Cleaning composition
12 claims: 7 independent, 5 dependent
- 1A cleaning composition comprising:(i) hydrogen peroxide or a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution;(ii) a first bleach activator comprising a precursor of peracetic acid;and, (iii) a second bleach activator comprising a precursor of C 8 to C 11 peroxyacid;wherein the composition comprises: (i) a protease;and, (ii) a lipase or an amylase or a mixture thereof.
- 5A cleaning composition as claimed in any one of the preceding claims wherein the second bleach activator is hydroxybenzoic acid derivative of the formula (I) in which R is C 8 -C 11 alkyl group.
- 7A cleaning composition as claimed in any one of the preceding claims wherein the composition further comprises a mannanase.
- 8A cleaning composition as claimed in any one of the preceding claims wherein the peroxygen bleach compound is selected from alkali metal salts of perborates or percarbonates.
Independent claims7
122 paragraphs, as filed
Field of the invention
0001The present invention relates to a cleaning composition for providing effective stain removal.
0002The invention has been developed primarily for use in detergent compositions and will be described hereinafter with reference to this application. However, it will be appreciated that the invention is not limited to this particular field of use.
Background of the invention
0003Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.
0004Peroxygen bleach compounds are well known for their ability to remove stains from substrates. Such bleaching agents include hydrogen peroxide, or substances that can generate perhydroxyl radical, such as inorganic or organic peroxides. Generally, the peroxygen bleach compound or hydrogen peroxide must be activated.
0005One method of activation is to employ wash temperatures greater than 60 °C. High temperatures required for activation of the peroxygen bleach compound often damage the fabric dyes, and can also cause premature damage to the substrate or fabric. Another known approach of activation is the use of organic precursor compounds along with peroxygen bleach compound. Addition of the organic precursors, often also referred to as bleach activators, into compositions having peroxygen bleach compound improves bleaching activity at lower wash temperatures, e.g. 40 to 60 °C. Examples of bleach activators are tetraacetylethylenediamine (TAED) and sodium nonanoyloxybenzenesulphonate(NOBS).
0006The bleach activators react with the perhydroxide anion (OOH-) of the hydrogen peroxide released by the peroxygen bleach compound in the aqueous solution to form a peroxyacid which is more reactive as a bleaching agent than the peroxide bleach alone.
0007Using a single bleach activator along with peroxygen bleach compound show limited action on stains depending on whether such stains are hydrophobic or hydrophilic. A hydrophobic bleach activator used with the peroxygen bleach compound is effective on hydrophobic bleachable stains, such as burnt fat (like butter), tomato-sauce, cosmetics (like lipstick), but have limited performance on hydrophilic bleachable stains, such as tea or red wine stains. Similarly, a hydrophilic bleach activator when used with peroxygen bleach compound is effective on hydrophilic bleachable stains, but shows limited performance on hydrophobic bleachable stains. Two or more bleach activators are often used together to activate peroxygen bleach compounds in order to make the bleach composition effective towards hydrophilic as well as hydrophobic stains.
0008Various attempts have been made to improve the overall bleaching performance on fabrics over a wide range of stains by using bleach activator combinations.
0009One such attempt was done in <patcit id="pcit0001" dnum="WO11117617A1"><text>WO11117617A1 (Reckitt & Colman, 2011</text></patcit>) which discloses a cleaning composition having a dispersion of a particle in acidic aqueous phase for providing stability before use and performance in use. The particle includes an admixture of tetraacetylethylenediamine (TAED) and decanoyloxybenzenecarboxylic acid (DOBA) coated with an acid stable coating.
0010<patcit id="pcit0002" dnum="US2009130224A1"><text>US 2009130224 A1 (Borchers et.al., 2009</text></patcit>) discloses an improved bleach activator and bleach activator compositions in the form of granules having TAED and DOBA for use in washing, cleaning and disinfectant compositions. The application discloses a granular bleach activating mixture of TAED and DOBA in which the mixture is free of binders.
0011<patcit id="pcit0003" dnum="US2008113036A1"><text>US 2008113036 A1 (Reinhardt et al. 2008</text></patcit>) discloses an improved bleach activator and bleach activator compositions having synergistic effects on difficult to remove stains such as grass and curry. The application discloses a mixture of bleach activators based on hydroxybenzoic acids and particular peracetic acid-releasing activators. This further discloses washing composition, cleaning composition and disinfectant having the activator mixtures in the form of co-granules of bleach component together with hydrogen peroxide-generating substance.
0012However there is still a need for cleaning composition which can provide for effective removal of tough stains like fruity stains, sebum stains, tomato and sunflower oil stains. Especially fruity stains are particularly difficult to remove. Tough stains like fruity stains require a significant amount of bleaching agent for their removal, which might also bleach the colour of the garment.
0013With growing trend towards eating healthier, people consume several servings of fruits or fruit juices and other fruit based products between meals at work as well as at home. As a result, incidents of fruity stains are on the rise. Thus there is a need for cleaning composition providing effective removal of the fruity stains from fabric especially from the white fabrics.
0014It is thus an object of the present invention to provide a cleaning composition which is effective against fruity stains which are otherwise considered to be difficult to remove.
0015It is another object of the present invention to provide a cleaning composition which can be used at lower wash temperatures.
0016It is yet another object of the present invention to provide a cleaning composition which is effective against sebum stains.
0017It is yet another object of the present invention to provide a cleaning composition which is particularly effective at cleaning fabrics.
0018Surprisingly it has been found that a cleaning composition having a combination of two specific bleach activators and a mixture of specific enzymes removes tough stains, which are otherwise considered to be difficult to be removed, especially fruity stains.
