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EP0634485B1 - Kombination aus Reinigungsmittel und Verpackung - Google Patents

Kombination aus Reinigungsmittel und Verpackung Download PDF

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Publication number
EP0634485B1
EP0634485B1 EP19940304781 EP94304781A EP0634485B1 EP 0634485 B1 EP0634485 B1 EP 0634485B1 EP 19940304781 EP19940304781 EP 19940304781 EP 94304781 A EP94304781 A EP 94304781A EP 0634485 B1 EP0634485 B1 EP 0634485B1
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EP
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Prior art keywords
units
composition
alkyl
group
mixtures
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Revoked
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EP19940304781
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English (en)
French (fr)
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EP0634485A1 (de
Inventor
Thomas Edward Cook
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from EP94304555A external-priority patent/EP0634484B1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP19940304781 priority Critical patent/EP0634485B1/de
Priority to CZ19953412A priority patent/CZ289726B6/cs
Priority to BR9407273A priority patent/BR9407273A/pt
Priority to HU9503864A priority patent/HU218571B/hu
Priority to MA23580A priority patent/MA23267A1/fr
Priority to JP7504678A priority patent/JPH09500170A/ja
Priority to CA002167163A priority patent/CA2167163C/en
Priority to PCT/US1994/007833 priority patent/WO1995002681A1/en
Priority to AU72207/94A priority patent/AU7220794A/en
Priority to TR00715/94A priority patent/TR27893A/xx
Priority to EG42894A priority patent/EG20794A/xx
Publication of EP0634485A1 publication Critical patent/EP0634485A1/de
Publication of EP0634485B1 publication Critical patent/EP0634485B1/de
Application granted granted Critical
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means

