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    • 专利摘要:
    CONCENTRATED ALKALINE LIQUID DETERGENT COMPOSITION. The present invention relates to a concentrated alkaline liquid detergent composition comprising: (a) 5 to up to 60% by weight of surfactant comprising anionic surfactant and optionally nonionic surfactant and optionally amphoteric surfactant and optionally soap of which at least 35% of the total surfactant it is non-soap anionic surfactant, (b) at least 30% water, (c) at least 0.25% by weight soil release polymer, characterized in that: (i) the soil release polymer has the formula ( I), and X-[(OCH 2 CH 2 } q -]-block -[(OCH 2 CH(CH 3 )) p ]-[(OC(O)-G 1 - C(O)O-G 2 ) n ]-OC(O)-G 1 - C(O)O-[((CH 3 )CHCH 2 0) p -]-block - [(CH 2 CH 2 0) q ]-X (I), wherein the G 1 components are all 1,4-phenylene components; the G 2 components are all ethylene components substituted with C 1-4 alkyl, each X is C 1-4 alkyl, preferably methyl or n-butyl; each q goes from 12 to 120; each p ranges from 1 to 10, preferably from 2 to 5; and n ranges from 2 to 10.
    公开号:BR112015001487B1
    申请号:R112015001487-9
    申请日:2013-07-02
    公开日:2021-05-04
    发明作者:Julie Bennett；Alyn James Parry
    申请人:Unilever Ip Holdings B.V.；
    IPC主号:
    专利说明:

    Field of Invention
    [0001] The present invention relates to concentrated alkaline aqueous liquid detergent compositions with low intrinsic foaming and, in particular, to liquids comprising substantial dirt release polymer (SRP) for polyester fabrics. In this description, unless otherwise indicated, no distinction is made between polymer and oligomer. Both are called polymers. Background of the Invention
    [0002] It has been proposed to use polyester based SRPs in detergent compositions, especially in laundry detergent compositions to promote improved dirt removal from polyester fabrics. Such polymers may have a polyester middle block with one or two polyethylene glycol end blocks attached to the middle block via ester bonds.
    [0003] The document US4759876 (Colgate) proposes an aqueous liquid concentrate comprising such SRP. Preferred liquids have about 80% by weight of the surfactant system as non-ionic, which provides such compositions with low foaming on wash and, in addition, is expected to provide concentrated compositions with low intrinsic foaming. The formulations are formulated to be acidic and free from triethanolamine to protect the SRP.
    [0004] The SRP used is a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate of molecular weight 22,000, with polyoxyethylene having a molecular weight of 3,400, with the molar ratio of polyethylene terephthalate units to polyoxyethylene terephthalate units being about 3: 1, and the ratio of ethylene oxide to phthalic component in the polymer being about 22:1.
    [0005] The document WO2009/153184 (Unilever) proposes to dose a surfactant in programmed wash at low levels so that the level of surfactant in the wash is lower than normal. This would lead to consequent unsatisfactory washing performance resulting from low levels of surfactant in the wash, which is stimulated by the inclusion of unusually high levels of specific polymers and enzymes in the liquid. A key polymer, preferably included at high levels in the composition, is the substantial SRP for polyester. The one used in the examples of WO2009/153184 belongs to polyester chemistry (terephthalic acid/propanediol condensation polymer with methoxy end PEG 750). It is sold under the brand name TexCare® SRN 170 by Clariant. The examples in this document suggest the use of a higher ratio of non-soap anionic surfactant to anionic compared to that found in the examples in US4759876.
    [0006] Detergent liquids concentrated following the principles established in WO2009/153184 can present high levels of intrinsic foam formation. The term intrinsic foaming is intended to mean that the concentrated composition itself forms a foam layer when subjected to aeration. This is a problem in the handling of compositions in the factory, particularly in the filling operation. However, this is a considerable problem when the consumer is dosing the composition using a volume measure, as is often the case with detergent compositions used in laundry washing. If a composition foams when it is dispensed through a nozzle or similar dispensing device, the mass dose will be too low relative to the measured volumetric dose and the consumer will not get the performance expected from their product. Compositions with increased levels of solvent-avid ingredients, in particular sequestrants, can exhibit even higher foaming. High levels of perfume, incorporation of ethoxylated polyethyleneimine, and use of amino-based counterions also tend to make foaming more significant.