Summary of the invention
0019According to the first aspect, the present invention provides for a cleaning composition comprising: <ol id="ol0001" compact="compact" ol-style=""><li>(i) hydrogen peroxide or a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution;</li><li>(ii) a first bleach activator comprising a precursor of peracetic acid; and,</li><li>(iii) a second bleach activator comprising a precursor of C<sub>8</sub> to C<sub>11</sub> peroxyacid;</li></ol> wherein the composition comprises: <ol id="ol0002" compact="compact" ol-style=""><li>(i) a protease; and,</li><li>(ii) a lipase or an amylase or mixtures thereof.</li></ol>
0020According to the second aspect, the present invention provides for a method of bleaching a bleachable substrate comprising the steps of: <ol id="ol0003" compact="compact" ol-style=""><li>(i) applying to the substrate a neat or diluted form of the composition of the first aspect;</li><li>(ii) optionally applying to the substrate a detergent composition; and, rinsing the substrate.</li></ol>
0021According to the third aspect disclosed is a use of the cleaning composition of the first aspect for bleaching stains.
0022According to a fourth aspect disclosed is a use of the cleaning composition of the first aspect for bleaching fruity or sebum stains on fabrics.
0023The invention will now be explained in more details.
Detailed description of the invention
0024According to the first aspect disclosed cleaning composition includes hydrogen peroxide or a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution, a first bleach activator, a second bleach activator, a protease and a lipase or an amylase or mixtures thereof.
Cleaning composition:
0025Disclosed cleaning composition may be in different forms including but not limited to powders, tablets, liquids, bars, crystals, gels, capsules or in the form of non-aqueous liquids or carried on sheets or other substrates or in pouches.
0026The cleaning composition described herein can be used to make any cleaning preparation which can be used for the purpose of bleaching any suitable substrate, for example, laundry cleaning, laundry bleaches, bleach pre-treaters, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.) or automatic dishwashing compositions.
0027Preferably the disclosed cleaning composition is a granular detergent composition. When the cleaning composition is a granular detergent composition it may be of a low to moderate bulk density. The known methods for manufacturing a granular detergent composition includes spray-drying, drum drying, fluid bed drying, and scraped film drying preferably using the wiped film evaporator.
0028Alternatively, the granular detergent composition may be in a 'concentrated' or 'compact' form. Such detergent composition may be prepared by mixing and granulating process, for example, using a high-speed mixer or granulator, or other non-tower process.
0029When the cleaning composition is a granular detergent composition the first bleach activator and the second bleach activator may be post dosed as particulates.
0030Preferably the pH of the aqueous solution on dissolution of the detergent composition is 6 to 12 and more preferably from 7 to 10.5.
Peroxygen bleach compound:
0031Disclosed composition includes a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in the art. Hydrogen peroxide sources are described in details in <nplcit id="ncit0001" npl-type="b"><text>Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300</text></nplcit> "Bleaching Agents (Survey)", and include the alkali metal salts of sodium perborates and sodium percarbonates, including various coated and modified forms.
0032Suitable peroxygen bleach compounds include hydrogen peroxide or any of its solid adducts such as organic peroxides example; urea peroxide and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Mixtures of two or more such compounds may also be suitable. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. Hydrogen peroxide is especially preferred in liquid cleaning compositions.
0033Percarbonate is stable during storage and dissolves quickly in the cleaning liquor and is especially preferred. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, enhances substrate bleaching performance. Highly preferred percarbonate is in uncoated or coated form. Preferably the average particle size of uncoated and coated percarbonate ranges from about 400 to about 1200 µm, most preferably from about 400 to about 600 µm. If coated percarbonate is used, the preferred coating materials include mixtures of carbonate and sulphate, zeolite, precipitated silica, waxes, borates, polymers, citrates, silicate, borosilicate or fatty acids.
0034Preferably the disclosed cleaning composition has 4 to 35 wt% of the peroxygen bleach compound. When the disclosed cleaning composition is in the form of a bleach additive for addition at the point of use either to wash liquor or to a non-bleaching detergent composition, the peroxygen bleach compound may be present at even higher levels of up to 90wt% of the composition. When the cleaning composition is a detergent composition the composition has 5 to 20 wt % more preferably 10 to 15 wt% of the peroxygen bleach compound.
Bleach activator:
0035Disclosed composition includes a first bleach activator and a second bleach activator. Preferably the ratio of the first bleach activator to the second bleach activator is from 5:1 to 1:5, preferably from 3:1 to 1:3 and further preferably from 2:1 to 1:2, and most preferably 1:1.
0036The bleach activator may be in the form of a powder or as particulate bodies having the bleach activator, a binder or agglomerating agent. It is preferred for reasons of stability and handling, that bleach activator is in the form of particulate bodies.
0037Preferably the weight ratio of bleach activator to hydrogen peroxide or peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution is from 1:2 to 1:20 more preferably from 1:2 to 1:15 and still preferably from 1:5 to 1:10.
First bleach activator:
0038Disclosed cleaning composition includes a first bleach activator having a precursor of peracetic acid. The first bleach activator is preferably a compound from the class of polyacylated alkylenediamines. Preferably the compound from the class of polyacylated alkylenediamines is tetraacetylethylenediamine (TAED).
0039Disclosed cleaning composition include 0.1 wt% to 20 wt%, preferably from 0.5 wt% to 10 wt% and optimal composition include 1 wt% to 5 wt% of the first bleach activator.
Second bleach activator:
0040Disclosed cleaning composition includes a second bleach activator having a precursor of C<sub>8</sub> to C<sub>11</sub> peroxyacid. Preferably the second bleach activator is hydroxybenzoic acid derivative of the formula (I) <chemistry id="chem0001" num="0001"><img file="EP2931864B1_D0001.tif" /></chemistry> in which R is C<sub>8</sub>-C<sub>11</sub> alkyl group.
0041Preferably the second bleach activator is decanoyloxybenzoic acid (DOBA) and derivatives thereof.
Enzyme:
0042Disclosed composition includes a protease and a lipase or amylase or a mixture thereof.
Protease:
0043Disclosed cleaning composition includes a protease. Suitable protease includes those of animal, vegetable or microbial origin. Protease from microbial origin is preferred. Protease may also be chemically modified or protein engineered mutant. Preferably the protease is a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Examples of alkaline proteases are subtilisins, especially those derived from Bacillus, examples include subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin147 and subtilisin 168 (described <patcit id="pcit0004" dnum="WO8906279A1"><text>WO8906279A1</text></patcit>). Examples of trypsin-like proteases are trypsin from porcine or bovine origin and the Fusarium protease described in <patcit id="pcit0005" dnum="WO8906270A1"><text>WO8906270A1</text></patcit> and <patcit id="pcit0006" dnum="WO9425583A1"><text>WO9425583A1</text></patcit>. The protease is preferably from B.subtilis. Preferred commercially available protease includes Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™, Maxatase™, Maxacal™, Maxapem™, Properase™, Purfast®, Effectenz®, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).
