WO2010079023A1

WO2010079023A1 - Anti-spray measured dosing system for viscous sheer thinning laundry liquids

Info

Publication number: WO2010079023A1
Application number: PCT/EP2009/066407
Authority: WO
Inventors: Paul Anthony Anderson; Glen Williams
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2009-01-09
Filing date: 2009-12-04
Publication date: 2010-07-15
Also published as: EP2376340A1; BRPI0923945A2; ZA201104613B

Abstract

Accordingly in a first aspect the invention provides a squeeze-operated container (1) comprising a storage chamber (3) containing a laundry fluid composition (13) which is shear thinning and has a viscosity of at least 100 Pa. s when in rest or up to a shear stress of 10 Pa; and a measuring chamber (5), the measuring chamber comprising a base (7) from which upwardly extends a dispensing spout (9) in fluid communication with the storage chamber; and a pour spout, wherein the storage container is squeezable to force the laundry fluid composition into the measuring chamber and the dispensing spout comprises a deflector cap (15) on the top of the dispensing spout and one or more lateral apertures (17) on the spout such that the viscous laundry fluid exits the spout laterally and downwardly, and characterised in that the or each of the apertures comprise annular sections of at least 60° and that the deflector cap extends radially outward of the apertures.

Description

ANTI-SPRAY MEASURED DOSING SYSTEM FOR VISCOUS SHEER THINNING

LAUNDRY LIQUIDS

The present invention relates to a measured-dosing system for laundry fluids.

In the use of laundry liquid products it is necessary to measure out a particular amount for use at any one time. This is more important with concentrated fluids as over-dosing or under-dosing is easier to effect with a concentrated fluid.

US2730270 discloses a capped squeeze bottle and liquid measuring and dispensing device attached thereto. A dip tube connects an outlet in the top of the cap with a measuring region above. The bottle is squeezed to force liquid up the dip tube and into the liquid measuring region. The bottle is inverted to dispense the measured amount of liquid.

The object of the present invention is to provide an improved measured-dosing system for laundry fluids.

Accordingly in a first aspect the invention provides a squeeze-operated container comprising a storage chamber containing a laundry fluid composition which is shear thinning and has a viscosity of at least 100 Pa. s when in rest or up to a shear stress of 10 Pa; and a measuring chamber, the measuring chamber comprising a base from which upwardly extends a dispensing spout in fluid communication with the storage chamber; and a pour spout, wherein the storage container is squeezable to force the laundry fluid composition into the measuring chamber and the dispensing spout comprises a deflector cap on the top of the dispensing spout and one or more lateral apertures the spout such that the viscous laundry fluid exits the spout laterally and downwardly, and characterised in that the or each of the apertures comprise annular sections of at least 60° and that the deflector cap extends radially outward of the apertures.

Preferably the apertures are laterally located.

With this arrangement when the fluid is forced into the measuring chamber by squeezing the storage chamber, the deflector cap prevents or reduces vertical spray of the laundry fluid composition which can be occasioned by excessive force applied to the storage chamber. This is especially advantageous with viscous shear thinning laundry liquids, where the dispensing apertures need to be large but, due to the thinning action on pressure application the risk exists of a large amount of liquid lost by inadvertent spraying when excessive pressure is applied, this is a particular problem in the case when the consumer is rushing to complete such chores as laundering.

Since the diameter of the plate is greater than that of the spout, the deflector cap skirt extends as a canopy over the or each aperture to deflect more effectively any inadvertent vertical directed spray.

The deflector cap may comprise a plate attached to the top of the spout, and may be attached by one or more depending arms such that there are multiple dispensing apertures, divided by said arm or arms.

Preferably the or each dispensing aperture is/are all located in a 180° region of the dispensing spout, and this region is aligned with the position of the pour spout. This offers the advantage of squeezing and pouring simultaneously so liquid is squeezed from the dispensing apertures toward the pour spout.

Preferably the deflector cap comprises a depending skirt extending at least partially around the circumference of the plate so that the lateral aperture or apertures are spaced apart from the top of the spout.

The measuring chamber may be integral with storage container or may be a separate device which may attached e.g. by a screw-fit or snap-fit attachment. The measuring chamber may be part of a closure device for the container.

The laundry fluid composition is may be a liquid or gel but is preferably a shear thinning e.g gel-type composition and the viscosity under shear stress is preferably less than 300 Pa. s, more preferably less than 100 Pa. s and even more preferably less than 5 Pa. s, even more preferably it is at most 1 Pa. s and most preferably it is at most 0.5 Pa. s. Shear thinning compositions may comprise a polymer gum, e.g. Xanthan gum or other gum capable of forming stable continuous gum networks which can suspend particles.

