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    ALKALINE LIQUID DETERGENT COMPOSITION FOR WASHING CLOTHES The present invention relates to an alkaline liquid laundry detergent composition comprising at least 1% by weight of triethanolamine, at least 5% by weight of non-soap surfactant and at least 0.5% by weight a polyester according to the following formula (I): (I) in which R1 and R2, independently of each other, are X- (OC2H4) n- (OC3H6) m, where X is C1-4 alkyl, the groups - (OC2H4) and groups - (OC3H6) are arranged in the form of blocks and the block consisting of groups- (OC3H6) is linked to a COO group or are HO- (C3H6), n is based on a molar mean that is a number from 12 to 120, preferably 40 to 50, m is based on a molar average which is a number from 1 to 10, and a is based on a molar average which is a number from 4 to 9. The compositions of the invention comprise polyesters that have an advantageous stability in their alkaline environment and also have advantageous dirt-releasing properties.
    公开号:BR112015001754B1
    申请号:R112015001754-1
    申请日:2013-07-24
    公开日:2021-03-16
    发明作者:John Francis Wells；Alyn James Parry；Robert John Carswell；Dirk Fischer；Thomas Lindner
    申请人:Unilever Ip Holdings B.V.；
    IPC主号:
    专利说明:

    Field of the Invention
    [0001] The present invention relates to alkaline liquid laundry detergent compositions comprising polyesters usable as dirt releasing agents in the compositions. Background of the Invention
    [0002] Laundry detergent compositions containing polyesters have been widely described in the state of the art.
    [0003] DE102007013217A1 and WO 2007 / 079850A1 describe anionic polyesters that can be used as dirt release components in washing and cleaning compositions.
    [0004] DE102007005532A1 describes aqueous formulations of dirt-releasing oligo- and polyesters with a low viscosity. Aqueous formulations can, for example, be used in washing and cleaning compositions.
    [0005] EP0964015A1 describes dirt-releasing oligoesters that can be used as dirt-releasing polymers in detergents and which are prepared using polyols comprising from 3 to 6 hydroxyl groups.
    [0006] EP1661933A1 is intended for amphiphilic and non-ionic oligoesters having fluidity at room temperature, which are prepared by the reaction of dicarboxylic acid compounds, polyol compounds and water-soluble alkylene oxide additives and their use as an additive in compositions of washing and cleaning. The main focus of this document is on polymers of high stability and polymers of high compatibility with respect to liquids. The performance of polymers compared to that of polymers of the then state of the art, with respect to polymers of release of polyester dirt, cannot be derivable from this document. The performance data, even for the freshly prepared polymer (oligoester) is not very surprising because, apparently, it was not used as would be conventional for a dirt-releasing polymer from a pre-washed fabric in the same composition. Thus, the person skilled in the art can take advantage of only little information on a probable practice for the benefit of washing performance of the claimed oligoesters.
    [0007] However, many of the polyesters described in the prior art need to have their stability improved in an alkaline environment, particularly when triethanolamine is also present. This material is usable to neutralize anionic surfactants for use in alkaline compositions, especially linear alkyl benzene sulfonate. Triethanolamine also catalyzes the alkaline hydrolysis of many polyesters that would be suitable for use in detergents, which thus lose their dirt-releasing power. In addition, especially in alkaline heavy-duty washing liquids, polyesters often show turbidity after incorporation.
    [0008] GB1466639 describes heavy-duty liquid detergent compositions containing non-ionic surfactants, anionic surfactants neutralized with ethanolamine, free ethanolamines and a polymeric dirt releasing agent. The non-ionic surfactant must be present in excess of the anionic surfactant to stimulate the removal of oily dirt. In column 6, lines 2 to 5, the fact is pointed out that the dirt release polymers of the type claimed are deposited under rinsing conditions. In the test protocol, the composition is applied through a non-specific pre-wash process. It seems that “prewash” is necessary to achieve the effect (polyester prewashed with compositions containing polymer outperforms those prewashed with the same composition without the polymer). It is a common and general knowledge that these preliminary types of dirt-releasing polymer do not deposit well during washing. As a result, they were not commercially stable. GB1466639 also explains the fact that the compositions comprising the polymers were stable in storage with triethanolamine. In several places it is also established that they were also stable in storage with amines, etc .; for example, in column 9, lines 36 to 43. This is not surprising because, unlike the polymers with modifications on the polyethoxylated end described in the previously discussed state of the art, this previous type of polymers with the polyethoxylation incorporated within the middle block of the polymer , instead of being at the end (s) do not disintegrate to produce non-functional polymers if they are hydrolyzed. Thus, the polymers in GB1466639 can be seen as compromising performance, but having greater stability than the newer polymers based on dirt release polymers developed mainly for powder applications. Starting from this state of the art, the person skilled in the art does not require a more stable polymer. Instead, it needs to look for a higher-performance polymer.