Definitions

  • the present invention relates to detergent compositions containing selected moisture-sensitive ingredients; it provides a combination between such compositions and a packaging system containing them, such a combination providing optimum protection against moisture to said selected ingredients, and thus excellent storage stability to the finished compositions.
  • the present invention is based on the finding that the selection of a particular packaging system, in combination with a careful control of the humidity level in the composition, can surprisingly solve the storage stability problem described above, for a series of particularly moisture-sensitive ingredients which are identified herein.
  • the present invention thus provides the combination of detergent compositions containing selected moisture-sensitive ingredients, and controlled humidity level, with a protecting system with selected moisture vapour transfer rate characteristics, as in claim 1.
  • the detergent composition is a mixture of the detergent composition
  • detergent composition herein is meant preferably laundry detergent compositions, although automatic dishwashing compositions and laundry additive compositions are also encompassed.
  • compositions are characterized by their Equilibrium Relative Humidity below 30% by weight at 35°C.
  • Equilibrium Relative Humidity is measured as follows : 300 g of product is place in a 1 liter container made of a water impermeable material and fitted with a lid capable of sealing the containers. The lid is provided with a sealable hole adapted to allow insertion of a probe into the container interior. The container and contents are maintained at a temperature of 35°C for 24 hours to allow temperature equilibration. A solid state Hygrometer (Hygrotest 6100, marketed by Testoterm Ltd, Old Flour Mill, Queen Street, Emsworth, Hampshire, England) is used to measure the water vapour pressure in the space over the products.
  • the probe Whilst the container is maintained at 35°C, the probe is inserted through the hole in the lid and measurements of the water vapour pressure has equilibrated, as evidenced by no change in two successive readings.
  • the instrument converts the water vapour pressure measurement into a direct read-out of the Equilibrium Relative Humidity.
  • compositions of the present invention can be prepared in a variety of ways so as to display an Equilibrium Relative Humidity below 30% at 35°C.
  • certain of the components of laundry detergent compositions which contain intrinsic moisture such as surfactant agglomerates or spray dried components, can be dried or further dried prior to mixing; dried zeolite can also be used in the preparation of surfactant agglomerates, as dry add, in spray-dried compositions, or in a final dusting step.
  • Polyhydroxy fatty acid amides may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • the preferred amine for use in the present invention is N-(R1)-CH2(CH2OH)4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester. Most preferred is the reaction product of N-methyl glucamine with C12-C20 fatty acid methyl ester.
  • Nonionic surfactant systems and granular detergents made from such systems have been described in WO 92 6160, published on 16th April, 1992.
  • This application describes (example 15) a granular detergent composition prepared by fine dispersion mixing in an Eirich RV02 mixer which comprises N-methyl glucamide (10%), nonionic surfactant (10%).
  • the polyhydroxy fatty acid amide may be present in compositions of the present invention at a level of from 0% to 40% by weight of the detergent component or composition, preferably from 1% to 30% by weight, even more preferably from 1% to 20% by weight.
  • Preferred choline ester derivatives having the following formula : wherein R is a C 5 to C 30 straight chain or branched chain alkyl or alkenyl, group and X is an anion, which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, preferably methyl sulfate, chloride, bromide or iodide. as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
  • p may be from 0 to 20.
  • the preferred choline-derivative cationic substances may be prepared by the direct esterification of a fatty acid of the desirec chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material.
  • the choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize.
  • Trimethylamine forming the desired cationic component.
  • Suitable choline esters for use herein have the formula: wherein t is 0 or 1, y is from 1 to 20, and R and X are as defined above.
  • the choline esters herein can be present at levels of from 0% to 50% by weight of the compositions, preferably from 1% to 30% by weight, even more preferably from 1% to 20% by weight.
  • Bleach activators are selected from the following species or mixtures thereof :
  • Alkanoyloxybenzenesulfonates - Suitable alkanoyloxybenzenesulfonate bleach activators which can be employed in the present invention are of the formula: wherein R 1 -C(O)- contains from about 8 to about 12, preferably from about 8 to about 11, carbon atoms and M is a suitable cation, such as an alkali metal, ammonium, or substituted ammonium cation, with sodium and potassium being most preferred.
  • Highly preferred hydrophobic alkanoyloxybenzenesulfonates are selected from the group consisting of nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyl-oxybenzenesulfonate, 2-ethylhexanoyloxybenzenesulfonate, octanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, dodecanoyloxybenzenesulfonate, and mixtures thereof.
  • Amido Derived Bleach Activators which can be employed in the present invention are amide substituted compounds of the general formulas: or mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group containing from about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene or alkarylene group containing from about 1 to about 14 carbon atoms, R 5 is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms, and L is essentially any suitable leaving group.
  • a leaving group is any group that is displaced from the bleaching activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • pKa of the conjugate acid of the leaving group although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those in which their conjugate acid has a pKa in the range of from about 4 to about 13, preferably from about 6 to about 11 and most preferably from about 8 to about 11.
  • Preferred bleach activators are those of the above general formula wherein L is selected from the group consisting of: wherein R 3 is as defined above and Y is -SO 3 - M + or -CO 2 - M + wherein M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
  • Preferred QSBA's herein are, on one hand, water-soluble, but on the other hand, have a tendency to partition to a definite extent into surfactant micelles, especially into micelles of nonionic surfactants.
  • Particularly preferred QSBA's have a caprolactam or valerolactam leaving group.
  • QSBA's useful in the present invention can be synthesized as follows: The following describes the synthesis in more detail.
  • 4-chloromethyl benzoyl acid chloride A 1-neck round bottom flask is fitted with an addition funnel, gas inlet and magnetic stirring and charged with 4-chloromethyl benzoic acid (0.5 mol), toluene (1.0 mol acid/350 ml) and a boiling stone under Argon. Thionyl chloride (1.0 mol) is added dropwise via an addition funnel. A reflux condenser is substituted for the additional funnel and the reaction is heated to toluene reflux for 4 hours under Argon. The reaction is cooled to room temperature. The solvent is evaporated.
  • 4-chloromethyl benzoyl caprolactam A 3-neck round bottom flask is fitted with mechanical stirring, reflux condenser, addition funnel, and gas inlet and is charged with caprolactam (0.5 mol), triethylamine (0.75 mol) and 75% of the required toluene (1.0 mol caprolactam/1.5 liters) under Argon. The solution is heated to toluene reflux. 4-chloromethyl benzoyl acid chloride (0.5 mol) suspended in remaining toluene is added in a slow stream. The reaction is stirred under Argon at toluene reflux for 6 hours, cooled slightly and filtered. The collected solids, triethylamine hydrochloride, is discarded and the filtrate is refrigerated to precipitate product. The product is collected by vacuum filtration, washed and dried.
  • N-[4-(triethylammoniomethyl)benzoyl] caprolactam, chloride salt - A 1-neck round bottom flask is fitted with magnetic stirring, addition funnel and gas inlet and is charged with 4-chloromethyl benzoyl caprolactam (0.5 mol) and acetonitrile (1 mole caprolactam/1.5 liters) under Argon. Triethylamine (1.0 mol) is added dropwise. A reflux condenser is substituted for the addition funnel and the reaction is heated to acetonitrile reflux for 4 hours under Argon. The reaction is cooled to room temperature and solvent is evaporated. Excess acetone is added to the flask with magnetic stirring to break apart the product. The mixture is heated to acetone reflux briefly then cooled to room temperature. The product is vacuum filtered, washed and dried.
  • the above synthesis may be repeated, but with substitution of valerolactam for caprolactam.
  • the synthesis may also be repeated with, for example, the substitution of trimethylamine for triethylamine. In each instance, the corresponding cationic bleach activator is secured.
  • the bleach activators herein are preferably incorporated at a level of from 1% to 20% by weight, more preferably from 2% to 10% by weight, most preferably from 3% to 5% by weight of the compositions.
  • Polymers - Polymers for use herein are selected from the group of :polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones, polyvinylimidazoles, polyaspartates, polyglutamates, or mixtures thereof, preferably having molecular weights around 10,000, terpolymers of maleic/acyclic acid and vinyl alcohols, preferably having a molecular weight ranging from 3000 to 70,000, and preferably a percentage of vinyl alcohol of from 5 to 60% - soil release agents, selected agents are sulfonated poly-ethoxy/propoxy end-capped ester oligomer and mixtures thereof.
