EP2092048A1 - Composition de détergent pour le linge - Google Patents

Composition de détergent pour le linge

Info

Publication number
EP2092048A1
EP2092048A1 EP07857257A EP07857257A EP2092048A1 EP 2092048 A1 EP2092048 A1 EP 2092048A1 EP 07857257 A EP07857257 A EP 07857257A EP 07857257 A EP07857257 A EP 07857257A EP 2092048 A1 EP2092048 A1 EP 2092048A1
Authority
EP
European Patent Office
Prior art keywords
laundry
detergent composition
indicator
handwash
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07857257A
Other languages
German (de)
English (en)
Inventor
Ian Eric Niven
Alyn James Parry
David Christopher Thorley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP07857257A priority Critical patent/EP2092048A1/fr
Publication of EP2092048A1 publication Critical patent/EP2092048A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes

Definitions

  • the present invention relates to a laundry detergent composition that incorporates a dosage indicator to indicate to the consumer when a sufficient amount of laundry detergent is present in a wash liquor.
  • Unit dose products are self contained doses of detergent product, such that the same amount of product can be delivered to each wash. This has found success in many machine-wash based markets.
  • Such an approach requires that a constant amount of water is present in each and every wash, to enable the concentration of actives in the wash liquor to be the same for each wash.
  • This fails to consider one of the problems associated with laundry handwash, namely that the amount of wash liquor varies greatly for different consumers, and generally follows the size of the ⁇ wash bowl container' available to the consumer.
  • Unit dose in handwash is therefore not a promising solution to fix the concentration of detergent ingredients in the wash liquor regardless of the ⁇ wash bowl container' used by the consumer.
  • the provision of a dosing cup, or similar is also limited via a similar argument .
  • sufficiency of detergent dosage has been judged via cues associated with either product appearance, for example, product volume, or else generated by the product on contact with the wash medium.
  • foam generation has been used for many years as a consumer cue for sufficiency of dosage - once a certain level of foam is achieved, the consumer takes this as a cue that there is an effective level of detergent present.
  • this learned cue has imposed a serious limitation on handwash product formulators in that they are now often forced to incorporate foam producing elements in their formulations.
  • variable water hardness for the same volume of water also presents another problem to the handwash detergent formulator.
  • the ratio of metal ion chelating agent to detergent is fixed in a product, harder water requires more product to be added, leading to more detergent being dosed.
  • Many handwash detergents have instructions to dose detergent product according to the water hardness. This is a problem because many consumers are not sure what water hardness they have in the water being used.
  • a visual consumer cue is disclosed in WO 2004/078896 (Unilever) .
  • the visual cue is a fabric pre-treatment cleaning method, whereby a textile is treated with a liquid detergent in the form of a foam and wherein the visual cue is a colour change to said foam.
  • the colour change is provided by a pH dependent chromophore and as such the reagent cannot then be buffered or else it could not change pH and so would not be able to work.
  • Another pH based indicator system is disclosed in CH313346.
  • the specific pH indicator disclosed is Alizarine Yellow R which changes colour from yellow to orange red as the solution pH rises from 10.1 to 12.1. As mentioned above, for a buffered laundry composition with a typical pH of 10.5 such an indicator system would be unsuitable to indicate sufficiency of dosage.
  • the indicator product comprises a substrate and a colour indicator component distributed on or in the substrate, and has a barrier present to isolate the colour indicator from the surrounding environment.
  • This product alerts the consumer that it has exhausted its capacity for releasing active material.
  • a method for softening water in a washing machine is disclosed in WO 2005/005329 (Reckitt Benckiser) , wherein hard water is contacted with a water insoluble product added to the washing machine, wherein the product has a different appearance after being contacted with the hard water.
  • An indicator for calcium and magnesium is disclosed in WO 02/084278 (Reckitt Benckiser) .
  • a product preferably a fibre product, having immobilised onto it an indicator dye, which can be used to detect metal ions in a liquid.
  • EP 0 597 900 Bl discloses a method for the colorimetric determination of magnesium ions in a fluid, particularly biological fluids such as blood serum, blood plasma and the like.
  • the method comprises contacting said fluid with a reagent comprising a metallochromic dye substance 2- (4, 5-dihydroxy-2, 7-disulpho-3- naphthylazo) benzene-arsonic acid [Arsenoaza I], together with a selective complexing agent, and determinating the formation of a magnesium-dye complex.
  • EP 0 513 564 Bl discloses a buffered reagent for determining the ionic strength and/or the specific weight of an aqueous liquid (urine) with the aid of a colour indicator, the reagent contains at least one detergent and one pH indicator .
  • Buffered laundry detergent compositions containing dyes that may change colour in response to certain cations are disclosed in WO 2006/041739. These compositions are stated to be for use to mask a red discolouration in the water. The compositions are not concentrated laundry powders. The problem of sufficiency of dosage is not addressed.
  • the invention provides a sufficiency of dosage indicator for laundry main wash, preferably in the field of handwash.
  • the composition when added to an aqueous medium provides a visual cue that signifies when an effective dosing of a laundry detergent composition is attained.