    [0009] Therefore, the aim of the present invention was to provide compositions comprising triethanolamine in combination with selected new polyesters that have an advantageous stability in an alkaline medium, have a beneficial solubility and, advantageously, are clearly soluble in alkaline compositions, such as liquids heavy-duty washing alkalis and also have advantageous dirt-releasing properties. Summary of the Invention
    [0010] According to the present invention, an alkaline liquid laundry detergent composition comprising at least 1% by weight of triethanolamine, at least 5% by weight of non-soap surfactant and at least 0.5% by weight of a polyester according to the following formula (I):
    in which: R1 and R2, independently of each other, are X- (OC2H4) n- (OC3H6) m, where X is C1-4 alkyl, the groups - (OC2H4) and groups - (OC3H6) are arranged in the form of blocks and the block consisting of groups - (OC3H6) is linked to a COO group, n is based on a molar mean which is a number from 40 to 50, m is based on a molar mean which is a number from 2 to 5, and a is based on a molar average that is a number from 6 to 7.
    [0011] Preferably, the composition additionally includes at least 2% by weight of nonionic alkoxylated polyethyleneimine with at least 3 moles of nitrogen alkoxylation.
    [0012] X is preferably methyl.
    [0013] The compositions are especially usable as concentrated liquid detergent compositions for washing.
    [0014] Preferably, the alkaline liquid detergent composition is isotropic. The composition can comprise at least 5% by weight of a non-soap anionic surfactant. Appropriately, 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 neutralized LAS acid, at least in part, with ASD. Amines can also be used as a counter ion for AES. For stability reasons, it is preferable to keep the total level of alkali metal ions below 1% by weight of the composition.
    [0015] To maximize the benefit of other cleaning technologies that are essentially or optionally included in the liquid, especially the anionic surfactant, the liquid is alkaline. It is preferable that the maximum pH of the concentrated composition is 8.4, more preferably a maximum of 8.2.
    [0016] The term "dirt release agent" is applied to materials that modify the surface of the fabric, minimizing the subsequent deposition of dirt and making it easier to clean the fabric in later washing cycles. Detailed Description of the Invention
    [0017] With reference to formula (I):
    [0018] The variable “a” based on a molar average is a number from 6 to 7.
    [0019] The variable “m” based on a molar average is a number from 2 to 5.
    [0020] The variable "n" based on a molar average is preferably a number from 43 to 47, more preferably it is a number from 44 to 46 and even more preferably it is 45.
    [0021] In a particularly preferred embodiment of the present invention, the composition comprises polyesters according to the following formula (I):
    in which: R1 and R2, independently of each other, are H3C- (OC2H4) n- (OC3H6) m, with groups - (OC2H4) and groups - (OC3H6) being arranged in the form of blocks and the block consisting of the groups - (OC3H6) is linked to a COO group, “n” is based on a molar average that is a number from 44 to 46, “m” is based on a molar average of 2, and “a” is based on a molar mean which is a number from 6 to 7.
    [0022] Among these polyesters, the polyesters of formula (I) are especially preferred:
    in which: R1 and R2, independently of each other, are H3C- (OC2H4) n- (OC3H6) m, with groups - (OC2H4) and groups - (OC3H6) being arranged in the form of blocks and the block consisting of the groups - (OC3H6) is linked to a COO group, “n” is based on a molar mean of 45, “m” is based on a molar mean of 2, and “a” is based on a molar mean which is a number from 6 to 7.