    [0007] It is possible to use an additional defoamer system. The introduction of silicone defoamer can be considered, but it cannot be stably incorporated into low-viscosity compositions that are more prone to intrinsic foaming. Also, if an external structuring system is to be used to suspend the silicone, it should add cost and increase valuable formulation space. Thus, a more efficient solution is desired.
    [0008] EP661933 (Sasol) describes non-ionic amphiphilic oligoesters which have dirt release properties after storage in alkaline detergent liquid. In the exemplary formula, a PO block of up to 10, but preferably 2 to 4, can be added between the middle block esters and the PEG end block. The material tested has 4 such repeating PO units added. The middle block is essentially 1,4-phenylene and 1,2-propylidene. Neither TEA nor ethoxylated polyethyleneimine is used with these polymers. The examples show that the dirt release performance of this polymer after storage is superior to a polymer that does not have a PO block. Invention Summary
    [0009] According to the present invention there is provided a concentrated alkaline liquid detergent composition comprising: (a) 5 to 60% by weight of surfactant comprising anionic surfactant and optionally nonionic surfactant and optionally amphoteric surfactant and optionally soap, of which at least 35% of the total surfactant is non-soap anionic surfactant, (b) at least 30% by weight of water, (c) at least 0.25% by weight of soil release polymer, characterized by the fact that: (i) the soil release polymer has the formula (I), and X-[(OCH2CH2}q-]-block-[(OCH2CH(CH3))p]-[(OC(O)-G1-C(O)O - G2)n]-OC(O)-G1-C(O)O-[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X (I), where the G1 components are all 1,4-phenylene components, each X is C1-4 alkyl, preferably methyl or n-butyl; each q ranges from 12 to 120, each p ranges from 1 to 10, preferably from 2 to 5; and n ranges from 2 to 10. The notation "block" is used herein as it is known in polymer chemistry to mean r that the parts of the main chain, each side of this imaginary division - for example, [(OCH2CH2)q] and [(OCH2CH(CH3))p], are not randomly polymerized, but they are formed as homogeneous blocks.
    The compositions are especially usable as laundry detergent compositions.
    [0011] Preferably, the compositions comprise at least 0.5% by weight of dirt release polymer.
    Preferably, the compositions comprise at least 0.5% by weight of triethanolamine, more preferably they comprise at least 1% by weight of triethanolamine.
    [0013] More preferably, the compositions comprise at least 0.5% by weight of soil release polymer and at least 1% by weight of triethanolamine.
    [0014] It has been surprisingly found that the soil release polymers of polyesters of formula (I) impart significant intrinsic anti-foaming benefits to concentrated detergent liquids.
    [0015] Preferably, the composition further includes at least 2% by weight of non-ionic alkoxylated polyethyleneimine with at least 3 moles of alkoxylation by nitrogen.
    [0016] The block polymers of formula (I) are linear block polyesters, n preferably ranging from 3 to 9, especially for polymers made from dimethyl terephthalate and 1,2-propylene glycol.
    [0017] The most preferred linear block polyesters are those in which n ranges from 6 to 8.
    [0018] More preferably, in formula (I), p is 2 and q ranges from 18 to 60.
    [0019] In one embodiment, at least 10% of the G2 groups are replaced with dimethylene. This optional modification helps to keep the esters in the middle block intact as fabric substantivity and otherwise soil release properties are lost and the improved hydrolysis resistance is of no practical significance. This modification to the middle block appears to make no difference to the anti-foaming properties of the polymer.
    [0020] The end blocks -[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X can both be present. Alternatively only one of the two possible end blocks needs to be present. Throughout this description and claims reference is made to end blocks as including the situation where an end block, or other blocks, is missing, unless the context requires otherwise. Preferably, the polymer has two end blocks. If one of the end blocks is missing, then the terminating group X will similarly be missing at that end.
    Alkaline liquid detergent compositions may comprise polymer (d) in amounts of up to 15% by weight, preferably from 1 to 10% by weight, more preferably from 1.5 to 7% by weight.
