filler suitably comprises a carbonate, sulfate, halide salt, phosphate, silicate, or a combination thereof. The filler may comprise an alkali metal or alkaline earth metal carbonate, an alkali metal or alkaline earth metal sulfate, an alkali metal or alkaline earth metal halide salt, an alkali metal or alkaline earth metal phosphate, or a combination thereof. Suitable fillers include sodium sulfate, sodium chloride, sodium carbonate, and sodium silicate. Suitable fillers may be anhydrous or hydrated. Preferably, the filler is anhydrous.

[0210] The filler can be present in the detergent formulation (e.g., solid toilet block) in any suitable amount, such as at least 10 wt %, such as at least 30 wt %, or even at least 50 wt %, based on the total weight of the detergent formulation. The filler can be present in the detergent formulation in an amount of 10 to 90 wt %, such as 30 to 70 wt %, or even 50 to 60 wt %, based on the total weight of the detergent formulation.

[0211] In some preferred embodiments, the cleaner formulation (eg, solid toilet block) further comprises an alkyl glucoside and / or a glycolipid, such as a sophorolipid, a rhamnolipid, and / or a mannosylerythritol lipid.

[0212] The cleaning agent formulation may comprise a hydrocarbyl glucoside. The hydrocarbyl glucoside suitably comprises an alkyl glucoside, an alkenyl glucoside or a combination thereof. The hydrocarbyl glucoside may comprise a fatty alcohol glucoside. Suitably, the hydrocarbyl glucoside comprises a C5-C 30 Alkyl or C5-C 30 Alkenyl glucosides, such as C 10 -C 20 Alkyl or C 10 -C 20 Alkenyl glucoside. Alkyl glucoside may include C5-C 30 Alkyl glucoside, such as C 10 -C 20 Alkyl Glucosides. Examples of suitable hydrocarbyl glucosides include octyl glucoside, decyl glucoside, octyldecyl glucoside, undecyl glucoside, lauryl glucoside, myristyl glucoside, cetearyl glucoside and coco glucoside. A suitable example of a hydrocarbyl glucoside is lauryl glucoside.

[0213] The hydrocarbyl glucoside may be present in the cleaner formulation (e.g., solid toilet block) in any suitable amount, for example in an amount of 0.1 to 5 wt%, such as 0.25 to 2 wt%, or even 0.5 to 1 wt%, based on the total weight of the cleaner formulation.

[0214] In some embodiments, the cleaner formulation (eg, solid toilet block) further comprises a nonionic surfactant, such as a fatty alcohol ethoxylate.

[0215] In some preferred embodiments, the cleaner formulation (eg, solid toilet block) may be substantially free or completely free of fatty alcohol ethoxylates.

[0216] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) further comprises an amphoteric surfactant (i.e., in addition to the amphoteric surfactant contained in the free-flowing granular composition), such as a betaine (e.g., cocamidopropyl betaine (CAPB)). When such an additional amphoteric surfactant is present, it can be free-flowing, but this is not required. In some preferred embodiments, the additional amphoteric surfactant is not free-flowing.

[0217] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) further comprises a chelating agent (i.e., in addition to the chelating agent contained in the free-flowing granular composition), such as a chelating agent described herein (e.g., a chelating agent selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, EDDS, citric acid, and salts and mixtures thereof, or a chelating agent selected from MGDA, GLDA, EDTA, EDDS, citric acid, and salts and mixtures thereof).

[0218] The total chelating agent content of the cleaner formulation (eg solid toilet blocks) may be from 2 to 5 wt%, wherein the chelating agent is present in the free-flowing granular composition and by further addition to the cleaner formulation when the cleaner formulation is prepared.

[0219] In some embodiments, the cleanser formulation may be a personal care composition such as shampoo, body wash, soap, beauty bar, cream, and conditioner.

[0220] Personal care compositions typically include ingredients such as surfactants (including anionic, amphoteric, nonionic and cationic surfactants); conditioning agents (including quaternary ammonium compounds, cationic polymers, cationic conditioning polymers, silicones, synthetic or natural oils or resins, etc.), fatty alcohols, electrolytes or other rheology modifiers, sunscreens / pearlescent agents, scalp benefit agents, fragrances, dyes, UV filters, penetration enhancers (e.g., propylene carbonate, benzyl alcohol, etc.), preservatives, antioxidants, emulsifiers, pH adjusters and buffers, and styling polymers (e.g., polyvinyl pyrrolidone, etc.).