    [0023] In another particularly preferred embodiment of the present invention, the inventive compositions comprise polyesters according to formula (I):
    in which: R1 and R2, independently of each other, are H3C- (OC2H4) n- (OC3H6) m, with groups - (OC2H4) and groups - (OC3H6) being arranged in the form of blocks and the block consisting of the groups - (OC3H6) is linked to a COO group, “n” is based on a molar average that is a number from 44 to 46, “m” is based on a molar average of 5, and “a” is based on a molar mean which is a number from 6 to 7.
    [0024] Among these polyesters, the polyesters of formula (I) are especially preferred:
    in which: R1 and R2, independently of each other, are H3C- (OC2H4) n- (OC3H6) m, with groups - (OC2H4) and groups - (OC3H6) being arranged in the form of blocks and the block consisting of the groups - (OC3H6) is linked to a COO group, “n” is based on a molar average of 45, “m” is based on a molar average of 5, and “a” is based on a molar average which is a number from 6 to 7.
    [0025] The groups -O-C2H4- in the structural units “H3C- (OC2H4) n- (OC3H6) m” are of the formula -O-CH2-CH2-.
    [0026] The groups -O-C3H6- of the structural units indexed with “a”, in the structural units “H3C- (OC2H4) n- (OC3H6) m” are of the formula -O-CH (CH3) - CH2- or - O-CH2-CH (CH3) -, that is, they are of the formula:

    [0027] Polyesters can advantageously be prepared by means of a process comprising heating dimethyl terephthalate (DMT), 1,2-propylene glycol (PG) and H3C- (OC2H4) n- (OC3H6) m-OH, the groups - (OC2H4) and groups - (OC3H6) are arranged in the form of blocks and the block consisting of the groups - (C3H6) is linked to the hydroxyl group -OH enem are as defined in formula (I), with the addition of a catalyst, at a temperature of 160 to 220 ° C, first at atmospheric pressure, and then, continuing the reaction, at reduced pressure at temperatures of 160 to 240 ° C.
    [0028] An appropriate process for the preparation of polyesters comprises heating the dimethyl terephthalate (DMT), 1,2-propylene glycol (PG) and H3C- (OC2H4) n- (OC3H6) m-OH, with the groups - ( OC2H4) and groups - (OC3H6) are arranged in the form of blocks and the block consisting of groups - (C3H6) is linked to the hydroxyl group -OH are defined as in formula (I), with the addition of a catalyst, to the temperature from 160 to 220 ° C, first at atmospheric pressure, and then, continuing the reaction, at reduced pressure at temperatures from 160 to 240 ° C.
    [0029] The reduced pressure preferably means a pressure of 10 to 90,000 Pa (0.1 to 900 mbar) and more preferably a pressure of 50 to 50,000 Pa (0.5 to 500 mbar).
    [0030] A preferred process is characterized by: (a) dimethyl terephthalate, 1,2-propylene glycol, H3C- (OC2H4) n- (OC3H6) m-OH and the catalyst are added to the reactor, heated in inert gas, preferably nitrogen, up to a temperature of 160 ° C to 220 ° C to remove methanol and then the pressure is reduced to below atmospheric pressure, preferably up to a pressure of 20,000 to 90,000 Pa (200 to 900 mbar) and more preferably to a pressure from 40,000 to 60,000 Pa (400 to 600 mbar) to complete the transesterification, and (b) in a second step, the reaction is continued at a temperature of 210 ° C to 240 ° C and a pressure of 10 to 1,000 Pa (0.1 to 10 mbar) and preferably from 50 to 500 Pa (0.5 to 5 mbar) to form the polyester.
    [0031] Sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) are preferably used as a catalytic system in the process.
    [0032] Unless they are explicitly stated differently, all percentages given are percentages by weight (% by weight or% by weight). General procedure for the preparation of polyesters
    [0033] The synthesis of polyester is carried out by the reaction of dimethyl terephthalate (DMT), 1,2-propylene glycol (PG) and methyl polyalkylene glycol using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as a catalyst system. Synthesis is a two-step procedure. The first stage is transesterification and the second stage is polycondensation. Transesterification
    [0034] Dimethyl terephthalate (DMT), 1,2-propylene glycol (PG), methyl polyalkylene glycol, sodium acetate (anhydrous) (NaOAc) and tetraisopropyl orthotitanate (IPT) are weighed in a reactor at room temperature.
