EP0786516B1 - Flüssiges Waschmittel - Google Patents

Flüssiges Waschmittel Download PDF

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Publication number
EP0786516B1
EP0786516B1 EP19970200106 EP97200106A EP0786516B1 EP 0786516 B1 EP0786516 B1 EP 0786516B1 EP 19970200106 EP19970200106 EP 19970200106 EP 97200106 A EP97200106 A EP 97200106A EP 0786516 B1 EP0786516 B1 EP 0786516B1
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EP
European Patent Office
Prior art keywords
polymer
hydrophobic
hazy
hydrophilic
polymers
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EP19970200106
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English (en)
French (fr)
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EP0786516A3 (de
EP0786516A2 (de
Inventor
Nancy Ann Falk
Barbara Helen Bory
Tamara Padron
Tirucherai Varahan Vasudevan
Diane Wolf
Jeanie Lum
Leslie Jo Morgan
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from US08/591,058 external-priority patent/US5719117A/en
Priority claimed from US08/591,789 external-priority patent/US5723434A/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0786516A2 publication Critical patent/EP0786516A2/de
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the present invention relates to so-called “isotropic” (i.e., non-structured) detergent compositions comprising certain hydrophobically modified polar polymers (i.e., soil anti-redeposition polymers) which have not previously been used in such isotropic formulations.
  • the hydrophobic modification allows formation of far more stable solutions (clear versus hazy) than otherwise possible.
  • Variables which make the compositions more hydrophobic i.e., use of appropriate hydrotrope; greater amounts of salt/electrolyte/builder; less anionic relative to nonionic are especially preferred.
  • the liquid detergent art may be broken down into those detergents in which all components of the liquid system are dissolved into one single liquid phase (e.g., the isotropic liquids); and those which contain sufficient surfactant and/or electrolyte to form a lamellar droplet comprising "onion" type layers dispersed in an electrolyte medium which is capable of suspending undissolved particles in the liquid.
  • these latter liquids are also known as so-called duotropic or structured liquids.
  • the viscosity is dependent on volume fraction of liquid occupied by the lamellar droplets. While increasing volume fraction is beneficial from a stability point of view, it also creates higher viscosity which may be undesirable from the point of view of dispensing as well as dispersion in the washing machine.
  • the polymers of the Montague et al. reference comprise a hydrophilic backbone which is generally a linear, branched or highly cross-linked molecular composition containing one or more types of hydrophilic monomer units; and hydrophobic side chains, for example, selected from the group consisting of siloxanes, saturated or unsaturated alkyl and hydrophobic alkoxy groups, aryl and aryl-alkyl groups, and mixtures thereof
  • hydrotrope is not taught in either US 5,147,576 to Montague et al. or US 4,759,868 to C-larke. Indeed, the use of hydrotrope is counterproductive in structured, lamellar liquids to the extent that it inhibits formation of the lamellar phase critical in such structured liquids (see column 19, line 17-24 of Montague et al.)
  • hydrotrope is essential in the isotropic liquid detergent formulations of the subject invention because those formulations not containing the hydrotrope have a much narrower formulation flexibility in terms of the surfactant composition and level as well as the electrolyte level.
  • the type and level of hydrotrope used may critically govern the solubility of the hydrophobically modified polymers of the type used in the subject invention. That is, while not wishing to be bound by theory, those hydrotropes which most enhance hydrophobicity of the composition are superior in terms of aiding solubilization of the polymer.
  • the criticality of the hydrotrope type used on the polymer solubility is shown in the examples
  • US 5,308,530 to Aronson et al. also discloses certain hydrophobically modified hydrophilic polymers.
  • the reference teaches a builder which is an interpolymer [A-B] m -[C] n where A and B are hydrophilic groups modified by hydrophobic monomer C.
  • A cannot equal B.
  • the hydrophilic chain is comprised of acrylate monomer only (i.e., is a homopolymer). These molecules are more soluble than those with mixtures of A and B.
  • liquids of the Aronson et al. reference are not pH jump liquids and do not contain sorbitol, such as the preferred liquids of the subject invention.
  • the pH of the Aronson et al. liquids is about 10 while the pH of the liquids of the invention is about 6 0 to about 8.0.
  • Montague et al. and Clarke are structured liquid references versus isotropic liquid references wherein the use of hydrotropes is not prescribed; and Aronson et al. contains polymers which are structurally different (A cannot equal B); and wherein compositional variables for enhancing solubility are not recognized in any event. Further, the liquids of Aronson et al. are not pH jump liquids.
  • H1200 acrylate/styrene copolymer
  • SEPAWA Seise Portum and Woschmicript Conference
  • composition according to the present invention contains a hydrophobic oil.
  • hydrocarbon oils and polymers in surfactant systems can be found, for example, in U.S. Patent No. 4,353,806 to Canter et al. and U.S. Patent No. 4,561,991 to Herbots et al.
  • the polymers disclosed in the above-mentioned art are not the hydrophobically modified polymers of the type discussed in the present application.
  • the use of hydrotropes is not discussed in U.S. Patent No. 4,353,806 to Canter et al.
  • the importance of the use of the hydrotrope and its criticality in polymer solubilization has already been discussed above.
  • the oil type discussed in U.S. Patent 4,561,991 to Herbots et al. are limited to terpenes and benzyl alcohol.
  • the suitable oils in the present disclosure are of a different type and will be discussed in the specification and examples below.