Other external structurants e.g. hydrogenated castor oil, micro crystalline cellulose may be used.

Another method useful is to change a non-gelled formulation so as to form an internal structure therein where the structure gives the desired properties to the thus-formed gel- type detergent. The composition may comprise a soap or fatty acid in combination with sodium sulphate and one or more surfactants may be used to form a gelled structure by the formation of lamellar phases.

The composition may comprise a lamellar phase dispersion from a micellar surfactant system, and additionally a structurant for establishing the lamellar phase, whereby said structurant may be a fatty alcohol.

The composition of the invention contains one or more surface active agents (surfactants) selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof. The preferred surfactant detergents for use in the present invention are mixtures of anionic and nonionic surfactants although it is to be understood that any surfactant may be used alone or in combination with any other surfactant or surfactants. The surfactant should comprise at least 10% by wt. of the composition, e.g., 1 1% to 85%, preferably at least 15% to 70% of the total composition, more preferably 16% to 65%; even more preferably 20% to 65%.

The composition may comprise nonionic synthetic organic detergents alone or in combination with other surfactants.

Nonionic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Typical suitable nonionic surfactants are those disclosed in U.S. Pat. Nos. 4,316,812 and 3,630,929. Usually, the nonionic detergents are polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of nonionic detergent is the alkoxylated alkanols wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the alkanol is a fatty alcohol of 9 to 1 1 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 alkoxy groups per mole.

Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. Neodol ™25-7 and

Neodol ™23-6.5, which products are made by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atoms content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5. The higher alcohols are primary alkanols.

Other useful nonionics are represented the class of nonionics sold under the trademark Plurafac. The Plurafacs are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Ci₃-Ci₅ fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, Ci₃-Ci₅ fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, Ci₃-Ci₅ fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, or mixtures of any of the above.

Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is an ethoxylated Cg-Cn fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 23-7 is an ethoxylated Ci₂-Ci₅ fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.

In the compositions of this invention, preferred nonionic surfactants include the Ci₂-Ci₅ primary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, and the Cg to Cu fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.

Another class of nonionic surfactants which can be used in accordance with this invention are glycoside surfactants. Glycoside surfactants suitable for use in accordance with the present invention include those of the formula:

RO-R'O-_y(Z)_x

wherein R is a monovalent organic radical containing from 6 to 30 (preferably from 8 to 18) carbon atoms; R' is a divalent hydrocarbon radical containing from about 2 to 4 carbons atoms; O is an oxygen atom; y is a number which can have an average value of from 0 to about 12 but which is most preferably zero; Z is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and x is a number having an average value of from 1 to about 10 (preferably from 1.5 to 10).

A particularly preferred group of glycoside surfactants for use in the practice of this invention includes those of the formula above in which R is a monovalent organic radical (linear or branched) containing from 6 to 18 (especially from about 8 to about 18) carbon atoms; y is zero; z is glucose or a moiety derived therefrom; x is a number having an average value of from 1 to about 4 (preferably from about 1 to 4).

Nonionic surfactants particularly useful for this application include, but are not limited to: alcohol ethoxylates (e.g. Neodol 25-9 from Shell Chemical Co.), alkyl phenol ethoxylates (e.g. Tergitol NP-9 from Union Carbide Corp.), alkylpolyglucosides (e.g. Glucapon™ 600CS from Henkel Corp.), polyoxyethylenated polyoxypropylene glycols (e.g.

Pluronic™L-65 from BASF Corp.), sorbitol esters (e.g. Emsorb™ 2515 from Henkel Corp.), polyoxyethylenated sorbitol esters (e.g. Emsorb™ 6900 from Henkel Corp.), alkanolamides (e.g. Alkamide™ DC212/SE from Rhone-Poulenc Co.), and N- alkypyrrolidones (e.g. Surfadone™LP-100 from ISP Technologies Inc.).

Nonionic surfactant is used in the formulation from about 0% to about 70%, preferably between 5% and 50%, more preferably 10-40% by weight. Mixtures of two or more of the nonionic surfactants can be used.