  • the above polymers are preferably used at levels ranging from 0.01 to 20% of the composition.
  • esters herein can be simply characterized as oligomers which comprise a substantially linear ester "backbone” and end-capping units which are derived from sulfonated monohydroxy polyethoxy/propoxy monomers, especially 2-(2-hydroxyethoxy)ethanesulfonate.
  • ester backbone a substantially linear ester "backbone” and end-capping units which are derived from sulfonated monohydroxy polyethoxy/propoxy monomers, especially 2-(2-hydroxyethoxy)ethanesulfonate.
  • end-capping units which are derived from sulfonated monohydroxy polyethoxy/propoxy monomers, especially 2-(2-hydroxyethoxy)ethanesulfonate.
  • the ester oligomer used herein preferably comprises : (i) from about 1 to about 2 moles of sulfonated poly-ethoxy/propoxy end-capping units of the formula (MO 3 S)CH 2 ) m (CH 2 ) m (CH 2 CH 2 O)(RO) n - wherein M is a salt forming cation selection from the group consisting of sodium and tetraalkylammonium, m is 0 or 1, R is ethylene, propylene or a mixture thereof, and n is from 0 to 2; (ii) from about 0.5 to about 66 moles of units selected from the group consisting of : a) oxyethyleneoxy units; b) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units wherein said oxyethyleneoxy units are present in an oxyethyleneoxy to oxy-1,2-propyleneoxy mole ratio ranging from 0.5:1 to about 10:1; and c) a mixture of a) or
  • the soil release compositions herein are not resinous, high molecular weight, macromolecular or fiber-forming polyesters but, instead, are relatively low molecular weight and contain species more appropriately described as oligomers rather than as polymers.
  • Individual ester molecules herein, including the end-capping units can have molecular weights ranging from about 500 to about 8,000.
  • Relevant for purposes of comparison with glycol - terephthalate fibrous polyesters is the molecular weight range from about 500 to about 5,000, within which molecules of the preferred esters of the invention which incorporate the essential units and 5-sulfoisophthalate are generally found.
  • the soil release agents used in the detergent composition of this invention are referred to as "oligomeric esters" rather than "polyester” in the colloquial sense of that term as commonly used to denote high polymers such as fibrous polyesters.
  • esters employed herein are all "substantially linear" in the sense that they are not significantly branched or crosslinked by virtue of the incorporation into their structure of units having more than two ester-bond forming sites.
  • a typical example of polyester branching or crosslinking of the type excluded in defining esters of the present invention see Sinker et al, U.S. Patent 4,554,328, issued November 19, 1985.
  • no cyclic esters are essential for the purposes of the soil release agent used herein but may be present in the detergent compositions of the invention at low levels as a result of side-reactions during ester synthesis.
  • cyclic esters will not exceed about 2 % by weight of the compositions; most preferably, they will be entirely absent from the compositions.
  • the term "substantially linear” as applied to the esters herein does, however, expressly encompass materials which contain side-chains which are unreactive in ester-forming or transesterification reaction.
  • oxy-1,2-propyleneoxy units are of an unsymmetrically substituted type; their methyl groups do not constitute what is conventionally regarded as "branching" in polymer technology (see Odian, Principles of Polymerization, Wiley, N.Y., 1981, pages 18-19, the disclosure of which is incorporated herein by reference and with which the present definitions are fully consistent) and are unreactive in ester-forming reactions.
  • Optional units in the esters of the soil release agent used herein can likewise have side-chains, provided that they conform with the same nonreactivity criterion.
  • the most preferable soil release polymer has the following general structure : wherein R is H or CH 3 in a ratio of 1.8:1.
  • ester molecules In the context of the structures of ester molecules disclosed herein it should be recognized that they encompass not only the arrangement of units at the molecular level but also the gross mixtures of ester which result from the reaction schemes herein and which have the desired range of composition and properties. Accordingly, when the number of monomer units or ratios of units are given, the numbers refer to an avarage quantity of monomer units present in oligomers of the composition.
  • the backbone is formed by oxyethyleneoxy and terephthaloyl units connected in alternation.
  • the backbone is formed by 5-sulfoisophthaloyl units, terephthaloyl units, oxyethyleneoxy or mixtures of oxyethyleneoxy, oxypropyleneoxy and poly(oxyethyleneoxy) units connected with alternation of the aryldicarbonyl and oxyalkyleneoxy units.
  • esters of the soil release agents used herein is a phrase which encompasses the novel doubly and singly end-capped compounds disclosed herein, mixtures thereof, and mixtures of said end-capped materials which may unavoidably contain some non-capped species. Although, levels of latter will be zero or at a minimum in all of the highly preferred compositions. Thus, when referring simply to an "ester” herein it is intended to refer, by definition, collectively to the mixture of sulfonated capped and uncapped ester molecules resulting from any single preparation.
  • ester molecules which are present in compositions of the invention which are not fully, i.e. doubly, end-capped by the end-capping units must terminate with units which are nut sulfonated poly-ethoxy/propoxy end-capping units. These termini will typically be hydroxyl groups or other groups attributable tot he unit-forming reactant. For example, in the structure b) above, a chain terminal position to which is attached -H forms of hydroxyl group. In other structures which may be constructed, units such as -(O)CC 6 H 4 C(O)-OCH 3 may be found in terminal positions. All the most highly preferred ester molecules herein will, however, as indicated above, have two sulfonated end-capping units and no backbone units occupying terminal positions.
  • the oxy-1,2-propyleneoxy units can have their methyl groups randonly alternating with one of the adjacent -CH 2 - hydrogen atoms, thereby lowering the symmetry of the ester chain.
  • the oxy-1,2-propyleneoxy unit can be depicted as having either the -OCH 2 CH(CH 3 )O- orientation or as having the opposite - OCH(CH 3 )CH 2 O- orientation.
  • Carbon atoms in the oxy-1,2-propylene units to which the methyl groups are attached are, furthermore, asymmetric, i.e., chiral; they have four nonequivalent chemical entities attached.
  • oxyethyleneoxy units In contrast to the oxy-1,2-propyleneoxy units, oxyethyleneoxy units cannot be used herein as a sole source of oxy-1,2-alkyleneoxy units without the addition of stabilizers since they lack the needed unsymmetrical character. It is the presence of the unsymmetrical units and/or of the stabilizers that inhibit the crystallization of the oligomer during manufacture and later when added to the wash liquor.
  • the use of oxyethyleneoxy units or high ratios of oxyethyleneoxy to oxypropyleneoxy units therefore, must be accompanied by the use of the stabilizers to retard the formation of crystals. Accordingly, such compositions herein contain sulfonate-type hydrotropes, linear or branched alkylbenzenesulfonates, paraffin sulfonates, and mixtures thereof integrated into the oligomer composition.
  • various optional units of a hydrophilicity-enhancing and nonpolyester substantive type can be incorporated into the esters.
  • the pattern of such incorporation will generally be random.
  • Preferred optional units are anionic hydrophiles, such as 5-sulfoisophthaloyl or similar units. Such units will, when incorporated into the ester backbone, generally divide it into two or more hydrophobic moieties separated by one or more hydrophilic moieties.
  • the essential non-charged aryldicarbonyl units herein need not exclusively be terephthaloyl units, provided that the polyester fabric-substantively of the ester is not harmed to a significant extent.
  • minor amounts of isomeric non-charged dicarbonyl units, such as isophthaloyl or the like, are acceptable for incorporation into the esters.
  • Poly(oxyethylene)oxy Units The optional poly(oxyethylene) oxy units comprising the esters of the soil release agent used herein have a degree of polymerization of from 2 to 40 and can constitute from 0 to about 25 mole percent of the total oxyalkyleneoxy units present.
  • poly(oxyethylene)oxy units are present when the backbone unit comprises 8 or more terephthaloyl units; however, at least some poly(oxyethylene)oxy units may be present in esters with as few as 1.5 terephthaloyl units.
  • the amount of poly(oxyethylene)oxy units present in the backbone is related to its degree of polymerization.
  • oxyethyleneoxyethyleneoxy units formed from diethylene glycol
  • the (oxyethylene) 3 units formed from triethylene glycol
  • the (oxyethylene) 3 units formed from tetraethylene glycol
  • the (oxyethylene) 3 units formed from tetraethylene glycol), which have a degree of polymerization of four, can constitute from 0 to 12 mole percent of the total oxyalkyleneoxy units present in the backbone.
  • End-Capping Units The end-capping units used in the esters of the soil release agents used herein are sulfonated polyethoxy/propoxy groups. These end-cap units provide anionic charged sites when the esters are dispersed in aqueous media, such as a laundry liquor. The end-caps serve to assist transport in aqueous media and to provide hydrophilic sites on the ester molecules.
  • esters herein are used as sodium salts, as salts of other alkali metals, as salts with nitrogen-containing cations (especially tetraalkylammonium), or as the dissociated ions in an aqueous environment.