  • WO 95/14,762 to Colgate Palmolive teaches microemulsion composition comprising 0.1-20% by wt. anionic, 0.1-50% by wt. cosurfactant; 0.1-10% by wt. "grease release agent" which may be a type of hydrophobically modified copolymer having structure defined by I (see abstract); and 0.1-10% by wt water insoluble hydrocarbon.
  • the copolymer defined by formula I is hydrophobically modified on every repeating monomeric unit, i.e., molar ratio of hydrophile to hydrophobe can be 1:1 and even less.
  • the ratio of the copolymers of the invention ranges from about 10 to about 40, i.e, there are far fewer pendant hydrophobic groups.
  • the oil of the Colgate reference must have a different function to that of the subject invention where oil is needed to enhance hydrophobicity and thereby helps in the dissolution of polymers.
  • the molecules of Colgate which are already highly hydrophobic, do not need addition of oil to further aid in dissolution.
  • HMPA of the reference dissolves in their system, it would not dissolve in a fully formulated detergent composition (i.e., which must contain at least one anionic) That is, the reference is not concerned with and, therefore, fails to teach or suggest that modifications must be made to solubilize polymers in detergent compositions. Specifically, the invention teaches that there not only must be a defined ratio of hydrophobic to hydrophilic groups, but that there is a MW ceiling (i.e., 20,000), that hydrotropes must be present, and that oil must be present.
  • nonionic active systems do not dissolve in liquids containing builder salts such as citrate. Also, pure nonionic systems perform poorly on particulate soils.
  • isotropic liquid compositions comprising (1) a surfactant or mixture of surfactants (e.g., mixture of anionic and nonionic surfactants); (2) a hydrotrope and (3) electrolyte, the use of polymer having a hydrophilic backbone (hydrophilic backbone made of one monomer only, e.g., acrylate) wherein there is a critical molar ratio of hydrophilic groups (e.g., the backbone) to hydrophobic "anchors" (“tail”) attached to the backbone (or in other words, molar ratio of hydrophilic to hydrophobic monomers), yields solutions which are more stable (e.g., clearer) and have better anti-redeposition properties than they otherwise would be if
  • isotropic liquid compositions comprising (1) a surfactant or a mixture of surfactants (e.g., mixture of anionic and nonionic surfactants wherein at least one anionic is required); (2) a hydrotrope; and (3) an aliphatic (saturated or unsaturated, straight or branched chained) hydrocarbon oil having specified molecular weight and/or carbon chain length, the use of polymer having a hydrophilic backbone wherein there is a critical molar ratio (i.e., below 10) of hydrophilic group (of the backbone) to hydrophobic "anchors" attached to the backbone (or in other words, molar ratio of hydrophilic to hydrophobic monomers), yields solutions which are clearer than they otherwise would be if the critical molar ratio and the oil criticalities were not met.
  • a surfactant or a mixture of surfactants e.g., mixture of anionic and nonionic surfactants wherein at least one anionic is required
  • a hydrotrope
  • the present invention relates to specific class of isotropic liquids (i.e having specific amounts and types of hydrotrope; preferred surfactants; and minimum electrolyte) containing specific polymers which polymers have a critical molar ratio of number of hydrophilic "backbone” groups (single monomer hydrophilic backbone) to number of hydrophobic "anchor” or tail groups.
  • the amount and type of hydrotrope, the ratio of anionic to nonionic surfactants and salt concentration may govern the solubility of the polymer.
  • nonionic hydrotropes, lower ratio of anionic to nonionic surfactants and higher electrolyte (encompassing both salts and builders) concentration tend to increase the solubility of the polymers by increasing the hydrophobicity of the micellar core and are therefore preferred.
  • use of some hydrotropes and some electrolyte is required.
  • the isotropic liquid according to the present invention is a liquid containing specific polymers having a critical molar ratio of number of hydrophilic "backbone” groups to number of hydrophobic “anchor” groups.
  • Molar ratio criticality is below 10, preferably below 7.
  • compositions of the subject invention are believed to result in clarity at ratios which need not be as low (i.e., the compound need not be as hydrophobic) as those of the companion case without oil because the oil makes the compositions even more hydrophobic.
  • a first aspect of the present invention provides an isotropic liquid detergent composition comprising:
  • the isotropic liquid detergent composition according to the invention further comprises a hydrocarbon oil from 4 to 19 carbons.
  • the total amount of surfactant in compositions according to the present invention is from 1 to 85% by weight.
  • the total amount of hydrotrope is from 0.1 to 25% by weight.
  • the total amount of polymer is from 0.1 to 10% by weight. All these amounts are expressed as weight precentage of the composition as a whole.
  • compositions of the invention may contain one or more surface active agents selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof.
  • surface active agents 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.
  • Anionic surface active agents which may be used in the present invention are those surface active compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophile group, i.e. water solubilizing group such as carboxylate, sulfonate or sulfate group or their corresponding acid form.
  • the anionic surface active agents include the alkali metal (e.g. sodium and potassium) water soluble higher alkyl aryl sulfonates, alkyl sulfonates, alkyl sulfates and the alkyl poly ether sulfates. They may also include fatty acid or fatty acid soaps.
  • One of the preferred groups of anionic surface active agents are the alkali metal, ammonium or alkanolamine salts of higher alkyl aryl sulfonates and alkali metal, ammonium or alkanolamine salts of higher alkyl sulfates.