  • the visual cue of the present invention is provided by a colour change indicator system. The colour desirably reverses during rinsing.
  • a first aspect of the present invention provides a laundry detergent composition comprising: -
  • a) detersive surfactant b) a colour change indicator system comprising: - i) an indicator dye capable of binding to divalent metal cations; and, ii) one or more other complexing agents for divalent metal cations, said complexing agent having a greater binding capacity than the indicator dye for said divalent metal cations at the pH of use; and, c) optionally carriers and adjuncts to 100 wt . % .
  • composition when contacted with an aqueous medium causes a colour change to said aqueous medium once an effective product dosing of the composition is attained.
  • the divalent metal cations are preferably Ca ++ and/or Mg ++ .
  • the amount of detersive surfactant in the composition is preferably at least 19.5wt%.
  • the amount of anionic surfactant is also preferably at least 18wt% of the composition.
  • a second aspect of the current invention provides the use of a composition according to the first aspect as a sufficiency of dosage indicator for laundry main wash, preferably in the field of handwash.
  • the laundry detergent composition is advantageously pH buffered to maintain the pH of the resulting wash liquor at a stable pH level suitable for laundry purposes. This is preferably from between pH 7 and 12, more preferably between pH 7.5 to 11.5 even more preferably 9 to 11.2.
  • the pH buffering of the composition can come entirely from the complexing agent, for example if a builder such as sodium tripolyphosphate (STP) is used as whole or part of the complexing agent.
  • STP sodium tripolyphosphate
  • An alternative embodiment of the composition of the invention has a separate pH buffer added as an additional component in the composition.
  • composition of the invention is a laundry detergent composition comprising : -
  • a) detersive surfactant b) a colour change indicator system comprising: - i) an indicator dye capable of binding to divalent metal cations; ii) one or more complexing agents for divalent metal cations, said complexing agent having a greater binding capacity than the indicator dye for said divalent metal cations at the pH of use; and, iii) pH buffer, which is preferably non- precipitating; and, c) optionally carriers and adjuncts to 100 wt . % .
  • composition of the present invention can advantageously be used to provide a visual cue once an effective product dosing of said laundry detergent composition in an aqueous medium is attained.
  • this is for the handwash field, and the visual cue prompts the end consumer to stop addition of the laundry detergent composition.
  • compositions of the invention one process of use for handwash comprises the following steps :-
  • the laundry handwash detergent composition is continued until a visual cue is provided by a colour change of the wash liquor.
  • the composition contains a buffer in sufficient quantity that the pH of the wash liquor is held constant.
  • the admixture may take place in any usual fashion that brings the composition and the aqueous medium into contact with each other.
  • the laundry handwash detergent composition is present in the aqueous medium in a dissolved or dispersed state.
  • the laundry handwash detergent composition can be any suitable form, such as a solid, liquid or paste.
  • it is a solid, particularly a particulate solid such as a powder or granular composition.
  • the indicator dye in the composition is selected to be non substantive to the laundry.
  • the primary field of use of the sufficiency of dosage composition will be as a handwash composition, it may also be adapted for washing machine use.
  • the colour change caused when the detergent dosing level is sufficient can be sensed not only by a human consumer, but also by a washing machine that is equipped with a sensor for detecting a colour change in a wash liquor.
  • Such compositions and uses thereof therefore also fall within the scope of the current invention.
  • Laundry handwash compositions, uses thereof and laundry handwash processes are preferred embodiments.
  • Laundry detergent compositions according to the present invention that utilise a colour change indicator system to provide a visual cue for the end consumer has one or more of the following associated advantages :-
  • a wider selection of surfactants can be incorporated, for example, the formulator is not limited by the necessity of incorporating a surfactant that produces a high level of foam, as an alternative visual cue other than foam can be provided; furthermore, foam boosters do not have to be in the formulation.
  • the visual cue is provided by a colour change indicator system, causing a colour change of the wash liquor due to interaction of the indicator dye, the complexing agents and hardness ions.
  • the colour change once an effective product dosing has been attained can conceivably be from colourless to coloured, or from coloured to colourless, preferably the colour change is from one colour to a second different colour.
  • the laundry detergent composition imparts a colour to the aqueous medium upon contact. For example, if the aqueous medium is water, the composition changes the colour from colourless to coloured upon initial contact, then once an effective dose of the composition is attained, the initial colour changes to a different colour to provide the visual cue to the consumer .
  • An effective product dosing of the laundry detergent composition can be considered to mean the provision of a sufficient amount of a laundry detergent system, for example a surfactant system and/or a hardness ion complexing agent, to provide the required fabric cleaning.
  • a laundry detergent system for example a surfactant system and/or a hardness ion complexing agent
