Polyester and its uses

Abstract

A polyester comprising at least one diacid-based building block, at least one diol-based building block, and at least one polyol-based building block, wherein the diacid-based building block is represented by the formula (I): [Formula 1] JPEG2025501467000012.jpg38170 (in the formula, R 1 is formula A 1 -O-(C=O)-CH2-O-(AO) x -X 1 where x is a number from 0 to 75; X 1 is hydrogen or methyl, AO is an alkylene oxide selected from ethylene oxide and a combination of ethylene oxide with at least one of propylene oxide and butylene oxide, and A1 is a branched or linear C2-C6-alkylene; the polyol building blocks are derived from a compound having y hydroxyl groups per molecule, where y is at least 3; The asterisk represents a bond to a diol or polyol building block through an ester oxygen atom; A polyester in which the molar ratio of diacid-based building blocks to the sum of diol and polyol building blocks (the latter multiplied by 2 / y) is in the range of 2:1 to 1:2.

Description

[Technical field]

[0001] The present invention relates to a polyester comprising at least one diacid-based constitutional unit, at least one diol-based constitutional unit, and at least one polyol-based constitutional unit, wherein the diacid-based constitutional unit is represented by formula (I): [ka] (In the formula, R 1 is formula-A 1 -O-(C=O)-CH2-O-(AO) x -X 1 where x is a number from 0 to 75; X 1 is hydrogen or methyl, AO is an alkylene oxide selected from ethylene oxide and a combination of ethylene oxide with at least one of propylene oxide and butylene oxide, 1 is a branched or preferably linear C2-C6-alkylene group, the polyol building blocks are derived from a compound having y hydroxyl groups per molecule, where y is at least 3; The asterisk represents a bond to a diol or polyol building block through an ester oxygen atom; For polyesters the molar ratio of diacid-based building blocks to the sum of diol and polyol building blocks (the latter multiplied by 2 / y) is in the range of 2:1 to 1:2. [Background technology]

[0002] Polyaspartates are polymers that contain mono-N-substituted aspartic acid units in their structure. Despite the name, such polymers are synthesized not from aspartic acid but from unsaturated polyesters (UPEs) and primary amines using aza-Michael addition. The product of this reaction contains a polyester backbone with side chains linked to the backbone through secondary amine groups.

[0003] U.S. Patent Application Publication No. 2005 / 0059791 A1, for example, describes flexible polyaspartic esters formed by reacting diethyl maleate with 1,4-butanediol, followed by addition of a polyamine such as 1,6-hexanediamine.

[0004] In laundry formulations, it is a common problem to disperse solid inorganic particles such as clay. Inorganic particles can be derived from soils such as clay, silica and oxide ions. During the washing process, they are removed from the laundry, dispersed in the washing liquor and removed together with the washing liquor. Several structures such as alkoxylated polytriethanolamine have been proposed, see for example WO2009 / 060409. However, the compounds proposed are generally not biodegradable.

[0005] Detergent formulators are continually challenged to develop improved products for removing various soils and stains from fabrics and hard surfaces. Removal of particulate stains has been a particularly challenging task. This challenge has been exacerbated in recent years by the growing interest and motivation to adopt sustainable bio-based and / or biodegradable components in laundry detergents and hand dishwashing. This has resulted in an increased market demand for detergent ingredients that combine a satisfactory performance profile with significantly improved biodegradability. Summary of the Invention [Problem to be solved by the invention]

[0006] It was therefore an object of the present invention to provide an additive for laundry formulations which exhibits good properties in laundry applications, for example with regard to cleaning properties, in particular with regard to dispersion of inorganic particles, and which is biodegradable. A further object of the present invention was to provide a process for producing such an additive, and an object to provide a laundry formulation with good solid inorganic particle dispersion properties, without the need to use non-biodegradable additives. [Means for solving the problem]

[0007] Accordingly, we have found the polyesters defined at the outset, hereinafter also referred to as the inventive polyesters, which are explained in more detail below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The polyester of the present invention comprises at least one diacid-based building block, at least one diol-based building block, and at least one polyol-based building block, the diacid-based building block being represented by formula (I): [ka] In formula (I), the asterisk represents attachment to the diol or polyol building block via the ester oxygen atom.