  • Preferred higher alkyl sulfates are those in which the alkyl groups contain 8 to 26 carbon atoms, preferably 12 to 22 carbon atoms and more preferably 14 to 18 carbon atoms.
  • the alkyl group in the alkyl aryl sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms.
  • a particularly preferred alkyl aryl sulfonate is the sodium potassium or ethanolamine C 10 to C 16 benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate.
  • the primary and secondary alkyl sulfates 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 describe in U.S. Patent Nos. 2,503,280, 2,507,088, 3,372,188 and 3,260,741 to obtain normal or secondary higher alkyl sulfates 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 2-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 C 10 to C 18 primary normal alkyl sodium and potassium sulfonates, with the C 10 to C 15 primary normal alkyl sulfonate salt being more preferred.
  • alkali metal or ethanolamine alkyl aryl sulfonate can be used in an amount of 0 to 70%, preferably 5 to 50% and more preferably 5 to 15% by weight.
  • the alkali metal or ethanolamine sulfate can be used in admixture with the alkylbenzene sulfonate in an amount of 0 to 70%, preferably 5 to 50% by weight.
  • normal alkyl and branched chain alkyl sulfates e.g., primary alkyl sulfates
  • anionic component e.g., sodium alkyl sulfates
  • the higher alkyl polyethoxy 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.
  • R 1 -O(CH 2 CH 2 O) p -SO 3 M The preferred higher alkyl polyethoxy sulfates used in accordance with the present invention are represented by the formula: R 1 -O(CH 2 CH 2 O) p -SO 3 M, where R 1 is C 8 to C 20 alkyl, preferably C 10 to C 18 and more preferably C 12 to C 15 ; 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 C 12 to C 15 alcohol sulfate having the formula C 12-15 -O-(CH 2 CH 2 O) 3 -SO 3 Na
  • alkyl ethoxy sulfates examples include C 12-15 normal or primary alkyl triethoxy sulfate, sodium salt, n-decyl diethoxy sulfate, sodium salt; C 12 primary alkyl diethoxy sulfate, ammonium salt; C 12 primary alkyl triethoxy sulfate, sodium salt; C 15 primary alkyl tetraethoxy sulfate, sodium salt; mixed C 14-15 normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyl pentaethoxy sulfate, sodium salt; and mixed C 10-18 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, sulfonates, or alkyl sulfates.
  • the alkali metal higher alkyl poly ethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfate, in an amount of 0 to 70%, preferably 5 to 50% and more preferably 5 to 20% by weight of entire composition.
  • Nonionic surfactants which can be used with the invention, alone or in combination with other surfactants are described below.
  • nonionic surfactants are characterized by the presence of a 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 US Patent Nos. 4,316,812 and 3,630,929.
  • the nonionic surfactants 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 11 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 10 to 15 carbon atoms and which contain about 5 to 9 ethylene oxide groups per mole, e.g. Neodol 25-9 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 9 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.
  • alkoxylated surfactants which can be used contain a precise alkyl chain length rather than an alkyl chain distribution of the alkoxylated surfactants described above. Typically, these are referred to as narrow range alkoxylates. Examples of these include the Neodol-1 (R) series of surfactants manufactured by Shell Chemical Company.
  • Nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac by BASF.
  • 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 C 13 -C 15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, C 13 -C 15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, C 13 -C 15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide or mixtures of any of the above.
  • Dobanol 91-5 is an ethoxylated C 9 -C 11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C 12 -C 15 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.
  • preferred nonionic surfactants include the C 12 -C 15 primary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 6 to 9 moles, and the C 9 to C 11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
  • 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 about 6 to about 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 1/2 to 4).
  • Nonionic surfactants which may be used include polyhydroxy amides as discussed in U.S. Patent No 5,312,954 to Letton et al. and aldobionamides such as disclosed in U.S. Patent No. 5,389,279 to Au et al.
  • nonionics would comprise 0-50% by wt., preferably 5 to 50%, more preferably 5 to 25% by wt. of the composition.
  • Mixtures of two or more of the nonionic surfactants can be used.
  • cationic surfactants are known in the art, and almost any cationic surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms is suitable in the present invention. Such compounds are described in "Cationic Surfactants", Jungermann, 1970.
  • compositions of the invention may use cationic surfactants alone or in combination with any of the other surfactants known in the art.
  • compositions may contain no cationic surfactants at all.
  • Ampholytic synthetic surfactants can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-soluble group, e.g. carboxylate, sulfonate, sulfate.
  • Examples of compounds falling within this definition are sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1-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-1-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.
  • the amount of active used may vary from 1 to 85% by weight, preferably 10 to 50% by weight.
  • preferred surfactant systems of the invention are mixtures of anionic and nonionic surfactants.
  • Particularly preferred systems include, for example, mixtures of linear alkyl aryl sulfonates (LAS) and linear alkoxylated (e.g., ethoxylated) sulfates (AES) with alkoxylated nonionics for example in the ratio of 1:2:1 (i.e., 3:1 anionic to nonionic).
  • LAS linear alkyl aryl sulfonates
  • AES linear alkoxylated e.g., ethoxylated sulfates
  • alkoxylated nonionics for example in the ratio of 1:2:1 (i.e., 3:1 anionic to nonionic).