    [0035] For the melting and homogenization process, the mixture is heated to 170 ° C for 1 hour and then to 210 ° C for an additional hour sprayed by means of a nitrogen stream. During transesterification, methanol is released from the reaction and is removed from the system by distillation (distillation temperatures <55 ° C). After 2 hours at 210 ° C, nitrogen is turned off and the pressure is reduced to 40,000 Pa (400 mbar) for 3 hours. Polycondensation
    [0036] The mixture is heated to 230 ° C. At 230 ° C, the pressure is reduced to 100 Pa (1 mbar) for 160 minutes. Once the polycondensation reaction has started, 1,2-propylene glycol is removed from the system by distillation. The mixture is stirred for 4 hours at 230 ° C and a pressure of 100 Pa. The reaction mixture is cooled to 140 - 150 ° C.
    [0037] The vacuum is released with nitrogen and the molten polymer is transferred to a glass bottle. Detergent Compositions
    [0038] In addition to the essential ingredients as claimed, detergent compositions may comprise one or more optional ingredients, for example, they may comprise conventional ingredients commonly used in detergent compositions, especially laundry detergent compositions. Examples of optional ingredients include, but are not limited to, anti-lime agents, bleaching agents, active bleaching compounds, bleach activators, bleach catalysts, photo bleaches, dye transfer inhibitors, color protection agents, redeposition, dispersing agents, fabric softening and anti-aesthetic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, bad odor reducers, preservatives, disinfectants, hydrotropes, fiber lubricants, anti-oxidants shrinkage, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for washing detergent or laundry compositions.
    [0039] The compositions according to the present invention comprising the polyesters of formula (I) have an advantageous stability in alkaline medium, have a favorable solubility and are advantageously clearly soluble in alkaline compositions, such as heavy-duty washing liquids and also they have advantageous dirt release properties. In washing or laundry detergent compositions, they result in advantageous washing performance, in particular also after storage. In addition, polyesters have advantageous foam suppression properties. This is not only advantageous when washing or washing detergent compositions are applied, but also advantageously reduces foaming during handling of the compositions. Surfactants
    [0040] Surfactants assist in removing dirt from textile materials and also assist in maintaining the removed dirt present in solution or in suspension in the washing 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. It is preferable that the ratio of nonionic surfactant to total surfactant is a maximum of 3: 2. Anionic
    Preferred alkyl sulfonates are alkyl benzene sulfonates, particularly linear alkyl benzene sulfonates having a C8-C15 alkyl chain length. 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.
    [0042] Linear alkyl benzene sulfonate surfactants can be LAS Detal with an alkyl chain length of 8 to 15, more preferably 12 to 14.
    [0043] It is also desirable that the composition comprises an anionic surfactant of alkyl polyethoxylate sulfate of formula (II): RO (C2H4O) ySO3-M + (II) where R is an alkyl chain having 10 to 22 carbon atoms, saturated or unsaturated, M is a cation that makes the compound soluble in water, especially an ammonium or substituted ammonium cation, or less preferably an alkali metal, and y ranges from 1 to 15.
    Preferably, R is an alkyl chain having from 12 to 16 carbon atoms, y ranges from 1 to 3, preferably y is 3; M can be ethanolamine, or another material chosen from the list of buffers, to avoid exchanging the sodium ion with the LAS counterion. However, since some sodium can be tolerated, the counterion can be sodium if low levels of this surfactant are used. The anionic surfactant lauryl ether sodium sulfate (SLES) can be used with the proviso that the total alkali metal salts in the composition remain low. An average of 3 moles of ethylene oxide per mole is preferred. Non-ionic
    [0045] Nonionic surfactants include primary and secondary alcohol ethoxylates, especially an ethoxylated C8-C20 aliphatic alcohol with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the primary and secondary C10 aliphatic alcohols -C25 ethoxylates 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 here, the composition contains from 0.1% 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 ethoxylate alcohol, nonylphenol ethoxylate, alkyl polyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy fatty acid amide, or N-acyl N-alkyl glucosamine derivatives ("glucamides").