[0221] The personal care compositions may comprise one or more surfactants as previously defined herein. They may also comprise a cationic surfactant.

[0222] Suitable cationic polymers will be known to those skilled in the art and comprise a plurality of quaternary ammonium residues bonded to a polymer backbone. Suitable cationic polymers include those known as polyquaterniums in the International Nomenclature of Cosmetic Ingredients (INCI List).

[0223] Preferred cationic polymers for use herein are polysaccharide compounds that have been functionalized with cationic residues such as quaternary ammonium groups. Particularly preferred cationic polymers are based on cellulose or guar gum. Compounds of this type will be known to those skilled in the art.

[0224] The personal care composition suitably comprises one or more ingredients selected from the group consisting of sodium acyl isethionate (e.g. sodium lauroyl isethionate or sodium cocoyl isethionate), sodium acyl alkyl isethionate (e.g. sodium lauroyl methyl isethionate or sodium cocoyl methyl isethionate), sodium alkyl amphoacetate, disodium cocoamphodiacetate, alkyl betaines, alkyl amidopropyl betaines, alkyl amidopropyl hydroxysultaines, alkyl propionates, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, acyl taurates (e.g. sodium lauroyl methyl taurate), acyl glycinates, acyl glutamates, acyl sarcosinates, alkyl polyglucosides, acyl lactylates, sodium acyl sulfoacetate, aliphatic esters, aromatic esters, glycerides, alcohol alkoxylates, fatty acid alkoxylates, biosurfactants (e.g. sophorolipids), fatty acids or mixtures thereof.

[0225] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 10 to 50 wt. %, e.g., 17 to 35 wt. %, of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; and 10 to 90% by weight, for example 30 to 70% by weight, of fillers, based on the total weight of the detergent formulation.

[0226] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 10 to 50 wt. %, e.g., 17 to 35 wt. %, of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; 10 to 90 wt %, e.g., 30 to 70 wt %, of filler, based on the total weight of the detergent formulation; and 1 to 30 wt%, such as 2 to 30 wt%, of a taurate surfactant (eg, alkyl acyl taurate), based on the total weight of the detergent formulation.

[0227] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 10 to 50 wt. %, e.g., 17 to 35 wt. %, of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; 10 to 90 wt %, e.g., 30 to 70 wt %, of filler, based on the total weight of the detergent formulation; and 0.1 to 5% by weight, for example 0.25 to 2% by weight, of hydrocarbyl glucoside, based on the total weight of the detergent formulation.

[0228] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 10 to 50 wt. %, e.g., 17 to 35 wt. %, of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; 10 to 90 wt %, e.g., 30 to 70 wt %, of filler, based on the total weight of the detergent formulation; and 1 to 5 wt%, such as 2 to 4 wt%, of chelating agent, based on the total weight of the detergent formulation.

[0229] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 10 to 50 wt. %, e.g., 17 to 35 wt. %, of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; 10 to 90 wt. %, for example 30 to 70 wt. %, of fillers, based on the total weight of the detergent formulation; 1 to 30 wt%, e.g., 2 to 30 wt%, of a taurate surfactant (e.g., alkyl acyl taurate), based on the total weight of the detergent formulation; and 0.1 to 5% by weight, for example 0.25 to 2% by weight, of hydrocarbyl glucoside, based on the total weight of the detergent formulation.

[0230] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 10 to 50 wt. %, e.g., 17 to 35 wt. %, of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; 10 to 90 wt. %, for example 30 to 70 wt. %, of fillers, based on the total weight of the detergent formulation; 1 to 30 wt%, e.g., 2 to 30 wt%, of a taurate surfactant (e.g., alkyl acyl taurate), based on the total weight of the detergent formulation; 0.1 to 5 wt. %, e.g., 0.25 to 2 wt. %, of an alkyl glucoside, based on the total weight of the detergent formulation; and 1 to 5 wt%, such as 2 to 4 wt%, of chelating agent, based on the total weight of the detergent formulation.

[0231] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 17 to 35 wt. % of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; 50 to 60 wt. % of filler, based on the total weight of the detergent formulation; 10% to 30% by weight, based on the total weight of the detergent formulation, of a taurate surfactant (such as an alkyl acyl taurate); and 0.5 to 1 wt. % of hydrocarbyl glucoside, based on the total weight of the detergent formulation.

