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    • 专利摘要:
    Liquid detergent composition. The present invention is directed to a liquid detergent composition comprising at least one anionic surfactant, at least one ethoxylated glycerin ester, at least one organic solvent comprising glycerin, water in an amount not greater than 10% by weight calculated in relation to the entire detergent composition, and optionally a fatty acid in partially or fully neutralized form. Said composition is suitable for use in unit doses which also comprise a water-soluble capsule for washing clothes. Furthermore, the invention is directed to said unit dose and to the methods for obtaining the composition and the unit dose. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2539732A1
    申请号:ES201330978
    申请日:2013-06-28
    公开日:2015-07-03
    发明作者:Carmen Mª PEY GUTIÉRREZ；Blanca Nogués López
    申请人:Kao Corp SA；
    IPC主号:
    专利说明:

    DESCRIPTIONLIQUID DETERGENT COMPOSITION Technical field
    The present invention relates to a liquid detergent composition for machine washing of clothes, to liquid unit doses comprising said liquid detergent composition and water-soluble capsules, as well as to methods of obtaining the detergent and liquid unit doses. State of the art
    The laundry detergent compositions available on the market are mainly classified into two types according to their physical appearance: conventional liquid detergents, with a water content of between 90, 50, or even 30% by weight depending on whether they are standard formulas or concentrated formulas; and powdered detergents, in solid form and with very little water. Liquid formulations are usually more suitable for washing clothes at moderate temperatures, given the greater ease of dispersion in water and the more respectful character with the tissues of its components. Both powder formulations and liquid formulations require the end user to dose them and put them in the washing machine. Often part of the product is in its case
    or in the conduits that lead said product to the drum. One of the most recent innovations in this regard is the appearance of formats in single-dose units, which have the advantage for the consumer and user of being easier to handle and dose than traditional formats and that can be introduced directly into the drum of the washing machine .
    In the case of liquid detergents, the unit dose or unit dose format is based on the use of concentrated liquid formulas packaged in water-soluble capsules. Liquid detergent formulations suitable for such use have as their main specific technical requirement their low water content (necessary condition to avoid dissolving the capsule, which must be produced during washing when contacting with water).
    The formulation of detergent compositions with low water content is a technically complex challenge that often leads to problems in relation to the preparation of the appropriate formulations of the ingredients, that is, the adequate incorporation and miscibility of these in a homogeneous, stable composition. without turbidity problems and with an adequate viscosity.


    One of the solutions adopted to reconcile non-miscible ingredients is the use of capsules with designs that minimize the interaction between them. For example, international patent application WO2003052042 describes a liquid detergent composition contained in a water-soluble package in the form of polyhedron, preferably a tetrahedron. The composition consists of at least two layers, hydrophilic and hydrophobic, the hydrophobic layer being preferably at the top. By virtue of the shape of the package, the interface between the upper layer and the lower layer is minimized, resulting in greater stability of the ingredient in the upper layer.
    It should be said that the use of special designs in relation to the structure / shape of the capsule usually entails greater complexity in the manufacturing process of the capsule, and consequently additional economic costs.
    Another solution adopted to overcome these problems is the incorporation of solvents in the formulations. For example, EP1120459 discloses a detergent formula suitable for washing clothes comprising a substantially anhydrous isotropic liquid detergent formulation encapsulated in a water soluble film based on polyvinyl alcohol. The formulation is characterized by the use of propylene glycol, (non-renewable material of origin), an alkanolamine and ethanol (a volatile organic compound), and by the preferred use of ethoxylated C13 / C15 fatty alcohol surfactants (a chain surfactant hydrocarbon that is not of plant / animal origin). The solution described in said publication is one of the most used solutions to solve the problem of the miscibility of the ingredients of the detergent formula in a practically non-accusative medium. In fact, the majority of liquid detergents concentrated in the market in the form of water-soluble capsules are based on the use of propylene glycol and low molecular weight alkanolamines (especially monoethanolamine or triethanolamine) as solvents and ethoxylated C13 / C15 alcohol. However, it would be desirable to be able to have formulations based on materials of renewable origin.
    There are some approaches to more sustainable formulations such as the one described in patent application publication EP2441824 A1. Said publication refers to compositions free of volatile organic compounds. The term "volatile organic compounds" refers to organic chemical compounds characterized by significant vapor pressures. VOCs are generally relatively non-toxic, but due to their volatile, fat-soluble and flammable nature they can affect the environment and human health, chronic effects. Thus, EP2441824 A1 describes refers to a liquid cleaning composition comprising (i) at least one non-ionic surfactant, (ii) at least one anionic surfactant, (iii)


    at least one non-aqueous solvent, and (iv) water, characterized, as appropriate, by a water content of less than 10% by weight. The invention is especially directed to the use of nonionic surfactants of the alkyl (oligo) glycosides and / or ethoxylated fatty alcohols type. However, the examples specify the use of a solvent formed by the mixture of glycerin, propylene glycol and monoethanolamine in proportions in which the glycerin ratio: (propylene glycol + monoethanolamine) fails to overcome a 1.1: 1 ratio.
    Also publication EP1516917 is an example of the state of the art relevant to the present invention. The authors describe the problem associated with non-aqueous or low-water detergent compositions, and mention the drawbacks associated with the use of high amounts of non-aqueous, and expensive, solvents necessary to maintain a fluid fluid and homogeneous single phase liquid. In particular, they emphasize the fact that although fatty acids provide significant cleaning advantages, it is difficult to incorporate high levels of fatty acids in single phase liquid unit dose compositions with low water content due to their limited solubility. The technical problem treated is solved by neutralizing the liquid detergent composition so that the composition comprises a combination of non-neutralized soap and neutralized soap soap. The soap: neutralized soap molar ratio is 5: 1 to 1: 5, preferably 1: 1 to 1: 5.
    For all the above, liquid detergent compositions with compositions suitable for single-dose water-soluble capsules that have adequate detergency in a wide range of programs are needed. Brief Description of the Invention
    In the field of liquid detergent compositions for water-soluble capsules, there is a need to have compositions with a low water content, with an effective detergent surfactant system, such compositions being homogeneous compositions, stable, without turbidity problems, preferably transparent, capable to disperse in water at moderate temperatures and even in cold water quickly enough and based on ingredients primarily from renewable sources (raw materials of animal and / or plant origin).
    The present invention offers an efficient solution to the aforementioned requirements, providing a liquid detergent composition for washing clothes capable of satisfying the different technical requirements related to liquid compositions for water-soluble capsules as well as environmental requirements:


    - Water content less than 10%
    - Stable and transparent formulas
    - Compositions dispersible in water at room temperature and in cold water at
    high enough speed
    - Adequate detergent capacity
    - Reduction of solvents of non-renewable origin
    - Use of non-ionic surfactants of fundamentally natural origin (structure
    hydrocarbon of vegetable / animal origin) Thus, in one aspect the present invention provides a liquid detergent composition comprising:
    a) at least one anionic surfactant,
    b) at least one ethoxylated glycerin ester,
    c) at least one organic solvent comprising
    c1. glycerin
    c2. optionally one or more organic solvents other than glycerin
    d) water in an amount not exceeding 10% by weight calculated in relation to the
    entire detergent composition,
    e) optionally a partially or totally neutralized fatty acid
    In another aspect the present invention also provides a method for the preparation of liquid detergent compositions according to the invention. Said method comprises mixing the components of the composition of the invention at the appropriate temperature for homogenization, preferably at room temperature.
    The present invention also provides a liquid unit dose comprising a water-soluble capsule with at least one compartment and a liquid housed therein, characterized in that said liquid is the liquid detergent composition according to the invention.
    The present invention also provides a method for preparing a liquid unit dose according to the invention. Said method comprises encapsulating in a water-soluble capsule the liquid detergent composition of the invention.
    The present invention also provides a method for cleaning clothes comprising the use of water-soluble capsules containing a liquid detergent composition according to the invention.
    The present invention also provides the use of liquid unit doses of the invention for cleaning clothes.

    Detailed description of the invention
    The present invention relates to a liquid detergent composition comprising:
    a) at least one anionic surfactant,
    5 b) at least one ethoxylated glycerin ester, c) at least one organic solvent comprising c1. glycerin c2. optionally one or more organic solvents other than glycerin d) water in an amount not exceeding 10% by weight calculated in relation to the
    The entire detergent composition, e) optionally a partially or totally neutralized fatty acid.
    a) Anionic surfactant
    The present invention comprises a component (a) comprising at least one anionic surfactant.
    In accordance with the present invention, it is preferable that said anionic surfactant is selected from the group consisting of alkylarylsulfonates, alkyl ether sulphonates, primary or secondary alkenesulfonates, alkyl sulfates, alkyl ether sulfates, carboxylic alkyl acids and / or their salts and sulphosuccinates, or mixtures thereof .
    Preferably alkyl ether sulfates, alkylethercarboxylic acids and / or their salts and sulphosuccinates, more preferably alkyl ether sulfates.
    As anionic surfactants of the alkylaryl sulfonate type, alkali metal salts or alkanolamines of alkyl benzenesulfonates are preferred. The alkyl group in the alkylbenzenesulfonate preferably contains 8 to 16 carbon atoms and more
    Preferably 10 to 15 carbon atoms. A particularly preferred alkyl benzenesulfonate is dodecyl benzene sulfonate.
    An example of anionic surfactant of the commercially available alkyl benzenesulfonate type is the one that responds to the commercial reference SULFONAX® (INCI designation dodecylbenzene sulfonic acid), containing 95% active and marketed by
    30 KAO Chemicals Europe.


    As anionic surfactants of the alkyl sulfate type, C6-C22 alkyl sulfates are preferred, the metal salts of said C6-C22 alkyl sulfates being used as well as the ammonium salts or salts of organic amines with alkyl or hydroxyalkyl substituents. Alkyl sulfates with an alkyl chain containing between 10 and 18 carbon atoms, more preferably between 12 and 16 carbon atoms are preferred. Especially preferred are sodium lauryl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate and mono-, di- and triethanolamine lauryl sulfates, or mixtures thereof.
    Examples of commercially available alkyl sulfate anionic surfactants are those that respond to the trade reference EMAL ® 10N or EMAL ® 10G, (INCI name Sodium Lauryl Sulfate), containing 95% active ingredient, EMAL ® 30E (INCI name Sodium Lauryl Sulfate ), containing 30% active ingredient, and EMAL ® 40TE (INCI TEA name Lauryl Sulfate), containing 40% active ingredient, all of them marketed by KAO Chemicals Europe.
    As anionic surfactants of the alkyl ether sulfate type, C6-C22 alkyl sulfates containing 0.5 to 5, preferably 0.8 to 3 moles of ethylene oxide, are preferred, the metal salts of said C6-C22 alkyl ether being used sulfates as well as ammonium salts or salts of organic amines with alkyl or hydroxyalkyl substituents. Alkyl ether sulfates with an alkyl chain containing between 10 and 18 carbon atoms, more preferably between 12 and 16 carbon atoms, and containing 0.5 to 5, preferably 0.8 to 3 moles of ethylene oxide are preferred .
    Especially preferred are sodium lauryl ether sulfate, potassium lauryl ether sulfate, ammonium lauryl ether sulfate and mono-, di- and triethanolamine lauryl ether sulfates, containing 0.8 to 3 moles of ethylene oxide, or mixtures thereof.
    Examples of commercially available alkyl ether sulfate anionic surfactants are those that respond to the EMAL ® 270D or EMAL ® 270E (INCI Sodium Laureth Sulfate) trade name, containing 70% active ingredient and with an average degree of ethoxylation of 2, EMAL ® 227D or EMAL ® 227E (INCI name Sodium Laureth Sulfate), containing 27% of active ingredient and with an average degree of ethoxylation of 2, all of them marketed by KAO Chemicals Europe.
    As anionic surfactants of the alkyl carboxylic acid type and / or its salts, carboxylic alkyl ether acids and / or their salts containing 0.5 to 15, preferably 2 to 12 moles of ethylene oxide, are preferred, the metal salts of said C6-C22 carboxylic alkyl ether acids as well as ammonium salts or salts of organic amines with alkyl or hydroxyalkyl substituents.