    [0022] Preferably, the concentrated alkaline liquid detergent composition is isotropic. The composition may comprise at least 5% by weight of non-soap anionic surfactant. Suitably, the liquid may comprise linear alkyl benzene sulfonate (LAS), non-ionic alkyl ether sulfate (AES) and optionally an amine or betaine oxide, the LAS being formed from LAS acid, neutralized, at least in part, with TEA . Amines can also be used as the counterion for AES. For stability reasons, it is preferable to keep the total alkali metal ion level at a value less than 1% by weight of the composition.
    [0023] To maximize the benefit of other cleaning technologies that are essentially or optionally included in the liquid, especially anionic surfactant, the liquid is alkaline. It is preferred that the maximum pH of the concentrate composition is 8.4, more preferably at most 8.2. Detailed Description of the Invention
    [0024] The present invention is a combination of a select group of polyester dirt release polymers with amazing anti-foaming properties and a liquid detergent base that has high intrinsic foaming.
    [0025] All percentages are percentages by weight unless otherwise stated or when the context makes it obvious that something else is intended. Polyester dirt release polymer (with anti-foaming properties)
    [0026] The present invention requires the selection of a dirt release polymer with a polyester middle block and its incorporation into a concentrated alkaline detergent liquid comprising surfactant and triethanolamine.
    [0027] SRPs having appropriate anti-foaming effect have the formula (I): X-[(OCH2CH2}q-]-block-[(OCH2CH(CH3))p]-[(OC(O)- G1-C(O)O-G2)n]-OC(O)-G1-C(O)O-[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X (I) X-[(OCH2CH2}q-]-block-[(OCH2CH(CH3))p]- and -[((CH3)CHCH2O)p-]-block- [(CH2CH2O)q]-X, in general, are connected at the ends of the polymer backbone or at the middle block. The middle block is responsible for making the polymer substantial for fabric, particularly for polyester fabrics. The terminations of large blocks of EO groups are highly hydrophilic and can be considered to be they leave the fabric to provide the surface modification that promotes dirt release. Thus, it is an essential aspect of the polymers of the present invention that they have EO end block(s) The polymer will be non-ionic. Ionic polymers are generally unstable in alkaline liquid detergent concentrates. Middle Block or Main Chain
    [0028] The middle block -[(OC(O)-G1-C(O)O-G2)n]-OC(O)-G1-C(O)O- is responsible for making the polymer substantive to tissue , particularly for polyester fabrics. It has little effect on the anti-foaming properties of the polymer.
    [0029] In practice, the esters in the middle block can be formed anyway.
    [0030] The G1 components comprise 1,4-phenylene components.
    [0031] The G2 components are substituted with ethylene components having C1-4 alkyl substituents. A preferred mono-substituted ethylene component is 1,2-propylene, which is derived from the condensation of 1,2-propane diol.
    For G2 components, the most preferred substituted ethylene components are monomethyl substituted G2 formed from 1,2-propylene diol, and substituted dimethyl G2 formed from 2,3-butylene diol. The use of substituted 1,2-dimethyl ethylene shows superior protection of adjacent ester bonds, which is due to the fact that the case will always occur where there is a methyl group on the carbon atom adjacent to the ester. This contrasts with the situation of the monomethyl material formed from 1,2-propane diol. In this case, the methyl group may be arranged by itself adjacent to the ester or it may alternatively be arranged by itself on the ethylene carbon which is located more remotely from the ester.
    [0033] 2,3-Butylene is a meso-stereoisomeric compound. It is believed that, once reacted to form the polymer chain, the different shapes behave similarly as far as the difficulty of hydrolysis is involved. The optically active RR or SS diastereoisomers are preferred over the RS (meso) diastereoisomer. Thus, the preferred form of the 2,3-butylene glycol used is the optically active forms RR or SS alone, or as a racemic mixture. In practice, it has been verified that the mixture of meso and racemic forms gives satisfactory results.
    [0034] A preferred diol to form the desired G2 group may be selected from the group of diols of formula (II): Syn n+1, n+2 alkylene diol (II) n being an integer from 1 to c-3, where c is the number of carbon atoms in the alkylene chain
    [0035] The most preferred diols are syn 2,3-butane diol and 1,2-propane diol.
    [0036] G2 can comprise up to 20 mol% of components derived from 2,3-butane diol derivatives, i.e. an ethylene component with a substituted methyl group on each carbon in the main chain.