  • applicants have increased the ratio of anionic (such as LAS or AES) relative to nonionic. While not wishing to be bound by theory, this appears to make the compositions less hydrophobic and, therefore, makes the compositions less stable (e.g., polymer won't dissolve as readily into micelles, perhaps because the micelles are less hydrophobic).
  • the nonionic should comprise, as a percentage of an anionic/nonionic system, at least 20%, more preferably at least 25%, up to about 75% of the total surfactant system
  • a particularly preferred surfactant system comprises anionic:nonionic in a ratio of 3:1.
  • compositions of the invention are all unstructured, isotropic compositions
  • the detergent compositions of the invention are also preferably pH jump compositions.
  • a pH jump heavy duty liquid (HDL) is a liquid detergent composition containing a system of components designed to adjust the pH of the wash liquor.
  • a pH jump system can be employed in this invention to keep the pH of the product low for enzyme stability in multiple enzyme systems (e.g., protease and lipase systems) yet allow it to become moderately high in the wash for detergency efficacy.
  • One such system is borax 10H 2 O/ polyol. Borate ion and certain cis 1,2 polyols complex when concentrated to cause a reduction in pH. Upon dilution, the complex dissociates, liberating free borate to raise the pH.
  • polyols which exhibit this complexing mechanism with borax include catechol, galacitol, fructose, sorbitol and pinacol. For economic reasons, sorbitol is the preferred polyol.
  • Sorbitol or equivalent component i.e., 1,2 polyols noted above
  • Sorbitol or equivalent component is used in the pH jump formulation in an amount from about 1 to 25% by wt., preferably 3 to 15% by wt. of the composition.
  • Borate or boron compound is used in the pH jump composition in an amount from about 0.5 to 10.0% by weight of the composition, preferably 1 to 5% by weight.
  • hydrotropes Another ingredient required by the subject invention is hydrotropes.
  • addition of hydrotropes helps to incorporate higher levels of surfactants into isotropic liquid detergents than would otherwise be possible due to phase separation of surfactants from the aqueous phase.
  • Hydrotropes also allow a change in the proportions of different types of surfactants, namely anionic, nonionic, cationic and zwitterionic, without encountering the problem of phase separation.
  • Hydrotropes function through either of the following mechanisms: i) they increase the solubility of the surfactant in the aqueous phase by changing the solvent power of the aqueous phase; short chain alcohols such as ethanol,isopropanol and also glycerol and propylene glycol are examples in this class and ii) they prevent formation of liquid crystalline phases of surfactants by disrupting the packing of the hydrocarbon chains of the surfactants in the micelles; alkali metal salts of alkyl aryl sulfonates such as xylene sulfonate, cumene sulfonate and alkyl aryl disulfonates such as DOWFAX (R) family of hydrotropes marketed by Dow Chemicals are examples in this class.
  • hydrotrope i.e., this second class of hydrotropes
  • a more weight efficient hydrotrope e.g., a hydrotrope such as cumene sulfonate which, for a given surfactant system, is a better hydrotrope
  • a less weight efficient hydrotrope e.g., xylene sulfonate
  • the preferred hydrotropes of this invention are the less weight efficient, but solubility enhancing, hydrotropes of Class I.
  • the hydrotrope in the composition of the present invention is a polyol, which may also act as enzyme stabilizers, selected from propylene glycol, ethylene glycol, glycerol, sorbitol, mannitol, glucose, and mixtures thereof.
  • hydrotropes are present in an amount of about 1% to 25% by wt., more preferably 1% to 10% by wt. of the composition.
  • compositions of the invention further contain an aliphatic hydrocarbon oil which is believed to make the compositions more hydrophobic and so help the stability (i.e., clarity) of the solution.
  • the aliphatic group is a saturated or unsaturated, straight or branch chained hydrocarbon having 4 to 19, preferably 8 to 18 carbons.
  • the molecular weight of these oils will generally be 50 to 300.
  • Examples of such oil include, but are not limited to heptanes, octanes, nonanes, decanes, through C 18 ; olefines such as octenes, nonenes, through C 18 ; and all isomeric variations (e.g., isooctane) thereof.
  • the oil can be used at levels varying from about 0.1 to 20% by weight, preferably 0.5 to 10%, more preferably 0 5% to 5% by weight of the composition.
  • Builders which can be used according to this invention include conventional alkaline detergency builders, inorganic or organic, which should be used at levels from about 0.1% to about 20.0% by weight of the composition, preferably from 1.0% to about 10.0% by weight, more preferably 2% to 5% by weight.
  • Electrolyte may be used any water-soluble salt. 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 sulphate or chloride. Preferably the inorganic builder comprises all or part of the electrolyte. That is the term electrolyte encompasses both builders and salts.
  • suitable inorganic alkaline detergency builders which may be used are water-soluble alkalimetal phosphates, polyphosphates, borates, silicates and also carbonates.
  • Specific examples of such salts are sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates and carbonates
  • 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. Patent No.
  • water-soluble polyphosphonates including specifically, sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-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-1,1,2-triphosphonic acid
  • Other examples include the alkali metal salts of ethane-2-carboxy-1,1-diphosphonic acid hydroxymethanediphosphonic acid, carboxyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid; (4) water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent No 3,308,067.
  • 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/TDS).
  • 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 ( y AlO 2 .SiO 2 ), 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. CaCO 3 /g. and a particle diameter of from about 0.01 micron to about 5 microns.