    [0046] Nonionic surfactants that can be used include primary and secondary alcohol ethoxylates, especially C8-C20 ethoxylated aliphatic alcohols with an average of 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially aliphatic alcohols primary and secondary C10-C15 ethoxylates with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Amine Oxide
    [0047] The composition may comprise up to 10% by weight of an amine oxide of formula (III): R4N (O) (CH2R3) 2 (III) in which R4 is a long chain component, each of CH2R3 is a component short chain. R3 is preferably selected from hydrogen, methyl and -CH2OH. In general R4 is a primary or branched hydrocarbyl component that can be saturated or unsaturated, preferably R4 is a primary alkyl component. R4 is a hydrocarbyl component having a chain length of about 8 to about 18.
    Preferred amine oxides have R4 which is a C8-C18 alkyl, and R3 is H. These amine oxides are illustrated by C12-C14 amyldimethyl oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
    [0049] 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 brand name Empigen®OB. Amine oxides suitable for use in this case are also available from Akzo Chemie and Ethyl Corp (see McCutcheon compilation and Kirk-Othmer review article for alternative amine oxide manufacturers).
    [0050] Although, in certain cases of the preferred embodiments, R4 is H, it is possible to have R4 slightly greater than H. Specifically, R4 can be CH2OH, for example: hexadecylbis oxide (2-hydroxyethyl) amine, sebobis oxide ( 2-hydroxyethyl) amine, stearylbis oxide (2-hydroxyethyl) amine and oleylbis (2-hydroxyethyl) amine oxide. Preferred amine oxides have the formula: O- - N + (Me) 2R5 (IV) where R5 is C12-16 alkyl, preferably C12-14 alkyl; Me is a methyl group. Zwiterionic
    [0051] Non-ionic systems with up to 95% by weight of LAS can be used with the proviso 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 particulate dirt detergency in the compositions of the present invention. Additional Surfactants
    [0052] Other surfactants other than the preferred LAS, AES and non-ionic surfactants can be added to the mixture of detersive surfactants. However, preferably, cationic surfactants are substantially absent.
    [0053] Although less preferred, some alkyl sulfate surfactant (PAS) can be used, especially non-ethoxylated primary and secondary C12-15 alkyl sulfates. Soap can be used. The soap levels are preferably less than 5% by weight, more preferably less than 3% by weight and more preferably still less than 1% by weight. EPEI
    [0054] To stimulate detergency, it is advantageous to use a second polymer with the dirt-releasing polymers in the compositions of the present invention. This second polymer is preferably a polyalkoxylated polyethyleneimine. Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, when branched, hydrogen in nitrogen is replaced by another chain of 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 described in US Patent No. 2,182,306, Ulrich et al., Published December 5, 1939; US patent 3,033,746, Mayle et al., published May 8, 1962; US patent 2,208,095, Esselmann et al., published July 16, 1940; US Patent 2,806,839, Crowther, published September 17, 1957; and US2,553,696, Wilson, published May 21, 1951.
    Preferably, EPEI comprises a main chain of polyethyleneimine of average molecular weight of about 300 to about 10,000; and polyalkoxylation comprises polyethoxylation. The polymer is non-ionic and does not have a permanent quaternization of the polyamine nitrogens, although, depending on the pH, they can be protonated. 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 mole of ethoxylation per nitrogen atom in the polyethyleneimine backbone. The ethoxylation can vary from 3 to 40 ethoxy components per polyalkoxy chain, preferably in the range of 16 to 26, more preferably still from 18 to 22. A minority of the ethoxy units can be replaced by propoxy units.
    [0056] When present, the alkoxylated polyethyleneimine polymer is present in the composition at a level between 0.01 and 25% by weight, preferably at a level of at least 2% by weight and / or less than 9.5% by weight , most 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
    [0057] 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 inhibiting polymers, anti-redeposition polymers and polymers release of cotton dirt, especially those based on modified cellulose materials. Especially when EPEI is not present, the composition can additionally comprise a polymer of polyethylene glycol and vinyl acetate, for example, the slightly grafted copolymers described in WO 2007/138054. 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 having the ability to provide a reduction in surfactant levels while maintaining high levels of oily dirt removal. Hydrotrope
    [0058] In the context of the present invention, a hydrotrope is a solvent that is neither water nor a conventional surfactant that aids in the solubilization of surfactants and other components, especially polymer and scavenger, in the liquid to make it isotropic. Among the appropriate hydrotropes, the following may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulfonate, ethanol, other glycols, for example, dipropylene glycol, diethers and urea. MPG and glycerol are the preferred hydrotropes. Enzymes
    [0059] It is preferable that at least one or more selected enzymes of protease, mannanase, pectate lyase, cutinase, esterase, lipase, amylase and cellulase may be present in the composition. Additional less preferred enzymes can be selected from peroxidase and oxidase. The enzymes are preferably present with the corresponding enzyme stabilizers. The total enzyme content is preferably at least 2% by weight, even higher than at least 4% by weight. Kidnappers
    [0060] Preferably kidnappers are included. Preferred sequestrants include organic phosphonates, alkane hydroxy phosphonates and carboxylates, available under the brand name DEQUEST from Thermphos.