    [0037] It has been found that the value of n needs to be at least 2 so that the anti-foaming polymers used in the invention have sufficient substantivity for polyester. The maximum value of n can range up to 26. By comparison, polyesters used in fiber making typically have a much higher molecular weight with n ranging from 50 to 250. Typically, n ranges from 2 to 16, preferably from 4 to 9 , most preferably from 6 to 8. In general, the higher the value of n, the less soluble the polymer. Because it is an average, n is not necessarily an integer for the polymer as a whole. End Block
    [0038] The following examples suggest that it is the propoxylation of the end blocks that gives the anti-foaming benefit. The degree of propoxylation should be 1 to 10 propylene oxide units on average per end-block. It takes place in a block. The 2 to 5 PO range is preferred because it has the right balance of anti-foaming properties. The anti-foaming benefit does not appear to increase linearly with the amount of propoxylation.
    [0039] The polymers have an EO block that has more alkoxy units than the PO block, preferably the EO block has at least 1.5 times the number of moles or units (q) compared to the PO block (p ), more preferably at least 5 times, and even 10 times the number of moles (p), or more, q is at least 6, and is preferably at least 10. The value of q usually ranges from 18 to 80. Typically , the value of q is in the range from 30 to 70, preferably from 40 to 70.
    [0040] The X-termination at the terminal end in EO blocks is preferably as small as possible. X is preferably methyl, ethyl or n-butyl and most preferably methyl or n-butyl.
    [0041] As the value of q increases, the value of n in the middle block must be increased so that the polymer will deposit well on the fabric during laundry washing.
    [0042] As p and q are produced through anionic polymerization routes, this results in blocks with discrete block lengths, in contrast to the middle block which is made through polycondensation routes. Molecular weight
    [0043] Preferred polymers for use in liquid detergent compositions have molecular weights (PM) within the range of 1,000 to 20,000, preferably from 1,500 to 10,000. Preferably the molecular weight is greater than 4,000. Polydispersion of polymers is preferred as being less than 3. Polymer Preparation
    [0044] The soil release polymers of the present invention can be prepared by methods known to the person skilled in the art. Documents US4702857 and US4711730 describe a synthetic method that can be adapted to produce the block polymers of the present invention.
    [0045] In one process, the end blocks are produced in a separate process and then are added to the middle block. A suitable process for making block copolymers for end blocks is described below. End Block Manufacturing
    [0046] [0046] PO/EO end blocks can be produced by anionic polymerization of propylene oxide using a preformed monofunctional PEG as initiator. Such a process is, for example, described in M.I. Malik, B. Trathnigg, C.O. Kappe, Macromol. Chern. Phys., 2007, 208, 2510-2524.
    [0047] The reaction scheme is presented below:

    [0048] Reaction A: Sodium hydride reacts with PEG to produce activated chain ends.
    [0049] Reaction B: Addition of PO proceeds to the ends of the PEG chains to form a block of PO.
    [0050] An alternative process forms the middle block and reacts it with PO and mPEG. Middle Block Manufacturing
    [0051] The middle block can be formed by condensing terephthalic acid methyl esters with an appropriate aliphatic diol, preferably using an excess of one of them as shown in greater detail in the examples below. If the dicarboxylic acid is used in the ester form, the reaction is suitably carried out in the presence of a base catalyst, at an elevated temperature, for example from 120 to 180°C, and, if desired, under reduced pressure. The lower alcohol, usually methanol, generated during the reaction is removed by distillation.
    [0052] Suitable catalysts include alkali or alkaline earth metals, eg lithium, sodium, calcium and magnesium, as well as transition metals and Group IIB, eg antimony, manganese, cobalt and zinc. Catalysts are usually used as oxides, carbonates or acetates. A preferred catalyst comprises antimony trioxide and calcium acetate.
    [0053] The esters and oligomers produced in the condensation reaction (ester exchange) can then be polymerized to the desired molecular weight, by further temperature increase, typically up to 180 to 250°C.