The composition may comprise anionic surface active agents and preferably are those surface active compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophilic group, i.e.; water solubilizing group such as sulfonate or sulfate group. The anionic surface active agents include the alkali metal (e.g. sodium and potassium) water soluble higher alkyl benzene sulfonates, alkyl sulfonates, alkyl sulfates and the alkyl polyether sulfates. They may also include fatty acid or fatty acid soaps. The preferred anionic surface active agents are the alkali metal, ammonium or alkanolamide salts of higher alkyl benzene sulfonates and alkali metal, ammonium or alkanolamide salts of higher alkyl sulfonates. Preferred higher alkyl sulfonates are those in which the alkyl groups contain 8 to 26 carbon atoms, preferably 12 to 22 carbon atoms and more preferably 14 to I8 carbon atoms. The alkyl group in the alkyl benzene sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms. A particularly preferred alkyl benzene sulfonate is the sodium or potassium dodecyl benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate. The primary and secondary alkyl sulfonates can be made by reacting long chain alpha-olefins with sulfites or bisulfites, e.g. sodium bisulfite. The alkyl sulfonates can also be made by reacting long chain normal paraffin hydrocarbons with sulfur dioxide and oxygen as described in U.S. Pat. Nos. 2,503,280, 2,507,088, 3,372,188 and 3,260,741 to obtain normal or secondary higher alkyl sulfonates suitable for use as surfactant detergents.

The alkyl substituent is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulfonates can be employed, although they are not as good with respect to biodegradability. The alkane, i.e. alkyl, substituent may be terminally sulfonated or may be joined, for example, to the carbon atom of the chain, i.e. may be a secondary sulfonate. It is understood in the art that the substituent may be joined to any carbon on the alkyl chain. The higher alkyl sulfonates can be used as the alkali metal salts, such as sodium and potassium. The preferred salts are the sodium salts. The preferred alkyl sulfonates are the Cio to Cis primary normal alkyl sodium and potassium sulfonates, with the Cio to Cis primary normal alkyl sulfonate salt being more preferred.

Mixtures of higher alkyl benzene sulfonates and higher alkyl sulfonates can be used as well as mixtures of higher alkyl benzene sulfonates and higher alkyl polyether sulfates.

The alkali metal alkyl benzene sulfonate can be used in an amount of 0 to 70%, preferably 10 to 50% and more preferably 10 to 20% by weight.

The alkali metal sulfonate can be used in admixture with the alkylbenzene sulfonate in an amount of 0 to 70%, preferably 10 to 50% by weight.

Also normal alkyl and branched chain alkyl sulfates (e.g., primary alkyl sulfates) may be used as the anionic component.

The higher alkyl polyether sulfates used in accordance with the present invention can be normal or branched chain alkyl and contain lower alkoxy groups which can contain two or three carbon atoms. The normal higher alkyl polyether sulfates are preferred in that they have a higher degree of biodegradability than the branched chain alkyl and the lower poly alkoxy groups are preferably ethoxy groups.

The preferred higher alkyl poly ethoxy sulfates used in accordance with the present invention are represented by the formula:

R^O(CH₂CH₂O)_P-SO₃M,

where R' is C₈ to C₂o alkyl, preferably Cio to Ci₈ and more preferably Ci₂ to Ci₅; P is 2 to 8, preferably 2 to 6, and more preferably 2 to 4; and M is an alkali metal, such as sodium and potassium, or an ammonium cation.

The sodium and potassium salts are preferred.

A preferred higher alkyl poly ethoxylated sulfate is the sodium salt of a triethoxy Ci₂ to Ci₅ alcohol sulfate having the formula:

Ci_2-I5-O-(CH₂CH₂O)₃-SO₃Na Examples of suitable alkyl ethoxy sulfates that can be used in accordance with the present invention are C₁₂-₁5 normal or primary alkyl triethoxy sulfate, sodium salt; n-decyl diethoxy sulfate, sodium salt; C₁₂ primary alkyl diethoxy sulfate, ammonium salt; C₁₂ primary alkyl triethoxy sulfate, sodium salt: Ci₅ primary alkyl tetraethoxy sulfate, sodium salt, mixed C-_H-I5 normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyl pentaethoxy sulfate, sodium salt; and mixed C₁0-₁8 normal primary alkyl triethoxy sulfate, potassium salt.

The normal alkyl ethoxy sulfates are readily biodegradable and are preferred. The alkyl poly-lower alkoxy sulfates can be used in mixtures with each other and/or in mixtures with the above discussed higher alkyl benzene, alkyl sulfonates, or alkyl sulfates.

The alkali metal higher alkyl poly ethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfonate or sulfonate, in an amount of 0 to 70%, preferably 10 to 50% and more preferably 10 to 20% by weight of entire composition.

