Patent Application
20120067764
This invention relates to a product and to its use in a machine washing method.
Many different delivery formats and packaging methods for detergent compositions for use in automatic washing formulations have been proposed and are used. These include solid detergent in the form of tablets or a granular composition, liquids and packaged compositions. The packaged compositions may be packaged in cardboard boxes, tubs, bags, bottles, flow wrappers or other packaging means.
For detergent compositions packaged in cardboard storage stability has proven to be an issue when the compositions are hygroscopic. Bottles and tubs provide good protection against moisture but use a lot of plastic. Bags are a reasonable compromise on plastic use and moisture barrier but due to their transparency to light are susceptible to discoloration in case the packed material is reactive.
This poor colour stability is often exacerbated by the contents of the package which can be aggressive towards the package materials, e.g. bleach components such as percarbonate compounds, which as oxidising agents are typically aggressive to the packaging materials.
It is an object of the present invention to obviate/mediate the problems outlined above.
In accordance with a first aspect of the present invention there is provided a detergent product comprising a container containing a detergent composition, which includes a percarbonate compound in an amount of greater than 20 wt %, preferably greater than 35% the container being formed of an insoluble material, wherein the detergent composition comprises a silicate in an amount of greater than 0.5 wt %.
The packaging may comprise from 100 g to 5000 g of the composition. Preferably from 300 g to 2000 g.
With the combination of a silicate/percarbonate in the detergent composition it has been found that the detrimental interaction of the detergent composition with the packaging material is greatly reduced. This has knock-on effects in that the overall stability of the package and hence its associated efficacy in a washing operation is greatly enhanced.
Without being bound to theory we believe that the silicate helps to passivate packaging material surfaces as well as interaction between granules of the composition.
As well as the percarbonate other bleaches may be present in the composition. Examples of bleaches that may be used are oxygen bleaches.
Peroxygen bleaching actives are: perborates, peroxides, peroxyhydrates, persulfates. A preferred compound is sodium percarbonate and especially the coated grades that have better stability. The percarbonate can be coated with silicates, borates, waxes, sodium sulfate, sodium carbonate and surfactants solid at room temperature.
Optionally, the compositions may additionally comprise from 0.01 to 30% wt, preferably from 2 to 20% wt of bleach precursors. Suitable bleach precursors are peracid precursors, i.e. compounds that upon reaction with hydrogen peroxide product peroxyacids. Examples of peracid precursors suitable for use can be found among the classes of anhydrides, amides, imides and esters such as acetyl triethyl citrate (ATC), tetra acetyl ethylene diamine (TAED), succinic or maleic anhydrides.
When a surfactant is present in the composition, it may be present in an amount of, for example, from 0.01 to 50% wt, ideally 0.1 to 30% wt and preferably 0.5 to 10% wt.
Suitable surfactants that may be employed include anionic or nonionic surfactants or mixture thereof. The nonionic surfactant is preferably a surfactant having a formula RO(CH2CH2O)nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about 1 to about 12. Examples of other non-ionic surfactants include higher aliphatic primary alcohol containing about twelve to about 16 carbon atoms which are condensed with about three to thirteen moles of ethylene oxide per mole of alcohol (i.e. equivalents).
Other examples of nonionic surfactants include primary alcohol ethoxylates (available under the Neodol tradename from Shell Co.), such as C11 alkanol condensed with 9 equivalents of ethylene oxide (Neodol 1-9), C12-13 alkanol condensed with 6.5 equivalents ethylene oxide (Neodol 23-6.5), C12-13 alkanol with 9 equivalents of ethylene oxide (Neodol 23-9), C12-15 alkanol condensed with 7 or 3 equivalents ethylene oxide (Neodol 25-7 or Neodol 25-3), C14-15 alkanol condensed with 13 equivalents ethylene oxide (Neodol 45-13), C9-11 linear ethoxylated alcohol, averaging 2.5 moles of ethylene oxide per mole of alcohol (Neodol 91-2.5), and the like.
Other examples of nonionic surfactants suitable for use include ethylene oxide condensate products of secondary aliphatic alcohols containing 11 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 equivalents of ethylene oxide. Examples of commercially available non-ionic detergents of the foregoing type are C11-15 secondary alkanol condensed with either 9 equivalents of ethylene oxide (Tergitol 15-S-9) or 12 equivalents of ethylene oxide (Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of Dow Chemical.
Octylphenoxy polyethoxyethanol type nonionic surfactants, for example, Triton X-100, as well as amine oxides can also be used as a nonionic surfactant.
Other examples of linear primary alcohol ethoxylates are available under the Tomadol tradename such as, for example, Tomadol 1-7, a C11 linear primary alcohol ethoxylate with 7 equivalents EO; Tomadol 25-7, a C12-15 linear primary alcohol ethoxylate with 7 equivalents EO; Tomadol 45-7, a C14-15 linear primary alcohol ethoxylate with 7 equivalents EO; and Tomadol 91-6, a C9-11 linear alcohol ethoxylate with 6 equivalents EO.
Other nonionic surfactants are amine oxides, alkyl amide oxide surfactants.