    [0054] The degree of polymerization can be monitored by means of gel permeation chromatography, NMR and endgroup titration. Detergent liquids
    [0055] Following the approach proposed in WO2009/153184, preferred liquids have high amounts of dirt release polymer, EPEI, enzymes and scavengers with respect to the total level of detersive surfactants. By carefully selecting these performance ingredients so that they are the ones that perform best when surfactant levels in the wash are low, the total detergency of the wash liquor can be adjusted to match that of a wash liquor made available from a conventional liquid that has broadly similar levels of performance additives and higher levels of surfactants in the wash liquor. The results with such an approach with respect to concentration are doubled. First, additives that have this high performance property must be found in combination, and then they need to be stably incorporated into the concentrated liquid, which has surfactants in the normal range or slightly lower than normal, for a concentrated liquid, but containing performance additives that are included at much higher levels than normal in the concentrated liquid. Because of this degree of difficulty in making the complete formulation with so many restrictions in selecting a multifunctional soil release polymer, it is highly advantageous and unexpected for the expert in the liquid detergent formulation technique that it does not only provide effective soil release performance. dirt, but also solve the problem of intrinsic foaming.
    [0056] The amount of surfactant makes up up to at least 5% by weight of the total liquid composition, preferably it makes up from 12 to 60% by weight. Compositions in accordance with the present invention most preferably have total detersive active surfactant levels of at least 15% by weight.
    [0057] The compositions may be concentrated laundry detergent compositions designed to be added to 10 liters of wash in small doses that require them to be diluted to at least 500 times their own volume of water to form a scheduled wash liquor comprising maximum 0.5 g/L of surfactant. They can also be concentrated compositions designed for manual washing or for automatic top loading washing machines. In manual washing less water can be used and in top loading automatic washing machines a larger amount of water can normally be used.
    [0058] The dose of liquid detergent is accordingly adjusted to provide similar concentrations of washing liquor. Surfactants
    [0059] Surfactants aid in the removal of dirt from textile materials and also help to keep the removed dirt in solution or suspension in the wash liquor. Anionic surfactants or mixtures of anionic and nonionic surfactants are a preferred aspect of the present invention. The amount of anionic surfactant is preferably at least 5% by weight.
    [0060] To obtain the full benefit of the present invention, it is preferable that the ratio of nonionic surfactant to total surfactant is at most 3:2. Compositions with higher levels of non-ionic are not subjected to intrinsic foaming at this intensity. anionic
    Preferred alkyl sulfonates are alkyl benzene sulfonates, particularly linear alkyl benzene sulfonates having an alkyl chain length of C8-C15. The preferred counterion for concentrated alkaline liquids is one or more ethanolamines, for example, monoethanolamine (MEA) and triethanolamine (TEA). This introduces TEA into the composition.
    Linear alkyl benzene sulfonate surfactants can be Detal LAS with an alkyl chain length from 8 to 15, more preferably from 12 to 14.
    [0063] It is further desirable that the composition comprises an anionic alkyl polyethoxylate sulfate surfactant of formula (II): RO(C2H4O)xSO3-M+ (II) where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound soluble in water, especially an ammonium or substituted ammonium cation, or less preferably an alkali metal, where x ranges from 1 to 15.
    [0064] Preferably, R is an alkyl chain having from 12 to 16 carbon atoms, x ranges from 1 to 3, preferably, x is 3; M can be an ethanolamine, or another material chosen from the list of buffers, to prevent sodium ion exchange with the LAS counterion. However, to the extent that some sodium can be tolerated, the counterion may be sodium if low levels of this surfactant can be used. The anionic surfactant sodium lauryl ether sulfate (SLES) can be used, provided that the total alkali metal salts remain low in the composition. An average of 3 moles of ethylene oxide per mole is preferred. non-ionic
    [0065] Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C8-C20 alcohol ethoxylate with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of non-ionic surfactants can be used. When included herein, the composition contains from 0.2% by weight to 40% by weight, preferably from 1% by weight to 20% by weight, more preferably from 5 to 15% by weight of a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide or N-acyl N-alkyl glucosamine derivatives ("glucamides").
    [0066] Nonionic surfactants that can be used include primary and secondary alcohol ethoxylates, especially ethoxylated C8-C20 aliphatic alcohols with an average of 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially alcohols ethoxylated primary or secondary aliphatic C10C15 with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Amine Oxide
    [0067] The composition may comprise up to 10% by weight of an amine oxide of the formula (III): R1N(O)(CH2R2)2 (III) in which R1 is a long chain component and each CH2R2 are chain components short. R2 is preferably selected from hydrogen, methyl and -CH2OH. In general, R1 is a primary or branched hydrocarbyl component which may be saturated or unsaturated, preferably R1 is a hydrocarbyl component having a chain length of from about 8 to about 18. Preferred amine oxides have R1 which is C8 alkyl -C18, and R2 is H. Such amine oxides are illustrated by C12-14 alkyl dimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
    [0068] A preferred amine oxide material is lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such amine oxide material is commercially available from Huntsman under the tradename Empigen®OB.