  • end-capping groups include sodium isethionate, sodium 2-(2-hydroxyethoxy) ethanesulfonate, sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethane sulfonate, sodium 5-hydroxy-4-methyl-3-oxa-pentanesulfonate sodium alpha-3-sulfopropyl-omega-hydroxy-poly-(oxy-1,2-ethane diyl) (with an average degree of ethoxylation of 1-2), sodium 5-hydroxy-3-oxa-hexanesulfonate, and mixtures thereof.
  • the soil release agent herein will preferably comprise from about one to about two moles of the sulfonated end-capping units per mole of the ester.
  • the esters are doubly end-capped; i.e. there will be two moles of end-capping units present per mole of the esters. From the viewpoint of weight composition, it will be clear that the fractional contribution of end-capping units to the molecular weight of the esters will decrease as teh molecular weight of the ester backbone increases.
  • Optional Crystalline Reducing Stabilizers - Stabilizers useful in the detergent composition of the invention should be water soluble or water dispersible.
  • the stabilizing agents that are useful herein include sulfonate-type hydrotropes, linear or branched alkylbenzenesulfonates, paraffin sulfonates, and other thermally-stable alkyl sulfonate variations with from about 4 to 20 carbon atoms.
  • Preferred stabilizers include sodium dodecylbenzenesulfonate, sodium cemenesulfonate, sodium toluenesulfonate, sodium xylenesulfonate, and mixtures thereof. When higher levels of stabilizers are used, mixtures of hydrotropes and/or other stabilizers are preferred over pure components to insure full integration into the oligomer and to reduce the possibility of crystallization of the stabilizer.
  • the level of such stabilizers should be kept as low as possible while providing the primary benefit, i.e. the reduction in the amount of crystallization that the soil release agent undergoes during manufacture, storage and when introduced to the wash liquor.
  • the composition may comprise from about 0.5% to about 20% stabilizer.
  • the ester soil release agents comprise an amount sufficient to reduce the crystallization of the oligomer during manufacture and when introduced to the wash liquor, i.e., at least 3% by weight.
  • the stabilizers may be added to the soil release agent in various ways.
  • the stabilizers are added to the oligomer reagents in the initial stages prior to full oligomerization.
  • the stabilizers thereby integrate uniformly into the oligomer.
  • Another method would entail first melting the pre-formed oligomer and then uniformly mixing the stabilizer into the molten oligomer.
  • Alkylbenzenesulfonates when used as surfactants in detergent compositions do not provide the stabilizing and crystallization-reducing effect, during dissolution of the soil release agent in the laundry liquor, that the stabilizer does when it is added as directed above.
  • Selected polymeric dye transfer inhibiting agents herein are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl-oxazolidones and polyvinylimidazoles or mixtures thereof. These polymers are used as levels of from 0.001 to 10%, preferably from 0.01% to 2%.
  • polyamine N-oxide polymers suitable for use contain units having the following structure formula : wherein
  • the N-O group can be represented by the following general structures : wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
  • R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
  • R groups can be aromatic such as phenyl.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000.
  • the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.
  • the polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
  • the amine oxide unit of the polyamine N-oxides has a PKa ⁇ 10, preferably PKa ⁇ 7, more preferred PKa ⁇ 6.
  • the polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • the N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 20,000-200,000.
  • Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
  • the average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern Methods of Polymer Characterization".
  • Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.
  • the N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
  • the N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4.
  • the detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP" having an average molecular weight of from
  • PVP polyvinylpyrrolidone
  • the detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent.
  • Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • the detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles have an average about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are preferably used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution, but can also be used as bleaching agents.
  • Peroxidase enzymes are known in the art, and include, for example, horseardish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO89/099813 and in WO91/05839.
  • the level should be such as to provide an activity in the range of from 0.10 to 1.00 PoDU/ml wash liquor.
  • the peroxidase will typically be added as a component of a laundry detergent composition and may be added in an amount of 0.01 to 100 mg enzyme per liter of wash liquid, preferably in an amount of 0.04 to 0.1 mg enzyme per liter.
  • composition herein can also comprise an amylase enzyme.
  • Suitable amylases include, for example, ⁇ -amylases obtained from a special strain of B. licheniforms, described in more detail in GB-1,296,839 (Novo).
  • Preferred commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc. and Termamyl, sold by Novo Nordisk A/S.
  • amylases are fungal species such as Fungamyl® commercially available from Novo Nordisk A/S.
  • the amylase should be used at levels of from 0.05 to 1.5% by weight of the detergent composition.
  • the level of amylase should be such as to provide an activity typically in the range of 1 to 500 KNU/100 g of detergent composition (Kilo Novo Units).
  • the level should be such as to provide an activity in the range of from 1 to 5,000 FAU/100g of detergent composition (Fungal Apha Amylase Unit).
  • EDDS ethylenediamine disuccinate
  • the EDDS is typically used at a level of from 0.1% to 10% by weight of the compositions herein, preferably from 0.12% to 5%.
  • Perfume encapsulates in form of particles, can be present in the composition herein at levels of from 0.001% to 10%, preferably 0.1 to 3%.
  • Perfume encapsulates comprise perfume dispersed in certain carrier materials.
  • perfume means any odoriferous material or any material which acts as a malodor counteractant. In general, such materials are characterized by a vapor pressure greater than atmospheric pressure at ambient temperatures.
  • the perfume or deodorant materials employed herein will most often be liquid at ambient temperatures, but also can be solids such as the various tamphoraceous perfumes known in the art.
  • a wide variety of chemicals are known for perfumery uses, including materials such as aldehydes, ketones, esters and the like. More commonly, naturally occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfumes, and such materials can be used herein.
  • the perfumes herein can be relatively simple in their composition or can comprise highly sophisticated, complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor.
  • Perfumes which are normally solid can also be employed in the present invention. These may be admixed with a liquefying agent such as a solvent prior to incorporation into the particles, or may be simply melted and incorporated, as long as the perfume would not sublime or decompose upon heating.
  • a liquefying agent such as a solvent
  • the invention also encompasses the use of materials which act as malodor counteractants. These materials, although termed “perfumes” hereinafter, may not themselves have a discernible odor but can conceal or reduce any unpleasant odors. Examples of suitable malodor counteractants are disclosed in U.S. Patent No. 3,102,101, issued August 27, 1963, to Hawley et al.
  • capsules provided by microencapsulation.
  • the perfume comprises a capsule core which is coated completely with a material which may be polymeric.
  • U.S. Patent 4,145,184, Brain et al, issued March 20, 1979, and U.S. Patent 4,234,627, Schilling, issued November 18, 1980, teach using a tough coating material which essentially prohibits the diffusions out of the perfume.
  • the perfume is delivered to fabric via the microcapsules and is then released by rupture of the microcapsules such as would occur with manipulation of the fabric.
  • encapsulated material to be used in the perfume particles of the present invention will depend to some degree on the particular perfume to be used. Some perfumes will require a greater amount of protection than others and the encapsulating material to be used therewith can be chosen accordingly.
  • the encapsulating materials of the perfumed particles can be a water-insoluble or water-soluble encapsulating material.
  • Nonlimiting examples of useful water-insoluble materials include polyethylenes, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyacrylates, vinyl polymers and polyurethanes and mixtures thereof.
  • Nonlimiting examples of suitable water-soluble coating materials include such substances as methyl cellulose, maltodextrin and gelatin. Such coatings can comprise from about 1% to about 25% by weight of the particles.
  • Especially suitable water soluble encapsulating materials are capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616.
  • Suitable water soluble or water dispersible encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials are N-Lok ®, manufactured by National Starch, Narlex ® (ST and ST2), and Capsul E ®. These encapsulating materials comprise pregelatinised waxy maize starch and, optionally, glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.