[0009] Preferably, the polyesters of the invention contain more than one constitutional unit according to formula (I) per molecule, for example from 2 to 20, preferably from 3 to 10.

[0010] It is generally understood that the polyester of the present invention is not one type of pure compound, but a mixture of various compounds containing the same constitutional units but with different arrangements, and has a molecular weight distribution as described below.

[0011] R 1 is represented by the general formula -A 1 -O-(C=O)-CH2-O-(AO) x -X 1 where x is a number from 0 to 75, preferably 0 or 12 to 30. 1 may be methyl or hydrogen, preferably X 1 is methyl.

[0012] A 1is a branched or preferably linear C2-C6-alkylene, for example, CH2-CH2, (CH2)3, (CH2)4, (CH2)6, CH(CH3)-CH2, CH2-CH(CH3), CH(C2H5)-CH2, CH2-CH(C2H5), CH(n-C3H7)-CH2, CH2-CH(n-C3H7), of which linear ones such as CH2-CH2, (CH2)3, (CH2)4, (CH2)5 and (CH2)6 are preferred, and CH2-CH2 is more preferred.

[0013] AO is an alkylene oxide selected from ethylene oxide (CH2CH2-O, hereinafter also referred to as EO) and a combination of EO with at least one of propylene oxide (CH2CH(CH3)-O, hereinafter also referred to as PO) and butylene oxide (CH2CH(C2H5)-O, hereinafter also referred to as BuO).

[0014] In one embodiment of the present invention, x is 0 or in the range of 1 to 30, and R 1 The majority of AO in R is ethylene oxide, and more preferably, x is in the range of 12 to 30, and the majority of all AO is EO. 1 is the formula (EO) x1 (PO) x2 -H, where x1 is in the range of 8 to 20 and x2 is in the range of 1 to 5.

[0015] In certain embodiments, x ranges from 12 to 25 and all AO are EO.

[0016] In particular, in embodiments where x is greater than 2, for example between 2 and 75, the value of x represents an average value, which refers to a number average.

[0017] The diol building blocks may be based on an aliphatic or cycloaliphatic diol, such as a C2-C8 alkanediol or a C4-C7 cycloalkanediol, preferably a C2-C8 alkanediol, which is unsubstituted or substituted by one or more methyl or ethyl groups. The diol building blocks may be derived from one or at least two different aliphatic or cycloaliphatic diols, preferably one. "Based on" in this context means that the majority of the hydroxyl groups are included in the polyester of the invention in esterified form.

[0018] Examples of C2-C8 alkanediols are ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethyl-propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2,3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane- 1,6-diol, hexane-2,5-diol, heptane-1,2-diol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,5-hexadiene-3,4-diol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and pinacol. Preferred examples are ethylene glycol, triethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2,5-dimethyl-2,5-hexanediol and 2-ethyl-1,3-hexanediol.

[0019] Examples of C4-C7 cycloalkanediols are 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cycloheptanediol. The aforementioned usually exist as mixtures of isomers.

[0020] In another embodiment of the present invention, the diol building block is diethylene glycol, triethylene glycol, tetraethylene glycol or an alkylene glycol having an average molecular weight M of, for example, 200 to 500 g / mol. n In another embodiment of the invention, the diol building block is based on a polyethylene glycol having an average molecular weight M of, for example, 280 to 750 g / mol. n The polypropylene glycol is based on