    [0069] Suitable amine oxides for use herein are also available from Akzo Chemie and Ethyl Corp (see McCutcheon compilation and Kirk-Othmer review article for alternative amine oxide manufacturers).
    [0070] Although, in certain preferred embodiments, R2 is H, it is possible to have R2 slightly larger than H. Specifically, R2 may be CH2OH, such as: hexadecylbis(2-hydroxyethyl)amine oxide, tallow(2-hydroxyethyl) oxide hydroxyethyl)amine, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide. Preferred amine oxides have the formula: O--N+(Me)2R1 (IV) where R1 is C12-16 alkyl, preferably C12-14 alkyl; Me is a methyl group. Zwitterionic
    [0071] Non-ionic free systems with up to 95% by weight of LAS can be used, provided that some zwitterionic surfactant, such as carbobetaine, is present. A preferred zwitterionic material is a betaine available from Huntsman under the brand name Empigen®BB. Betaine improves the detergency of particulate dirt in the compositions of the invention. Additional Surfactants
    [0072] Surfactants other than the preferred LAS and AES, and nonionic may be added to the detersive surfactant blend. However, cationic surfactants are preferably substantially absent.
    [0073] Although less preferred, some alkyl sulfate surfactant (PAS) can be used, especially non-ethoxylated C1215 primary and secondary alkyl sulfates. Soap can be used. Soap levels are preferably lower than 5% by weight, more preferably lower than 3% by weight and most preferably lower than 1% by weight. EPEI
    [0074] To boost detergency it is advantageous to use a second polymer with the dirt release polymers of the present invention, which is a polyalkoxylated polyethyleneimine.
    [0075] Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, when branched, the hydrogen in nitrogen is replaced by another chain and ethylene imine units. Such polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine backbones are disclosed in US Patents 2,182,306, Ulrich et al, issued Dec. 5, 1939; US 3,033,746, Mayle et al, published May 8, 1962; US 2,208,095, Esselmann et al, published July 16, 1940; US 2,806,839, Crowther, published September 17, 1957; and US 2,553,696, Wilson, published May 21, 1951.
    [0076] Preferably, the EPEI comprises a polyethyleneimine backbone of weight average molecular weight from about 300 to about 10,000; and polyalkoxylation comprises polyethoxylation. The polymer is non-ionic and does not permanently quaternize the polyamine nitrogens, although they can be protonated depending on pH. A preferred nonionic EPEI can be represented as PEI(X)YEO, where X represents the molecular weight of the unmodified PEI and Y represents the average amount of moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone. The ethoxylation can range from 3 to 40 ethoxy components per polyalkoxy chain, preferably it is in the range from 16 to 26, more preferably from 18 to 22. The minority of ethoxy units can be substituted by propoxy units.
    [0077] When present, the alkoxylated polyethyleneimine polymer is present in the composition at a level between 0.01 and 25% by weight, and preferably at a level of at least 2% by weight or less than 9.5% by weight, more preferably from 3 to 9% by weight and with a non-soap surfactant to EPEI ratio of 2:1 to 7:1, preferably from 3:1 to 6:1, or even up to 5:1. Other Polymers
    [0078] In addition to the polyester dirt release polymer with anti-foaming properties and the optional EPEI, the composition may comprise other polymeric materials, for example: dye transfer inhibition polymers, anti-redeposition polymers and polymers of cotton dirt release, especially those based on modified cellulosic materials. Especially when EPEI is not present, the composition may additionally comprise a polymer of polyethylene glycol and vinyl acetate, for example the lightly grafted copolymers described in WO2007/138054. Such amphiphilic grafted polymers based on water soluble polyalkylene oxides as a graft base and side chains formed by polymerization of a vinyl ester component have the ability to enable the reduction of surfactant levels while maintaining high levels of oily dirt removal. hydrotrope
    [0079] In the context of the present invention, a hydrotrope is a solvent that is neither water nor conventional surfactant that assists in the solubilization of surfactants and other components, especially polymer and sequestrant, in the liquid to make it isotropic. Among suitable hydrotropes, there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, for example dipropylene glycol, diethers and urea. MPG and glycerol are preferred hydrotropes. Enzymes
    It is preferred that at least one or more enzymes selected from protease, mannanase, pectate lyase, cutinase, esterase, lipase, amylase and cellulase are present in the compositions. Additional less preferred enzymes can be selected from peroxidase and oxidase. Preferably the enzymes are present with corresponding enzyme stabilizers. The total enzyme content is preferably at least 2% by weight, even as high as at least 4% by weight. kidnappers
    [0081] There is no space to include high levels of anti-limescale agents in concentrated compositions. Thus, scavengers are preferably included. Such materials tend to have low solubility in concentrated liquids so the multifunctionality of the anti-foam dirt release polymer aids in the stable incorporation of these materials into the compositions.