  • This ion exchange builder is more fully described in British Pat. 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 [(AlO 2 ) y .(SiO 2 )]xH 2 O, 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 about 15 to about 264; said aluminosilicate ion exchange material having a particle size diameter from about 0.1 micron to about 100 microns; a calcium ion exchange capacity on an anhydrous basis of at least about 200 milligrams equivalent of CaCO 3 hardness per gram; and a calcium exchange rate on an anhydrous basis of at least about 2 grains/gallon/minute/gram.
  • These synthetic aluminosilicates are more fully described in British Patent No. 1,429,143.
  • the more electrolyte that is used the more hydrophobic are the micelles and, according to what applicants believe to be the theoretical mechanism of the invention, the better for the hydrophobically modified polymer to dissolve.
  • One or more enzymes as described in detail below, may be used in the compositions of the invention.
  • the lipolytic enzyme may be either a fungal lipase producible by Humicola lanuginosa and Thermomyces 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.
  • TJ lipase 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 immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950).
  • 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 with 2 ml samples of the emulsion according to the following scheme:
  • 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 Ouchterlony procedure. A 2 5 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 hereabove 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.
  • 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 .
  • 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.
  • lipase enzymes 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 .1-10, more preferably .5-7, most preferably 1-2 g/liter.
  • 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.
  • 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 Industri a/S; Maxatase and Maxacal of Gist-Brocades; Kazusase of Showa Denko; BPN and BPN' proteases; Optimase from Solvay and so on.
  • the amount of proteolytic enzyme, included in the composition ranges from 0.05-50,000 GU/mg. preferably 0. to 50 GU/mg, based on the final composition. Naturally, mixtures of different proteolytic enzymes may be used.
  • 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.
  • lipases or proteases 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.
  • enzymes having mutations at various positions e.g., enzymes engineered for performance and/or stability enhancement
  • Durazym (R) from Novo.
  • the enzyme stabilization system may comprise calcium ion; boric acid, propylene glycol and/or short chain carboxylic acids.
  • the composition preferably contains from about 0.01 to about 50, preferably from about 0. to about 30, more preferably from about 1 to about 20 millimoles of calcium ion per liter.
  • the level of calcium ion should be selected sos that there is always some minimum level available for the enzyme after allowing for complexation with builders, etc., in the composition.
  • Any water-soluble calcium salt can be used as the source of calcium ion, including calcium chloride, calcium formate, calcium acetate and calcium propionate
  • a small amount of calcium ion is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • Another enzyme stabilizer which may be used in propionic acid or a propionic acid salt capable of forming propionic acid. When used, this stabilizer may be used in an amount from about 0.1% to about 15% by weight of the composition.
  • polyols containing only carbon, hydrogen and oxygen atoms are preferred. They preferably contain from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples include propylene glycol (especially 1,2 propane diol which is preferred), ethylene glycol, glycerol, sorbitol, mannitol and glucose.
  • the polyol generally represents from about 0.1 to 25% by weight, preferably about 1.0% to about 15%, more preferably from about 2% to about 8% by weight of the composition.
  • the composition herein may also optionally contain from about 0.25% to about 5%, most preferably from about 0.5% to about 3% by weight of boric acid.
  • the boric acid may be, but is preferably not, formed by a compound capable of forming boric acid in the composition. Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic acid and a p-bromo phenylboronic acid) can also be used in place of boric acid.
  • One preferred stabilization system is a polyol in combination with boric acid.
  • the weight ratio of polyol to boric acid added is at least 1, more preferably at least about 1.3.
  • pH jump system such as is taught in U.S. Patent No. 5,089,163 to Aronson et al.
  • Alkalinity buffers which may be added to the compositions of the invention include monoethanolamine, triethanolamine and borax.
  • 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 and calcium may be loosely combined.
  • the bentonite in its more purified form (i.e. free from any grit and sand) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq 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
  • detergent additives or 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 1.5%.
  • 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 carboxylmethyl cellulose having a 2:1 ratio of CM/MC which is sold under the tradename Relatin DM 4050
  • Optical brighteners for cotton, polyamide and polyester fabrics can be used.
  • Suitable optical brighteners include Tinopal LMS-X, stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene and benzidene sulfone, 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. silicon 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 Iragon Blue L2D, Detergent Blue 472/572 and ultramarine blue can be used.
  • 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
  • Iragon Blue L2D Detergent Blue 472/572 and ultramarine blue
  • soil release polymers and cationic softening agents may be used.
  • the polymer used in the composition of the invention is one which, as noted above, has previously been used in structured (i.e., lamellar) compositions such as those described in U.S. Patent No. 5,147,576 to Montague et al. This is because the polymer allows the incorporation of greater amounts of surfactants and/or electrolytes than would otherwise be compatible with the need for a stable, low-viscosity product as well as the incorporation, if desired, of greater amounts of other ingredients to which lamellar dispersions are highly stability-sensitive.
  • the polymer comprises a "backbone” component which is a monomer (single monomer) as discussed below and a “tail” portion which is a second monomer which is hydrophobic in nature (e.g., lauryl methacrylate or styrene).
  • the hydrophilic backbone generally is a linear, branched or highly cross-linked molecular composition containing one type of relatively hydrophilic monomer unit wherein the monomer is preferably sufficiently soluble to form at least a 1% by weight solution when dissolved in water.