[0021] The polyol building blocks are derived from compounds having at least three hydroxyl groups per molecule, for example three ("triol", y=3) or four ("tetrol", y=4) or six ("hexol", y=6), with triols being preferred. In the context of the present invention, the term "hydroxyl group" refers to a primary or secondary alcohol group. Examples of triol building blocks are glycerol, butane-1,2,3-triol, butane-1,2,4-triol, pentane-1,2,3-triol, pentane-1,2,4-triol, pentane-1,2,5-triol, hexane-1,2,3-triol, hexane-1,2,4-triol, hexane-1,2,5-triol, hexane-1,2,6-triol, hexane-1,3,4-triol, hexane-1,3,5-triol, hexane-1,3,6-triol, hexane-1,4,5-triol, tetrahydrofuran-2,3,4-triol, tetrahydrofuran-2,3,5-triol, 2-(hydroxymethyl)tetrahydrofuran-3,4-diol, 5-(hydroxymethyl)tetrahydrofuran-2,4-diol, (3-hydroxytetrahydrofuran-2,5-diol), 1-(3-hydroxytetrahydrofuran-2-yl)dimethanol, 1-(3-hydroxytetrahydrofuran-2-yl)ethane-1,2-diol, 1-(4-hydroxytetrahydrofuran-2-yl)ethane-1,2-diol, 2-(2-hydroxyethyl)tetrahydrofuran-3,4-diol, 2-(1-hydroxyethyl)tetrahydrofuran-3,4-diol, 6-(hydroxymethyl)tetrahydro-2H-pyran-2,3-diol, 6-(hydroxymethyl)tetrahydro-2H-pyran-2,4-diol, 6-(hydroxymethyl)tetrahydro-2H-pyran-2,5-diol, 1,trimethylolmethane, 1,1,1-trimethylolethane and 1,1,1-trimethylolpropane as well as their ethoxylated, propoxylated and / or butoxylated derivatives and mixtures of at least two of the aforementioned.Preferred examples of triol building blocks are those based on glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, n-hexane-1,3,6-triol, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpropane ("TMP"), 1,1,1-trimethylolethane, trimethylolmethane and mixtures of at least two of the foregoing. "Based on" and "derived from" in this context mean that the majority of the hydroxyl groups are included in the polyester of the invention in esterified form.

[0022] Further examples of triol building blocks are those derived from any of the ethoxylates and propoxylates described above, such as the ethoxylates and propoxylates of glycerol or TMP, in such embodiments, the molar ratio of ethoxylate or propoxylate per mole of glycerol or TMP, respectively, ranges from 1:1 to 50:1.

[0023] Examples of tetrol building blocks are those derived from pentaerythritol, diglycerol, trimethylolpropane dimer, erythritol or ethoxylate, propoxylate or mixed ethoxylate / propoxylate oligomers and polymers based on the aforementioned tetrols as starting components. More preferably, the tetrol building blocks are derived from pentaerythritol and diglycerol.

[0024] An example of a hexol building block is that derived from sorbitol.

[0025] In the polyesters of the invention, the molar ratio of diacid-based building blocks to the sum of diol and polyol building blocks (the latter multiplied by 2 / y) is in the range of from 2:1 to 1:2, preferably from 3:2 to 2:3, more preferably from 1.2:1 to 1:1.2, even more preferably from 1.1:1 to 1:1.1 and in particular 1:1.

[0026] Thus, (moles of diacid-based constitutional units) / [(moles of diol-based constitutional units)+2 / y (moles of polyol-based constitutional units)] is in the range of 2:1 to 1:2, preferably 3:2 to 2:3, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1, and particularly preferably 1:1.

[0027] In one embodiment of the present invention, the molar ratio of diol building blocks to polyol building blocks multiplied by 2 / y is in the range of 1:1 to 4:1.

[0028] In a preferred embodiment of the present invention, all of the polyol constituent units are triol constituent units, and the molar ratio of diol constituent units to triol constituent units multiplied by 2 / 3 is in the range of 2:1 to 1:1.5, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1, and particularly preferably 1:1.

[0029] In one embodiment of the present invention, the average molecular weight M of the polyester of the present invention is n The average molecular weight M is in the range of 2,000 to 75,000 g / mol, preferably 10,000 to 50,000 g / mol. n can be measured by gel permeation chromatography ("GPC"). Suitable mobile phases are hexafluoroisopropanol ("HFIP"), dimethylacetamide ("DMAc"), tetrahydrofuran ("THF") and water.

[0030] In one embodiment of the present invention, the average molecular weight M of the polyester of the present invention is w The average molecular weight M is in the range of 10,000 to 200,000, preferably 20,000 to 175,000 g / mol. w can be measured by GPC. Suitable mobile phases are HFIP, DMAc, THF and water.

[0031] In one embodiment of the present invention, the polydispersity M of the polyester of the present invention w / M nis in the range of 1:10, preferably 1.5 to 7, and more preferably 2 to 5.