    The preferred scavenger 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, for providing inferior cleaning results is Dequest® 2066 (Diethylenetriamine penta acid) (phosphonic methylene or heptasodium DTPMP).
    [0062] In addition to the 1% TEA, the presence of buffer is preferred for pH control. 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 can be selected from the group consisting of amino alcohol compounds having a molecular weight above 61 g / mol, which include MEA. In addition to the materials already mentioned, suitable materials also include: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoamino hexanol, 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
    [0063] It may be advantageous to include fluorescent and / or bleach catalyst in the compositions as additional high-performance performance additives. Its inclusion is also made easier by making it possible to reduce soap by including the propoxylated polyester dirt release polymers. Perfume and dyes will desirably be included in the compositions. The compositions may contain viscosity modifiers, foaming stimulating agents, preservatives (for example, bactericides), pH buffering agents, polyelectrolytes, anti-shrink agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents , draping agents, anti-static agents and ironing aids. The compositions may additionally comprise pearls and / or opacifiers or other visual effects and tint dyes. Packaging and Dosing
    [0064] The liquids can be packaged in unit doses in polymeric film soluble in the washing water. Alternatively, liquids can be supplied in multidose plastic packaging with a top or bottom closure. A dosage measurement can be provided with the package, as part of the lid or as a cover system.
    [0065] The present invention will now be further described with reference to the following non-limiting examples. EXAMPLES Example I:

    [0066] An appropriate polyester is obtained according to formula (I), where: R1 and R2 are H3C- (OC2H4) n- (OC3H6) m, in which groups - (OC2H4) and groups - (OC3H6 ) are arranged in the form of blocks and the block consisting of groups - (OC3H6) is linked to a COO group, “n” is based on a molar average of 45, “m” is based on a molar average of 5, and “ a ”is based on a molar mean that is a number from 6 to 7. Example II: Table 2

    [0067] An appropriate polyester is obtained according to formula (I), where: R1 and R2 are H3C- (OC2H4) n- (OC3H6) m, in which groups - (OC2H4) and groups - (OC3H6 ) are arranged in the form of blocks and the block consisting of groups - (OC3H6) is linked to a COO group, “n” is based on a molar average of 45, “m” is based on a molar average of 2, and “ a ”is based on a molar mean that is a number from 6 to 7. Example III: Comparative Example Table 3

    [0068] A comparative polyester of formula (I ') is obtained
    where: R1 'and R2' are H3C- (OC2H4) n '- (OC3H6) m', in which groups - (OC2H4) and groups - (OC3H6) are arranged in the form of blocks and the block consisting of groups - (OC3H6) is linked to a COO group, n 'is based on a molar average of 45, m' is based on a molar average of 2, and a is based on a molar average of 2 to 3. Example IV : Comparative Example Table 4

    [0069] A comparative polyester of formula (I ') is obtained
    where: R1 'and R2' are H3C- (OC2H4) n '- (OC3H6) m', in which groups - (OC2H4) and groups - (OC3H6) are arranged in the form of blocks and the block consisting of groups - (OC3H6) is linked to a COO group, n 'is based on a molar average of 45, m' is based on a molar average of 2, and a is based on a molar average which is a number of approximately 10. Test of Stability in Detergent Formulation
    [0070] 1% by weight (based on the total weight of the detergent formulation used) of the polyesters of Examples I through IV and the commercially available dirt release polymer “TexCare SRN100” was dissolved in a test detergent formulation (the composition of this formulation test detergent is given in Table 1 below) and the pH value was adjusted with caustic solution to pH 8.2. The turbidity of the formulations was determined. The prepared formulations were stored at 60 ° C for 8 days. Thereafter, the hydrolysis of the polyesters was calculated and compared with the hydrolysis of the commercially available dirt release polymer “TexCare SRN 100” by GPC analysis. The results are given in Table 2 below.