    Preferred are carboxylic alkyl ether acids and / or their salts with an alkyl chain containing between 10 and 18 carbon atoms, more preferably between 12 and 18 carbon atoms, and containing from 0.5 to 15, preferably from 2 to 12 moles. of ethylene oxide.
    Especially preferred are carboxylic lauryl ether, sodium carboxylate lauryl ether, potassium carboxylate lauryl ether, ammonium carboxylate lauryl ether, carboxylic myristyl ether, sodium carboxylate myristyl ether, potassium carboxylate myristyl ether and myristyl ether 2 to carboxylate 2 moles to carboxylate 2 moles to carboxylate 2 moles of ethylene oxide, or technical mixtures thereof.
    Examples of anionic surfactants of the alkyl carboxylic acid type and / or their commercially available salts are those that correspond to the commercial reference AKYPO ® RLM 25 CA (INCI name Laureth-4 Carboxylic Acid), AKYPO ® RLM 45 N (INCI name Sodium Laureth- 6 Carboxylate), AKYPO ® SOFT 45 NV (INCI designation Sodium Laureth-6 Carboxylate), AKYPO ® RLM 70 (INCI designation Laureth-8 Carboxylic Acid), AKYPO ® RLM 100 (INCI designation Laureth-11 Carboxylic Acid), AKYPO ® SOFT 100 BVC (INCI name Sodium Laureth-11 Carboxylate) all of them sold by KAO Chemicals Europe.
    As anionic surfactants of the sulphosuccinate type, mono- and dialkyl C6-C22 sulfosuccinates and mono- and di-C6-C22 alkyl ether sulphosuccinates containing 0.5 to 10, preferably 1 to 5 moles of ethylene oxide, are preferred. or mixtures thereof, the metal salts of said mono- and di-C6-C22 alkyl sulfosuccinates and mono- and di-C6-C22 alkyl ether sulfosuccinates being used, as well as the ammonium salts or salts of organic amines with alkyl substituents or hydroxyalkyl
    Mono- and di-alkyl sulfosuccinates and mono- and di-alkyl ether sulfosuccinates with alkyl chains containing between 8 and 18 carbon atoms, more preferably between 12 and 18 carbon atoms are preferred.
    Especially preferred are sodium di-octyl sulfosuccinate, potassium di-octyl sulfosuccinate, sodium bis (2-ethylhexyl) sulfosuccinate, potassium bis (2-ethylhexyl) sulfosuccinate, di-isotridecyl sulfosuccinate, potassium di-isotridecyl sulphosuccinate, di-sodium mono-lauryl ether sulfosuccinate containing 0.5 to 5 moles of ethylene and di-potassium mono-lauryl ether sulfosuccinate containing 0.5 to 5 moles of ethylene, or mixtures thereof. Even more preferred are di-sodium mono-lauryl ether sulfosuccinate containing 0.5 to 5 moles of ethylene and mono-lauryl ether


    di-potassium sulfosuccinate containing 0.5 to 5 moles of ethylene, or mixtures thereof.
    Examples of commercially available sulphosuccinate type anionic surfactants are those that respond to the commercial reference SUCCIDET ® NES or SUCCIDET ® S 30 5 (INCI designation Disodium Laureth Sulfosuccinate), marketed by KAO Chemicals Europe
    b) Ethoxylated glycerin esters
    The present invention comprises a component b) ethoxylated glycerin ester comprising at least one component of the formula (II).
    (II)
    wherein said formula (II) comprises the components of formula i), ii), iii) and / or iv), being
    i) component represented by formula (II), where, independently, one of the symbols B1, B2, B3 represents an acyl group represented by –CO-R and the rest represents H
    Ii) component represented by formula (II) where, independently, two of the symbols B1, B2, B3 represent an acyl group represented by -CO-R and the remainder represents H;
    iii) component represented by formula (II) where, independently, each of the symbols B1, B2, B3 represents an acyl group represented by -CO25 R;


    iv) component represented by formula (II), where each of B1, B2 and B3 represent H;
    each of m, n or l independently represents a number from 0 to 40, the sum of m, n, l being in the range of 2 to 100, preferably 2 to 40.
    R ’represents H or CH3, preferably H,
    characterized in that in the acyl group represented by–CO-R, R represents an alkyl or alkenyl group, linear or branched, of 3 to 21 atoms ofcarbon, preferably 5 to 17 carbon atoms.
    In a preferred embodiment of the invention component b) according to the inventionit comprises at least two different components of formula (II): one of formula (i), (ii) or (iii),and another of formula (iv); the proportion by weight of the components [(i) + (ii) + (iii)] / (iv)between 30.0: 0.3 and 0.5: 3.0.In a more preferred embodiment of the invention component b) according toThe invention comprises components of formulas (i), (ii), (iii) and (iv); being the proportion incomponent weight [(i) + (ii) + (iii)] / (iv) between 15: 0.3 and 1: 3.0.
    It is also preferred that the degree of alkoxylation, that is, the sum of m, n and l bebetween 2 and 100, more preferably 2 and 40, even more preferable between 3 and 30, even moremore preferably between 4 and 25.
    In a preferred embodiment the degree of alkoxylation, that is, the sum of m, n and l isbetween 10 and 100 and the proportion by weight of the components [(i) + (ii) + (iii)] / (iv)It is greater than 50.
    In another preferred embodiment of the invention the degree of alkoxylation ie the sum ofm, n and l is between 3 and 7 and the proportion by weight of the components[(i) + (ii) + (iii)] / (iv) is less than 50.
    Examples of ethoxylated glycerin esters according to the invention availablecommercially they are those that respond to the commercial references Levenol® C-421(INCI designation Glycereth-2 Cocoate), Levenol® H&B (INCI designation Glycereth-2Cocoate), Levenol® F-200 (INCI designation Glycereth-6 Cocoate), Levenol® C-301(INCI designation Glycereth-7 Cocoate), EMANON® HE (INCI designation Glycereth-7Cocoate), Levenol® C-201 (INCI designation Glycereth-17 Cocoate), EMANON® XLF(INCI designation Glycereth-7 Caprylate / Caprate), EMANON® EVE (INCI designationGlycereth-7 Caprate / Caprylate).


    c) Organic solvent
    The present invention comprises a component c) solvent comprising
    c.1. glycerin
    5 c.2. optionally one or more organic solvents other than glycerinIn a preferred embodiment component c) comprises
    c.1. glycerin
    c.2. optionally one or more organic solvents other than glycerin with a weight ratio c.1: c.2 greater than 1.5, preferably greater than 2, more preferably greater
    10 to 2.4. In a more preferred embodiment component c) consists of
    c.1. glycerin, and
    c.2. one or more organic solvents that do not comprise propylene glycol.In another preferred embodiment component c) consists of glycerin.
    c.2. Organic solvent other than glycerin The present invention comprises a component (c) ocpionally comprising an organic solvent other than glycerin. Examples of c.2 solvents according to the invention include ethanol, isopropanol, 1,2-propanediol, 1,3-propanediol, propylene glycol, dipropylene glycol, methylpropane diol and mixtures thereof. You can also use others
    lower alcohols, C1-C4 alkanolamines, such as monoethanolamine, diethanolamine, methyldiethanolamine, methylisopropylamine and triethanolamine and mixtures thereof. In a preferred embodiment of the invention the solvent c) according to the invention is
    Choose from propylene glycol, dipropylene glycol, methylpropanoldiol, monoethanolamine. 25 diethanolamine, methyldiethanolamine and triethanolamine, more preferably propylene glycol, monoethanolamine and triethanolamine.
    e) Fatty acid
    The present invention optionally comprises a partially or totally neutralized fatty acid. According to the invention, fatty acids are preferably