Anionic surfactants particularly useful for this application include, but are not limited to: linear alkyl benzene sulfonates (e.g. Vista™ C-500 from Vista Chemical Co.), alkyl sulfates (e.g. Polystep™ B-5 from Stepan Co.), polyoxyethylenated alkyl sulfates (e.g. Standapol™ ES-3 from Stepan Co.), alpha olefin sulfonates (e.g. Witconate™ AOS from

Witco Corp.), alpha sulfo m ieetthhyl esters (e.g. Alpha-Step™ MC-48 from Stepan Co.) and isethionates (e.g. Jordapon™ Cl from PPG Industries Inc.).

Anionic surfactant is used in the formulation from about 0% to about 60%, preferably between 5% and 40%, more preferably 8 to 25% by weight.

The composition may comprise cationic surfactants and preferably cationic surfactants having at least one long chain alkyl group of about 10 to 24 carbon atoms are used.

Specific cationic surfactants which can be used as surfactants in the subject invention are described in detail in U.S. Pat. No.4,497,718.

As with the nonionic and anionic surfactants, the compositions of the invention may use cationic surfactants alone or in combination with any of the other surfactants known in the art. Of course, the compositions may contain no cationic surfactants at all. The composition may comprise ampholytic synthetic detergents, being derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be a straight chain or a branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.

Examples of compounds falling within this definition are sodium 3(dodecylamino)propionate, sodium 3-(dodecylamino)propane-l-sulfonate, sodium 2- (dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N- carboxymethyldodecylamino)propane 1 -sulfonate, disodium octadecyl-imminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2- sulfato-3-dodecoxypropylamine. Sodium 3-(dodecylamino)propane-l-sulfonate is preferred.

Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic group, straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Specific examples of zwitterionic surfactants which may be used are set forth in U.S. Pat. No. 4,062,647.

The amount of amphoteric used may vary from 0 to 50% by weight, preferably 1 to 30% by weight.

It should be noted that the compositions of the invention are preferably isotropic (by which is generally understood to be a homogenous phase when viewed macroscopically) and either transparent or translucent.

Total surfactant used must be at least 10%, preferably at least 15%, more preferably at least 20% by wt.

The invention preferably comprises builders including conventional alkaline detergency builders, inorganic or organic, which can be used at levels from about 0% to about 50% by weight of the composition, preferably from 3% to about 35% by weight.

As used herein, the term electrolyte means any water-soluble salt.

Preferably the composition comprises at least 1.0% by weight, more preferably at least 5.0% by weight, most preferably at least 10.0% by weight of electrolyte. The electrolyte may also be a detergency builder, such as the inorganic builder sodium tripolyphosphate, or it may be a non-functional electrolyte such as sodium sulfate or chloride. Preferably the inorganic builder comprises all or part of the electrolyte.

The composition may comprise at least 1%, preferably at least 3%, preferably 3% to as much as 50% by weight electrolyte.

The compositions of the invention are capable of suspending particulate solids, although particularly preferred are those systems where such solids are actually in suspension.

The solids may be undissolved electrolyte, the same as or different from the electrolyte in solution, the latter being saturated electrolyte. Additionally, or alternatively, they may be materials which are substantially insoluble in water alone. Examples of such substantially insoluble materials are aluminosilicate builders and particles of calcite abrasive.

Examples of suitable inorganic alkaline detergency builders which may be used are water-soluble alkali metal phosphates, polyphosphates, borates, silicates and also carbonates. Specific examples of such salts are sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates, and carbonates. Examples of suitable organic alkaline detergency builder salts are: (1 ) water-soluble amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2 hydroxyethyl)- nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates (see U.S. Pat. No. 2,379,942); (3) water- soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-1-hydroxy-l,1-diphosphonic acid; sodium, potassium and lithium salts of methylene diphosphonic acid; sodium, potassium and lithium salts of ethylene diphosphonic acid; and sodium, potassium and lithium salts of ethane-l,l,2-triphosphonic acid. Other examples include the alkali metal salts of ethane-2-carboxy-l,l-diphosphonic acid hydroxymethanediphosphonic acid, carboxyldiphosphonic acid, ethane-1-hydroxy- l,l,2-triphosphonic acid, ethane-2-hydroxy-1 ,l,2-triphosphonic acid, propane-1 , 1 ,3,3- tetraphosphonic acid, propane-1 , 1 , 2, 3-tetraphosphonic acid, and propane-1 ,2, 2, 3-tetra- phosphonic acid; (4) water-soluble salts of polycarboxylates polymers and copolymers as described in U.S. Patent No. 3,308,067.

In addition, polycarboxylate builders can be used satisfactorily, including water-soluble salts of mellitic acid, citric acid, and carboxymethyloxysuccinic acid, salts of polymers of itaconic acid and maleic acid, tartrate monosuccinate, tartrate disuccinate and mixtures thereof (TMS/TPS).