0044Protease from a strain of Bacillus having maximum activity throughout the pH range of 8 to 12 is highly preferred and includes commercially available Esperase™ and Savinase™.
0045Preferably the cleaning composition of the present invention include 0.001 wt% to 10 wt% more preferably from 0.01 wt% to wt% of protease depending upon their activity.
Lipase:
0046Disclosed cleaning composition includes a lipase. Lipase catalyses hydrolysis of ester bonds of edible fats and oils, i.e. triglycerides, into free fatty acids, mono- and diglycerides and glycerol.
0047Preferred lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola species (incl. Thermomyces. species) which includes lipase from H. lanuginosus (T. lanuginosus) as described in <patcit id="pcit0007" dnum="EP0258068B1"><text>EP0258068B1</text></patcit> and <patcit id="pcit0008" dnum="EP0305216B1"><text>EP0305216B1</text></patcit> or from H. insolens as described in <patcit id="pcit0009" dnum="WO9613580A1"><text>WO9613580A1</text></patcit> or lipases from Pseudomonas species which includes lipase from P. alcaligenes or P. pseudoalcaligenes (<patcit id="pcit0010" dnum="EP0218272A1"><text>EP0218272 A1</text></patcit>), P. cepacia (<patcit id="pcit0011" dnum="EP0331376B1"><text>EP0331376B1</text></patcit>), P. stutzeri (<patcit id="pcit0012" dnum="GB1372034A"><text>GB 1 ,372,034</text></patcit>), P. fluorescens, Pseudomonas species strain SD 705 (<patcit id="pcit0013" dnum="WO9506720A"><text>WO95/06720</text></patcit> and <patcit id="pcit0014" dnum="WO9627002A"><text>WO96/27002</text></patcit>), P. wisconsinensis (<patcit id="pcit0015" dnum="WO9612012A"><text>WO96/12012</text></patcit>) or lipases from Bacillus species which includes lipases from B. subtilis (<nplcit id="ncit0002" npl-type="s"><text>Dartois et al. (1993), Biochemica et Biophysica Acta, 1131 , 253-360</text></nplcit>), B. stearothermophilus (<patcit id="pcit0016" dnum="JP64744992B"><text>JP64/744992</text></patcit>) or B. pumilus (<patcit id="pcit0017" dnum="WO9116422A"><text>WO 91/16422</text></patcit>). Other examples include lipase variants such as those described in <patcit id="pcit0018" dnum="WO9205249A"><text>WO92/05249</text></patcit>, <patcit id="pcit0019" dnum="WO9401541A"><text>WO94/01541</text></patcit>, <patcit id="pcit0020" dnum="EP407225A"><text>EP407225</text></patcit>, <patcit id="pcit0021" dnum="EP260105A"><text>EP260105</text></patcit>, <patcit id="pcit0022" dnum="WO9535381A"><text>WO95/35381</text></patcit>, <patcit id="pcit0023" dnum="WO9600292A"><text>WO96/00292</text></patcit>, <patcit id="pcit0024" dnum="WO9530744A"><text>WO95/30744</text></patcit>, <patcit id="pcit0025" dnum="WO9425578A"><text>WO94/25578</text></patcit>, <patcit id="pcit0026" dnum="WO9514783A"><text>WO95/14783</text></patcit>, <patcit id="pcit0027" dnum="WO9522615A"><text>WO95/22615</text></patcit>, <patcit id="pcit0028" dnum="WO9704079A"><text>WO97/04079</text></patcit> and <patcit id="pcit0029" dnum="WO9707202A"><text>WO97/07202</text></patcit>.
0048Preferred commercially available lipases are available under the trademarks Lipoclean®, Lipolase®, Lipolase® Ultra and Lipex®. LIPEX® is particularly preferred, and LIPEX® 100 T is further particularly preferred. The activity of commercial lipase is commonly expressed as Lipase Units or LU. Different lipase preparations may have different activities. For fungal lipases these may range from 2,000 to 2,000,000 LU per gram. Preferred compositions include lipase having 5 to 20000LU/g.
0049In order to prevent accidents and to alleviate safety concerns, commercial lipases are always coated with an inert material. Therefore, commercial lipases that are used for detergent powders, bars and tablets are in granular form containing very low amount of active lipase and balance of adjunct materials. Such granulates contain lipase concentrate, inorganic salt, binders and coating materials. They are free-flowing so that there is no lumping, and the granulate dissolve faster. Lipases are also available in liquid form, example LIPEX ® 100 L.
0050Preferred cleaning composition has 0.0001wt% to 0.3wt% lipase, more preferably from 0.0001 to 0.1wt% lipase and further preferably 0.0009wt% to 0.00186 wt% lipase.
Amylase:
0051Disclosed cleaning composition includes an amylase. Suitable amylases (alpha-amylase and/or beta-amylase) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of amylase suitable for the present invention includes alpha-amylase obtained from Bacillus species which includes special strain of B. licheniformis, described in more detail in <patcit id="pcit0030" dnum="GB1296839A"><text>GB 1,296,839</text></patcit>, or the Bacillus species strains disclosed in <patcit id="pcit0031" dnum="WO95026397A"><text>WO 95/026397</text></patcit> or <patcit id="pcit0032" dnum="WO00060060A"><text>WO 00/060060</text></patcit>. Other suitable examples of amylases are the variants described in <patcit id="pcit0033" dnum="WO9402597A"><text>WO 94/02597</text></patcit>, <patcit id="pcit0034" dnum="WO9418314A"><text>WO 94/18314</text></patcit>, <patcit id="pcit0035" dnum="WO9623873A"><text>WO 96/23873</text></patcit>, <patcit id="pcit0036" dnum="WO9743424A"><text>WO 97/43424</text></patcit>, <patcit id="pcit0037" dnum="WO01066712A"><text>WO 01/066712</text></patcit>, <patcit id="pcit0038" dnum="WO02010355A"><text>WO 02/010355</text></patcit> and <patcit id="pcit0039" dnum="WO02031124A"><text>WO 02/031124</text></patcit> (which references all incorporated by reference).