    selected with a number of C atoms between 6 and 22. C6-C22 fatty acids can be selected from natural and / or synthetic origin. Natural acids are not normally produced in pure form and therefore are preferably used for the purposes of the invention in the form of mixtures. Consequently, the fatty acids are preferably selected from hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, 9-hexadecenoic acid, 9,12-octadecadienoic acid, 9,12,15octadecatrienoic acid, 5,8,11,14 - Eicosatetraenoic acid, 4,8,12,15,19 docosapentaenoic acid, coconut oil acid, oleic acid, resin oil acid, sunflower oil acid, flax seed oil acid, and / or oil acid of rapeseed.
    In one embodiment of the invention, the C6-C22 fatty acids are optionally alkoxylated, preferably ethoxylated with 1 to 20 moles of ethylene oxide, preferably with 1 to 10 moles of ethylene oxide.
    In a different embodiment of the invention the C6-C22 fatty acids are not ethoxylated.
    The composition of the invention.
    The compositions according to the invention provide a liquid detergent composition comprising:
    a) at least one anionic surfactant,
    b) at least one ethoxylated glycerin ester,
    c) at least one organic solvent comprising
    c1. glycerin
    c2. optionally one or more organic solvents other than glycerin
    d) water in an amount not exceeding 10% by weight calculated in relation to the
    entire detergent composition,
    e) optionally at least one partially or totally neutralized fatty acid
    In a preferred embodiment, the composition according to the present invention comprises the:
    e) at least one partially or totally neutralized fatty acid.
    In a particular embodiment the composition according to the invention comprises:
    f) at least one sequestering agent, preferably phosphonate and / or citrate.
    In another embodiment the composition according to the invention comprises:
    g) at least one optical bleach.


    In one embodiment the composition according to the invention comprises:
    h) at least one or more enzymes
    In a preferred embodiment of the invention, the compositions according to the invention
    5 comprise: -between 1% and 90%, preferably between 5% and 60%, more preferably between 10 and 40%, even more preferably between 20 and 30% of component a), -between 1% and 90%, preferably between 5% and 60%, more preferably between 10 and 40%, more preferably between 16 and 35% of component b), and
    10-between 1% and 30%, preferably between 15% and 25%, of component c); - between 0 and 40% of component e), preferably between 5 and 30% by weight, more preferably between 8 and 25%, referring to such ranges considering that the whole acid is neutralized, in relation to the calculation of the molecular weight thereof,
    15 - between 0 and 6 of component f), preferably between 0.05% and 5% - between 0 and 1% of component g), preferably between 0.001 and 0.3%
    - between 0 and 3%, more preferably between 0.0001 and 2% of component h), preferably mixture of protease, amylase and mannanase.
    each of the indicated amounts being expressed as a percentage by weight of the active substance referred to in relation to the total active weight of the composition.
    It is preferred that the ratio of the weight ratio between component (a) and component (b) is between 0.5 and 2.0%.
    25 The ratio of the ratio between component e) (in neutralized form) and the sum of components a + b is between 0 and 0.5.
    The ingredients g), h) and i) used in preferred embodiments of the invention are defined below. 30 f) sequestering agent
    The compositions of the present invention may optionally contain a sequestering agent additive.


    Suitable sequestering agents include polycarboxylate type compounds. Especially preferred are citrate sequestering agents, e.g. eg, citric acid and soluble salts thereof (particularly sodium salt). They are of particular importance for liquid detergent formulations for intensive cleaning because of their availability from renewable resources and their biodegradability. However, they have some difficulty in being incorporated into low water formulations such as those described in this invention.
    Other preferred sequestering agent type additives include, ethylenediamine diisuccinic acid and salts thereof (ethylenediamine diisuccinates, EDDS), ethylenediaminetetraacetic acid and salts thereof (ethylenediaminetetraacetates, EDTA), and diethylenetriaminepentaacetic acid and salts thereof (ethylenediaphthiaphene (ethylenediaphthiaphene) ethylenediaphthioethyleneterephthosphene (ethylenediaphthiaphene) ethylenediaphthio (ethylenediaphthiaphene) ethylenediaphthio (ethylenediaphthioethyleneterethiaphene) HEDP), ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP), aluminosilicates such as zeolites A, B
    or MAP; fatty acids or salts, preferably sodium salts thereof, preferably saturated and / or unsaturated C12-C18 fatty acids; and alkali or alkaline earth metal carbonates preferably sodium carbonate. g) optical bleaching agent
    The compositions of the present invention also contain additional components that can dye items that are being cleaned, such as fluorescent bleaching agent.
    Any fluorescent whitening agent suitable for use in a laundry detergent composition may be used in the composition of the present invention.
    Suitable fluorescent bleaching agents include derivatives of diaminoestylbenzene disulfonic acid and its alkali metal salts. Particularly preferred are salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2-isulfonic acid, and related compounds in which the morpholino group it is substituted with another moiety comprising nitrogen. Also preferred are brighteners of the 4,4'-bis (2-sulfostyryl) biphenyl type, which may optionally be combined with other fluorescent bleaching agents at the option of the formulator.
    Typical levels of fluorescent bleaching agents in the preparations of the present invention range from 0.001% to 1%, although a level between 0.1% and 0.3%, by mass, is usually used. Commercial supplies of acceptable fluorescent bleaching agents


    they can be purchased, for example from Ciba Specialty Chemicals (High Point, N.C.) and Bayer (Pittsburg, Pa.). h) enzymes
    The compositions of the present invention may contain one or more enzymes that provide cleaning performance and / or tissue care benefits.
    Detersive enzymes suitable for use in this invention include, but are not limited to, hemicellulases, peroxidases, proteases, other cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mananases, pectate liases, keratinases, reductases, oxidases, phenoxase , lipoxygenase, ligninases, pululanases, tanases, pentosanases, malanases, [beta] -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
    Enzymes can be used at levels recommended by suppliers such as Novozymes and Genencor.
    A typical combination is an enzyme cocktail that can comprise, for example, a protease and in conjunction with amylase.
    When present in a cleaning composition, the aforementioned additional enzymes may be present at levels of about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to about 0.5 % enzymatic protein by weight of the composition. Additives of the composition according to the invention
    In addition to the essential elements mentioned above, the composition according to the invention may comprise other components with the aim of improving any technical aspect of the composition such as stability, detergent capacity or sensory aspects related to consumer perception.
    Although it is not necessary for these elements to be present for the practice of the invention, the use of such materials is often very useful for making the formulation acceptable during consumer use.
    Examples of optional components include, but are not limited to: additional nonionic and anionic surfactants, amphoteric and hybrid ion surfactants, cationic surfactants,