    Preferred scavengers include organic phosphonates, alkane hydroxy phosphonates and carboxylates available under the tradename DEQUEST from Thermphos.
    The preferred sequestrant level is less than 10% by weight and preferably less than 5% by weight of the composition. A particularly preferred scavenger is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), for example, sold as Dequest 2010. Also suitable, but less preferred, as it gives inferior cleaning results, is Dequest® 2066 (diethylenetriamine penta(methylene) phosphonic acid or Hepta sodium DTPMP). Buffers
    [0084] In addition to 1% TEA, the presence of a pH control buffer is preferred. Preferred buffers are MEA and TEA. They are preferably used in the composition at levels of 5 to 15% by weight, including 1% TEA. Other suitable buffer materials may be selected from the group consisting of amino alcohol compounds having a molecular weight above 61 g/mol, which includes MEA. In addition to the materials already mentioned, suitable materials also include: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoaminohexanol, 2-[(2-methoxyethyl)methylamino]-ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanolamine, isobutanolamine, monopentanolamine, 1- amino-3-(2-methoxyethoxy)-2-propanol, 2-methyl-4-(methylamino)-2-butanol and mixtures thereof. Additional Optional Ingredients
    [0085] It may be advantageous to include fluorescent and/or bleach catalyst in the compositions as additional high efficiency performance additives. Their inclusion is also made easier by the soap reduction made possible by the inclusion of propoxylated polyester dirt release polymers. Perfume and colorants will desirably be included in the compositions. Compositions may contain viscosity modifiers, foam stimulating agents, preservatives (eg bactericides), pH buffering agents, polyelectrolytes, anti-shrink agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, agents which provide drapery, antistatic agents and ironing aids. The compositions may additionally comprise pearlizers and/or opacifiers or other visual cues, and tint coloring. Packaging and Dosing
    [0086] Alternatively, liquids can be supplied in multi-dose plastic containers with a top or bottom closure. A dose measure can be supplied with the packaging as a part of the cap or as an integral system.
    [0087] The present invention will now be further described with reference to the following non-limiting examples. Examples
    [0088] Legend for Ingredients Used:

    Example 1 - Concentrated Liquid Compositions with SRP
    [0089] A series of compositions designed to be dosed in 35 ml per wash without SRP, with prior art SRPs and with propoxylated SRPs were formulated. The compositions are given in Table 1. They were subjected to a foam evaluation using the following protocol:
    [0090] A 30 ml sample of the concentrated detergent composition was added to a 100 ml measuring cylinder. The cylinder was hermetically sealed and shaken 20 times to generate foam. The cylinder was left to rest for 1 minute and the foam height was measured. The protocol was repeated up to 6 times for each sample and the mean was calculated. The results are given in Table 2.