[0232] In some preferred embodiments, the cleaner formulation (e.g., solid toilet block) comprises: 17 to 35 wt. % of a free-flowing granular composition, based on the total weight of the detergent formulation, wherein the free-flowing granular composition comprises at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents; 50 to 60 wt. % of filler, based on the total weight of the detergent formulation; 10% to 30% by weight, based on the total weight of the detergent formulation, of a taurate surfactant (such as an alkyl acyl taurate); 0.5 to 1 wt. % of a hydrocarbyl glucoside, based on the total weight of the detergent formulation; and 2 to 4 wt% chelating agent, based on the total weight of the detergent formulation.

[0233] In the preferred embodiments described above, the detergent formulation may be substantially free or completely free of hydrocarbyl sulfates and / or alkylbenzene sulfonates.

[0234] In the preferred embodiments described above, the detergent formulation may be substantially free or completely free of hydrocarbyl sulfates and / or fatty alcohol ethoxylates.

[0235] In the preferred embodiments described above, the detergent formulation may be substantially free or completely free of hydrocarbyl sulfates, alkylbenzene sulfonates, and fatty alcohol ethoxylates.

[0236] According to a fifth aspect of the present invention, there is provided the use of a free-flowing granular composition comprising at least 50 wt. % of one or more amphoteric surfactants and at least 0.1 wt. % of one or more chelating agents in household cleaning (e.g. toilet bowl care), hand dishwashing, laundry, fabric care, kitchen care, carpet cleaning, vehicle care, polishing products, machine cleaning and maintenance, pesticides, insecticides, fungicides, herbicides, oilfield chemical applications, marine applications, personal care or institutional / industrial cleaning formulations.

[0237] According to a sixth aspect of the present invention, there is provided a toilet cleaning device comprising the detergent formulation of the fourth aspect (preferably a solid detergent formulation) and an attachment element for attaching the device to the toilet. Suitably, the device is attachable to the rim of the toilet bowl. The attachment element may be in the form of an arm or a hook. The device may include a holder for holding the detergent formulation. The holder may be in the form of a housing such as a basket. When the toilet is flushed, water suitably contacts a portion of the detergent formulation, for example by passing through the basket, to dissolve a portion of the detergent formulation and provide cleaning for the toilet.

[0238] According to a seventh aspect of the present invention, there is provided a method of providing cleaning to a toilet, the method comprising securing a detergent formulation (preferably the solid detergent formulation of the fourth aspect, such as a solid toilet block) to the rim of the toilet or placing the detergent formulation (preferably the solid detergent formulation of the fourth aspect, such as a solid toilet block) in a toilet tank.

[0239] Preferred features of the fifth, sixth and seventh aspects are as defined in relation to the first and second aspects.Preferred features of the cleaner formulation apply when the cleaner formulation is a solid toilet block (eg a rim block or tank block).

[0240] The invention will now be further defined with reference to the following non-limiting examples.

[0241] Example 1 A solid composition comprising the ingredients listed in Table 1 was prepared.

[0242] Table 1 Composition 1 2 3 4 CAPB (wt% active substance) 76 73 79 76 Sodium citrate (wt% active substance) 2.5 Water (weight %) 1.8 1.7 0.8 1.7 NaCl (wt%) 14.8 13.9 14.2 14.6 MGDA (wt% active substance) 6 Others*(wt%) to 100 to 100 to 100 to 100 *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0243] CAPB is derived from palm kernel oil which contains a mixture of C12-C18 fatty acids.

[0244] MGDA is provided as the trisodium salt.

[0245] Example 2 The composition of Example 1 was tested for caking according to the following procedure. The results are shown in Table 2.

[0246] Compaction test on dry product 1. Scope and Principle This method is used to evaluate the degree of agglomeration of dry products in the form of powders, agglomerates, granules or needles.

[0247] The degree of caking is defined as the proportion of powder that appears as lumps and does not pass through a 2 mm sieve after applying pressure under a 25 kg weight for 1 hour.

[0248] 2. Equipment Plastic resealable bag (8x10cm) 25kg weight 2mm sieve 3. Analytical procedures.

[0249] Weigh 100 mL of the material to be analyzed (W i ).

[0250] The material was sealed in an 8 x 12 cm resealable plastic bag.

[0251] A 25 kg weight was placed on the bagged material for 1 hour.