    [0071] TexCare SRN 100 is a polyester comprising -OOC- (1,4-phenylene) -COO- structural units and -O-CH2-CH2-O structural units. Table 5 - Detergent Test Formulation

    [0072] Keyword for Ingredients Used: MPG is mono propylene glycol TEA is triethanolamine NI 7EO is C12-15 ethoxylated alcohol 7EO nonionic - Neodol® 25-7 (ex Shell Chemicals) LAS acid is C12- linear alkylbenzene acid 14 sulfonic SLES 3EO is sodium lauryl ether sulfate with 3 moles of EO Empigen® BB is carbobetaine ex Huntsman Empigen® OB is amine oxide ex Huntsman Prifac® 5908 is saturated lauric fatty acid ex Croda Dequest® 2010 is HEDP (acid 1 - hydroxyethylidene-1,1 diphosphonic) ex Thermphos EPEI is Sokalan HP 20 - polyethylene imine ethoxylated cleaning polymer: PEI (600) 2EO ex BASF Perfume is an oil-free perfume TexCare SRN-100 is a dirt release polymer ex Clariant Table 6: Turbidity of the Formulation Comprising Polyester and Polyester Stability in It

    [0073] Values in% for polyesters of Examples I to IV in comparison / in relation to TexCare SRN 100. Dirt Release Test
    [0074] The polyesters of Examples I and II were tested for their dirt release performance according to the “Dirty Engine Oil” Test (DMO Test).
    [0075] The polyesters of Examples I and II were used in concentrations of 1% by weight (based on the total weight of the detergent formulation used) and the formulations were stored according to the stability test. The formulations were those described above for the stability test. As a test fabric, a standard white polyester fabric (30A) was used. The pre-washed fabrics (the fabrics were pre-washed with the stocked detergent formulations comprising the polyesters of Examples I and II) were soiled with dirty motor oil. After 1 hour, the soiled fabrics were washed again with the stocked detergent formulations comprising the polyesters of Examples I and II. The washing conditions for the “pre-wash” and for the washing procedure after the fabrics are soiled with dirty engine oil were as given in Table 3. Table 7: Washing Conditions

    [0076] The washing results obtained for the stock formulations comprising the polyesters of Examples I and II are shown in Table 4. Table 4 also shows the washing result obtained for a detergent formulation comprising 1% by weight of TexCare SRN 100. The composition of this detergent formulation comprising TexCare SRN 100 was as described above for the stability test. In the case of TexCare SRN 100, the conditions for “pre-wash” and for the washing procedure after the fabrics were soiled were similar to the conditions used for detergent formulations comprising the polyesters of Examples I and II, but with the exception of that in the case of TexCare SRN 100, the “pre-wash” and the washing procedure, after the fabrics were soiled with dirty engine oil, were made using “freshly prepared” detergent formulation (without alkaline storage). Table 8: Test Results (Wash Performance)

    Test on an Additional Detergent Composition
    [0077] To verify that the dirt release polymers were stable and provided good performance over a range of liquids, the polymer of Example II was additionally tested on the concentrated liquid laundry composition given in Table 5. This composition is designed to be dosed in 20 ml per wash in a typical European automatic front-loading washing machine. Table 9

    [0078] In this case, the washing performance was evaluated using the thergotometer washing protocol. Details of which can be found in Table 6. Table 10: Washing Conditions in a Tergotometer

    [0079] Three clean polyester mesh control fabrics were used in each vessel. In the two pre-washings, they were free of stains. The appropriate 25: 1 liquor: fabric ratio was achieved using a mixture of 50% polyester mesh and 50% woven cotton. After the washing stage, two 1-minute rinses were performed and the ballast was discarded. After a second pre-wash and dry cycle, the control fabrics were then stained with dirty motor oil and left to dry before being washed for a final time to evaluate the performance of the composition. Before and after washing, the color of the stains was measured using Hunterlab Ultrascan XE and expressed in terms of the difference between the stained and clean fabric, giving values ΔE * (before washing) or ΔE * (after washing), respectively. The ΔE values are the color differences defined as the Euclidean distance between the stained and cleaned tissue in the L * a * b * color space. The AE * values (after washing) have been converted to Stain Removal Index values (SRI) by applying the standard transformation: SRI = 100 - ΔE * (after washing)
    [0080] Using this composition, an average SRI value of 91.3 (standard deviation 5.8) was obtained after storage at 60 ° C for 8 days. If this performance is compared with the performance of the freshly prepared SRN 100, as per our previous example, it would equal a washing performance of 91%.