  • the only limitation to the structure of the hydrophilic backbone is that a polymer corresponding to the hydrophilic backbone made from the backbone monomeric constituents is relatively water soluble (solubility in water at ambient temperature and at pH of 3.0 to 12.5 is preferably more than I g/l).
  • the hydrophilic backbone is also preferably predominantly linear, e.g., the main chain of backbone constitutes at least 50% by weight, preferably more than 75%, most preferably more than 90% by weight.
  • the hydrophilic backbone is composed of one monomer unit selected from a variety of units available for polymer preparation and linked by any chemical links including
  • the hydrophobic side chains are part of a monomer unit which is incorporated in the polymer by copolymerizing hydrophobic monomers and the hydrophilic monomer making up the backbone.
  • a "tail” group preferably comprises a monomer unit comprising the hydrophobic side chains which are incorporated in the "tail” monomer.
  • the polymer is made by copolymerizing hydrophobic monomers (tail group comprising hydrophobic groups) and the hydrophilic monomer making up the backbone.
  • the hydrophobic side chains preferably include those which when isolated from their linkage are relatively water insoluble, i.e., preferably less than 1 g/l, more preferred less than 0.5 g/l, most preferred less than 0.1 g/l of the hydrophobic monomers, will dissolve in water at ambient temperature at pH of 3.0 to 12.5.
  • the hydrophobic moieties are selected from siloxanes, saturated and unsaturated alkyl chains, e.g., having from 5 to 24 carbons, preferably 6 to 18, most preferred 8 to 16 carbons, and are optionally bonded to hydrophilic backbone via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, polypropoxy, or butyloxy (or mixtures of the same) linkage having from 1 to 50 alkoxylene groups.
  • the hydrophobic side chain can be composed of relatively hydrophobic alkoxy groups, for example, butylene oxide and/or propylene oxide, in the absence of alkyl or alkenyl groups. Another preferred hydrophobic group include styrene.
  • Monomer units which make up the hydrophilic backbone include:
  • Monomeric units comprising both the hydrophilic backbone and hydrophobic side chain may be substituted with groups such as amino, amine, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxy, carboxyl and oxide groups.
  • the hydrophilic backbone is composed of one unit.
  • the backbone may also contain small amounts of relatively hydrophobic units such as those derived from polymers having a solubility of less than 1 g/l in water provided the overall solubility of the polymer meets the requirements discussed above. Examples include polyvinyl acetate or polymethyl methacrylate.
  • the polymer preferably has the formula :
  • z is 1; x:z (i.e., hydrophilic backbone to hydrophobic tail) is less than 10; in which the monomer units may be in random order, and n is at least 1: R 1 represents -CO-O-, -O-, -O-CO-, -CH 2 -, -CO-NH- or is absent;
  • the group (defined by z) can be substituted benzene group such as, for example styrene.
  • the present invention is directed to the observation that, when polymers such as those described above (known as deflocculating or decoupling polymers in the "structured liquid” art) are used in isotropic liquids and further when there is a criticality of hydrophilic groups to hydrophobic groups, (as well as required hydrotrope and electrolyte levels; and preferred hydrotropes and surfactants used) the liquids are far more stable (i.e., they do not phase separate and become hazy, but rather stay clear) than if these required or preferred variables had not been met.
  • the molar ratio of hydrophilic to hydrophobic monomer is less than 10 (i.e., 0.5 to 10), preferably, less than 7 to 1 (i.e., preferably greater than or equal to 1)
  • an isotropic liquid which would otherwise be unstable (less clear) hazy becomes clear.
  • Minimal amounts of hydrotrope and electrolytes are required. It is possible to achieve optimal clarity when conditions are appropriately manipulated.
  • the second aspect of the present invention is based on the observation that, when such polymers (known as deflocculating or decoupling polymers in the "structured liquid” art) are used in isotropic liquids and further when there is a criticality of hydrophilic group to hydrophobic groups and oil is added, the liquids are for more stable (i.e., they do not phase separate and become hazy, but rather stay clear) than if this criticality had not been met.
  • the polymer should be used in an amount comprising 0.1 to 10% by wt , preferably 0.25% to 5% by wt. of the composition.
  • Linear alkylbenzene sulfonic acid was purchased from Vista Chemicals; alcohol ethoxy sulfate (AES Neodol 25-3S) and ethoxylated alcohols (Neodol 25-9) were purchased from Shell Chemicals.
  • Hydrophobically modified acrylate and acrylate/lauryl methacrylate based polymers decoupling polymers
  • hydrophobically modified acrylate styrene based polymers such as H100 and H1200 from National Starch and Chemicals.
  • Hydrotropes Sodium Cumene sulfonate (SCS) and sodium xylene sulfonate (SXS) were supplied by Stepan Chemicals and propylene glycol was purchased from Fisher Scientific.
  • Hydrocarbon oils are supplied by Fisher Scientific and Aldrich; and Shell Sol 71 is C 12 -C 14 saturated hydrocarbon oil from Shell.
  • the formulations were prepared by adding to water, sodium citrate, sorbitol, borate, hydrotrope and sodium hydroxide in a beaker and stirred at 35 - 50"C until the solution became clear This was followed by the addition of LAS acid and Neodol25-9. The mixture was then cooled to 25°C and the desired amount of Neodol 25-3S (59% AES) was added.Required amount of polymer was then added to the base formulation at room temperature (18 - 23°C).