  • the amount of the laundry detergent system present will vary depending on the formulation specification, and the region in which it will be sold.
  • ⁇ laundry process' and ⁇ laundry detergent compositions and products' should be taken to mean the actual laundering process itself (whether handwash or by machine) and products classed as ⁇ main wash' detergent products. Accordingly, the present invention is not concerned with pre- and post fabric treatments, nor with so-called ⁇ rinse' products.
  • the aqueous medium is water or predominantly water. Once a laundry detergent product has been added to the aqueous medium, for example water, the resulting medium is commonly known as a ⁇ wash liquor' .
  • the wash liquor may be at any pH level suitable for laundry wash purposes. This may be, for example, between pH 4 and 12. However preferentially, the pH of the wash liquor is 7 or above, for example, between 7 and 12.
  • the wash liquor may change pH during the laundry wash.
  • the indicator dye and complexing agents are chosen such that the colour change occurs independently of pH range.
  • the pH of the wash liquor may vary during the wash, preferably the pH of the wash liquor is maintained at a stable pH.
  • a component that can act as a pH buffer This may be achieved, for example, by the complexing agent included in compositions of the invention, by addition of builder or the addition of a separate pH buffer.
  • the wash liquor is advantageously maintained at a pH of from 7 to 12, more preferably it is kept stable at a level between pH 7.5 and 11.5, more preferably still at a level between pH 8 and 11, for example between pH 8.5 and 10.5.
  • the pH is kept stable by incorporating a pH buffer into the composition.
  • Useful pH buffers compatible with laundry main wash and handwash are well known to the skilled formulator.
  • the colour change indicator system is present in the wash liquor to provide a visual cue once an effective level of laundry detergent composition is present.
  • it is incorporated within the wash liquor in a dissolved or dispersed state, preferably a dissolved state.
  • the colour change indicator system is provided as part of a laundry detergent composition, i.e. incorporated as part of the laundry detergent product.
  • the species that the colour change indicator is responsive to are the hardness ions Ca ++ and/or Mg ++ already present in the aqueous medium prior to contact with the laundry detergent composition.
  • the colour change indicator system is pH independent, i.e. the colour change is not mediated by hydrogen or hydronium cations, so that it is not affected by pH within the normal pH ranges used in laundry main wash or handwash.
  • the laundry composition comprises a pH buffer. It is usual for laundry detergents to be buffered to maintain the pH of the wash liquor at a stable level. Preferably this stable level is in the range of from pH 7 to 12, preferably between pH 7.5 and 11.5, more preferably still between pH 8 and 11, for example between pH 8.5 and 10.5. In this way, the pH of the wash liquor is stable, and as such hydrogen ions would be unsuitable to use as the species to which the colour change indicator is responsive .
  • the colour change indicator system comprises an indicator dye capable of binding to divalent metal cations and one or more complexing agents for divalent metal cations.
  • the complexing agent (or one complexing agent from a mixture of two or more complexing agents) has a stronger affinity, measured, for example, by binding capacity, for the divalent metal cation to which it is responsive than the indicator dye .
  • Binding capacity is one way of measuring the affinity of one species to another, and can be equated to values for the stability constant of the metal cation (s) with either complexing agent and indicator dye.
  • the metal- indicator dye complex is less stable than the metal- complexing agent complex.
  • the complexing agent should have a greater binding capacity than the indicator dye for the metal cation.
  • the difference in binding capacities is at least one order of magnitude; with the greater binding capacity belonging to the complexing agent. More preferably the difference is two orders of magnitude.
  • Suitable complexing agents are chelating agents for metal cations especially divalent metal cations which cause or are associated with hard water. Chelating agents have two or more species capable of co-ordinating to a metal cation. It is well within the ambit of the person skilled in the art to be able to choose suitable chelating agents in combination with textbook knowledge such as that present in "Vogel's Textbook of Quantitative Chemical Analysis" 6 th Edition
  • Useful chelating agents can include any of those known to those skilled in the art such as amino carboxylates, phosphates (such as STP) , phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
  • Suitable phosphonate chelating agents for use herein may include alkali metal ethane 1-hydroxy diphosphonates (HEDP) , alkylene poly (alkylene phosphonate) , as well as amino phosphonate compounds, including amino aminotri (methylene phosphonic acid) (ATMP) , nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP) .
  • 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 phosphonate (DTPMP) and ethane 1- hydroxy diphosphonate (HEDP) .
  • DTPMP diethylene triamine penta methylene phosphonate
  • HEDP ethane 1- hydroxy diphosphonate
  • 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 substitutes 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.
  • Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA) , N- hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA) , both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • 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) .
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di- acetic acid
  • carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
  • the composition incorporates a material that acts as a pH buffer.