Certain zeolites or aluminosilicates can be used. One such aluminosilicate which is useful in the compositions of the invention is an amorphous water-insoluble hydrated compound of the formula Na_x[ (AIO₂) _Y-SiO₂), wherein x is a number from 1.0 to 1.2 and y is 1 , said amorphous material being further characterized by a Mg++ exchange capacity of from about 50 mg eq. CaCO₃/g. and a particle diameter of from 0.01 mm to 5 mm. This ion exchange builder is more fully described in British Patent No. 1 ,470,250.

A second water-insoluble synthetic aluminosilicate ion exchange material useful herein is crystalline in nature and has the formula Na_z[(AIO₂)y(SiO₂)]_xH₂O, wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from 15 to 264; said aluminosilicate ion exchange material having a particle size diameter from 0.1 mm to 100 mm; a calcium ion exchange capacity on an anhydrous basis of at test about 200 milligrams equivalent of CaCO₃ hardness per gram; and a calcium exchange rate on an anhydrous basis of at least 2 grains/gallon/minute/gram. These synthetic aluminosilicates are more fully described in British Patent No. 1 ,429,143. Preferably the composition comprises enzymes which may be used in the subject invention are described in greater detail below.

If a lipase is used, the lipolytic enzyme may be either a fungal lipase producible by Humicola lanuginosa and Thermomvces lanuginosus, or a bacterial lipase which show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Chromobacter viscosum var. lipolyticum NRRL B-3673. This microorganism has been described in Dutch patent specification 154,269 of Toyo Jozo Kabushiki Kaisha and has been deposited with the Fermentation Research Institute, Agency of Industrial Science and Technology, Ministry of International Trade and Industry, Tokyo, Japan, and added to the permanent collection under nr. KO Hatsu Ken Kin Ki 137 and is available to the public at the United States Department of Agriculture, Agricultural Research Service, Northern Utilization and Development Division at Peoria, III., USA, under the nr. NRRL B-3673. The lipase produced by this microorganism is commercially available from Toyo Jozo Co., Tagata, Japan, hereafter referred to as "TJ lipase". These bacterial lipases should show a positive immunological cross-reaction with the TJ lipase antibody, using the standard and well-known immune diffusion procedure according to Ouchterlony (Acta. Med. Scan., 133. pages 76-79 (1930).

The preparation of the antiserum is carried out as follows:

Equal volumes of 0.1 mg/ml antigen and of Freund's adjuvant (complete or incomplete) are mixed until an emulsion is obtained. Two female rabbits are injected 45 with 2 ml samples of the emulsion according to the following scheme: day 0: antigen in complete Freund's adjuvant day 4: antigen in complete Freund's adjuvant day 32: antigen in incomplete Freund's adjuvant day 64: booster of antigen in incomplete Freund's adjuvant

The serum containing the required antibody is prepared by centrifugation of clotted blood, taken on day 67. The titre of the anti-TJ-lipase antiserum is determined by the inspection of precipitation of serial dilutions of antigen and antiserum according to the Ouchteriony procedure. A dilution of antiserum was the dilution that still gave a visible precipitation with an antigen concentration of 0.1 mg/ml.

All bacterial lipases showing a positive immunological cross reaction with the TJ-lipase antibody as here above described are lipases suitable in this embodiment of the invention. Typical examples thereof are the lipase ex Pseudomonas fluorescens IAM 1057 (available from Amano Pharmaceutical Co., Nagoya, Japan, under the trade-name Amano-P lipase), the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade-name Amano B), the lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P1338, the lipase ex Pseudomonas sp. (available under the trade-name Amano CES), the lipase ex Pseudomonas cepacia, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRL B-3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp. USA and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.

An example of a fungal lipase as defined above is the lipase ex Humicola lanuginosa available from Amano under the tradename Amano CE; the lipase ex Humicola lanuginosa as described in the aforesaid European Patent Application 0,258,068 (NOVO), as well as the lipase obtained by cloning the gene from Humicola lanuginosa and expressing this gene in Aspergillus oryzae, commercially available from NOVO industri A/S under the tradename "Lipolase". This lipolase is a preferred lipase for use in the present invention.

While various specific lipase enzymes have been described above, it is to be understood that any lipase which can confer the desired lipolytic activity to the composition may be used and the invention is not intended to be limited in any way by specific choice of lipase enzyme.

The lipases of this embodiment of the invention are included in the liquid detergent composition in such an amount that the final composition has a lipolytic enzyme activity of from 100 to 0.005 LU/ml in the wash cycle, preferably 25 to 0.05 LU/ml when the formulation is dosed at a level of about 0.1-10, more preferably 0.5-7, most preferably 1-2 g/liter.