  • Base Formulation Component Wt.% Remarks Sodium alkyl benzene sulfonate (LAS) 2.6 - 23 0 Anionic surfactant Alcohol ethoxy sulfate C 12 -C 15 , 3EO (AES) 2.6 - 23.0 Anionic surfactant Alcohol ethoxylate C 12 -C 15 , 9EO 2.6 - 23.0 Nonionic surfactant Sodium citrate 2 aq. 0 - 5.0 Builder Sodium borate 10 aq.
  • Polymer having a ratio below 10, preferably below 7, produce clear liquid while those having a ratio above 20 produce a hazy liquid.
  • backbone group e.g., acrylate
  • tail group e.g., lauryl methacrylate
  • the clarity of the liquid depends on the ratio between the number of hydrophilic backbone monomers and hydrophobic tail groups.As in formulations containing only 2.5 weight sodium citrate 2 aq., in formulations containing 3.75 wt.% sodium citrate polymer having hydrophilic to tail ratio below 10, preferably below 7 are clear, and, those above 10 are unclear.
  • propylene glycol instead of cumene sulfonate, see Example 1
  • polymer having the above defined ratio value of below 10 preferably below 7 produced a clear liquid This is believed to be true because the core of the micelles formed in the presence of cumene sulfonate are less hydrophobic than those formed in presence of propylene glycol.
  • propylene glycol is preferred
  • backbone group e.g., acrylate
  • tail group e.g., lauryl methacrylate
  • the example shows that some electrolyte is required.
  • compositions with high levels of nonionic are more hydrophobic than compositions with high levels of anionic.This in turn makes hydrophobically modified polymer more soluble.
  • Formulations used in the evaluation are listed in table below: Ingredient Formulation 1 Formulation 2 Alcohol ethoxy sulfate, C 12 -C 15 , 3EO 14.0 14.0 Sodium alkyl benzene sulfonate, C 11 -C 15 8.0 8.0 Alcohol ethoxylate, C 12 -C 15 , 9EO 8.0 8 0 Sodium citrate dihydrate 5.0 5.0 Propylene glycol 4.0 4.0 Sodium borate pentahydrate 3.1 3.1 Sorbitol 4.5 4.5 Ethanol 2.3 2.3 Glycerol 2.7 2.7 Enzymes 1.1 1.1 Acrylate/lauryl methacrylate copolymer 0.0 2.0 Minors (fluorescer, perfume, colorant, preservative) >0.5 >0.5 Water to 100% to 100%
  • Swatches were prewashed in a dye free commercial liquid laundry detergent five times to age the material, remove spinning oils, and increase absorbency of the cloth.Cotton swatches were type TIC429 (Textile Innovators, Inc.); 50/50 polyester/cotton blend swatches were type TIC7403 (Textile Innovators,Inc.); polyester swatches were type TF730 (Textile Fabrics, Inc.)
  • test formulations were then added (0.4 cup) to a filled (95°F, 120 ppm, 2:1 Ca:Mg) standard top-loading washing machine (Lady Kenmore model 80 heavy duty washer by Sears, Roebuck, and Co.) and allowed it to mix for one minute.
  • the machine was then stopped and soiled test cloths treated with test formulation were added (4 each of cotton, 50/50 cotton/polyester blend, and polyester). The cloths then continued washing on the cotton/sturdy cycle of the washing machine, then were dried in a static dryer.
  • stain removal index 100 - [(L c -L w ) 2 + (a c -a w ) 2 + (b c -b w ) 2 ] 1/2 where the subscripts c and w represent clean swatches (before staining) and washed stained swatches, respectively.
  • formulation 2 which contains acrylate/lauryl methacrylate copolymer, clearly removes the stain better than does the formulation without polymer on cotton and on the poly/cotton blend.
  • test formulations were added (0.4 cup) to a filled (95°F, 120 ppm hardness, 2:1 Ca:Mg) standard top-loading washing machine (Lady Kenmore model 80 heavy duty washer by Sears, Roebuck, and Co ) and allowing it to mix for one minute.
  • the machine was then stopped and test cloths (soiled by the procedure described in the previous example) were added (4 each of cotton, 50/50 cotton/polyester blend, and polyester).
  • the washer was restarted and allowed to agitate for 90 seconds; then the unsoiled cloths were added (3 each of cotton, blend, and polyester; cotton first, then blend, then polyester) without stopping the machine.
  • the cloths then continued to wash on the cotton/sturdy cycle of the washing machine, then were dried in a static dryer.
  • the clarity of the liquid depends on the molar ratio between the number of hydrophilic monomers and the number of hydrophobic anchors per molecule.
  • formulations containing 2.5 weight percent sodium citrate 2 aq. formulations containing polymer having the above defined ratio of lower than about 10 are clear and those containing polymers having ratio above about 20 are unclear.
  • the polymer having a molar ratio between the number of hydrophilic monomers and the number of hydrophobic anchors per molecule below 10 produced hazy liquid although the liquid containing propylene glycol and LAS, AES and Neodol 25-9 in the ratio of 1:2:1 produced a clear liquid when polymers having the above defined ratio of below 10 was added (see Example 11).
  • the micelles containing high LAS concentration are less hydrophobic (and, therefore, presumably do not interact well with hydrophobic polymer).