[0252] Record the weight of the 2 mm sieve.

[0253] The bag was opened and the material was poured onto a 2 mm sieve.

[0254] The sieve was shaken gently for 30 seconds.

[0255] Record the weight of the sieve and the amount of product that did not pass through the sieve and subtract the initial weight of the sieve (W from the total weight). f ).

[0256] 4. Plotting the results The percentage of compacted material (%CM) can be calculated using the following formula: Table 2 Composition 1 2 3 4 Agglomeration degree (%) 68.5 0.8 0.0 74.3 Example 3 After a storage period of 6 or 24 months, the flowability of the composition of Example 1 was evaluated by the following method. The results are provided in Table 3.

[0257] Method for measuring the flowability of dry products ○Instrument: Plastic tube, ⌀ 4 cm, volume 500 mL ■ Support device for plastic pipes (with a base containing a 1.5 cm hole and an opening / closing system) ■Empty container (to be placed under the instrument) ■Scales ■Stopwatch ○ Procedure: ■Insert the tube into the support device and close the hole ■ Fill the tube with (500 mL) the dry product to be analyzed.

[0258] ■Weigh the empty container and place it under the device (Wi) ■ Open the hole and start a stopwatch after the dry product begins to flow; if the dry product does not flow immediately, gently tap the base of the support.

[0259] ■ When the flow of dry product stops, stop the meter and record the time (t); if some dry product is still in the tube, after 10 seconds of no flow, you can gently hit the base of the device to help flow. If most of the solids are still in the tube after 3 attempts, the dry product is not flowing.

[0260] ■Weighing container (Wf) ■ Liquidity will be measured using the following formula: Table 3 Composition 1 2 3 4 Storage period 24m 24m 6m 6m Flowability (g / s) 0.7 22.4 24.4 0.1 The results of 22.4 g / s and 24.4 g / s at 6 and 24 months for compositions 2 and 3 in Table 3 above illustrate excellent flowability. For comparative compositions 1 and 4, very poor flowability was achieved.

[0261] Example 4 The average particle size of the composition of the present invention can be determined according to the following method for evaluating the particle size of solid materials in the form of powders, agglomerates, granules or needles.

[0262] equipment: -Sieves of different mesh sizes: Plate, 75μm, 125μm, 250μm, 500μm, 1000μm -Vibrating screen with timer -Weight scale Analytical procedure: - Take the sieves and weigh each of them - Stack the sieves starting with the sieve with the smallest mesh size and increasing in size.

[0263] - Pour about 100 g of dry product on the top sieve.

[0264] - Place the sieve on the vibrating wire mesh, cover with the lid and vibrate for 60 seconds.

[0265] -Weigh each sieve again and record the data.

[0266] -Subtract the weight of each sieve from the final weight of the sieve containing the powder.

[0267] The results can be normalised and plotted on a graph to illustrate the particle size distribution. In the example below, the mesh size of each sieve is plotted on the X-axis and the amount of product found (in g) is plotted on the Y-axis.

[0268] Example 5 Solid toilet block formulations 5 to 8 were prepared containing the ingredients listed in Table 4. The amount of each ingredient is given as weight % active.

[0269] To prepare the toilet block formulation, the solid ingredients shown in Table 4 were weighed and added to the mixing chamber of a horizontal mixer with counter-rotating sigma blades and mixed to obtain a uniform mixture. The mixing speed was 10 rpm and the mixing chamber temperature was set to 25°C. The liquid ingredients shown in Table 4 were then weighed and added to the pre-mixed solid ingredients under mixing. Once a uniform granular mixture was obtained, the mixer was stopped. The granular mixture was then added to a single-screw plodder and extruded in the desired shape using a screw speed of 1 rpm. The temperatures of the barrel and conical head of the plodder were set to 18.5°C and 30°C, respectively. The extrudability of the composition was considered "OK" if the mixture retained its shape and did not break or crack during extrusion.