Preferred anionic surfactants are frequently provided as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or magnesium salts. Contemplated as useful are one or more sulfate or sulfonate compounds including: alkyl benzene sulfates, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.
Other surfactants which may be used are alkyl naphthalene sulfonates and oleoyl sarcosinates and mixtures thereof.
Any suitable soil catcher may be employed. Unlike detergents or surfactants, which simply aid in the removal of soils from surfaces, the soil catcher actively binds to the soil allowing it to be removed from the surface of the laundry. Once bound, the soil is less likely to be able to redeposit onto the surface of the laundry. Preferred soil catchers have a high affinity to both oily and water-soluble soil. Preferably, the soil catcher is a mixture of two or more soil catchers, each soil catcher may have a different affinity for different soils. Preferred soil catchers for oily soils have a non polar structure with high absorption capability. Preferred water based soil catchers are generally charged and have a high surface area in order to attract the soil by electrostatic charge and collect it.
Suitable soil catchers include polymers, such as acrylic polymers, polyesters and polyvinylpyrrolidone (PVP). The polymers may be crosslinked, examples of which include crosslinked acrylic polymers and crosslinked PVP. Super absorbing polymers are mainly acrylic polymers and they are useful for the scope of this patent.
Other important polymers are ethylidene norbene polymers, ethylidene norbene/ethylene copolymers, ethylidene norbene/propylene/ethylidene ter-polymers. Inorganic materials may also be employed. Examples include zeolites, talc, bentonites and active carbon. The latter may be used to absorb and/or degrade coloured parts of stain and/or absorb odours. Alginates, carrageneans and chitosan may also be used. Preferred water insoluble agents are selected from at least one of acrylic polymer, polyester, polyvinylpyrrolidone (PVP), silica, silicate, zeolite, talc, bentonites, active carbon, alginates, carrageneans, ethylidene morbene/propylene/ethylidene ter-polymers and chitosan in the manufacture of a detergent composition as an active agent for binding soil. Preferably the detergent composition is a laundry cleaning composition or stain-removing composition.
Preferred examples of water-insoluble soil catcher compounds comprise a solid cross-linked polyvinyl N-oxide, or chitosan product or ethylidene norbene/propylene/ethylidene ter-polymers or blend of the same, as discussed more fully hereafter.
Water soluble polymeric soil catcher agents that are suitable to be bound to insoluble carriers, or to be made insoluble via cross-linking are those polymers known in the art to inhibit the transfer of dyes from coloured fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash. Especially suitable polymeric soil catcher agents are polyamine N-oxide polymers, polymers and copolymers of N-vinylpyrrolidone and N-vinylimidazole, vinyloxazolidones, vinylpyridine, vinylpyridine N-oxide, other vinylpyridine derivatives or mixtures thereof.
The soil catcher may be present in the detergent composition in an amount of 0.01 to 100% wt of the composition, preferably from 1 to 90% wt, more preferably from 5 to 50% wt.
The composition advantageously additionally comprises cleaning agents selected from the group consisting of, fillers, builders, chelating agents, activators, fragrances, enzymes or a mixture thereof. These active agents are generally water soluble, so dissolve during the wash. Thus the additional active agents are released over a period of time when exposed to water in the laundry washing machine.
Suitable fillers include bicarbonates and carbonates of metals, such as alkali metals and alkaline earth metals. Examples include sodium carbonate, sodium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate and sesqui-carbonates of sodium, calcium and/or magnesium. Other examples include metal carboxy glycine and metal glycine carbonate. Chlorides, such as sodium chloride; citrates; and sulfates, such as sodium sulfate, calcium sulfate and magnesium sulfate, may also be employed.
The filler may be present in an amount of 0.1 to 80% wt, preferably 1 to 60% wt.
The composition may comprise at least one builder or a combination of them, for example in an amount of from 0.01 to 80% wt, preferably from 0.1 to 50% wt. Builders may be used as chelating agents for metals, as anti-redeposition agents and/or as alkalis.
Examples of builders are described below:
Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in GB-A-1,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.
Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarobyxlates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in GB-A-1,398,421, GB-A-1,398,422 and U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed citrates described in GB-A-1,439,000.
Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
Suitable polymer water-soluble compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in GB-A-1,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.
Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarobyxlates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in GB-A-1,398,421, GB-A-1,398,422 and U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed citrates described in GB-A-1,439,000.
Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6-hexane-hexacarboxyfates and carboxymethyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
More preferred polymers are homopolymers, copolymers and multiple polymers of acrylic, fluorinated acrylic, sulfonated styrene, maleic anhydride, methacrylic, isobutylene, styrene and ester monomers.
Examples of these polymers are Acusol supplied from Rohm & Haas, Syntran supplied from Interpolymer and the Versa and Alcosperse series supplied from Alco Chemical, a National Starch & Chemical Company.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Examples of bicarbonate and carbonate builders are the alkaline earth and the alkali metal carbonates, including sodium and calcium carbonate and sesqui-carbonate and mixtures thereof. Other examples of carbonate type builders are the metal carboxy glycine and metal glycine carbonates.