  • the polymer having a molar ratio between the number of hydrophilic monomers and the number of hydrophobic anchors per molecule below 10 produced hazy liquid although the liquid containing propylene glycol and LAS, AES and Neodol 25-9 in the ratio of 1:2:1 produced a clear liquid when polymers having the above defined ratio of below 10 was added (same as Example 14). This is again believed to be because the micelles containing high AES concentration are less hydrophobic.
  • This formulation is similar to that of the formulation containing LAS, AES and Neodol 25-9 in the ratio of 1:2 1 (Example 11) in that it even produced a clear liquid upon addition of polymers having a molar ratio between the number of the hydrophilic monomers and the number of hydrophobic anchors per molecule of below 10.
  • This is again due to the fact that micelles containing high levels of nonionic surfactants (Neodol 25-9) are more hydrophobic than those containing high levels of anionic surfactants. The more hydrophobic the micelles are, the higher will be the interaction between the micelle and the hydrophobically modified polymer and the better is the chance of producing a clear liquid.
  • Neodol 25-3 (AES 25-3S) 23.7 Neodol 25-9 8.0
  • Oil Chain Length Type Amount Wt.% 1.0 2.0 3.0 n-Heptane C 7 Aliphatic - saturated Sol. Sol. Insol. Toluene C 7 Aromatic Sol. Insol. Insol. 1-Octene C 8 Aliphatic - unsaturated Sol. Sol. Sol. Octane C 8 Aliphatic - saturated Sol. Sol. Sol. Dodecane C 12 Aliphatic - saturated Sol. Sol. Sol. Shellsol 71 C 12-14 Aliphatic - saturated Sol. Sol. Sol. Tetradecane C 14 Aliphatic - saturated Sol. Sol. Sol. Hexadecane C 16 Aliphatic - saturated Sol. Sol. Sol.

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Claims (7)

  1. Isotrope flüssige Detergens-Zusammensetzung, umfassend:
    (1) Tensid
    (2) eine hydrotrope Komponente, ausgewählt aus Propylenglycol, Ethylenglycol, Glycerin, Sorbit, Mannit, Glucose und deren Mischungen;
    (3) Elektrolyt; und
    (4) Polymer mit
    (a) einem hydrophilen Grundgerüst, das Monomer-Einheiten umfasst, die ausgewählt sind aus:
    (i) einem oder mehreren ethylenisch ungesättigten hydrophilen Monomeren, die ausgewählt sind aus der Gruppe bestehend aus ungesättigten (C1-6)-Säuren, Ethern, Alkoholen, Aldehyden, Ketonen oder Estern; und/oder
    (ii) einer oder mehreren polymerisierbaren hydrophilen cyclischen Monomer-Einheiten; und/oder
    (iii) einem oder mehreren nicht ethylenisch ungesättigten polymerisierbaren hydrophilen Monomeren, die ausgewählt sind aus der Gruppe bestehend aus Glycerin und anderen mehrwertigen Alkoholen;
    wobei ein oder mehrere der Monomere gegebenenfalls mit einer oder mehreren Amino-, Amin-, Amid-, Sulfonat-, Sulfat-, Phosphonat-, Hydroxy-, Carboxyl- oder Oxidgruppen substituiert sind;
    (b) mindestens einem Monomer, das eine seitenständige hydrophobe Gruppe aufweist;
    wobei das Polymer ein MG von 1000 bis 20000 aufweist;
    wobei das Molverhältnis der hydrophilen Monomere zu der oder den seitenständigen hydrophoben Gruppe(n) weniger als 10 beträgt.
  2. Zusammensetzung nach Anspruch 1, umfassend:
    (a) 1 bis 85 Gewichts-% des Tensids;
    (b) 0,1 bis 25 Gewichts-% der hydrotropen Komponente; und
    (c) 0,1 bis 10 Gewichts-% des Polymers.
  3. Zusammensetzung nach Anspruch 1 oder Anspruch 2, weiter umfassend ein Kohlenwasserstoff-Öl mit 4 bis 19 Kohlenstoffatomen.
  4. Zusammensetzung nach Anspruch 3, in der das Kohlenwasserstoff-Öl ein (C10-C16)-Alkan umfasst.
  5. Zusammensetzung nach Anspruch 3 oder Anspruch 4, in der die Menge an hydrotroper Komponente 0,1 bis 25 Gewichts-% der Gesamtzusammensetzung beträgt.
  6. Zusammensetzung nach irgendeinem vorangehenden Anspruch, in der das Tensid eine Mischung aus anionischen und nichtionischen Tensiden umfasst.
  7. Zusammensetzung nach Anspruch 6, in der die Tenside in einem Verhältnis anionisch zu nichtionisch von etwa 3:1 und darunter verwendet werden.
EP19970200106 1996-01-25 1997-01-16 Flüssiges Waschmittel Revoked EP0786516B1 (de)

Applications Claiming Priority (4)

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US08/591,058 US5719117A (en) 1996-01-25 1996-01-25 Isotropic liquids comprising hydrophobically modified polar polymers plus aliphatic hydrocarbon oils
US591789 1996-01-25
US591058 1996-01-25
US08/591,789 US5723434A (en) 1996-01-25 1996-01-25 Isotropic liquids comprising hydrophobically modified polar polymer

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DE69728701D1 (de) 2004-05-27
CA2195511A1 (en) 1997-07-26
CA2195511C (en) 2006-06-20
DE69728701T2 (de) 2004-10-07
ES2218636T3 (es) 2004-11-16
EP0786516A2 (de) 1997-07-30

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