  • Water-soluble encapsulating materials are especially suitable when perfume has to be incorporated into a dry granular or powder product. Such a water-soluble capsule will then protect perfume during storage in product from other conventional laundry composition compounds such as bleach, enzymes and clay.
  • a material that is pH sensitive i.e., a material that will remain as a coating on the particle in one pH environment but which would be removed from the particle in a different pH environment.
  • a material that is pH sensitive i.e., a material that will remain as a coating on the particle in one pH environment but which would be removed from the particle in a different pH environment.
  • a material that is pH sensitive i.e., a material that will remain as a coating on the particle in one pH environment but which would be removed from the particle in a different pH environment.
  • a material that is pH sensitive i.e., a material that will remain as a coating on the particle in one pH environment but which would be removed from the particle in a different pH environment.
  • such a material could be used to encapsulate the perfume in a liquid fabric softening composition having a pH of about 3.
  • the coating material could be stripped away. This would allow for further protection of perfume in liquid compositions over long storage periods, i.e., the perfume would
  • the perfume may also be encapsulated with a material that makes the particles more substantive to the surface being treated for example, fabric in the laundry process. Such materials. help to deliver the particles to the fabric and maximize perfume release directly on the fabric. Generally, these materials are water-insoluble cationic materials. Examples of useful material include any of the cationic (including imidazolinium) compounds listed in U.S. Patent 3,686,025, Morton, issued August 22, 1972, incorporated herein by reference.
  • Such materials are well known in the art and include, for example, the quaternary ammonium salts having at least one, preferably two, C 10 -C 20 fatty alkyl substituent groups; alkyl imidazolinium salts wherein at least one alkyl group contains a C 8 -C 25 carbon "chain”; the C 12 -C 20 alkyl pyridinium salts, and the like.
  • the encapsulated perfume particles can be made by mixing the perfume with the encapsulating matrix by spray-drying emulsions containing the encapsulating material and the perfume.
  • the particle size of the product from the spray-drying tower can be modified. These modifications can comprise specific processing steps such as post-tower agglomeration steps (e.g. fluidised bed) for enlarging the particle size and/or processing steps wherein the surface properties of the encapsulates are modified, e.g. dusting with hydrophobic silica in order to reduce the hygroscopicity of the encapsulates.
  • a particularly preferred encapsulation process is an emulsification process followed by spray-drying and finally dusting with silica.
  • the emulsion is formed by :
  • perfume loading would allow for aesthetically pleasing fragrance of the composition itself. Upon opening the package containing the composition and as the product is added to water, this immediate release of fragrance may be desirable.
  • This perfume would be added via conventional means, e.g., mixing, as is, into a liquid composition or spraying onto dry product compositions.
  • the laundry additive according to the composition of the present invention can be incorporated into a wide variety of compositions which deliver a perfume to a fabric including detergent and rinse added compositions.
  • the packaging system containing the detergent compositions of the present invention is characterized by it contains at least one unit having a Moisture Vapour Transfer Rate, 1g/m 2 /day to 20g/m 2 /day, preferably 1g/m 2 /day to 15g/m 2 /day.
  • the Moisture Vapour Transfer Rate can be measured by known methods such as described in ASTM Standard E-96-53T, test for measuring Water Vapor transmission of Materials in Sheet form,
  • the packaging system containing the detergent compositions of the present invention is as in claim 1.
  • the Moisture Vapour Transfer Rate can be measured by known methods such as described in ASTM Standard E-96-53T, test for measuring Water Vapor transmission of Materials in Sheet form, and TAPPI Standard T464 m-45, Water Vapor Permeability of Sheet Materials at high temperature and Humidity.
  • the method used in the context of the present invention is referred to as the procon test, using a Permatran-W TWIN equipment.
  • test sample is cut out from the material to be tested.
  • Another test sample from uniform protective sheet of material of known MVTR is used as control (e.g. bitumen laminated liner or wax-laminated board).
  • the MVTR is recorded in g/m 2 /24 hours and calculated as follows :
  • the packaging system herein being the recipient for detergent compositions of the present invention; typically a consumer unit such as a bag/pouch containing the composition of the invention and designed to be used/stored as such in the consumer homes.
  • the amount of detergent composition contained in the packaging systems herein can vary from 250 g (individual small consumer units) to 20 kg, (bundles consumer units).
  • the consumer units of the present packaging systems are bags/pouches, and such units are typically used in refill bags.
  • Refill bags are readily collapsible containers which have been designed in order to reduce the amount of plastic packaging material disposed in the environment;
  • Refill bags can be used by emptying their content into a permanent package such as plastic or metal cannister or a carton container that the consumer uses for storing the detergent products;
  • the refill bag is not reclosable; however, reclosable bags/pouches are encompassed by the present invention as well.
  • the bags/pouches herein can be pillow bags or gusseted bags; either ones, but specifically the gusseted bags, may have reduced or no head space; they can be made either from raw stock of from preformed and/or prefolded material, and can be sealed by various means, e.g. by heat, adhesives/glue, tapes.
  • Plastic, meterials are typically polyolefines, and both plastic and paper can be virgin or recycled material; the films herein can be printer in different ways, typically gravure, flexo, offset.
  • films with moisture barrier properties obtained by resins, either coextruded or in different laminated layers, or coating by e.g. lacquers.
  • compositions herein in addition to the one or more of the selected ingredients listed hereinabove, may also contain other ingredients such as described hereinbelow.
  • the granular laundry detergent compositions herein also contain a (non-enzymatic) bleaching agent; however bleach-free granular detergent compositions are also desirable, particular for the treatment of certain fabrics requiring special care; therefore, such bleach-free detergent compositions are also encompassed by the present invention.
  • the moisture sensitive selected materials of the present invention are preferably chosen from the group of choline esters, polyaspartate, polyglutamate, maleic/acyclic acids/vinyl alcohol terpolymers, sulfonated polyethoxy/propoxy end-capped ester oligomers, peroxidase enzyme and mixtures thereof
  • the bleaching agent is either an inorganic persalt such as perborate, persulfate, percarbonate or a preformaced organic peracid or perimidic acid, such as N,N phtaloylaminoperoxy caproic acid, 2-carboxy-phtaloylaminoperoxy caproic acid, N,N phtaloylaminoperoxy valeric acid, Nonyl amide of peroxy adipic acid, 1,12 diperoxydodecanedoic acid, Peroxybenzoic acid and ring substituted peroxybenzoic acid, Monoperoxyphtalic acid (magnesium salt, hexhydrate), Diperoxybrassylic acid.
  • an inorganic persalt such as perborate, persulfate, percarbonate or a preformaced organic peracid or perimidic acid, such as N,N phtaloylaminoperoxy caproic acid, 2-carboxy-phtaloylamin
  • the bleach-containing laundry detergent herein typically contain from 1% to 40%, preferably from 3% to 30% by weight, most preferably from 5% to 25% by weight of bleaching agent.
  • the perborate bleach is usually in the form of its sodium salt, and present in the monohydrate of tetrahydrate form).
  • the percarbonate bleach is usually in the form of the sodium saltand a mean size from 250 to 900 micrometers, preferably 500 to 700 micrometers.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na 2 CO 3 3H 2 O 2 .
  • the percarbonate bleach can be coated with e.g. a further mixed salt of an alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799, granted to Interox on 9th March 1977.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:2000 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Suitable coating materials are sodium silicate, of SiO 2 :Na 2 O ratio from 1.6:1 to 2.8:1, and magnesium silicate.
  • carbonate/sulphate coated percarbonate bleach may include a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an aminophosphonate, that is incorporated during the manufacturing process.
  • a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an aminophosphonate
  • Preferred heavy metal sequestrants for incorporation as described herein above include the organic phosphonates and amino alkylene poly(alkylene phosphonates) such as the alkali metal ethane 1-hydroxy diphosphonates, the nitrilo trimethylene phosphonates, the ethylene diamine tetra methylene phosphonates and the diethylene triamine penta methylene phosphonates.
  • organic phosphonates and amino alkylene poly(alkylene phosphonates) such as the alkali metal ethane 1-hydroxy diphosphonates, the nitrilo trimethylene phosphonates, the ethylene diamine tetra methylene phosphonates and the diethylene triamine penta methylene phosphonates.
  • the preferred laundry detergent compositions herein contain a surfactant selected from the following species :