In the context of the present application it will be appreciated that builders are compounds that sequester metal ions associated with the hardness of water, e.g. calcium and magnesium, whereas chelating agents are compounds that sequester transition metal ions capable of catalysing the degradation of oxygen bleach systems. However, certain compounds may have the ability to do perform both functions.
Suitable chelating agents to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof. Chelating agents when used, are typically present herein in amounts ranging from 0.01 to 50% wt of the total composition and preferably from 0.05 to 10% wt.
Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly(alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates. The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates. Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST™.
Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. Pat. No. 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.
A preferred biodegradable chelating agent for use herein is ethylene diamine N,N′-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. Ethylenediamine N,N′-disuccinic acids, especially the (S,S) isomer have been extensively described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins. Ethylenediamine N,N′-disuccinic acid is, for instance, commercially available under the tradename ssEDDS™ from Palmer Research Laboratories.
Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine diacetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS™ and methyl glycine di-acetic acid (MGDA).
The detergent compositions may comprise a solvent. Solvents can be used in amounts from 0.01 to 30% wt, preferably in amounts of 0.1 to 3% wt. The solvent constituent may include one or more alcohol, glycol, acetate, ether acetate, glycerol, polyethylene glycol with molecular weights ranging from 200 to 1000, silicones or glycol ethers. Exemplary alcohols useful in the compositions include C2-8 primary and secondary alcohols which may be straight chained or branched, preferably pentanol and hexanol.
Preferred solvents are glycol ethers. Examples include those glycol ethers having the general structure Ra—O—[CH2—CH(R)—(CH2)-0]n-H, wherein Ra is C1-20 alkyl or alkenyl, or a cyclic alkane group of at least 6 carbon atoms, which may be fully or partially unsaturated or aromatic; n is an integer from 1 to 10, preferably from 1 to 5; and each R is selected from H or CH3. Specific and preferred solvents are selected from propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, isopropanol, ethanol, methanol, diethylene glycol monoethyl ether acetate, and, especially, propylene glycol phenyl ether, ethylene glycol hexyl ether and diethylene glycol hexyl ether.
The composition may, for example, comprise one enzyme or a combination of them, for example in an amount of from 0.01 to 10% wt, preferably from 0.1 to 2% wt. Enzymes in granular form are preferred. Examples of suitable enzymes are proteases, modified proteases stable in oxidisable conditions, amylases, lipases and cellulases.
Most preferably the detergent composition comprises the following admixture:—
55 wt % sodium percarbonate
20 wt % sodium bicarbonate
17 wt % sodium sulphate
4.0 wt % anionic surfactant
0.5 wt % nonionic surfactant
0.5 wt % soil catcher
0.5 wt % soil suspending polymer
0.2 wt % enzyme
0.5 wt % TAED
0.1 wt % fragrance.
Rest—water and minors
The detergent composition is preferably in the form of a powder. By “powder” we mean any solid, flow able composition. Thus the powder may, for example, be in the form of granules or agglomerated particles. It may, however, be in the form of a loose agglomeration of particles. The d50 particle size of the particles may range from 0.001 □m to 10 mm, preferably from 0.01 □m to 2 mm, and more preferably from 0.1 □m to 2 mm, for example 1 □m to 1 mm.
The detergent composition is enclosed in a container which is impermeable to water and to components dissolved therein. Such an enclosed product may be used in the washing cycle of a laundry washing machine.
Suitable materials for forming the enclosing wall are a polyolefin, such as polyethylene or polypropylene, or another polymer such as a polyester or polyamide. One or more of the walls may comprise an admixture of different components. Furthermore/alternatively one or more of the walls may comprise a laminated structure comprising a plurality of layers, with each of the layers having an identical or more preferably a non-identical composition.
In this regard it is preferred that the container material comprises a laminate whereby the inner layer comprises PE (e.g. of 140 micron thickness) and the outer layer comprises any other polyolefin such as PP, PE or PET, preferably PET (e.g. of 20 micron thickness).
For this container material it has been found that in storage yellowing/oxidation of the inner container material is largely prevented hindered using the detergent composition specified above.
The invention is further illustrated with reference to the following non-limiting Example.
Powders were stored in a pouch made of plastic foil.
The foil was composed of a laminate of 140 micron layer of PE and a 20 micron layer of PET. The PE material was the inner material of the pouch formed of such film. 1 kg of the testing powder formulation was filled in the formed pouch and the pouches were closed by sealing. 5 pouches were used per product and were assessed after 6 weeks of storage at 40° C. and 75% rH. For the assessment the pouches were cut open after cooling to room temperature and a panel of 5 persons assessed the degree of yellowing of the inner pouch material.
The formulae used in the test were:
The evaluations of the results was been done with a visual panel test versus the original virgin foil.
The evaluation scale was the following:
1=like the original
2=slightly different from the original
3=clearly different from the original
4=strongly different from the original
5=completely yellowed
It resulted that the formula with silicate scored 1 while the one without scored 3.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0902959.6 | Feb 2009 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/GB10/00291 | 2/19/2010 | WO | 00 | 9/30/2011 |