0052Commercially available amylases are Duramyl(TM), Termamyl(TM), Termamyl Ultra(TM), Natalase(TM), Stainzyme(TM), Stainzyme Plus(TM), Fungamyl(TM) and BAN(TM) (Novozymes A/S), Rapidase(TM) and Purastar(TM) (from Genencor International Inc.).
Mannanase:
0053Preferably the disclosed composition includes mannanase. Examples of suitable mannanase include those of bacterial or fungal origin. Preferably the mannanase is derived from a strain of a filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus (<patcit id="pcit0040" dnum="WO9425576A"><text>WO 94/25576</text></patcit>). <patcit id="pcit0041" dnum="WO9324622A"><text>WO 93/24622</text></patcit> disclosing a mannanase isolated from Trichoderma reese is also preferred. Mannanases have also been isolated from several bacteria, including Bacillus species. For example, <nplcit id="ncit0003" npl-type="s"><text>Talbot et al.,Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990</text></nplcit>) describes a beta-mannanase derived from Bacillus stearothermophilus. <nplcit id="ncit0004" npl-type="s"><text>Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551 -555 (1994</text></nplcit>) describes a beta-mannanase derived from Bacillus subtilis. <patcit id="pcit0042" dnum="JP03047076A"><text>JP-A-03047076</text></patcit> discloses a beta-mannanase derived from Bacillus sp. <patcit id="pcit0043" dnum="JP63056289A"><text>JP-A-63056289</text></patcit> describes the production of an alkaline, thermostable beta- mannanase. <patcit id="pcit0044" dnum="JP63036775A"><text>JP-A-63036775</text></patcit> relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase. <patcit id="pcit0045" dnum="JP08051975A"><text>JP-A-08051975</text></patcit> discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001. A purified mannanase from Bacillus amyloliquefaciens is disclosed in <patcit id="pcit0046" dnum="WO9711164A"><text>WO 97/11164</text></patcit>. Examples of preferred commercially available mannanases include Mannaway(TM) available from Novozymes A/S Denmark.
Surfactant:
0054Disclosed cleaning composition preferably includes a surfactant. The surfactant may be a soap or an anionic, nonionic, amphoteric, zwitterionic or cationic surfactant or mixtures thereof. In general, the nonionic and anionic surfactant may be chosen from the surfactants described in "<nplcit id="ncit0005" npl-type="b"><text>Surface Active Agents" Vol. 1, by Schwartz and Perry, Interscience 1949</text></nplcit>, <nplcit id="ncit0006" npl-type="b"><text>Vol. 2 by Schwartz, Perry and Berch, Interscience 1958</text></nplcit>, in the current edition of "<nplcit id="ncit0007" npl-type="b"><text>McCutcheon ' s Emulsifiers and Detergents" published by Manufacturing Confectioners Company</text></nplcit> or in "<nplcit id="ncit0008" npl-type="b"><text>Tenside-Taschenbuch", H.Stache, 2nd Edn., Carl Hauser Verlag, 1981</text></nplcit>.
0055Suitable anionic surfactant includes water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl includes the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic surfactant are sodium and potassium alkyl sulphates. Especially preferred are the sodium and potassium sulphates obtainable by sulphating higher C<sub>8</sub> to C<sub>18</sub> alcohols for example from tallow or coconut oil. Other preferred anionic surfactant include sodium and potassium alkyl C<sub>9</sub> to C<sub>20</sub> benzene sulphonates, particularly sodium linear secondary alkyl C<sub>10</sub> to C<sub>15</sub> benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
0056Most preferred anionic surfactants are sodium lauryl ether sulfate (SLES), particularly preferred are anionic surfactant with 1 to 3 ethoxy groups, sodium C<sub>10</sub> to C<sub>15</sub> alkyl benzene sulphonates (LAS) and sodium C<sub>12</sub> to C<sub>18</sub> alkyl sulphates (PAS). Alkyl ester suphonates such as methyl ester sulphonates (MES) may be preferably used for replacing a portion or completely replacing the anionic surfactant.
0057Other suitable surfactants are those described in <patcit id="pcit0047" dnum="EP328177A"><text>EP-A-328 177</text></patcit> (Unilever), which shows resistance to salting-out, the alkyl polyglycoside surfactants described in <patcit id="pcit0048" dnum="EP070074A"><text>EP-A-070 074</text></patcit> and alkyl monoglycosides. The surfactant chain may be branched or linear.
0058Suitable nonionic surfactants include the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Preferred nonionic surfactants are C<sub>6</sub> to C<sub>22</sub> alkyl phenol-ethylene oxide condensates, generally having 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C<sub>8</sub> to C<sub>18</sub> primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 50 EO. Preferably, the non-ionic is 10 to 50 EO, more preferably 20 to 35 EO. Alkyl ethoxylates are particularly preferred.
0059Soaps may also be present. The fatty acid soap used preferably contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration. Preferred soap may be derived from saturated and non-saturated fatty acids obtained from natural sources and synthetically prepared. Examples of such fatty acids include capric, lauric, myristic, palmitic, stearic, oleic, linoleic and linolenic acid. The anionic contribution from soap is preferably from 0 to 30 wt% of the total anionic.
0060Preferred surfactant systems are mixtures of anionic with nonionic surfactant, in particular the groups and examples of anionic and nonionic surfactants pointed out in <patcit id="pcit0049" dnum="EP346995A"><text>EP-A-346 995</text></patcit> (Unilever).
0061Amounts of amphoteric or zwitterionic surfactants can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic surfactants are used, it is generally in small amounts in combinations with anionic and nonionic surfactants.