A Lipase Unit (LU) is that amount of lipase which produces 1/mmol of titratable fatty acid per minute in a pH state under the following conditions: temperature 3O⁰C; pH =9.0; substrate is an emulsion of 3.3 wt. % of olive oil and 3,3% gum arabic, in the presence of 13 mmol/l Ca²⁺ and 20 mmol/l NaCI in 5 mmol/l Trisbuffer.

Naturally, mixtures of the above lipases can be used. The lipases can be used in their non-purified form or in a purified form, e.g. purified with the aid of well-known absorption methods, such as phenyl sepharose absorption techniques.

If a protease is used, the proteolytic enzyme can be of vegetable, animal or microorganism origin. Preferably, it is of the latter origin, which includes yeasts, fungi, molds and bacteria. Particularly preferred are bacterial subtilisin type proteases, obtained from e.g. particular strains of B. subtilis and B licheniformis. Examples of suitable commercially available proteases are Alcalase™, Savinase™, Esperase™, all of NOVO lndustri A/S; Maxatase™ and Maxacal™ of Gist-Brocades; Kazusase™ of Showa Denko; BPN and BPN' proteases and so on. The amount of proteolytic enzyme, included in the composition, ranges from 0.05-50,000 GU/mg. preferably 0.1 to 50 GU/mg, based on the final composition. Naturally, mixtures of different proteolytic enzymes may be used.

While various specific enzymes have been described above, it is to be understood that any protease which can confer the desired proteolytic activity to the composition may be used and this embodiment of the invention is not limited in any way be specific choice of proteolytic enzyme.

In addition to lipases or proteases, it is to be understood that other enzymes such as cellulases, oxidases, amylases, peroxidases and the like which are well known in the art may also be used with the composition of the invention. The enzymes may be used together with cofactors required to promote enzyme activity, i.e., they may be used in enzyme systems, if required. It should also be understood that enzymes having mutations at various positions (e.g., enzymes engineered for performance and/or stability enhancement) are also contemplated by the invention. One example of an engineered commercially available enzyme is Durazym from Novo.

The formulation may be enzyme free i.e. 0% by weight of enzymes.

In addition to the enzymes mentioned above, a number of other optional ingredients may be included.

Alkalinity buffers which may be added to the compositions of the invention include monoethanolamine, triethanolamine, borax, sodium silicate and the like.

Hydrotropes which may be added to the invention include ethanol, sodium xylene sulfonate, sodium cumene sulfonate and the like.

Other materials such as clays, particularly of the water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hydrated aluminum silicate in which about 1/6th of the aluminum atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc. may be loosely combined, he bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitable for detergents contains at least 30% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meg per 100g of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1 , 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British Patent No. 401 ,413 to Marriott and British Patent No. 461 ,221 to Marriott and Guam.

In addition, various other detergent additives of adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature.

Improvements in the physical stability and anti-settling properties of the composition may be achieved by the addition of a small effective amount of an aluminum salt of a higher fatty acid, e.g., aluminum stearate, to the composition. The aluminum stearate stabilizing agent can be added in an amount of 0 to 3%, preferably 0.1 to 2.0% and more preferably 0.5 to l.5%.

There also may be included in the formulation, minor amounts of soil suspending or anti- redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preferred anti-redeposition agent is sodium carboxyl methyl cellulose having a 2:1 ratio of CM/MC which is sold under the tradename Relatin DM 4050.

Another minor ingredient is soil releasing agents, e.g. deflocculating polymers. In general, a deflocculating polymer comprises a hydrophilic backbone and one or more hydrophobic side chains.

The deflocculating polymer of the invention is described in greater detail in U.S. Pat. No. 5,147,576.

The deflocculating polymer generally will comprise, when used, from 0.1 to 5% of the composition, preferably 0.1 to 2% and most preferably, 0.5 to 1.5%.

Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include Tinopal™, stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dimorpholine dianilino stilbene sulfonate.

Anti-foam agents, e.g. silicone compounds, such as Silicane L 7604, can also be added in small effective amounts.

Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, e.g. formalin, ultraviolet absorbers, anti- yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume and dyes and bluing agents such as lragon Blue L2D, Detergent Blue 472/372 and ultramarine blue can be used.

Also, soil release polymers and cationic softening agents may be used.

The list of optional ingredients above is not intended to be exhaustive and other optional ingredients which may not be listed, but are well known in the art, may also be included in the composition.