[0032] In one embodiment of the invention, the hydroxyl number according to DIN 53240 (2013) of the unsaturated polyester after step (a) is in the range of 5 to 150 mg KOH / g.

[0033] In one embodiment of the invention, the polyesters of the invention have an overall amino number according to DIN 9072 in the range of 3 to 50 mg KOH / g.

[0034] In one embodiment of the present invention, the polyester of the present invention has a glass transition temperature in the range of -5°C to 41°C as measured by differential scanning calorimetry (DSC).

[0035] In one embodiment of the present invention, the polyesters of the present invention have some carbon-carbon double bonds. Such carbon-carbon double bonds preferably have the (E) configuration (or trans-, etc.). These are 1 This can be determined by H-NMR spectroscopy. In one embodiment of the present invention, the molar percentage of carbon-carbon double bonds corresponds to a range of 5-10% of the ester building blocks.

[0036] In one embodiment of the present invention, the polyester of the present invention may contain additional units based on alkanedicarboxylic acids, such as adipic acid, succinic acid or glutaric acid, for example, the molar ratio of diacid-based units according to formula (I) to alkanedicarboxylic acid-based units is in the range of 10:1 to 2:1. In that case, such alkanedicarboxylic acid-based units will be replaced by diacid-based units according to formula (I) in terms of the molar ratio of diol and polyol units. However, in a preferred embodiment, the polyester of the present invention does not contain such additional units.

[0037] Preferably, the polyester of the present invention does not contain any constitutional units derived from monoalkanols and monocarboxylic acids.

[0038] It has been found that the above-mentioned good properties can be obtained by using a mixture of diols and polyols in a specific range, i.e., 2:1 to 1:2 molar ratio based on hydroxyl groups, to adjust the branching degree of the polyester of the present invention. It has been found that the solution viscosity of the polyester of the present invention is significantly low. In addition, the polyester of the present invention is biodegradable.

[0039] Thus, another aspect of the invention is a process for producing the polyester of the invention, comprising the steps of: (a) reacting an activated α,β-ethylenically unsaturated dicarboxylic acid with a mixture of at least one diol and at least one polyol, wherein the activated unsaturated dicarboxylic acid is selected from activated maleic acid, activated itaconic acid, and activated fumaric acid, and the molar ratio of the carboxyl groups of the activated α,β-ethylenically unsaturated dicarboxylic acid to the sum of the hydroxyl groups of the diol and polyol is in the range of 2:1 to 1:2; (b) The product obtained in step (a) is treated with HO-A 1 -NH2, and most preferably reacting with HO-CH2-CH2-NH2; (c) The product obtained in step (b) is reacted with HOOC-CH2-O-(AO) x -X 1 and converting using The process includes:

[0040] The process is also referred to as the process of the present invention, and the steps are also referred to as step (a) or step (b) or step (c), respectively. The activated α,β-ethylenically unsaturated dicarboxylic acid and the diol and polyol are also collectively referred to as starting materials. The process of the present invention is described in more detail below.

[0041] In step a), an activated α,β-ethylenically unsaturated dicarboxylic acid is reacted with a mixture of at least one diol and at least one polyol.

[0042] Examples of α,β-ethylenically unsaturated dicarboxylic acids are maleic acid, itaconic acid, fumaric acid, with maleic acid being preferred. Since harsh reaction conditions are required when carrying out step (a) using the acid itself, for example maleic acid, step (a) is carried out using so-called activated α,β-ethylenically unsaturated dicarboxylic acids. Activation can be carried out by using the dichlorides of the respective α,β-ethylenically unsaturated dicarboxylic acids, C1-C4 alkyl diesters of the α,β-ethylenically unsaturated dicarboxylic acids, or anhydrides in the case of maleic acid.

[0043] Particularly preferred examples are the dimethyl ester of maleic acid, the diethyl ester of maleic acid and maleic anhydride.