0062The compositions according to the invention include 2 wt% to 70wt% of surfactant more preferably 10 to 30wt%. Preferred compositions include anionic or non-ionic surfactants. More preferred compositions include a mixture of the two.
Builders and Sesquestrants:
0063Disclosed cleaning composition may include builders. Builders may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
0064Examples of calcium sequestrant materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetraacetic acid.
0065Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
0066Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives and includes zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in <patcit id="pcit0050" dnum="EPO384070A"><text>EP-A-O, 384, 070</text></patcit>. It is preferred that when an insoluble inorganic builder for example zeolite is used, the size is in the range 0.1 to 10 µm (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex Malvern™).
0067When the cleaning composition is a detergent composition in the form of granular, spray- dried or dry-blended powder, the level of builder is preferably from 1 to 40 wt%.
0068Preferably the detergent composition includes zeolite and carbonate (including bicarbonate and sesquicarbonate) builders. The composition may also contain other builders including crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably sodium aluminosilicate. Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. The term phosphate includes diphosphate, triphosphate, and phosphonate species.
0069Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst). Builders or complexing agent as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid may also be included. Many builders are also bleach- stabilising agents by virtue of their ability to complex metal ions.
Other ingredients:
0070Disclosed cleaning composition may include one or more of other ingredients selected from bleach stabiliser, polymers, perfumes, fluorescers, soil release polymers, germicides, colourants and coloured speckles such as blue speckles. This list is not intended to be exhaustive.
0071Disclosed composition may include a bleach stabiliser. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), ethylenediamine disuccinate (EDDS), and the aminopolyphosphonates such as ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate (DETPMP).
0072When present the composition may include one or more polymers. Examples include carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. Suitable commercially available polymer includes Sokalan CP5 (ex BASF) which is a polyacrylate, namely maleic acid-acrylic acid copolymer, with a sodium salt.
0073Disclosed cleaning composition may also include perfumes. When present the perfumes could be of natural origin or synthetic. They include single compounds or mixtures of compounds. By perfume in this context is not only meant a fully formulated product delivering fragrance, but includes selected components of that fragrance, particularly those which are prone to loss, such as the so-called top notes. The perfume may be used in the form of neat oil or in an encapsulated form.
0074Disclosed composition may also include fluorescent agent (optical brightener). Fluorescent agents are well known and many fluorescent agents are commercially available. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt%, more preferably 0.01 to 0.1 wt%. Preferred fluorescent agent includes but not limited to distyryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, diamine stilbene disulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH and pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2- (4-styryl-3-sulfophenyl) -2H-napthol [I,2-d]triazole, disodium 4, 4'-bis {[(4-anilino-6- (N methyl-N-2 hydroxyethyl) amino 1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2' disulfonate and disodium 4,4'- bis (2-sulfoslyryl) biphenyl. Tinopal® DMS is the disodium salt of disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate. Tinopal® CBS is the disodium salt of disodium 4,4'-bis(2-sulfostyryl)biphenyl.
0075Disclosed composition may include a soil release polymer, for example sulphonated and unsulphonated PET/PEOT polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22. Especially preferred soil release polymer are the sulphonated non-end-capped polyesters described and claimed in <patcit id="pcit0051" dnum="WO9532997A"><text>WO9532997A</text></patcit> (Rhodia Chimie).
0076The invention will now be explained in details with the help of non-limiting exemplary embodiments.
<u>Examples</u>
0077<u>Evaluation of the preferred and the comparative compositions in removal of blackberry</u>
stain and tomato-sunflower stain:
a) Measurement of Soil Release Index (SRI)
0078Soil release index (SRI) is a measure of the amount of a stain present on fabric that is removed during a washing process. The intensity of any stain after washing is measured by means of a spectrophotometer and expressed in terms of the difference between the stained fabric and a clean fabric giving ΔE* for each stain. It is defined as ΔE* and is calculated as: <maths id="math0001" num=""><math display="block"><mrow><mi mathvariant="normal">ΔE</mi><mo>=</mo><msqrt><mrow><msup><mfenced separators=""><mi mathvariant="normal">L</mi><msub><mrow><mo>*</mo></mrow><mrow><mi mathvariant="normal">stain</mi><mo>−</mo><mi mathvariant="normal">after</mi></mrow></msub><mo>−</mo><mi mathvariant="normal">L</mi><msub><mrow><mo>*</mo></mrow><mrow><mi mathvariant="normal">clean</mi><mo>−</mo><mi mathvariant="normal">cloth</mi></mrow></msub></mfenced><mn mathvariant="normal">2</mn></msup><mo>+</mo><msup><mfenced separators=""><mi mathvariant="normal">a</mi><msub><mrow><mo>*</mo></mrow><mrow><mi mathvariant="normal">stain</mi><mo>−</mo><mi mathvariant="normal">after</mi></mrow></msub><mo>−</mo><mi mathvariant="normal">a</mi><msub><mrow><mo>*</mo></mrow><mrow><mi mathvariant="normal">clean</mi><mo>−</mo><mi mathvariant="normal">cloth</mi></mrow></msub></mfenced><mn mathvariant="normal">2</mn></msup><mo>+</mo><msup><mfenced separators=""><mi mathvariant="normal">b</mi><msub><mrow><mo>*</mo></mrow><mrow><mi mathvariant="normal">stain</mi><mo>−</mo><mi mathvariant="normal">after</mi></mrow></msub><mo>−</mo><mi mathvariant="normal">b</mi><msub><mrow><mo>*</mo></mrow><mrow><mi mathvariant="normal">clean</mi><mo>−</mo><mi mathvariant="normal">cloth</mi></mrow></msub></mfenced><mn mathvariant="normal">2</mn></msup></mrow></msqrt></mrow></math><img file="EP2931864B1_D0002.tif" /></maths>
0079L*, a*, and b* are the coordinates of the CIE 1976 (L*, a*, b*) colour space, determined using a standard spectrophotometer. ΔE* can be measured before and after the stain is washed, to give ΔE*bw (before wash) and ΔE*aw (after wash).
0080ΔE after wash is the difference in L a b colour space between the clean (unwashed) fabric and the stained fabric after wash. So a ΔE after wash of zero means that a stain is completely removed.