    权利要求:
    Claims (17)
    [0001]
    1. Alkaline liquid detergent composition for washing, characterized by comprising at least 1% by weight of triethanolamine, at least 5% by weight of non-soap surfactant and at least 0.5% by weight of a polyester according to following formula (I):
    [0002]
    2. Composition, according to claim 1, characterized by the fact that “n” is based on a molar mean that is a number from 43 to 47.
    [0003]
    3. Composition, according to claim 2, characterized by the fact that “n” is based on a molar average that is a number from 44 to 46.
    [0004]
    4. Composition, according to claim 3, characterized by the fact that “n” is based on a molar mean that is 45.
    [0005]
    5. Composition according to any one of claims 1 to 4, characterized by the fact that R1 and R2, independently of each other, are H3C- (OC2H4) n- (OC3H6) m, with groups - (OC2H4) and the groups - (OC3H6) are arranged in the form of blocks and the block consisting of groups - (OC3H6) is linked to a COO group, “n” is based on a molar mean that is a number from 44 to 46, “m ”Is based on a molar average that is 2, and“ a ”is based on a molar average that is a number from 6 to 7.
    [0006]
    6. Composition, according to claim 5, characterized by the fact that “n” is based on a molar mean that is 45.
    [0007]
    7. Composition according to any one of claims 1 to 4, characterized by the fact that R1 and R2, independently of each other, are H3C- (OC2H4) n- (OC3H6) m, with groups - (OC2H4) and the groups - (OC3H6) are arranged in the form of blocks and the block consisting of groups - (OC3H6) is linked to a COO group, “n” is based on a molar mean that is a number from 44 to 46, “m ”Is based on a molar average that is 5, and“ a ”is based on a molar average that is a number from 6 to 7.
    [0008]
    8. Composition, according to claim 7, characterized by the fact that “n” is based on a molar mean that is 45.
    [0009]
    Composition according to any one of the preceding claims, characterized in that it comprises at least 2% by weight of alkoxylated imine polyethylene.
    [0010]
    10. Composition according to any of the preceding claims, characterized by the fact that it comprises at least 5% by weight of anionic surfactant.
    [0011]
    11. Composition according to any one of the preceding claims, characterized by the fact that it comprises the anionic alkyl ether sulfate surfactant.
    [0012]
    12. Composition according to any one of the preceding claims, characterized in that it comprises linear alkyl benzene sulfonate (LAS), the LAS being neutralized from LAS acid, at least in part, with triethanolamine (TEA).
    [0013]
    13. Composition according to any one of the preceding claims, characterized in that it comprises at least 2% by weight of the polyester.
    [0014]
    14. Composition according to any one of the preceding claims, characterized in that it comprises at least 0.5% by weight of amine oxide.
    [0015]
    15. Composition according to any one of the preceding claims, characterized by the fact that it comprises up to 25% by weight of hydrotrope.
    [0016]
    16. Composition according to any one of the preceding claims, characterized in that it comprises a maximum of 1% by weight of alkali metal ions.
    [0017]
    17. 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, more preferably still less than 1% by weight.
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    同族专利:
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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 art. 34 industrial property law|
    2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2021-01-12| B09A| Decision: intention to grant|
    2021-02-09| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |
    2021-03-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12178621.4|2012-07-31|
    EP12178621|2012-07-31|
    PCT/EP2013/065583|WO2014019903A1|2012-07-31|2013-07-24|Alkaline liquid laundry detergent compositions comprising polyesters|
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