[0270] Table 4 Composition 5 6 7 8 <![CDATA[Sodium sulfate anhydrous]]> 56.25 54.25 56.25 54.25 Sodium citrate ternary dihydrate 3 3 3 3 anhydrous sodium carbonate 1.5 1.5 1.5 1.5 <![CDATA[Sodium methyl oleoyl taurate [1] > 0 13.65 0 13.65 <![CDATA[Cocamidopropyl betaine (present as a free-flowing particulate composition of the present invention) [2] > 27.3 13.65 27.3 13.65 <![CDATA[Lauryl glucoside [3] > 0.62 0.62 0 0 <![CDATA[Cocamidopropyl betaine [4] > 0 0 0.44 0.22 <![CDATA[Sodium methyl oleoyl taurate [5] > 0 0 0 0.19 spices 3 3 3 3 Mixing time (minutes) 85 45 80 30 Extrudability OK OK OK OK Flash foam (mL) (time 0 seconds) 183 87 151 62 Stable foam (mL) (time 300 seconds) 171 80 142 58 Lifespan (N° flushing) 143 237 126 237 [1] Commercially available as a powder containing 70% by weight of active substance [2] Solid free-flowing composition 3 of Example 1 comprising 79% by weight of active substance [3] Commercially available as a liquid containing 50% by weight of active substance [4] Commercially available as a liquid containing 35% by weight of active substance [5] Commercially available as a liquid containing 30% by weight of active substance The flash foam test is performed as follows: Foam test The foaming curves of the formulations in Table 4 were tested according to ASTM D1173-53 (2001) "Foaming properties of Surface Active Agents" and UNI 26001 "Cosmetic And Personal Hygiene Products - Foaming Power Determination Of Detergent Products Containing Surface Active Agents", 1995, using the well-known Ross Miles pour foam method (J. Ross, GD Miles: An Apparatus for Comparison of Foaming Properties of Soaps and Detergents, Oil & Soap, May 1941, pp. 99-102).

[0271] The test conditions are as follows: Toilet Block Concentration About 0.18g / L, w / w Water hardness <![CDATA[Approximately 330 ppm CaCO3 (tap water)]]> water temperature 15℃ Number of repetitions 3 Measuring the foam time 0 seconds, 60 seconds, 300 seconds Foam volume unit mL The foaming properties of the solid toilet block formulations are reported in Table 4 as flash foam (mL of initial foam at time 0 seconds) and steady foam (mL of foam after 300 seconds).

[0272] The life test was performed as follows: Life test The longevity of the formulations in Table 4 was tested by flushing a toilet at random intervals 18 times per day with a cage containing 1 x 35g of the formulation block attached to the rim. The toilet was a Duract Duracplus Sudan model with an approximately 6L flush. The water hardness was approximately 330 ppm CaCO3 (tap water) and the water temperature was approximately 15±5°C.

[0273] Lifespan was determined as the point in time at which the formulation was completely consumed.

[0274] Example 6 Additional solid compositions were prepared comprising the ingredients listed in Table 5: Table 5 Composition 9 10 11 12 13 14 15 16 17 CAPB (wt% active substance) 74 74 74 80 72 <![CDATA[LAPB 1 (wt% active substance)]]> 95 87.5 <![CDATA[LAPO 2 (wt% active substance)]]> 90.8 <![CDATA[LAA 3 (wt% active substance)]]> 54 Sodium citrate (wt% active substance) 2.5 3.8 1.5 1.8 NaCl (wt%) 14.1 14.3 14 <1 <1 14.5 14.2 16.2 Water (weight %) 1.2 1.1 1.4 3.6 4.1 0.5 1.7 1.8 2.3 Sodium sulfate (weight %) 2 10.3 MGDA (wt% active substance) 5 6.2 2.5 5 STPP (wt% active substance) 5 EDDS (wt% active substance) 5 Glycerol (weight %) 6.3 Sodium carbonate (weight %) 9.8 Others*(wt%) to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0275] 1 Lauramidopropyl Betaine (Desalted) 2 Lauramidopropylamine oxide 3 Sodium lauroamphoacetate.

[0276] Example 7 The compositions of Example 6 were tested shortly after preparation according to the methods described in Examples 2 and 3 to determine the degree of caking and flowability. The results are shown in the table. The results and appearance of these compositions are detailed in Table 6.

[0277] Table 6 Example Appearance Flowability (g / s) Agglomeration degree (%) 9 particulate matter 25.7 <1 10 particulate matter 27.8 <1 11 particulate matter 23.4 <1 12 (Comparison) fine powder <5 62.7 13 fine powder 15.8 <1 14 Small particles 26 <1 15 Fine powder / granular matter 17.3 <1 16 Small particles 16.5 <1 17 Small particles 33.6 <1 Example 8 Another solid composition of the present invention was prepared comprising cocamidopropyl hydroxysultaine (75 wt %), MGDA (4 wt %), sodium citrate (1 wt %), water (4.2 wt %), and sodium chloride (13.8 wt %). The remaining material came from impurities in the components or residual starting materials.