0081SRI is defined as: <maths id="math0002" num=""><math display="block"><mrow><mi>SRI</mi><mo>=</mo><mn>100</mn><mo>−</mo><mi mathvariant="normal">ΔE</mi><msub><mrow><mo>*</mo></mrow><mi>aw</mi></msub></mrow></math><img file="EP2931864B1_D0003.tif" /></maths>
0082A SRI of 100 means complete removal of a stain. The higher the SRI value, the greater is the stain removal potential.
0083The clean (or virgin) fabric is an "absolute standard" which is not washed. For each experiment, it refers to an identical piece of fabric to that to which the stain is applied. Therefore, its point in L a b colour space stays constant.
b) Preparation of the preferred and control detergent composition
0084A control detergent composition (Control) was prepared with a ratio between first bleach activator (TAED) to second bleach activator (DOBA) of 1:1. Control composition was formulated with no enzymes. Other standard laundry detergents were also included. The composition of Control is provided in Table 1.
0085Preferred detergent composition Ex 1 and Ex 2 had a ratio between first bleach activator (TAED) to second bleach activator (DOBA) of 1:1. Ex 1 was formulated with a combination of protease and amylase. Ex 2 was formulated with a combination of protease and lipase. The composition of preferred detergent compositions is provided in Table 1.
c) Washing protocol for determining SRI-values
0086For the determination of the SRI-values, a standard protocol was used, called the machine wash protocol.
0087Said machine wash protocol is as follows: <ol id="ol0004" compact="compact" ol-style=""><li>(a) A set of 6 cotton swatches were taken.</li><li>(b) Each cotton swatch was stained at two different and marked locations with a blackberry fruit stain and a Tomato sunflower oil stain.</li><li>(c) Colour of the two stains on the cotton swatches were measured before washing to get ΔE*<sub>bw</sub> (before wash).</li><li>(d) 7gpl of the control composition was added to a Miele Washing machine Softronic W4165.</li><li>(e) A normal white wash cotton intensive cycle 1 hour 56 minutes was selected with water temperature of 40°C. The total wash liquor used was 6 liters. The water used had a hardness 24° French hardness. The wash load was 1.5 kg.</li><li>(f) The wash load included the stained cotton swatches and two SBL soil strips and the liquor to cloth ratio was 4:1. The stained cotton swatches were not soaked before washing.</li><li>(g) Post washing the cotton swatches was dried overnight.</li><li>(h) The after wash reading of the stain on the 6 cotton swatches were recorded.</li></ol>
0088Similarly the stained cotton swatches were prepared and washed as described in the above steps (a) to (h) with a preferred composition and the reading of the swatches before and after wash was recorded.
<u>d) Measurement of the delta SRI values</u>
0089The delta SRI value after wash was determined as the difference between the absolute SRI value for a stained cotton swatch washed with the preferred composition and absolute SRI value for a stained cotton swatch washed with the control composition. <maths id="math0003" num=""><math display="block"><mrow><mi>Delta SRI</mi><mo>=</mo><mfenced><mi>absolute SRI of stained cotton swatch washed with preferred composition</mi></mfenced><mo>−</mo><mfenced><mi>absolute SRI of stained cotton swatch washed with control composition</mi></mfenced></mrow></math><img file="EP2931864B1_D0004.tif" /></maths>
0090A delta SRI value higher than the LSD (Least significant difference) value indicates a statistically significant difference between the absolute SRI values of stained swatch washed with the preferred composition and the absolute SRI value of stained swatch washed with control composition.
0091The SRI and the delta SRI values of the cotton swatches stained with blackberry fruit stain and tomato - sunflower oil stain and thereafter washed with the control or the preferred compositions with the machine wash protocol described above are provided in Table 2. <tables id="tabl0001" num="0001"><table frame="all"><title>Table1</title><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="93mm" /><colspec colnum="2" colname="col2" colwidth="16mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="15mm" /><thead><row rowsep="0"><entry valign="middle" /><entry align="center" valign="middle">Control</entry><entry align="center" valign="middle">Ex 1</entry><entry align="center" valign="middle">Ex 2</entry></row><row><entry valign="middle">Ingredients</entry><entry align="center" valign="middle">(wt%)</entry><entry align="center" valign="middle">(wt%)</entry><entry align="center" valign="middle">(wt%)</entry></row></thead><tbody><row><entry valign="middle">Na-LAS</entry><entry align="center" valign="middle">11.69</entry><entry align="center" valign="middle">11.69</entry><entry align="center" valign="middle">11.69</entry></row><row><entry valign="middle">Non-Ionic 7EO</entry><entry align="center" valign="middle">1.17</entry><entry align="center" valign="middle">1.17</entry><entry align="center" valign="middle">1.17</entry></row><row><entry valign="middle">Sodium Soap</entry><entry align="center" valign="middle">0.63</entry><entry align="center" valign="middle">0.63</entry><entry align="center" valign="middle">0.63</entry></row><row><entry valign="middle">Na disilicate</entry><entry align="center" valign="middle">6.60</entry><entry align="center" valign="middle">6.60</entry><entry align="center" valign="middle">6.60</entry></row><row><entry valign="middle">Soda Ash</entry><entry align="center" valign="middle">20.64</entry><entry align="center" valign="middle">20.64</entry><entry align="center" valign="middle">20.64</entry></row><row><entry valign="middle">Sodium Sulphate</entry><entry align="center" valign="middle">34.579</entry><entry align="center" valign="middle">34.129</entry><entry align="center" valign="middle">34.309</entry></row><row><entry valign="middle">SOKLAN CP5 (ex BASF, polymer of maleic acid and acrylic acid)</entry><entry align="center" valign="middle">0.39</entry><entry align="center" valign="middle">0.39</entry><entry