Optionally, the inventive compositions may contain all or some the following ingredients: zwitterionic surfactants (e.g. Mirataine™ BET C-30 from Rhone-Poulenc Co.), cationic surfactants (e.g. Schercamox™ DML from Scher Chemicals, Inc.), fluorescent dye, antiredeposition polymers, antidye transfer polymers, soil release polymers, protease enzymes, lipase enzymes, amylase enzymes, cellulase enzymes, peroxidase enzymes, enzyme stabilizers, perfume, opacifiers, UV absorbers, builders, and suspended particles of size range 300-5000 microns.

The composition is preferably transparent or translucent. The deflector cap is especially advantageous with transparent/translucent compositions because sprayed transparent/translucent compositions would be more difficult to locate due to the lack of colour. It is therefore more important to prevent vertical spray of such compositions.

The compositions of the invention have at least 50% transmittance of light using a 1 centimeter cuvette, at a wavelength of 410-800 nanometers, preferably 570-690 nm wherein the composition is substantially free of dyes.

Alternatively, transparency of the composition may be measured as having an absorbency in the visible light wavelength (about 410 to 800 nm) of less than 0.3 which is in turn equivalent to at least 50% transmittance using cuvette and wavelength noted above. For purposes of the invention, as long as one wavelength in the visible light range has greater than 50% transmittance, it is considered to be transparent/translucent. Measurement of Absorbency and Transmittance

Instrument: Milton Roy Spectronic 601

Procedure:

1. Both the spectrophotometer and the power box were turned on and allowed to warm up for 30 minutes.

2. Set the wavelength type in the desired wavelength on the keypad (i.e., 590, 640, etc.) press the [second function] key press the "go to 8" [yes] key machine is then ready to read at the chosen wavelength.

3. Zero the instrument press the [second function] key press the"zero A" [% T/A/C] instrument should then read "XXX NM 0.000 A T"

4. Open the cover, place sample vertically and in front of the sensor.

5. Close the lid and record reading (ex. 640 NM 0.123 A T)

^*Note: all readings are taken in "A" mode (absorbency mode)

^*Note: zero instrument with every new wavelength change and/or new sample. Non limiting embodiments are described below by way of example only.

FIG. 1. is an enlarged perspective view of one embodiment of the invention; and FIGS. 2a,2b,2c are a schematic side view of the container in use.

Referring to FIG 1 squeeze-operated container 1 comprises a storage chamber 3 (shown partially in Fig 1 but wholly in figs 2a-2c) containing a laundry fluid 13 and a measuring chamber 5. The measuring chamber 5 comprises a base 7 from which upwardly extends a spout 9 which is in fluid communication with the storage chamber 3.

The storage container 3 is squeeze operated and squeezing forces the laundry fluid 13 into the measuring chamber 5. The spout 9 comprises a deflector cap 15 on the top of the spout 9 with two diametrically opposed lateral apertures 17 on the spout such that the laundry fluid 3 exits the spout laterally as shown by arrows 21. The lateral apertures 17 are 60° annular sections of the spout and the deflector cap extends radially outward beyond the radial extent of the apertures 17. The 60° annular sections allow egress from the container by a viscous laundry composition . When the fluid is forced into the measuring chamber by squeezing the storage chamber, the deflector cap prevents or reduces vertical spray of the fluid which can be occasioned by excessive force applied to the storage chamber. This is especially useful with laundry liquids, where upward vertical spray would be highly undesirable.

The deflector cap in forming a canopy over the apertures enhances spray control providing lateral and downward spray, given the large dispensing apertures.

The deflector cap here comprises a plate section connected by diametrically opposing arms 23 to the top of the spout.

In a further embodiment, not shown the deflector cap comprises a depending skirt which extends all the way around the circumference of the plate so that the lateral aperture or apertures are spaced apart from the top of the spout. In a yet further embodiment the diameter of the plate is greater than that of the spout, such that the deflector cap skirt extends as a canopy over the or each aperture to deflect more effectively any inadvertent vertical directed spray.

The measuring chamber may be integral with the storage container or may be a separate device which may be attached e.g. by a screw-fit or snap-fit attachment. The measuring chamber here is a part of a closure device for the container. The closure device 30 is flip- top cap, the body of which remains attached the container and houses the measuring chamber, and the flip-top is moved between an open/closed position by the user.

Exemplary Laundry Formulation A

The following gel laundry detergent compositions were prepared, of which composition A is according to the invention.