  • Some builder materials when incorporated in accordance with the present invention as a complexing agent can also provide a pH buffering function to the composition.
  • a separate pH buffer is incorporated in the composition, such that it is an additional component other than any dual purpose pH buffering complexing agent/builder.
  • the pH buffer is non-precipitating.
  • the pH buffer may also be non-responsive (i.e. a non- divalent cation complexing buffer) to the metal cations to which the colour change system is responsive.
  • the pH buffer should have little or no affinity for Ca ++ or Mg ++ .
  • the pH buffer may, in certain embodiments of - I i
  • the invention also be the complexing agent.
  • many common laundry builders such as sodium tripolyphosphate (STP)
  • STP sodium tripolyphosphate
  • pH buffers will be well known to skilled laundry detergent formulators.
  • additional buffering may be achieved by the use of a separate buffering system that is typically based on materials such as carbonate, bicarbonates, protonic acids and/or co-ordinatively unsaturated metals or non metals.
  • the pH buffer if added as a separated additional component is preferably present in the pH buffered laundry detergent composition at a level of from 1 to 95 wt.%, more preferably 2 to 85 wt.%.
  • the weight ratio of the pH buffer to total surfactant in the laundry detergent composition is preferably from 15:1 to 1:50, more preferably from 15:1 to 1:25.
  • the weight ratio of the pH buffer to complexing agent in the laundry detergent composition is preferably from 15:1 to 1:15, more preferably from 12:1 to 1:12.
  • the indicator dye is preferably present in the laundry detergent composition at a level of from 0.001 to 5 wt.%, more preferably 0.01 to 2.5 wt.%, for example from 0.05 to 2 wt.%, alternatively from 0.1 to 1 wt.%.
  • the absolute concentration of dye in solution should be sufficiently high to ensure that the colour change, when it occurs, is sufficiently intense to allow perception by the user.
  • the weight ratio of the indicator dye to total surfactant is from 1:1 to 1:500, more preferably from 1:1 to 1:350.
  • the indicator dye is chosen from those that exhibit a colour change in the aqueous medium/wash liquor, between its state when complexed to a divalent metal cation and its non- complexed state.
  • a dye may be colourless when complexed to a metal cation, but be coloured when in its free non-complexed state or vice versa.
  • the indicator dye exhibits one colour when it is bound to the divalent metal cation, and a second, different colour when it is in its free, non-complexed state.
  • Preferred indicator dyes are those which operate in the pH region of pH 7 to 12. Suitable indicator dyes can be found in "Indicators", by Edmund Bishop, published by Elsevier 1972. Although most indicator dyes will work to some extent over a range of pH values, they generally will have a preferred pH range where the colour change will be particularly sharp. The skilled person can therefore choose a suitable dye according to the pH of the final laundry formulation. It is highly preferable that the indicator dye is non substantive to the fabric being laundered. Optionally the indicator dye can be non-light fast, meaning that the colour produced by the dye fades upon exposure to light, especially U. V. light.
  • An example of an embodiment of a colour change indicator system is the combination of TRIS buffer, EDTA (a complexing agent) and Calmagite Indicator (an indicator dye) .
  • this and similar embodiments function by being responsive to calcium and/or magnesium cations that are naturally present in water.
  • divalent alkali earth metal ion levels can vary (different water hardness values) ; they are well known for each country/region, and so the formulation can be tailored to match the local calcium level in water (water hardness) .
  • the aqueous medium turns pink as there is excess divalent metal ion present in the water, enough to bind to both the complexing agent and the indicator dye, which turns pink when complexed to the divalent metal ion.
  • the complexing agent preferentially binds the divalent metal ions over the dye, and when the free divalent metal ions in the aqueous medium are all bound, the complexing agent then strips divalent metal ions away from the indicator dye. This produces a blue colour (the colour of non-complexed indicator dye) and is the visual cue for the consumer to stop addition of composition because there is enough composition present.
  • This system can therefore be used to provide an effective dose of detersive surfactant and other laundry actives.
  • the laundry detergent compositions of the invention comprises surfactant.
  • This can be a single surfactant or a mixture of two or more surfactants.
  • any surfactant may be used, including anionic, non-ionic, cationic, amphoteric and zwitterionic surfactants.
  • the surfactant is anionic, non-ionic or a mixture of the two.
  • the surfactant incorporated in the laundry detergent composition is detersive surfactant.
  • the surfactant, or at least one surfactant of any surfactant mixture provides a detersive, i.e. cleaning effect to textile fabrics treated as part of a laundering process.
  • Other surfactants which may or may not be detersive surfactants can be used as part of the composition .
  • the detersive surfactant is suitable of handwash purposes.
  • the non-ionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon ' s Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. It is preferred if the surfactant chosen is an anionic surfactant, a non- ionic surfactant or a mixture of one or more anionic surfactants with one or more non-ionic surfactants.
  • Preferred non-ionic surfactants are detailed below.
  • non-ionic surfactant shall be defined as amphiphilic molecules with a molecular weight of less than about 10,000, unless otherwise noted, which are substantially free of any functional groups that exhibit a net charge at the normal wash pH of 6-11.