align="center" valign="middle">0.39</entry></row><row><entry valign="middle">SCMC(sodium carboxy methyl cellulose)</entry><entry align="center" valign="middle">0.23</entry><entry align="center" valign="middle">0.23</entry><entry align="center" valign="middle">0.23</entry></row><row><entry valign="middle">Tinopal CBSx</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry></row><row><entry valign="middle">Zeolite</entry><entry align="center" valign="middle">2.613</entry><entry align="center" valign="middle">2.613</entry><entry align="center" valign="middle">2.613</entry></row><row><entry valign="middle">TAED</entry><entry align="center" valign="middle">1.35</entry><entry align="center" valign="middle">1.35</entry><entry align="center" valign="middle">1.35</entry></row><row><entry valign="middle">DOBA</entry><entry align="center" valign="middle">1.35</entry><entry align="center" valign="middle">1.35</entry><entry align="center" valign="middle">1.35</entry></row><row><entry valign="middle">Sodium Percarbonate</entry><entry align="center" valign="middle">12.00</entry><entry align="center" valign="middle">12.00</entry><entry align="center" valign="middle">12.00</entry></row><row><entry valign="middle">EDTMP Ca/Na salt (Dequest 2047)</entry><entry align="center" valign="middle">0.369</entry><entry align="center" valign="middle">0.369</entry><entry align="center" valign="middle">0.369</entry></row><row><entry valign="middle">Citric Acid anhydrous</entry><entry align="center" valign="middle">1.90</entry><entry align="center" valign="middle">1.90</entry><entry align="center" valign="middle">1.90</entry></row><row><entry valign="middle">EHDP (Dequest 2016D)</entry><entry align="center" valign="middle">0.246</entry><entry align="center" valign="middle">0.246</entry><entry align="center" valign="middle">0.246</entry></row><row><entry valign="middle">Antifoam</entry><entry align="center" valign="middle">0.40</entry><entry align="center" valign="middle">0.40</entry><entry align="center" valign="middle">0.40</entry></row><row><entry valign="middle">Savinase 24GTT (protease)</entry><entry align="center" valign="middle">0</entry><entry align="center" valign="middle">0.173</entry><entry align="center" valign="middle">0.173</entry></row><row><entry valign="middle">Lipex 100TB (lipase)</entry><entry align="center" valign="middle">0</entry><entry align="center" valign="middle">0</entry><entry align="center" valign="middle">0.10</entry></row><row><entry valign="middle">Stainzyme Plus 12GT (amylase)</entry><entry align="center" valign="middle">0</entry><entry align="center" valign="middle">0.10</entry><entry align="center" valign="middle">0</entry></row><row><entry valign="middle">Repelotex SF2</entry><entry align="center" valign="middle">0.123</entry><entry align="center" valign="middle">0.123</entry><entry align="center" valign="middle">0.123</entry></row><row><entry valign="middle">Dimorpholino Fluorescer Granular</entry><entry align="center" valign="middle">0.20</entry><entry align="center" valign="middle">0.20</entry><entry align="center" valign="middle">0.20</entry></row><row><entry valign="middle">Blue Carbonate Speckles</entry><entry align="center" valign="middle">1.00</entry><entry align="center" valign="middle">1.00</entry><entry align="center" valign="middle">1.00</entry></row><row><entry valign="middle">Moisture, Salts, NDOM</entry><entry align="center" valign="middle">2.87</entry><entry align="center" valign="middle">2.87</entry><entry align="center" valign="middle">2.87</entry></row><row><entry valign="middle">TOTAL</entry><entry align="center" valign="middle">100.00</entry><entry align="center" valign="middle">100.00</entry><entry align="center" valign="middle">100.00</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="19mm" /><colspec colnum="4" colname="col4" colwidth="17mm" /><colspec colnum="5" colname="col5" colwidth="17mm" /><thead><row><entry valign="top" /><entry valign="top">SRI</entry><entry valign="top">Delta SRI</entry><entry valign="top">LSD95p</entry><entry valign="top">LSD95n</entry></row></thead><tbody><row><entry namest="col1" nameend="col5" align="left">Tomato-sunflower oil stain</entry></row><row><entry>Control</entry><entry>88.0292</entry><entry>0.0000</entry><entry>3.9490</entry><entry>-3.9490</entry></row><row><entry>Ex 1</entry><entry>92.0873</entry><entry>4.0582</entry><entry>3.9490</entry><entry>-3.9490</entry></row><row><entry>Ex 2</entry><entry>89.9515</entry><entry>1.9224</entry><entry>3.9490</entry><entry>-3.9490</entry></row><row><entry namest="col1" nameend="col5" align="left">Blackberry fruit stain</entry></row><row><entry>Control</entry><entry>88.9981</entry><entry>0.0000</entry><entry>4.4120</entry><entry>-4.4120</entry></row><row><entry>Ex 1</entry><entry>94.6586</entry><entry>4.6605</entry><entry>4.4120</entry><entry>-4.4120</entry></row><row><entry>Ex 2</entry><entry>95.1835</entry><entry>5.1854</entry><entry>4.4120</entry><entry>-4.4120</entry></row></tbody></tgroup></table></tables>
0092The results in Table 2 clearly shows that the delta SRI of the preferred compositions (Ex 1 and Ex 2) having a combination of TAED, DOBA and enzymes protease and amylase (Ex 1) or protease and lipase (Ex 2) shows statistically significant improvement in removal of blackberry fruit stain when compared to the control composition. It is also clear from Table 2 that preferred composition (Ex2) is comparatively better than control composition in removal of tomato-sunflower oil stain and the preferred composition (Ex 1) shows statistically significant improvement in removal of tomato and sunflower oil stain when compared to the control composition.
Evaluation of the preferred and the comparative compositions in removal of sebum stains:
0093Commercially available detergent powder ArielTM Actilift UK (ex Proctor and Gamble) was used as Control.
0094The preferred granular detergent composition Comp 3 was prepared with a ratio between first bleach activator (TAED) to second bleach activator (DOBA) of 1:1 and having the enzymes protease, amylase and lipase. Other standard laundry detergents were also included. The formulation of Comp 3 is provided in Table 3.