  • Alkyl sulfate surfactants hereof are water soluble salts or acids or the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quarternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 5, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate C 12 -C 18 E(3.0), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulphonates, C 8 -C 22 primary or secondary alkanesulphonates, C 8 -C 24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C 9 -C 20 linear alkylbenzenesulphonates C 8 -C 22 primary or secondary alkanesulphonates
  • alkylpolyglycolethersulfates (containing up to 10 moles of ehtylene oxide); acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • Preferred surfactants for use in the compositions herein are the alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof.
  • the laundry detergent compositions of the present invention typically comprise from about 1 % to about 40 %, preferably from about 3 % to about 20 % by weight of such anionic surfactants.
  • the present laundry detergent compositions preferably also comprise a nonionic surfactant.
  • nonionic surfactant While any nonionic surfactant may be normally employed in the present invention, two families of nonionics have been found to be particularly useful. These are nonionic surfactants based on alkoxylated (especially ethoxylated) alcohols, and those nonionic surfactants based on amidation products of fatty acid esters and N-alkyl polyhydroxy amine. The amidation products of the esters and the amines are generally referred to herein as polyhydroxy fatty acid amides. Particularly useful in the present invention are mixtures comprising two or more nonionic surfactants wherein at least one nonionic surfactant is selected from each of the groups of alkoxylated alcohols and the polyhydroxy fatty acid amides.
  • Suitable nonionic surfactants include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants such as the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with an average of up to 25 moles of ethylene oxide per more of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • nonionic surfactant of the surfactant system of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986 having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to 16 carbon atoms and a polysaccharide, e.g. a polyglycoside hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglucosides have the formula R 2 O(C n H 2n O) t (glucosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably from about 1.3 to about 3, most preferably from 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
  • the additional glycosyl units can then be attached betweentheir 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
  • the laundry detergent compositions of the present invention may also contain cationic surfactants, ampholytic, zwitterionic, and semi-polar surfactants, (other than those already described above) and other nonionic surfactants, including the semi-polar nonionic amine oxides described below.
  • Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldi- or tri-methylammonium compounds, and those surfactants having the formula : [R 2 (0R 3 )y][R 4 (OR 3 )y] 2 R 5 N+X- wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH
  • the laundry detergent compositions of the present invention typically comprise from 0 % to about 25 %, preferably form about 3 % to about 15 % by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched chain.
  • One of the aliphatic substituents contains at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
  • the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 10 % by weight of such ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivates of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quarternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at columns 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants.
  • the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 10 % by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting af alkyl groups and hydrocyalkyl groups containing form about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of form about 10 to about 18 carbon atoms and 2 moieties selected form the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula :
  • the preferred laundry detergent compositions contain a builder, preferably non-phosphate detergent builders, although phosphate-containing species are not excluded in the content of the present invention. These can include, but are not restricted to alkali metal carbonates, bicarbonates, silicates, aluminosilicates, carboxylates and mixtures of any of the foregoing.
  • the builder system is present in an amount of from 1% to 80% by weight of the composition, typically preferable from 20% to 60% by weight in granular laundry detergent compositions herein, and from 1% to 30% in liquid laundry detergent compositions herein.
  • Suitable silicates are those having an SiO 2 : Na 2 O ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of SiO 2 : Na 2 O ratios from 2.0 to 2.8 being preferred.
  • crystalline layered sodium silicates of general formula NaMSi x O 2x + 1 ⁇ yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2,3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the form of Na 2 Si 2 O 5 .
  • Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • preferred sodium aluminosilicate zeolites have the unit cell formula Na z [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
  • the term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite X, P and MAP, the latter species being described in EPA 384070.
  • the crystalline aluminosilicate ion exchange material is a Zeolite A having the formula Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ xH 2 O wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.
  • Suitable carboxylate builders containing one carboxy group include lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686 and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829,1, and the 1,2,2-ethane tetracarboxylates ,1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis,cis,cis-tetracarboxylates, 2,5-tetrahydrofuran -cis- dicarboxylates, 2,2,5,5,-tetrahydrofuran- tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carbxoymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivates disclosed in British Patent No. 1,425,343.
  • ingredients which are known for use in detergent compositions may also be used as optional ingredients in the various embodiments of the present invention, such as other bleach activators, other chelating agents, other enzymes, suds suppressing agents, fabric softening agents, in particular fabric softening clay, as well as dyes, fillers, optical brighteners, pH adjusting agents, non builder alkanity sources, enzyme stability agents, hydrotopes, solvents, perfumes.
  • bleach activator include N-,N,N'N' tetra acetylated compounds of the formula where x can be O or an integer between 1 and 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD Tetraacetyl hexylene diamine
  • R 1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from about 1 to about 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R 1 preferably contains from about 6 to 12 carbon atoms.
  • R 2 preferably contains from about 4 to 8 carbon atoms.
  • R 1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 . The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl. R 1 and R 5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • the detergent compositions herein may contain other iron and/or manganese chelating agents than EDDS.
  • Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraprionates, triethylenetetraamine-hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorous are permitted in detergent compositons, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • enzymatic materials than peroxidase and amylase can be incorporated into the detergent compositions herein. Suitable are proteases, lipases, cellulases, and mixtures thereof.
  • a suitable lipase enzyme is manufactured and sold by Novo Industries A/S (Denmark) under the trade name Lipolase and mentioned along with other suitable lipases in EP-A-0258068 (Novo Nordisk).
  • Suitable cellulases are described in e.g. WO-91/17243 and WO 91/17244 (Novo Nordisk).
  • Preferred commercially available protease enzymes include those sold under the trade names Alcalase and Savinase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130 756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130 756, Bott et al, published January 9, 1985).
  • part or all of the surfactant contained in the finished composition is incorporated in the form of separate particles; said particles may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • the most preferred way to process the particles is by agglomerating powders (such as e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits.
  • Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).
  • a high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant is used.
  • the surfactant system may comprise any of the groups of anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants, or mixtures of these.
  • the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • a particularly suitable process of making surfactant particles from high active surfactant pastes is more fully described in EP 510 746, published on 28th October, 1992.
  • the free-flowing surfactant particles made by the process described above are then mixed with other detergent components, in order to produce a finished detergent composition.
  • This mixing may take place in any suitable piece of equipment.
  • Liquid detergents such as nonionic surfactant and perfume may be sprayed on to the surface of one or more of the constituent granules, or onto the finished composition.
  • compositions When the above compositions are stored in a 35°C/80% eRH environment in plastic or polyethylene laminate refill bags with a measured MVTR of 5g/m2/day, (or plastic cannisters of a measured MVTR of 0,5g/m2/day which is outside the claimed range), the composition showed excellent stability after 4 weeks of storage, the eRH measured at 35°C of the composition ranging from 10 after packing to 28 after 4 weeks of storage.