  • non-ionic surfactant Any type of non-ionic surfactant may be used, although preferred materials are further discussed below.
  • Highly preferred are fatty acid alkoxylates, especially ethoxylates, having an alkyl chain of from C8-C35, preferably C8-C30, more preferably C10-C24, especially C10-C18 carbon atoms .
  • R 1 O(EO) .
  • R 1 represents an alkyl chain of between 4 and 30 carbon atoms
  • (EO) represents one unit of ethylene oxide monomer
  • n has an average value between 0.5 and 20.
  • R 1 may be linear or branched.
  • Such chemicals are generally produced by oligomerizing fatty alcohols with ethylene oxide in the presence of an effective amount catalyst, and are sold in the market as, for example, Neodols from Shell (Houston, Tex.) and Alfonics from Sasol (Austin, Tex.).
  • the fatty alcohol starting materials which are marketed under trademarks such as Alfol, Lial and Isofol from Sasol
  • Neodol from Shell
  • Commercial alcohol ethoxylates are typically mixtures, comprising varying chain lengths of R 1 and levels of ethoxylation . Often, especially at low levels of ethoxylation, a substantial amount of unethoxylated fatty alcohol remains in the final product, as well .
  • fatty alcohol ethoxylates wherein R 1 represents an alkyl chain from 10-18 carbons and n is an average number between 5 and 12 are highly preferred.
  • R 2 represents a linear or branched alkyl chain ranging from 4 to 30 carbons
  • Ar is a phenyl (CeH 4 ) ring and (EO) n is an oligomer chain comprised of an average of n moles of ethylene oxide.
  • R 2 is comprised of between 8 and 12 carbons, and n is between 4 and 12.
  • Such materials are somewhat interchangeable with alcohol ethoxylates, and serve much the same function.
  • a commercial example of an alkylphenol ethoxylate suitable for use in this invention is Triton X-IOO, available from Dow Chemical (Midland, Mich.).
  • EO represents an ethylene oxide unit
  • PO represents a propylene oxide unit
  • x and y are numbers detailing the average number of moles ethylene oxide and propylene oxide in each mole of product.
  • Such materials tend to have higher molecular weights than most non-ionic surfactants, and as such can range between 1,000 and 30,000 Daltons.
  • BASF Mount Olive, N.J. manufactures a suitable set of derivatives and markets them under the Pluronic trademarks.
  • non-ionic surfactants should also be considered within the scope of this invention. These include condensates of alkanolamines with fatty acids, such as cocamide DEA, polyol-fatty acid esters, such as the Span series available from Uniqema (Wlimington, Del.), ethoxylated polyol-fatty acid esters, such as the Tween series available from Uniqema (Wilmington, Del.), Alkylpolyglucosides, such as the APG line available from Cognis (Gulph Mills, Pa.) and n- alkylpyrrolidones, such as the Surfadone series of products marketed by ISP (Wayne, N.J). Furthermore, non-ionic surfactants not specifically mentioned above, but within the definition, may also be used.
  • Preferred anionic surfactants are outlined below.
  • the anionic surfactants used in this invention can be any water soluble anionic surfactant other than soap.
  • Water soluble surfactants are, unless otherwise noted, here defined to include surfactants which are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25°C.
  • “Anionic surfactants” are defined herein as amphiphilic molecules comprising one or more functional groups that exhibit a net anionic charge when in aqueous solution at the normal wash pH of between 6 and 11.
  • Preferred anionic surfactants are the alkali metal salts of organic sulphur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulphonic and sulphuric acid ester radicals.
  • anionic surfactant hereinafter described can be used, highly preferred anionic surfactants are the alkali and alkaline earth metal salts of both fatty alcohol sulphates, preferably primary alkyl sulfates, more preferably they are ethoxylated, for example alkyl ether sulfates, and alkylebenzene sulfonates or mixtures thereof.
  • alkyl Ether Sulphates preferably primary alkyl sulfates, more preferably they are ethoxylated, for example alkyl ether sulfates, and alkylebenzene sulfonates or mixtures thereof.
  • R 3 is a primary alkyl group of 8 to 18 carbon atoms
  • n has an average value in the range from 1 to 6 and M is a solubilising cation.
  • the alkyl group R 3 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 3 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 3 is coconut alkyl, for example.
  • n has an average value of 2 to 5.
  • Ether sulphates have been found to provide viscosity build in certain of the formulations of this invention, and thus are considered a preferred ingredient.
  • R 4 is an alkyl group of 6 to 16 atoms
  • R "5 is an alkyl group of 1 to 4 carbon atoms
  • M is a solubilising cation.
  • the group R 4 may have a mixture of chain lengths. Preferably at least two-thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety R 8 CH (-) CO 2 (-) is derived from a coconut source, for instance. It is preferred that R 15 is a straight chain alkyl, notably methyl or ethyl.
  • R 6 is an alkyl group of 8 to 18 carbon atoms
  • Ar is a benzene ring (CeH 4 ) and M is a solubilising cation.
  • the group R 6 may be a mixture of chain lengths. A mixture of isomers is typically used, and a number of different grades, such as "high 2-phenyl” and “low 2-phenyl” are commercially available for use depending on formulation needs.
  • Paraffin sulphonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. They are usually produced by the sulphoxidation of petrochemically- derived normal paraffins. These surfactants are commercially available as, for example, Hostapur SAS from Clariant (Charlotte, N. C).
  • Olefin sulphonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
  • U.S. Patent No. 3,332,880 contains a description of suitable olefin sulphonates, and is incorporated herein by reference. Such materials are sold as, for example, Bio-Terge AS-40, which can be purchased from Stepan (Northfield, 111.)