0095One set of 6 cotton swatches stained with sebum stain was rinsed in the machine wash protocol as described above. The SRI values for the stained cotton swatch after wash were determined with the procedure as described above and the results were provided in Table 3. The Delta SRI value were also determined and provided in Table 4. <tables id="tabl0003" num="0003"><table frame="all"><title>Table 3</title><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="54mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><thead><row><entry valign="top">Ingredients</entry><entry valign="top">Comp 3 (wt%)</entry></row></thead><tbody><row><entry>Na-LAS</entry><entry align="center">11.69</entry></row><row><entry>sNon-Ionic 7EO</entry><entry align="center">1.17</entry></row><row><entry>Sodium Soap</entry><entry align="center">0.63</entry></row><row><entry>Na disilicate</entry><entry align="center">6.23</entry></row><row><entry>Soda Ash</entry><entry align="center">20.64</entry></row><row><entry>Sodium Sulphate</entry><entry align="center">34.129</entry></row><row><entry>CP5</entry><entry align="center">0.39</entry></row><row><entry>SCMC</entry><entry align="center">0.23</entry></row><row><entry>Tinopal CBSx</entry><entry align="center">0.02</entry></row><row><entry>Zeolite 4 A</entry><entry align="center">2.613</entry></row><row><entry>TAED</entry><entry align="center">1.35</entry></row><row><entry>DOBA</entry><entry align="center">1.35</entry></row><row><entry>Sodium Percarbonate</entry><entry align="center">12.00</entry></row><row><entry>EDTMP Ca/Na salt (Dequest 2047)</entry><entry align="center">0.369</entry></row><row><entry>Citric Acid anhydrous</entry><entry align="center">1.90</entry></row><row><entry>EHDP (Dequest 2016D)</entry><entry align="center">0.246</entry></row><row><entry>GAG</entry><entry align="center">0.40</entry></row><row><entry>Savinase 24GTT (protease)</entry><entry align="center">0.173</entry></row><row><entry>Lipex 100TB (lipase)</entry><entry align="center">0.10</entry></row><row><entry>Mannaway 4T (mannanase)</entry><entry align="center">0.082</entry></row><row><entry>Stainzyme Plus 12GT (amylase)</entry><entry align="center">0.100</entry></row><row><entry>Repelotex SF2</entry><entry align="center">0.123</entry></row><row><entry>Dimorpholino Fluorescer Granular</entry><entry align="center">0.20</entry></row><row><entry>Blue Carbonate Speckles</entry><entry align="center">1.00</entry></row><row><entry>Moisture, Salts, NDOM</entry><entry align="center">2.87</entry></row><row><entry>TOTAL</entry><entry align="center">100.00</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="all"><title>Table 4</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="30mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="19mm" /><colspec colnum="4" colname="col4" colwidth="17mm" /><colspec colnum="5" colname="col5" colwidth="17mm" /><thead><row><entry valign="top" /><entry valign="top">SRI</entry><entry valign="top">Delta SRI</entry><entry valign="top">LSD95p</entry><entry valign="top">LSD95n</entry></row></thead><tbody><row><entry>Sebum stain</entry><entry /><entry /><entry /><entry /></row><row><entry>Ariel™ Actilift UK</entry><entry>88.41</entry><entry>0</entry><entry>4.872</entry><entry>-4.872</entry></row><row><entry>Comp 3</entry><entry>93.39</entry><entry>4.979</entry><entry>4.872</entry><entry>-4.872</entry></row></tbody></tgroup></table></tables>
0096The results in Table 4 clearly shows that the preferred composition (Comp 3) having a combination of bleach activators TAED, DOBA and enzymes protease, lipase and amylase shows statistically significant improvement in removal of sebum stain when compared to the commercially available comparative composition (ArielTM Actilift UK ).
0097It will be appreciated that the illustrated examples provide for a detergent compositions having specific bleach activators and enzymes.
0098It should be understood that the specific forms of the invention herein illustrated and described are intended to be representative only as certain changes may be made therein without departing from the clear teachings of the disclosure.
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| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Opposition filedOppositionORIGINAL CODE: 0009260PLBI | PLBI | EP | |
| Opposition filed against patentOppositionR026 | R026 | DE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Deletion acc. to par. 5 (withdrawal of the translation of the ep patent)MK05 | MK05 | AT | |
| Invalidated european patentMG4D | MG4D | LT | |
| Patent invalid in the netherlands as no translation has been filedMP | MP | NL | |
| Dpma publication of mentioned ep patent grantGrantedR096 | R096 | DE | |
| Reference to at number (ep patent validated in austria)REF | REF | AT | |
| European patents granted designating irelandGrantedFG4D | FG4D | IE | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| Designated contracting statesAK | AK | EP | |
| European patent grantedGrantedFG4D | FG4D | GB | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Grant fee paidORIGINAL CODE: EPIDOSNIGR3GRAS | GRAS | EP | |
| Intention to grant announcedINTG | INTG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOSNIGR1GRAP | GRAP | EP | |
| Request for extension of the european patent (deleted)DAX | DAX | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Request for extension of the european patentAX | AX | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 2931864
- Publication, DOCDB
- 2931864
- Publication, EPODOC
- EP2931864
- Application
- 13799259
- Application, DOCDB
- 13799259
- Application, EPODOC
- EP20130799259
Titles3
- German
- REINIGUNGSZUSAMMENSETZUNG
- English
- CLEANING COMPOSITION
- French
- COMPOSITION DE NETTOYAGE
Classification
- CPC, 4
- C11D3/38618
- C11D3/38627
- C11D3/391
- C11D3/3917
- IPC, 2
- C11D3 386
- C11D3 39
Designated states38
- Contracting states, 38
- Albania
- Austria
- Belgium
- Bulgaria
- Switzerland
- Cyprus
- Czechia
- Germany
- Denmark
- Estonia
- Spain
- Finland
- France
- United Kingdom
- Greece
- Croatia
- Hungary
- Ireland
- Iceland
- Italy
- Liechtenstein
- Lithuania
- Luxembourg
- Latvia
and 14 moreShow fewer
- Monaco
- North Macedonia
- Malta
- Netherlands (Kingdom of the)
- Norway
- Poland
- Portugal
- Romania
- Serbia
- Sweden
- Slovenia
- Slovakia
- San Marino
- Türkiye