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  • Oil, Petroleum & Natural Gas (AREA)
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Claims (8)

  1. Kombination aus einer granulären Reinigungsmittelzusammensetzung, enthaltend mindestens einen feuchtigkeitsempfindlichen Bestandteil, gewählt aus der Gruppe:
    nichtionische Polyhydroxyfettsäureamid-Tenside
    kationische Cholinester-Tenside
    Bleichaktivatoren, gewählt aus Alkanoyloxybenzolsulfonaten, Amido-derivatisierte Spezies, Spezies vom Benzoxazin-Typ, substituierte quaternäre Spezies und Mischungen hiervon,
    Polymere, gewählt aus Polyamin-N-oxiden, Copolymeren aus N-Vinylpyrrolidon und N-Vinylimidazol, Polyvinyl-oxazolidonen und Polyvinylimidazolen, Polyaspartat, Polyglutamat, Maleinsäure/Acrylsäure/Vinylalkohol-Terpolymeren, sulfonierten Polyethoxy/Propoxy-endverkappten Esteroligomeren und Mischungen hiervon,
    Peroxidaseenzyme
    Amylaseenzyme
    Ethylendiamindibernsteinsäure-Komplexbildner
    Parfümeinkapselungen,
    Mischungen hiervon,
    mit einem Verpackungssystem, welches die Zusammensetzung enthält, dadurch gekennzeichnet, daß die Zusammensetzung eine relative Gleichgewichtsfeuchtigkeit von weniger als 30% bei 35°C aufweist, und daß das Verpackungssystem aus einer Tasche oder einem Beutel aus einer Monoschicht oder laminiertem Papier und/oder Kunststofffolie besteht, wobei das Verpackungssystem eine Feuchtigkeitsdampfdurchgangsrate von 1 g/m2/Tag bis 20 g/m2/Tag aufweist.
  2. Kombination nach Anspruch 1, wobei die Einheit in dem Verpackungssystem eine Feuchtigkeitsdampfdurchgangsrate von 1 g/m2/Tag bis 15 g/m2/Tag aufweist.
  3. Kombination nach Anspruch 1, wobei der Beutel oder die Tasche ein wiederbefüllbarer Beutel ist.
  4. Kombination nach den Ansprüchen 1 bis 3, wobei die granuläre Reinigungsmittelzusammensetzung eine Wäschewaschmittelzusammensetzung ist, welche ein oberflächenaktives Mittel und einen Builder enthält.
  5. Zusammensetzung nach Anspruch 4, wobei die Zusammensetzung eine Schüttdichte von mehr als 650 g/l aufweist.
  6. Kombination nach Anspruch 5, wobei mindestens ein Teil des Tensids in der Zusammensetzung über ein Agglomerat oder ein Extrudat zugeführt wird.
  7. Kombination nach den Ansprüchen 4 bis 6, wobei die Zusammensetzung ein Persauerstoff- oder Peroxysäure-Bleichmittel enthält.
  8. Kombination nach den Ansprüchen 4 bis 7, wobei die Zusammensetzung bleichmittelfrei ist, und die feuchtigkeitsempfindlichen Bestandteile gewählt sind aus:
    kationischen Cholinester-Tensiden
    Polymeren, gewählt aus: Polyaspartat, Polyglutamat, Maleinsäure/Acrylsäure/Vinylalkohol-Terpolymeren, sulfonierten Polyethoxy/Propoxy-endverkappten Esteroligomeren
    Peroxidaseenzymen
    und Mischungen hiervon.
EP19940304781 1993-07-14 1994-06-30 Kombination aus Reinigungsmittel und Verpackung Revoked EP0634485B1 (de)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EP19940304781 EP0634485B1 (de) 1993-07-14 1994-06-30 Kombination aus Reinigungsmittel und Verpackung
BR9407273A BR9407273A (pt) 1993-07-14 1994-07-13 Conbinação detergente-embalagem
JP7504678A JPH09500170A (ja) 1993-07-14 1994-07-13 洗剤‐パッケージの組合せ
AU72207/94A AU7220794A (en) 1993-07-14 1994-07-13 Detergent-package combination
HU9503864A HU218571B (hu) 1993-07-14 1994-07-13 Mosószer készítmény - csomagolórendszer kombináció
MA23580A MA23267A1 (fr) 1993-07-14 1994-07-13 Combinaison de compositions detergentes sensibles a l'humidite et du systeme d'emballage les contenant.
CZ19953412A CZ289726B6 (cs) 1993-07-14 1994-07-13 Kompozice granulovaného detergentního prostředku
CA002167163A CA2167163C (en) 1993-07-14 1994-07-13 Detergent-package combination
PCT/US1994/007833 WO1995002681A1 (en) 1993-07-14 1994-07-13 Detergent-package combination
TR00715/94A TR27893A (tr) 1993-07-14 1994-07-14 Secilmis denge nispi nemi ve nem buhari transfer oranina sahip deterjan-paket kombinasyonu.
EG42894A EG20794A (en) 1993-07-14 1994-07-14 Detergent package combination