    [0091] It can be seen from Table 2 that TexCare® SRN240, a polymer of similar molecular weight and construction with respect to those of the propoxylated SRPs (but without any propoxylation), makes the composition foam and is very similar to that of the base alone and TexCare® SRN170. All three propoxylated SRPs cause a significant reduction in foaming. Table 1 - Liquid Detergent Compositions

    Table 2
    权利要求:
    Claims (19)
    [0001]
    1. Concentrated alkaline liquid detergent composition, characterized in that it comprises: (a) 5 to 60% by weight of surfactant comprising anionic surfactant and optionally non-ionic surfactant and optionally amphoteric surfactant and optionally soap of which at least 35% of the total surfactant is a non-soap anionic surfactant, (b) at least 30% by weight of water, (c) at least 0.25% by weight of soil release polymer, in that the soil release polymer has the formula I , and X-[(OCH2CH2)q-]-block-[(OCH2CH(CH3))p]-[(OC(O)-G1-C(O)O-G2)n]-OC(O)-G1 -C(O)O-[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X(I), the G1 components being all 1,4-phenylene components; the G2 components are all C14 alkyl substituted ethylene components, each X is C1-4 alkyl, preferably methyl or n-butyl; each q ranges from 12 to 120; each p ranges from 1 to 10, preferably from 2 to 5; and n ranges from 2 to 10.
    [0002]
    2. Composition according to claim 1, characterized in that it additionally comprises at least 0.5% by weight of triethanolamine (TEA).
    [0003]
    3. Composition according to claim 2, characterized in that it comprises at least 1% by weight of triethanolamine.
    [0004]
    4. Composition according to any one of the preceding claims, characterized in that it comprises at least 0.5% by weight of the dirt release polymer (c).
    [0005]
    5. Composition according to any one of the preceding claims, characterized in that the ratio of non-soap anionic surfactant to dirt release polymer is at most 9:1.
    [0006]
    6. Composition according to any one of the preceding claims, characterized in that each G2 has one or two C1-4 alkyl substituents with at most one on each carbon.
    [0007]
    7. Composition according to any one of the preceding claims, characterized in that the C1-4 alkyl components are methyl components.
    [0008]
    8. Composition according to any one of the preceding claims, characterized in that it comprises at least 2% by weight of alkoxylated polyethylene imine.
    [0009]
    9. Composition according to any one of the preceding claims, characterized in that it comprises at least 5% by weight of anionic surfactant.
    [0010]
    10. Composition according to any one of the preceding claims, characterized in that it comprises anionic surfactant of alkyl ether sulfate.
    [0011]
    11. Composition according to any one of the preceding claims, characterized in that it comprises linear alkyl benzene sulphonate (LAS), the LAS being neutralized from LAS acid, at least in part, with triethanolamine (TEA).
    [0012]
    12. Composition according to any one of the preceding claims, characterized in that it comprises at least 2% by weight of the dirt release polymer (c).
    [0013]
    13. Composition according to any one of the preceding claims, characterized in that it comprises at least three enzymes.
    [0014]
    14. Composition, according to any one of the preceding claims, characterized in that it comprises at least 1% by weight of sequestrant.
    [0015]
    15. Composition according to any one of the preceding claims, characterized in that it comprises at least 0.5% by weight of amine oxide.
    [0016]
    16. Composition according to any one of the preceding claims, characterized in that it comprises up to 25% by weight of hydrotrope.
    [0017]
    17. Composition according to any one of the preceding claims, characterized in that it comprises at most 1% by weight of alkali metal ions.
    [0018]
    18. Composition according to any one of the preceding claims, characterized in that it has a viscosity measured at 23 s-1 and 25°C of less than 0.1 Pa.s.
    [0019]
    19. Composition according to any one of the preceding claims, characterized in that it comprises less than 5% by weight of soap, preferably less than 3% by weight and even more preferably less than 1% by weight.
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    同族专利:
    公开号 | 公开日
    MX2015000894A|2015-04-17|
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    EP2692842B1|2014-07-30|
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    IN2015MN00104A|2015-10-16|
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    WO2014019792A1|2014-02-06|
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    AU2013298898A1|2015-02-05|
    AR091933A1|2015-03-11|
    PL2880143T3|2016-09-30|
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    法律状态:
    2018-01-23| B11A| Dismissal acc. art.33 of ipl - examination not requested within 36 months of filing|
    2018-03-20| B11N| Dismissal: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 11.1 NA RPI NO 2455 DE 23/01/2018 POR TER SIDO INDEVIDA. |
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |
    2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12178620.6|2012-07-31|
    EP12178620.6A|EP2692842B1|2012-07-31|2012-07-31|Concentrated liquid detergent compositions|
    PCT/EP2013/063967|WO2014019792A1|2012-07-31|2013-07-02|Concentrated liquid detergent compositions|
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