  • Sulphosuccinate esters R 7 OOCCH 2 CH (SO 3 ⁇ M + ) COOR 8 are also useful in the context of this invention.
  • R 7 and R 8 are alkyl groups with chain lengths of between 2 and 16 carbons, and may be linear or branched, saturated or unsaturated.
  • a preferred sulphosuccinate is sodium bis (2- ethylhexyl) sulphosuccinate, which is commercially available under the tradename Aerosol OT from Cytec Industries (West Paterson, N.J.) .
  • Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol. Also included are non-ionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the non-ionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
  • fatty acid ester sulphonates with formula:
  • R 11 OSO 3 M wherein R 11 is a primary alkyl group of 10 to 18 carbon atoms and M is a sodium cation; and paraffin sulphonates, preferably with 12 to 16 carbon atoms to the alkyl moiety.
  • anionic surfactants preferred for use with this formulation include isothionates, sulphated triglycerides, alcohol sulphates, ligninsulphonates, naphthelene sulphonates and alkyl naphthelene sulphonates and the like. Additional anionic surfactants, falling into the general definition but not specifically mentioned above, should also be considered within the scope of this invention.
  • R 12 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilising cation.
  • the alkyl group R 12 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 12 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 12 is coconut alkyl, for example.
  • the solubilising cation may be a range of cations which are in general monovalent and confer water solubility.
  • An alkali metal, notably sodium, is especially envisaged.
  • Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
  • R 13 COOM where R 13 is a primary or secondary alkyl group of 3 to 29 carbon atoms and M is a solubilising cation.
  • the alkyl group represented by R 13 may represent a mixture of chain lengths and may be saturated or unsaturated, although it is preferred that at least two thirds of the R 13 groups have a chain length of between 7 and 17 carbon atoms.
  • suitable alkyl group sources include the fatty acids derived from coconut oil, tallow, tall oil and palm kernel oil. For the purposes of minimising odour, however, it is often desirable to use primarily saturated carboxylic acids.
  • solubilising cation may be any cation that confers water solubility to the product, although monovalent such moieties are generally preferred.
  • acceptable solubilising cations for use with this invention include alkali metals such as sodium and potassium, which are particularly preferred, and amines such as triethanolammonium, ammonium and morpholinium.
  • a product according to the invention may take any suitable form, such as a solid, liquid or paste composition. Preferably it is in a solid form, particularly in a powder or granular form.
  • suitable form such as a solid, liquid or paste composition.
  • the formulation may include one or more optional ingredients. While it is not necessary for these elements to be present in order to practice this invention, the use of such materials is often very helpful in rendering the formulation acceptable for consumer use.
  • optional components include, but are not limited to: additional nonionic and anionic surfactants, amphoteric and zwitterionic surfactants, cationic surfactants, hydrotropes, fluorescent whitening agents, photobleaches, fibre lubricants, reducing agents, enzymes, enzyme stabilising agents, powder finishing agents, defoamers, builders, bleaches, bleach catalysts, soil release agents, antiredeposition agents, dye transfer inhibitors, buffers, colorants, fragrances, pro-fragrances, rheology modifiers, anti-ashing polymers, preservatives, insect repellents, soil repellents, water-resistance agents, suspending agents, aesthetic agents, structuring agents, sanitisers, solvents, fabric finishing agents, dye fixatives, wrinkle-reducing agents, fabric conditioning agents and deodorizers.
  • additional nonionic and anionic surfactants include, but are not limited to: additional nonionic and anionic surfactants, amphoteric and zwitterionic surfactants, cationic sur
  • one or more detergency builders may be added.
  • Builders are often added to fabric cleaning compositions to complex and remove alkaline earth metal ions, which can interfere with the cleaning performance of a detergent by combining with anionic surfactants and removing them from the wash liquor.
  • Soluble builders such as alkali metal carbonates and alkali metal citrates, are particularly preferred, especially for the liquid embodiment of this invention.
  • Other builders as further detailed below, may also be used, however. Often a mixture of builders, chosen from those described below and others known to those skilled in the art, will be used.
  • Alkali and alkaline earth metal carbonates are suitable for use as builders in the compositions of this invention. They may be supplied and used either in anhydrous form, or including bound water. Particularly useful is sodium carbonate, or soda ash, which both is readily available on the commercial market and has an excellent environmental profile.
  • the sodium carbonate used in this invention may either be natural or synthetic, and, depending on the needs of the formula, may be used in either dense or light form.
  • Natural soda ash is generally mined as trona and further refined to a degree specified by the needs of the product it is used in.
  • Synthetic ash is usually produced via the Solvay process or as a coproduct of other manufacturing operations, such as the synthesis of caprolactam. It is sometimes further useful to include a small amount of calcium carbonate in the builder formulation, to seed crystal formation and increase building efficacy.
  • Organic detergent builders can also be used as builders in the present invention.