    hydrotropes, fiber lubricants, reducing agents, enzyme stabilizing agents, defoamers, adjuvants, chemical whiteners, bleaching catalysts, dirt removal agents, anti-redeposition agents, color transfer inhibitors, buffers, dyes, fragrances, pro-fragrances, rheology modifiers, antifouling polymers, preservatives, insect repellent biocides, dirt repellents, water resistance agents, suspending agents, aesthetic agents, structuring agents, sanitizers, textile finishing agents, color fixers, agents wrinkle reducers, textile conditioning agents and deodorants. Fragrance
    The composition according to the invention may contain certain amounts of perfumes, fragrances, dyes or dyes or other components intended to improve its appearance or sensory experience of the user or intended to solve any practical issue.
    Suitable examples of perfumes according to the invention include aldehydes, esters, ketones and the like.
    Suitable aldehydes for the present invention may be one or more, but not limited to, of the following group of aldehydes: phenylacetaldehyde, p-methyl phenylacetaldehyde, pisopropyl phenylacetaldehyde, methylnonyl acetaldehyde, phenylpropanal, 3- (4-t-butylphenyl) -2 -methyl propanal, 3- (4-t-butylphenyl) -propanal, 3- (4-methoxyphenyl) -2-methylpropanal, 3- (4-isopropylphenyl) -2methylpropanal, 3- (3,4-methylenedioxyphenyl) -2- methylpropanal, 3- (4-ethylphenyl) -2,2-dimethylpropanal, phenylbutanal, 3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex-3-enal, heptanal, cis4-heptenal, 2- ethyl-2-heptenal, 2,6-dimethyl-5-heptenal (melonal), 2,6-dimethylpropanal, 2,4-heptadienal, octanal, 2-octenal, 3,7-dimethyloctanal, 3,7-dimethyl-2,6 -octadien-1-al, 3,7dimethyl-1,6-octadien-3-al, 3,7-dimethyl-6-octenal, 3,7-dimethyl-7-hydroxyoctan-1-al, nonanal, 6nonenal, 2 , 4-nonadienal, 2,6-nonadienal, decanal, 2-methyl decanal, 4-decenal, 9-decennial, 2,4-decadienal, undecanal, 2-methyldecanal, 2-methylundecanal, 2,6,10-trimethyl- 9-undecenal, undec-10-enil aldehyde, undec-8-dwarf, dodecanal, tridecanal, tetradecanal, anisaldehide, bourgenonal, cinnamic aldehyde ald, -amylcinnam-aldehyde, -hexyl cinnamaldehyde, methoxy cinnarondehyde, citroxy cinnaronylidene , isociclocitral, citronellil oxyacetaldehyde, cortexaldehyde, cumminic aldehyde, cyclamem aldehyde, florhydral, heliotropin, hydrotropic aldehyde, lilial, vanillin, ethyl vaniline, benzaldehyde, p-methyl benzaldehyde, 3,4-4-hydroxy-4-4-hydroxy-4 -methyl-pentyl) -3-cyclohexene-1-caroxaldehyde, 2,4


    dimethyl-3-cyclohexene-1-carboxaldehyde, 1-methyl-3-4-methylpentyl-3-cyclohexencarboxaldehyde, and p-methylphenoxyacetaldehyde.
    Examples of ketones suitable for the present invention may be one or more, but not limited to, of the following group of ketones: -damascona, -damascona, -damascona, damascenone, muscona, 6,7-dihydro-1, 1,2,3,3-pentamethyl-4 (5H) -indanone, cashmeran, cisjasmona, dihydrojasmona, methyl dihydrojasmonate, -ionone, -ionone, dihydro--ionone, methyl ionone, -iso-methyl ionone , 4- (3,4-Methylenedioxyphenyl) butan-2-one, 4- (4-hydroxyphenyl) butan-2-one, methyl -naphthyl ketone, methyl cedril ketone, 6-acetyl-1,1,2,4,4 , 7-hexamethyltetralin (tonalid), 1-carvone, 5-cyclohexadecen-1-one, acetophenone, decatone, 2- [2 (4-methyl-3-cyclohexenyl-1-yl) propyl] cyclopentan-2-one, 2-sec -butylcyclohexanone, -dihydro ionone, allyl ionone, -irone, -ketone, -irisone, acetanisola, geranyl acetone, 1- (2-methyl-5isopropyl-2-cyclohexenyl) -1-propanone, acetyl diisoamilene, methyl cyclocytrona, 4-t-pentyl cyclohexanone, pt-butylcyclohexanone, ot-butylcyclohexanone, ethyl amyl ketone, ethyl penti l Ketone, chin, methyl-7,3-dihydro-2H-1,5-benzodioxepine-3-one, fenchone, methyl naphthyl ketone, propyl naphthyl ketone and methyl hydroxynaphthyl ketone.
    The present invention also provides a liquid unit dose comprising a water-soluble capsule with at least one compartment and a liquid housed therein, characterized in that said liquid is the liquid detergent composition according to the invention.
    The composition according to the present invention is suitable for use in a water-soluble capsule or bag. Said bag is preferably formed of a film material that is soluble or dispersible in water. More preferably the film has a water solubility of at least 50%, preferably at least 75% or even at least 95%. Preferred bag-shaped materials are polymeric materials, preferably polymers that are formed into a film or sheet. The bag-shaped material can be obtained, for example, by casting, blow molding, extrusion or blow extrusion of the polymeric material, as is known in the art. Preferred polymers, copolymers or derivatives thereof suitable for use as a bag-shaped material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, poly (alkylene oxides), acrylamide, acrylic acid, cellulose, cellulose ethers, esters of cellulose, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids
    or peptides, polyamides, polyacrylamide, copolymers of maleic / acrylic acids, polysaccharides including starch and gelatin, natural gums, such as xanthan and carrageenan, polyacrylates and water soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose,


    dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates and most preferably are selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methylcellulose (HPMC) and combinations thereof, PVA films known under the Monosol M8630 brand, films known with the commercial reference PT film or the K series of films marketed by Aicello or VF-HP film marketed by Kuraray.
    Other additives include functional detergent additives that are released into the wash water, for example, organic polymer dispersants, etc.
    The bags can be of any size or shape, comprising at least one compartment. The compositions according to the invention are homogeneous if they need to use more than one compartment, however they are compatible with two-compartment or three-compartment or multi-compartment capsules.
    The water-soluble capsule according to the invention is preferably a polyvinyl alcohol capsule.
    The present invention also provides a method for the preparation of liquid detergent compositions according to the invention comprising mixing the components according to the invention at the temperature suitable for homogenization, preferably at room temperature.
    The present invention also provides a method for preparing the liquid unit dose according to the invention which comprises encapsulating the liquid detergent composition in a water-soluble capsule.
    Encapsulation methods:
    The encapsulation methods in the present invention relate to full load or also to partial loading of the capsule. Air or other gas may also be trapped in the capsule.
    The person skilled in the art knows the encapsulation methods, as an example two possible methods of encapsulating the liquid detergent composition in a water-soluble capsule are presented.
    (a) Horizontal encapsulation
    PVOH-based water-soluble packages can be manufactured according to any of the horizontal encapsulation procedures described in any of the documents


    WO-A-00/55044, WO-A-00/55045, WOA-00/55046, WO-A-00/55068, WO-A-00/55069 and WOA-00/55415.
    By way of example, a thermoforming process is described below in which a series of packages according to the invention are produced from two sheets of water-soluble material. In this respect, recesses are formed in the film sheet using a forming mold having a plurality of cavities with dimensions corresponding, in general, to the dimensions of the packages to be produced. In addition, a single heating plate is used for thermoforming the film for all cavities and in the same way a simple sealing plate is described.
    A first sheet of PVOH film is removed on a forming mold, so that the film is placed on the plurality of cavity formation in the mold. In this example, each cavity generally has a dome shape that has a round edge, the edges of the cavities are also rounded to eliminate all sharp edges that could damage the film during the formation or sealing stages of the procedure.
    Each cavity also includes a raised flange surrounding it. In order to maximize the strength of the package; The film is released in the forming mold in a fold-free form and with minimal tension. In the formation step, the film is heated to 100-120 ° C, preferably at about 110 ° C, for up to 5 seconds, preferably 700 microseconds. A heating plate is used to heat the film, in which the plate is placed superimposed on the forming mold.
    During this preheating stage, a vacuum of 50 kPa crosses the preheating plate to ensure close contact between the film and the preheating plate, this close contact ensures that the film is heated evenly and homogeneously (the extent of the vacuum depends of the thermoforming conditions and the type of film used, however, in the present context it was found that a vacuum of less than 0.6 kPa was adequate).
    Non-uniform heating results in a formed package that has weak points. In addition to the vacuum, it is possible to blow air against the film to force close contact with the preheating plate.
    The thermoformed film is molded into the cavities that blow the film from the heating plate by blowing and / or by absorbing the film into the cavities so that a plurality of recesses are formed in the film, which, once formed , they are preserved in their thermo-formed orientation by applying a vacuum


    through the walls of the cavities. This vacuum is maintained at least until the packages are sealed.
    Once the recesses have been formed and held in place by vacuum, a liquid detergent composition according to the invention is added to each of the recesses. Then, a second sheet of polyvinyl alcohol film is superimposed on the first line through the loaded recesses and heat sealed using a sealing plate. In this case, the heat-heating plate, which is generally flat, operates at a temperature of approximately 140-160 ° C and contacts the films for 1 to 2 seconds with a force of 8 to 30 kg / cm2, preferably of 10 to 20 kg / cm2. The raised tabs surrounding each cavity ensure that the films are sealed along the flange to form a continuous sack. The rounded edge of each cavity is formed, at least partially, by a resiliently deformable material, such as, for example, silicone rubber. This results in the application of less force on the inner edge of the sealing flange to avoid damage caused by heat / pressure on the film.
    Once sealed, the packages formed are separated from the web of sheet film using cutting means. At this stage, it is possible to release the vacuum in the mold and eject the formed packages from the forming mold. In this way the packages are formed, loaded and sealed while they are introduced into the forming mold. In addition, they can also be cut while in the forming mold.
    During the formation, loading and sealing stages of the process, the relative humidity of the atmosphere is controlled to approximately 50% humidity. This is done to maintain the heat seal characteristics of the film. When thinner films are handled, it may be necessary to reduce the relative humidity to ensure that the films have a relatively low degree of plasticization and are therefore harder and easier to handle.
    (b) Vertical encapsulation
    In the vertical encapsulated technique, a continuous tube of flexible plastic film is extruded. It is sealed, preferably by heat or ultrasonic sealing, at the bottom, loaded with the liquid composition, sealed again above the liquid film and then removed from the continuous tube by, for example, cutting.
    Those skilled in the art will know encapsulation procedures for other water-soluble films, such as those based on PVP or PEO.


    The present invention also provides a method for cleaning clothes comprising the use of water-soluble capsules containing a liquid detergent composition according to the invention.
    Examples 1. Concentrated compositions of liquid laundry detergents in accordance with the invention: preparation, appearance and dissolution capacity in water.
    Tables 1-3 summarize the compositions according to the invention (1-8), as well as the comparative examples (C1-C5), indicating the percentages of active material of each of the ingredients.
    The compositions are prepared at room temperature, following a normal process of mixing the components, stirring after each addition, until they are completely homogenized.
    Tables 1-3 also summarize the appearance and dissolution capacity in water of the concentrated compositions.
    The aspect is evaluated visually at room temperature, designating as "correct" that aspect in which the formula is transparent and homogeneous, and "incorrect" in case the composition has turbidity or phase separation.
    The dissolution capacity in water is evaluated visually and corresponds to the time it takes for the detergent composition to dissolve completely in water. 0.5g of the composition to be evaluated is weighed on a glass container 1.5cm high. Said container is in turn inserted into the base of a second larger glass container. 1000 mL of 20ºHF hard water (544ppm Ca2 + and 156ppm Mg2 +) are introduced into this second container, allowing it to slide slowly along the wall to avoid turbulence (speed around 3.0-3.5 mL / s). After one minute after adding the water, the mixture begins to stir at 200 rpm until complete dissolution of the composition to be evaluated. The solution in water is considered to be correct when the time does not exceed 160 s (average time corresponding to compositions of liquid detergents for water-soluble capsules present in the market).
    The results shown in Table 1 show that the compositions according to the invention (1,3) have a transparent and homogeneous appearance, unlike the comparative examples C2 and C3 based on ethoxylated fatty alcohol as a nonionic surfactant alternative to the ester of ethoxylated glycerin. In the case of comparative example C1 in the