[0044] Examples of suitable diols and polyols are as disclosed above. Preferred examples are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and ethylene glycols having an average molecular weight M of, for example, 200 to 500 g / mol. n In another embodiment of the invention, the diol is dipropylene glycol, tripropylene glycol, tetrapropylene glycol or polyethylene glycol having an average molecular weight M of, for example, 280 to 750 g / mol. n The polypropylene glycol is selected from those having the formula:

[0045] The polyols are, for example, selected from compounds having at least three hydroxyl groups per molecule, for example three ("triols", y=3) or four ("tetrols", y=4) or six ("hexols", y=6), with triols being preferred. Examples of preferred triols are glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, n-hexane-1,3,6-triol, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpropane ("TMP"), 1,1,1-trimethylolethane, trimethylolmethane and mixtures of at least two of the foregoing.

[0046] Further examples of triols are the ethoxylates and propoxylates of any of the foregoing, such as the ethoxylates of glycerol or TMP. In such embodiments, the molar ratio of ethoxylate or propoxylate per mole of glycerol or TMP, respectively, ranges from 1:1 to 50:1.

[0047] Examples of tetrols are pentaerythritol, diglycerol, trimethylolpropane dimer, ethoxylate, propoxylate or mixed ethoxylate / propoxylate oligomers and polymers based on erythritol or the aforementioned tetrols as starting components. More preferably, the tetrols are selected from pentaerythritol and diglycerol.

[0048] An example of a hexol is sorbitol.

[0049] In step (a), the molar ratio of the carboxyl groups of the activated α,β-ethylenically unsaturated dicarboxylic acid to the sum of the hydroxyl groups of the diol and polyol is in the range of 2:1 to 1:2, preferably 3:2 to 2:3, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1, and particularly preferably 1:1.

[0050] In one embodiment of step (a), an activated alkanedicarboxylic acid, such as an activated adipic acid, an activated succinic acid or an activated glutaric acid, is added, for example, such that the molar ratio of activated α,β-ethylenically unsaturated dicarboxylic acid to activated alkanedicarboxylic acid is in the range of 10:1 to 2:1. The addition of the activated alkanedicarboxylic acid does not change the overall molar ratio of activated carboxyl groups to activated hydroxyl groups. The activation of the carboxyl groups of the alkanedicarboxylic acid can be of the same type as that of the α,β-ethylenically unsaturated dicarboxylic acid, especially in the case of C1-C4 alkyl esters and succinic acid to anhydride.

[0051] Step (a) may be carried out in bulk or in the presence of a solvent. Examples of suitable solvents include hydrocarbons such as paraffins or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene isomer mixtures, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Examples of suitable solvents in the absence of an acid catalyst include ethers such as dioxane or tetrahydrofuran and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

[0052] The amount of solvent may be at least 0.1% by weight, preferably at least 1% by weight, more preferably at least 10% by weight, based on the mass of the starting materials to be reacted. It is also possible to use an excess amount of solvent, for example 1.01 to 10 times the mass of the starting materials to be reacted. If the amount of solvent exceeds 100 times the mass of the starting materials, the concentration of the reactants is significantly reduced, the reaction rate is significantly reduced, and the reaction time is uneconomically long, which is not advantageous.

[0053] Step (a) may be carried out in the presence of a moisture remover, which is added at the beginning of step (a). Suitable examples include molecular sieves, in particular molecular sieves 4Å, MgSO4 and Na2SO4. It is also possible to add additional moisture remover during the reaction or to replace the moisture remover with fresh moisture remover. It is also possible to distill off the water or alcohol formed during the reaction and to use, for example, a Dean-Stark apparatus.

[0054] Step (a) may be carried out in the absence of an acid catalyst. It is preferred to operate in the presence of an acid inorganic catalyst, an acid organometallic catalyst or an acid organic catalyst or a mixture of two or more acid catalysts.

[0055] Examples of the acidic inorganic catalyst in step (a) include sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid H3PO2, aluminum sulfate hydrate, alum, acidic silica gel (pH=6, particularly=5) and acidic alumina. Examples of the acidic inorganic catalyst include, for example, compounds represented by the general formula Al(OR 2 )3 and aluminum compounds of the general formula Ti(OR 2 Titanates of R 2 The groups are the same or different and independently represent C1 to C 10 Alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl, C3 to C6 12 Cycloalkyl is, for example, selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, with cyclopentyl, cyclohexyl and cycloheptyl being preferred.