  • organic builders include alkali metal citrates, succinates, malonates, sulphamic acid and/or water soluble salts thereof, fatty acid sulphonates, fatty acid carboxylates, nitrilotriacetates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulphonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopoly
  • Such carboxylates are described in U.S. Patent Nos. 4,144,226, 4,146,495 and 4,686,062.
  • Alkali metal citrates, nitrilotriacetates, oxydisuccinates, acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred nonphosphate builders.
  • compositions of the present invention may comprise sulphamic acid and/or water soluble salts thereof as whole or part of a soluble builder system.
  • the water soluble salt be a metal salt of sulphamate, such as an alkali or alkaline earth metal salt or sulphamate, or in some cases a transition metal counterion, such as lead or zinc sulphamate. Alternatively a non-metal counterion may be used, for example ammonium.
  • a water soluble salt of sulphamic acid is used, it is preferably an alkali or alkaline earth metal sulphamate, in particularly sodium sulphamate.
  • the sulphamic acid typically has the formula H2NSO3H. When present in a laundry detergent formulation, the sulphamic acid may be wholly or part in a zwitterionic form, of formula H 3 N + SO3 " .
  • compositions of the present invention which utilise a water-soluble phosphate builder typically contain this builder at a level of from 1 to 90% by weight of the composition.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from about 6 to 21, and salts of phytic acid. Sodium or potassium tripolyphosphate is most preferred.
  • the preferred compositions of this invention comprise phosphates at a level of less than about 10% by weight, more preferably less than about 5% by weight.
  • the most preferred compositions of this invention are formulated to be substantially free of phosphate builders.
  • Zeolites may also be used as builders in the present invention.
  • a number of zeolites suitable for incorporation into the products of this disclosure are available to the formulator, including the common zeolite 4A.
  • zeolites of the MAP variety such as those taught in European Patent Application EP-B-384, 070, which are sold commercially by, for example, Ineos Silicas (UK) , as Doucil A24, are also acceptable for incorporation.
  • MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, more preferably within the range of from 0.90 to 1.20.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the particle size of the zeolite is not critical.
  • Zeolite A or zeolite MAP of any suitable particle size may be used.
  • zeolites are insoluble matter, it is advantageous to minimise their level in the compositions of this invention.
  • the preferred formulations contain less than about 10% of zeolite builder, while especially preferred compositions compress less than about 5% zeolite.
  • zeolite to be absent .
  • enzyme stabiliser When enzymes, and especially proteases are used in liquid detergent formulations, it is often necessary to include a suitable quantity of enzyme stabiliser to temporarily deactivate it until it is used in the wash.
  • suitable enzyme stabilisers are well-known to those skilled in the art, and include, for example, borates and polyols such as propylene glycol. Borates are especially suitable for use as enzyme stabilisers because in addition to this benefit, they can further buffer the pH of the detergent product over a wide range, thus providing excellent flexibility.
  • a borate-based enzyme stabilisation system along with one or more cationic polymers that are at least partially comprised of carbohydrate moieties, stability problems can result if suitable co-stabilisers are not used. It is believed that this is the result of borates' natural affinity for hydroxyl groups, which can create an insoluble borate-polymer complex that precipitates from solution either over time or at cold temperatures. Incorporating into the formulation a co-stabiliser, which is normally a diol or polyol, sugar or other molecule with a large number of hydroxyl groups, can ordinarily prevent this.
  • sorbitol used at a level that is at least about 0.8 times the level of borate in the system, more preferably 1.0 times the level of borate in the system and most preferably more than 1.43 times the level of borate in the system, is sorbitol, which is effective, inexpensive, biodegradable and readily available on the market.
  • Similar materials including sugars such as glucose and sucrose, and other polyols such as propylene glycol, glycerol, mannitol, maltitol and xylitol, should also be considered within the scope of this invention.
  • composition was prepared according to table 1.
  • the example was formulated to provide an effective detergent dose of 2.25g/L.
  • Using the colour change indicator system one skilled in the art can easily vary the detergent dosing level depending on what is required locally.
  • SDS, EDTA and Calmagite were sourced from Sigma Aldrich, and TRIS was sourced from BDH.
  • Table 1 An example of colour change indicator system for the provision of a dosing of 2.25 g/L of composition to an aqueous medium. To show that this composition can effectively provide a visual cue to a consumer once an effective product dosing is attained; solutions of the formulation were prepared at concentration of 0.5, 1, 1.5, 2, 2.25, 2.5, 3, 3.5 & 4 g/L in demin. water that had been adjusted to 10 FH (French
  • the absorbance of the each solution was measured in a 1 cm cell over the range 400 to 700 nm (roughly the wavelength perceivable to the human eye) .
  • LAS linear alkylbenzene sulphonate
  • STP sodium tripolyphosphate
  • Calmagite was the same as for example 1.
  • This example depicts a different system to example 1.
  • the complexing agent is also acting as the pH buffer. It shows that the system is adaptable to be able to deliver an easily perceivable colour change, and that varying concentrations of detergent can be delivered.