Component: Wt %

Propylene glycol 8.0 sodium citrate 3.9

Borax 3.0

NaOH (50%) 1.1

Monoethanolamine 1.0

LAS-acid 4.4

Coconut fatty acid 1.5

Nonionic surfactant 1 1.1

Oleic acid 2.3

1-Dodecanol 5.0

Protease enzyme 0.3

Lipase enzyme 0.5

Perfume 0.2

Water balance to 100

wherein:

Borax : Sodium tetraborate (10aq) nonionic surfactant: ethoxylated alcohol with on average 9 ethylene oxide groups. The gel detergent composition exemplified by composition A was found to be shear thinning and stable. Furthermore, typical detergent particles of density between 0.8 and 0.9 g/cm3 and having a diameter up to 5000 microns could be stable suspended in this composition for more than 2 weeks without any observable net movement of the particles.

For obtaining the values shown in the above table, all rheological measurements were carried out at 25 ⁰C using a Cammed CSL100 rheometer with a cone and plate geometry specially roughed to prevent slip.

Viscosity was measured at varying shear rates from very low shear up to a shear regime in excess of 100 s^'\ Two situations are shown: the viscosity measured at relatively low shear (20 s^"1) and that measured at much higher shear (100 s^"1). It can be seen that the viscosity of composition A at high shear is much lower than that obtained at low shear, whereas composition B shows almost equal viscosity's for high and low shear. In other words composition A is clearly shear thinning, whereas composition B is not.

In addition, the critical stress is shown. This parameter represents the stress at which the material leaves the upper Newtonian plateau and thins under increasing shear. Also, "Eta 0"-values are shown, referring to the viscosity calculated for zero shear from creep flow measurements.

Finally, "Tan delta" values are shown, referring to the ratio of loss over storage moduli (G"/G') and reflecting the dominance of viscous over elastic properties such that materials giving very low "Tan delta"-values (tending to zero, such as composition A in the above table), will be much more elastic than those giving higher "Tan delta" values (tending to 90). Exemplary Laundry Formulation B

The following gel laundry detergent compositions were prepared of which composition C is according to the invention and composition D is a comparative composition according to the prior art:

Component: Wt %

Propylene glycol 4.75 sodium citrate 2.8

Borax 2.3

NaOH (50%) 0.43

Monoethanolamine 0.23

LAS-acid 6.0

Coconut fatty acid 0.77

Sodium alcohol EO sulphate 10.5

Nonionic surfactant 6.6

1-Decanol 6.0

Protease enzyme 0.45

Lipase enzyme 0.25

Perfume 0.2

Water balance to 100

wherein:

Borax : Sodium tetraborate (10aq) nonionic surfactant: ethoxylated alcohol with on average 9 ethylene oxide groups

Sodium alcohol EO sulphate: ethoxylated alcohol sulphate with on average 3 ethylene oxide groups.

Composition B was is a stable, transparent, pourable shear thinning liquid, capable of stable suspending typical detergent particles having a density of between 0.8 and 0.9 g/cm3 and a diameter of up to 5000 microns, for more than 2 weeks without any observable net movement of the particles. Critical rheological parameters for the two compositions are shown below.

For clarification of the rheological values shown in this table, reference is made to the description concerning the similar table shown in above example A.

It is of course to be understood that the invention is not intended to be restricted to the details of the above embodiments which are described by way of example only.

Claims

1. Accordingly in a first aspect the invention provides a squeeze-operated container comprising a storage chamber containing a laundry fluid composition which is shear thinning and has a viscosity of at least 100 Pa. s when in rest or up to a shear stress of 10 Pa; and a measuring chamber, the measuring chamber comprising a base from which upwardly extends a dispensing spout in fluid communication with the storage chamber; and a pour spout, wherein the storage container is squeezable to force the laundry fluid composition into the measuring chamber and the dispensing spout comprises a deflector cap on the top of the dispensing spout and one or more lateral apertures the spout such that the viscous laundry fluid exits the spout laterally and downwardly, and characterised in that the or each of the apertures comprise annular sections of at least 60° and that the deflector cap extends radially outward of the apertures.

2. A squeeze-operated container according to claim 1 wherein the deflector cap comprises a plate attached to the top of the spout.

3. A squeeze-operated container according to claim 2 wherein said plate is attached by one or more depending arms such that there are multiple lateral apertures, divided by said arm or arms.

4. A squeeze-operated container according to any preceding claim wherein the deflector cap comprises a depending skirt which extends at least partially around the circumference of the spout so that the lateral aperture or apertures are spaced apart from the top of the spout.

5. A squeeze-operated container according to any of claims 3 or 4 wherein the diameter of the plate is greater than that of the spout, such that the deflector cap skirt extends as a canopy over the or each aperture to deflect more effectively any inadvertent vertical directed spray.