    Since ethoxylated fatty alcohol is used, a transparent and homogeneous formulation is achieved by introducing a glycol type solvent into the composition. The dissolution capacity of those compositions that have a transparent and homogeneous appearance is correct in all cases.
    Also, the composition according to the invention (2) allows sodium citrate to be incorporated without losing the appearance and dissolution capacity in water required for this type of products.
    Table 1
    C1
    C2
    C3 1 2 3
    Chemical description%
    %
    %%%%
    Dodecylbenzene Acid 23.0
    23.0
    27.9
    23.0
    23.0
    27.9
    sulfonic 1
    C13-15 alcohol 7EO 2 18.2
    18.2
    22.1
    0.0
    0.0
    22.1
    Glycereth-6 Cocoate 3 0.0
    0.0
    0.0
    18.2
    18.2
    22.1
    Coconut Fatty Acid 14.9
    14.9
    7.4
    14.9
    14.9
    7.4
    Monoethanolamine (MEA) 9.0
    9.0
    8.1
    9.0
    9.0
    8.1
    Sodium citrate · 2H2O 0.0
    0.0
    0.0
    0.0
    4.0
    0.0
    Phosphonate 4 0.50
    0.50
    0.50
    0.50
    0.25
    0.50
    Optical bleach 5 0.15
    0.15
    0.15
    0.15
    0.15
    0.15
    Propylene Glycol 11.5
    0.00
    0.00
    0.00
    0.00
    0.00
    Glycerin 11.5
    23.0
    23.0
    23.0
    21.0
    23.0
    Water 6.5
    6.5
    6.0
    6.5
    7.6
    6.0
    Enzymes (protease, amylase, 1.6
    1.6
    1.6
    1.6
    1.6
    1.6
    tomorrow)
    Perfume, dyes, to 100
    to 100
    to 100 to 100 to 100 to 100
    minorities


    pH (100%) between 7.5 -8.5
    Appearance at room temperature ORXXOROROR
    Water dissolution capacity OR--OROROR
    1 SULFONAX at 95% a.m. supplied by KAO Chemicals Europe2 FINDET 1315/19 supplied by KAO Chemicals Europe3 LEVENOL F-200 supplied by KAO Chemicals Europe4 Diethylenetriamine penta (methylene phosphonate) sodium5 4, 4-Distyryl biphenyl derivative (DSBP)
    NOTES:The percentages shown in the table correspond to active matter.Referred to the appearance, the symbol "O" corresponds to transparent and stable compositions and
    5 the "X" to non-homogeneous compositions show turbidity or phase separation. The dissolution capacity of water is considered adequate "O" when it is at the level of market products. 2. Concentrated compositions of liquid laundry detergents
    according to the invention: effect of the chemical characteristics of ethoxylated glycerin esters
    Table 2 shows different examples of compositions according to the invention (4-6) in which the structural and chemical characteristics (ester chain length and degree of ethoxylation) of ethoxylated glycerin esters are varied.
    Table 2
    4 56
    Chemical description %%%
    Dodecylbenzene Sulfonic Acid 1 23.023.023.0
    Glycereth-7 Cocoate 2 18.20.00.0


    Glycereth-17 Cocoato 3 0.0
    18.2
    0.0 Glycereth-7 Caprilato / Caprato 4
    0.0
    0.0
    18.2 Coconut Fatty Acid
    14.9
    14.9 14.9 Monoethanolamine (MEA)
    9.0
    9.0
    9.0 Phosphonate 5
    0.50
    0.50
    0.50 Optical bleach 6
    0.15
    0.15
    0.15 Glycerin
    23.0
    23.0 23.0 Water
    6.5
    6.5
    6.5 Enzymes (protease, amylase, mannanase)
    1.6
    1.6 1.6 Perfume, dyes, minorities
    to 100 to 100
    to 100 pH (100%)
    between 7.5 -8.5 Aspect at room temperature
    O o
    O Water dissolution capacity
    O o o
    1 SULFONAX at 95% a.m. supplied by KAO Chemicals Europe2 LEVENOL C-301 supplied by KAO Chemicals Europe3 LEVENOL C-201 supplied by KAO Chemicals Europe4 EMANON XLF supplied by KAO Chemicals Europe5 Sodium diethylenetriamine penta (methylene phosphonate)6 4, 4-Distyryl biphenyl derivative (DSBP)
    3. Concentrated compositions of liquid laundry detergents according to the invention, based on lauryl ether sulfate.
    Table 3 shows some examples of compositions in which lauryl ether sulfate is used as an anionic surfactant. Examples 7 and 8 based on glycereth-6 cocoate provide homogeneous and stable formulations, and with good dissolution capacity. In contrast, comparative examples C4 and C5, based on ethoxylated fatty alcohol, give rise to non-homogeneous formulations, even using glycol type solvents in the composition (case of comparative example C4).
    Table 3


    C4 C5 7 8
    Chemical description%%%
    % Sodium Lauryl Ether Sulfate 1
    20.4
    20.4
    20.4
    20.4 C13-15 alcohol 7EO 2
    34.8
    34.8
    0.0
    0.0 Glycereth-6 Cocoate 3
    0.0
    0.0
    34.8 34.8 Coconut Fatty Acid
    5.5
    5.5
    5.5 5.5 Triethanolamine (ASD)
    9.8
    9.8
    9.8
    9.8 Phosphonate 4
    0.25
    0.25
    0.25
    0.25 Optical bleach 5
    0.10
    0.10
    0.10
    0.10 Propylene Glycol
    9.0
    0.0
    9.0
    0.0 Glycerin
    9.0
    18.0
    9.0
    18.0 Water
    5.5
    5.5
    5.5 5.5 Enzymes (protease, amylase,
    1.6
    1.6
    1.6
    1.6
    tomorrow)Perfume, dyes, minorities
    to 100 to 100 to 100
    to 100 pH (100%)
    between 7.5 -8.5 Aspect at room temperature
    X X O
    O Water dissolution capacity
    - O o
    1 EMAL 270 at 70% a.m. supplied by KAO Chemicals Europe 2 FINDET 1315/19 supplied by KAO Chemicals Europe 3 LEVENOL F-200 supplied by KAO Chemicals Europe 4 Diethylenetriamine penta (methylene phosphonate) sodium 5 4, 4-Distyryl biphenyl derivative (DSBP)
    4. Detergent capacity of the compositions according to the invention.
    Table 4 summarizes the experimental data corresponding to the evaluation of detersive efficacy. This efficiency is established by determining the percentage of dirt removal present in standard tissue samples. The efficacy tests are carried out