[0278] Example 9 Prepare a multifunctional hair, body and beard formulation that can be used as a shampoo, conditioner, body wash, face wash & pre-shave composition.

[0279] The composition contains the following ingredients: Element Weight% active substance Sodium Lauroyl Methyl Isethionate 10.72 glycerin 26.5 Guar Hydroxypropyltrimonium Chloride 0.50 Composition 1 of Example 3 (cocamidopropyl betaine) 5.00 Sodium Cocoyl Isethionate 25.93 Propoxytetramethylpiperidinyl polydimethylsiloxane 2.00 Phenoxyethanol 1.00 fragrances 1.00 other* to 100 *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0280] The composition may be provided in the form of a butter, paste, ointment or thick cream.

[0281] The composition provides a high-quality, creamy, foamy lather with mild ingredients and a desirable afterfeel.

[0282] Advantages of the composition include that it can be provided in reduced packaging or sustainable packaging, it contains less water than conventional products, it contains no sulfates and is multifunctional.

[0283] Example 10 The following solid shampoo formulation was prepared containing the following components Composition 20 21 22 23 24 Microcrystalline cellulose (% active substance by weight) 25.00 25.00 25.00 - - Sodium cocosulfate (wt% active ingredient) 39.38 39.38 39.38 85.82 85.82 D-Mannitol (wt% active substance) 25.00 25.00 25.00 - - Guar Hydroxypropyltrimonium Chloride (Weight % Active Ingredient) 0.30 0.30 0.30 0.30 0.30 water 3.60 5.60 - - 2 Composition 3 of Example 1 (cocamidopropyl betaine) 3.00 1.00 6.60 3 1 fragrances 0.30 0.30 0.30 0.3 0.3 Argan Oil - - - 3 3 other* to 100 to 100 to 100 to 100 to 100 Appearance tablet Great tablet Great Great

[0284] *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0285] Example 11 Two drain cleaning compositions were prepared comprising the following components: Element Formulation 1 (wt% active substance) Formulation 2 (wt% active substance) citric acid 50 50 sodium carbonate 20 20 Sodium dichloroisocianurate \ 10 Sodium percarbonate 10 \ <![CDATA[TAED 1 ]]> 1 \ Composition 3 of Example 1 (cocamidopropyl betaine) 4 4 MGDA 6 6 Probiotics 2 \ Sodium xylenesulfonate 1.9 1.9 Sodium chloride 4 7 other* to 100 to 100 pH: 5% 4.5 4.7 *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0286] 1 Tetraacetylethylenediamine The composition is prepared by mixing all the ingredients at ambient temperature until a homogeneous composition in powder form is obtained.

[0287] To use, add the composition directly to a sink with warm water.

[0288] Example 12 The toilet block composition was prepared by mixing the ingredients listed in the table below until homogenized, extruding, and then cutting into blocks. Element Weight% active substance sodium sulfate 43.45 Sodium citrate 3 sodium carbonate 1.5 Sodium methyl oleoyl taurate 3.5 Composition 3 of Example 1 (cocamidopropyl betaine) 7.6 Lauryl Glucoside 0.15 Cetyl Stearyl Alcohol 2 C12-16 Sodium Sulfate 30.4 spices 3 other* to 100

[0289] *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0290] Sodium methyloleoyl taurate is provided as a powder comprising 70% by weight of active substance.

[0291] Lauryl glucoside is provided as a solution comprising 50% by weight of active substance.

[0292] Cetylstearyl alcohol is provided as flakes comprising 90% by weight of active substance.

[0293] C12-16 sodium sulfate is provided as a powder containing 95% by weight of active substance.

[0294] Example 13 Provided is an effervescent toilet bowl cleaner comprising the following components: Element Weight% active substance Anhydrous citric acid 45 sodium carbonate 46 Composition 3 of Example 1 4 Sodium xylenesulfonate 1.9 Sodium dichloroisothiazide 2 other* to 100% *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0295] The composition is prepared by mixing all the ingredients at ambient temperature until a homogeneous composition in powder form is obtained.