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Abstract

La présente invention concerne une composition de détergent pour le linge qui donne une indication visuelle lorsque la dose efficace de produit est atteinte dans un milieu aqueux et un procédé de lavage à la main effectué avec la composition ainsi que l'utilisation de la composition pour fournir une indication suffisante de la dose de produit. La composition de détergent comprend: (a) un tensio-actif détergent; (b) un système d'indicateur changeant de couleur comprenant: (i) un colorant indicateur capable de se lier à des cations métalliques bivalents; (ii) un ou plusieurs autres agents complexants pour les cations métalliques bivalents, ledit agent complexant présentant une capacité de liaison supérieure au colorant indicateur pour lesdits cations métalliques bivalents dans des conditions de pH en utilisation, et (c) éventuellement des supports et des matières d'appoint pour atteindre les 100% en poids.
EP07857257A 2006-12-20 2007-12-05 Composition de détergent pour le linge Withdrawn EP2092048A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07857257A EP2092048A1 (fr) 2006-12-20 2007-12-05 Composition de détergent pour le linge

Applications Claiming Priority (3)

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EP06126722 2006-12-20
EP07857257A EP2092048A1 (fr) 2006-12-20 2007-12-05 Composition de détergent pour le linge
PCT/EP2007/063343 WO2008074635A1 (fr) 2006-12-20 2007-12-05 Composition de détergent pour le linge

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EP2092048A1 true EP2092048A1 (fr) 2009-08-26

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EP (1) EP2092048A1 (fr)
CN (1) CN101568631A (fr)
AR (1) AR064447A1 (fr)
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Publication number Priority date Publication date Assignee Title
WO2008117233A1 (fr) * 2007-03-26 2008-10-02 The Procter & Gamble Company Système de composition détergente liquide avec changement d'indication visuelle
EP2126029A1 (fr) * 2007-03-26 2009-12-02 The Procter & Gamble Système de composition liquide possédant un changement d'indication visuelle
CN106479759A (zh) * 2015-08-28 2017-03-08 上海家化联合股份有限公司 一种变色清洁组合物
CN115697689A (zh) 2020-06-09 2023-02-03 巴斯夫欧洲公司 回收粘接制品的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1731794A1 (ru) * 1989-12-19 1992-05-07 Научно-производственное объединение "СинтезПАВ" "Жидкое моющее синтетическое средство "Кама" дл стирки тканей"
WO2007147745A1 (fr) * 2006-06-21 2007-12-27 Ciba Holding Inc. Procédé de lessive à la main

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Publication number Priority date Publication date Assignee Title
CH313346A (de) * 1953-01-03 1956-04-15 Baerle & Cie Ag Wasch- bzw. Reinigungsmittel
GB2403719A (en) * 2003-07-07 2005-01-12 Reckitt Benckiser Nv Water-softening method
ES2324676T3 (es) * 2004-10-04 2009-08-12 The Procter And Gamble Company Composicion con un tinte formador de complejos con metales y un tensioactivo.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1731794A1 (ru) * 1989-12-19 1992-05-07 Научно-производственное объединение "СинтезПАВ" "Жидкое моющее синтетическое средство "Кама" дл стирки тканей"
WO2007147745A1 (fr) * 2006-06-21 2007-12-27 Ciba Holding Inc. Procédé de lessive à la main

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199317, Derwent World Patents Index; Class A97, AN 1993-141619, XP002397885 *
See also references of WO2008074635A1 *

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WO2008074635A1 (fr) 2008-06-26
AR064447A1 (es) 2009-04-01
CN101568631A (zh) 2009-10-28

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