    using a Miele Softtronic W5722 front-loading washing machine under the following conditions: synthetic / mixing program, spin speed 800 rpm, wash water temperature 20ºC, water hardness 20ºHF (544ppm Ca2 + and 156ppm Mg2 +), 2 kg towel load of pre-described cotton and 35 grams of the detergent to evaluate. In each test
    5 of detergency different types of standard dirt are used, placing 3 specimens (dimensions 5x5 cm) for each type of fabric, in each wash.
    After the washing step, the tissue samples are allowed to air dry, at room temperature.
    Determination of detersive efficacy is done by colorimetric measurements on
    10 standard soiled tissue before and after the washing process. These measurements are made using a colorimeter, for example the Datacolor International Spectraflash 600.
    Detersive efficacy is expressed as% detergency, calculated from the following mathematical formula, in which the CIE L * (Brightness) parameter is involved, coming from the colorimetric measurement.
    ∗ ∗
    ∗ −�
    % = · 100
    ∗ ∗
    � � −�
    15 The percentage of detergency detailed in the table corresponds to the average value corresponding to the three specimens used for each type of tissue.
    The values shown in Table 4 demonstrate that the composition according to the
    The invention (example 1) has a suitable cleaning power.
    Table 4:% Detergency
    one
    Standard fabric reference %
    E-101 37
    wfk-10TE 57

    E-123 fifty


    E-104
    E-101 Olive oil / Active carbon on cotton supplied by Empa Testmaterials
    E-104 Olive oil / Active carbon on cotton / polyester supplied by Empa Testmaterials
    wfk-10TE Clay on cotton supplied by Empa Testmaterials
    Specific dirt mix to assess low temperature detergency on cotton fabric, supplied by EMPA Testmaterials

    权利要求:
    Claims (12)
    [1]
    1. Liquid detergent composition comprising:
    5 a) at least one anionic surfactant,b) at least one ethoxylated glycerin ester,c) at least one organic solvent comprising
    c1. glycerin c2. optionally one or more organic solvents other than glycerin 10 d) water in an amount not exceeding 10% by weight calculated in relation to the entire detergent composition, e) optionally a partially or totally neutralized fatty acid
    [2]
    2. Liquid detergent composition according to claim 1 which additionally
    15 comprises: f) at least one sequestering agent, preferably phosphonate and / or citrate.
    [3]
    3. Composition according to claim 1 or 2 further comprising: g) at least one optical bleach.
    [4]
    4. Composition according to any one of claims 1 to 3 which
    additionally it includes:h) at least one or more enzymes.
    5. Composition according to any one of claims 1 to 4 wherein component a) is selected from alkyl ether sulfates, alkylethercarboxylic acids and / or their salts and sulphosuccinates, more preferably alkyl ether sulfates.
    [6]
    6. Composition according to any one of claims 1 to 5 wherein the weight ratio c1: c2 is greater than 1.5.
    [7]
    7. Composition according to claim 6 wherein the ratio c1: c2 is greater than 2, more preferably greater than 2.4.
    Composition according to any one of claims 1 to 7 wherein the solvent c2 is not propylene glycol.

    [9]
    9. Method for the preparation of liquid detergent compositions as defined in any one of claims 1 to 8 which comprises mixing the components according to the invention at the temperature suitable for their
    5 homogenization, preferably at room temperature.
    [10]
    10. Liquid unit dose comprising a water-soluble capsule of at least one compartment and a liquid housed therein, characterized in that said
    Liquid is a liquid detergent composition according to any one of claims 1 to 8.
    [11]
    eleven. Liquid unit dose according to claim 10 wherein the water-soluble capsule is a polyvinyl alcohol capsule.
    [12]
    12. Method for the preparation of a liquid unit dose as defined in claims 10 or 11 comprising encapsulating in a water-soluble capsule the liquid detergent composition according to any one of claims 1 to 9.
    13. Method for cleaning clothes comprising the use of liquid unit doses defined in any of claims 10 or 11.
    [14]
    14. Method for cleaning clothes comprising the use of liquid unit doses according to any of claims 1 to 8.
    [15]
    15. Use of a composition according to any one of claims 1 to 8 as a component of liquid unit doses for cleaning clothes.
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    同族专利:
    公开号 | 公开日
    JP2016525159A|2016-08-22|
    EP3015539A4|2017-02-15|
    US9611447B2|2017-04-04|
    EP3015539B1|2018-05-02|
    EP3015539A1|2016-05-04|
    HUE039180T2|2018-12-28|
    BR112015032697A2|2017-07-25|
    JP6535325B2|2019-06-26|
    MX2015017134A|2016-07-08|
    CA2914906C|2021-10-26|
    NO3015539T3|2018-09-29|
    ES2677649T3|2018-08-06|
    WO2014207286A1|2014-12-31|
    CA2914906A1|2014-12-31|
    DK3015539T3|2018-06-06|
    US20160130530A1|2016-05-12|
    BR112015032697B1|2022-01-11|
    ES2539732B1|2016-02-05|
    PL3015539T3|2018-10-31|
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    ES201330978A|ES2539732B1|2013-06-28|2013-06-28|Liquid detergent composition|ES201330978A| ES2539732B1|2013-06-28|2013-06-28|Liquid detergent composition|
    MX2015017134A| MX2015017134A|2013-06-28|2014-06-27|Liquid detergent composition.|
    US14/898,671| US9611447B2|2013-06-28|2014-06-27|Liquid detergent composition comprising an ethoxylated glycerol compound|
    CA2914906A| CA2914906C|2013-06-28|2014-06-27|Liquid detergent composition comprising an ethoxylated glycerol compound|
    PL14818514T| PL3015539T3|2013-06-28|2014-06-27|Liquid detergent composition|
    BR112015032697-8A| BR112015032697B1|2013-06-28|2014-06-27|LIQUID DETERGENT COMPOSITION|
    DK14818514.3T| DK3015539T3|2013-06-28|2014-06-27|LIQUID DETERGENT COMPOSITION|
    JP2016522669A| JP6535325B2|2013-06-28|2014-06-27|Liquid detergent composition|
    HUE14818514A| HUE039180T2|2013-06-28|2014-06-27|Liquid detergent composition|
    NO14818514A| NO3015539T3|2013-06-28|2014-06-27|
    EP14818514.3A| EP3015539B1|2013-06-28|2014-06-27|Liquid detergent composition|
    PCT/ES2014/070529| WO2014207286A1|2013-06-28|2014-06-27|Liquid detergent composition|
    ES14818514.3T| ES2677649T3|2013-06-28|2014-06-27|Liquid detergent composition|
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