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP93870141 1993-07-14
EP93870141 1993-07-14
EP94304555 1994-06-23
EP94304555A EP0634484B1 (de) 1993-07-14 1994-06-23 Reinigungsmittel-Verpackung-Kombination
EP19940304781 EP0634485B1 (de) 1993-07-14 1994-06-30 Kombination aus Reinigungsmittel und Verpackung

Publications (2)

Publication Number Publication Date
EP0634485A1 EP0634485A1 (de) 1995-01-18
EP0634485B1 true EP0634485B1 (de) 2001-09-05

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EP19940304781 Revoked EP0634485B1 (de) 1993-07-14 1994-06-30 Kombination aus Reinigungsmittel und Verpackung

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JP (1) JPH09500170A (de)
AU (1) AU7220794A (de)
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CA (1) CA2167163C (de)
CZ (1) CZ289726B6 (de)
EG (1) EG20794A (de)
HU (1) HU218571B (de)
MA (1) MA23267A1 (de)
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WO (1) WO1995002681A1 (de)

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GB9507659D0 (en) 1995-04-13 1995-05-31 Ass Octel Alkylation process
DE19542571C2 (de) * 1995-11-15 1998-02-26 Henkel Kgaa Verfahren zur Verpackung von Stoffgemischen
EP0778342A1 (de) 1995-12-06 1997-06-11 The Procter & Gamble Company Waschmittelzusammensetzungen
GB9704776D0 (en) * 1997-03-07 1997-04-23 Unilever Plc Detergent - packaging combination
US6245731B1 (en) * 1997-09-01 2001-06-12 The Procter & Gamble Company Detergent tablets-package combination
ES2230840T3 (es) * 1998-04-23 2005-05-01 THE PROCTER & GAMBLE COMPANY Particulas de perfume encapsulado y composiciones detergentes que contienen dichas particulas.
DE19848457A1 (de) * 1998-10-21 2000-04-27 Henkel Kgaa Wasch- und Reinigungsmittelformkörper/Verpackung-Kombination
WO2001016283A1 (de) * 1999-08-31 2001-03-08 Henkel Kommanditgesellschaft Auf Aktien Reinigungsmittelkomponente
DE19949981A1 (de) * 1999-10-16 2001-04-19 Henkel Kgaa Wasch- oder Reinigungsmittel-Portion mit einem Sprengmittel
AU1816300A (en) * 1999-11-09 2001-06-06 Procter & Gamble Company, The Detergent compositions comprising a fragrant reaction product
US6906012B1 (en) 1999-11-09 2005-06-14 Procter & Gamble Company Detergent compositions comprising a fragrant reaction product
WO2001040428A1 (en) * 1999-11-30 2001-06-07 The Procter & Gamble Company Process for making a detergent composition
GB0128946D0 (en) * 2001-12-03 2002-01-23 Unilever Plc Package for a water-soluble capsule
DE102005042053A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Zeolith- und parfümhaltige Teilchen mit verbesserten Dufteigenschaften
EP2270123A1 (de) * 2009-06-30 2011-01-05 The Procter and Gamble Company Verpackte partikelförmige Bleichzusammensetzungen
EP3197862B1 (de) 2014-09-25 2020-06-10 Basf Se Polyetheramine basierend auf 1,3-dialkoholen
US11512268B2 (en) * 2017-11-29 2022-11-29 Basf Se Storage-stable enzyme preparations, their production and use
WO2021151536A1 (en) * 2020-01-29 2021-08-05 Unilever Ip Holdings B.V. Laundry detergent product

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DE3813773A1 (de) * 1988-04-23 1989-11-02 Henkel Kgaa Waschmittelerzeugnis
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JPH04202600A (ja) * 1990-11-30 1992-07-23 Lion Corp 洗剤包装体

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HU218571B (hu) 2000-10-28
TR27893A (tr) 1995-10-11
MA23267A1 (fr) 1995-04-01
CA2167163C (en) 1999-11-23
AU7220794A (en) 1995-02-13
EP0634485A1 (de) 1995-01-18
CZ341295A3 (en) 1996-09-11
EG20794A (en) 2000-03-29
HU9503864D0 (en) 1996-02-28
JPH09500170A (ja) 1997-01-07
WO1995002681A1 (en) 1995-01-26
HUT73039A (en) 1996-06-28
CA2167163A1 (en) 1995-01-26
CZ289726B6 (cs) 2002-03-13

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