[0296] Example 14 Provided is an effervescent toilet bowl cleaner comprising the following components: Element Weight% active substance Sodium citrate 45 sodium carbonate 44 Composition 3 of Example 1 4 Sodium xylenesulfonate 1.9 Sodium dichloroisothiazide 1.5 C9-11 Pareth-8 1.5 fragrances 1 other* to 100% *Other components include unreacted starting materials and impurities present in commercial sources of ingredients.

[0297] The composition is prepared by mixing all the ingredients at ambient temperature until a homogeneous composition in powder form is obtained.

Claims

1. A free-flowing granular composition comprising at least 50% by weight of one or more amphoteric surfactants and at least 0.1% by weight of one or more chelating agents.

2. A free-flowing granular composition according to claim 1, wherein the one or more amphoteric surfactants are selected from the group consisting of betaine surfactants, sultaine surfactants, amphoacetate surfactants and mixtures thereof.

3. The free-flowing granular composition of claim 1, wherein the one or more amphoteric surfactants are selected from the group consisting of betaine surfactants, sultaine surfactants, amphoacetate surfactants, amine oxides and mixtures thereof.

4. The free-flowing granular composition of claim 2, wherein the one or more amphoteric surfactants comprises a betaine surfactant.

5. A free-flowing granular composition according to any one of the preceding claims, wherein the one or more amphoteric surfactants comprises cocamidopropyl betaine.

6. A free-flowing granular composition according to any one of the preceding claims, wherein the one or more amphoteric surfactants are present in an amount of 50 to 97 wt%, preferably 60 to 90 wt%, more preferably 70 to 85 wt%.

7. A free-flowing granular composition according to any one of the preceding claims, wherein the chelating agent is a polycarboxylic acid chelating agent.

8. A free-flowing granular composition according to any one of the preceding claims, wherein the one or more chelating agents are selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, NTA, AES, ASDA, DTPMPA, STPP and HEDTA.

9. A free-flowing granular composition according to any one of the preceding claims, wherein the chelating agent is selected from MGDA, GLDA, IDS, EDTA, DTPA, DETPMP, HEIDA, EDDS, citric acid and salts and mixtures thereof.

10. A free-flowing granular composition according to any one of the preceding claims, wherein the chelating agent is selected from MGDA, GLDA, EDTA, EDDS, citric acid and salts and mixtures thereof.

11. A free-flowing granular composition according to any preceding claim, wherein the one or more chelating agents are present in an amount of 0.1-20 wt%, preferably 0.5-15 wt%, preferably 1-10 wt%.

12. A free-flowing granular composition according to any preceding claim comprising sodium chloride.

13. The free-flowing granular composition according to claim 11, wherein the amount of sodium chloride is 10-30% by weight.

14. A free-flowing granular composition according to any preceding claim comprising less than 5% by weight water.

15. A free-flowing granular composition according to any preceding claim having a degree of agglomeration of less than 5% as measured by the method of Example 2.

16. A free-flowing granular composition according to any preceding claim having a flowability of at least 10 g / s as measured by the method of Example 3.

17. Use of one or more chelating agents for improving the flowability of a granular composition comprising at least 50% by weight of one or more amphoteric surfactants.

18. A method of preparing a free-flowing granular composition according to any one of claims 1 to 16, the method comprising: (i) providing an aqueous composition comprising one or more amphoteric surfactants and one or more chelating agents; as well as (ii) drying the composition obtained in step (i).

19. A cleaning agent formulation comprising the free-flowing granular composition according to any one of claims 1 to 16.

20. The cleanser formulation of claim 19 which is a solid personal care composition.

21. A solid toilet block (such as a rim block or tank block) comprising the free-flowing granular composition according to any one of claims 1 to 16.

22. Use of the free-flowing granular composition according to any one of claims 1 to 16 in household cleaning (e.g. toilet bowl care), hand dishwashing, laundry, fabric care, kitchen care, carpet cleaning, vehicle care, polishing products, machine cleaning and maintenance, pesticides, insecticides, fungicides, herbicides, oilfield chemical applications, marine applications, personal care or institutional / industrial cleaning formulations.

23. A toilet cleaning device comprising a detergent formulation (preferably a solid detergent formulation) according to claim 19 and an attachment element for attaching the device to a toilet.

24. A method of providing cleaning to a toilet, the method comprising attaching the detergent formulation of claim 19 to a toilet rim or placing the detergent formulation of claim 19 within a toilet tank.

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