[0056] Preferably, Al(OR 1 )3 and Ti(OR1 )4R 1 The groups are each the same and are selected from isopropyl or 2-ethylhexyl.

[0057] Preferred acidic organometallic catalysts are, for example, dialkyltin oxides R 1 2SnO, R 1 is as defined above. A particularly preferred example of an organometallic acid catalyst is di-n-butyltin oxide, which is commercially available in the form of oxotin. Further examples of organometallic catalysts are selected from dialkyltin dicarboxylates, such as dibutyltin dilaurate.

[0058] Preferred acidic organic catalysts are, for example, acidic organic compounds containing phosphoric acid groups, sulfonic acid groups, sulfuric acid groups or phosphonic acid groups. Particularly preferred are sulfonic acids such as paratoluenesulfonic acid. Acidic ion exchangers can also be used as acidic organic catalysts, an example of which is a polystyrene resin containing sulfonic acid groups and crosslinked with about 2 mol % divinylbenzene.

[0059] It is also possible to use a combination of two or more of the aforementioned catalysts. Another possibility is to use these organo- or organometallic, otherwise inorganic, catalysts in the form of separate molecules in immobilized form.

[0060] When it is desired to use an acidic inorganic, organometallic or organic catalyst, the amount of catalyst used in accordance with the present invention is from 0.1 to 10% by weight, preferably from 0.2 to 2% by weight.

[0061] Step (a) is preferably carried out under an inert gas atmosphere, such as carbon dioxide, nitrogen or a noble gas, among which mention may be made especially of argon.

[0062] In one embodiment of the present invention, step (a) is carried out at a temperature between 80° C. and 200° C. It is preferred to operate at temperatures between 130° C. and 180° C., in particular between 140° C. and 170° C. or less. Particularly preferred is a maximum temperature of up to 165° C., very preferably up to 160° C.

[0063] The pressure conditions of step (a) are not critical. It is possible to operate under a significant reduced pressure, for example from 10 to 500 mbar. Step (a) of the invention can also be carried out at pressures above 500 mbar. To simplify step (a), it is preferred to carry it out at atmospheric pressure, but it is also possible to carry it out at slightly higher pressures, for example up to 1200 mbar. A further option is to increase the pressure significantly, for example to work at up to 10 bar. It is preferred to carry out step (a) at atmospheric pressure.

[0064] In one embodiment of the present invention, the duration of step (a) is from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours, more preferably from 1 hour to 20 hours.

[0065] An unsaturated polyester is obtained from step (a). The term "unsaturated" refers to the presence of carbon-carbon double bonds in the polyester obtained in step (a). It is observed that a portion of the C-C double bonds, for example 5-20% of the double bonds, are isomerized during step (a).

[0066] After step (a), the obtained unsaturated polyester can be easily isolated, for example by removing the catalyst by filtration, and concentrating the filtrate, usually under reduced pressure.Another suitable work-up method includes adding water, followed by precipitation, followed by washing and drying.In another embodiment, the obtained unsaturated polyester is used without further purification.

[0067] In one embodiment of the present invention, the unsaturated polyesters obtained from step (a) have an average molecular weight Mn (gel permeation chromatography GPC in DMAc) of 500 to 10,000 g / mol, preferably 600 to 5,000 g / mol, more preferably 700 to 2,500 g / mol. They are usually easily soluble in polar solvents, i.e. even with up to 50% by weight, and in some cases even up to 80% by weight, of the polyesters of the present invention, clear solutions can be prepared that are free of gel particles detectable by the naked eye. Examples of polar solvents are tetrahydrofuran (THF), ethanol, diethylene glycol, propylene glycol.

[0068] In one embodiment of the present invention the unsaturated polyester from step (a) has a hydroxyl number according to DIN 53240 (2013) in the range of 5 to 150 mg KOH / g.

[0069] In step (b), the unsaturated polyester obtained in step (a) is reacted with an amino alcohol HO-A 1 -NH2, for example 1-aminopropan-2-ol, 1-aminobutan-2-ol, preferably HO-CH2-CH2-NH2, HO-(CH2)3-NH2 (3-amino-1-propanol), 5-amino-1-pentanol, 6-amino-1-hexanol, in particular HO-CH2CH2-NH2. 1 is selected such that the hydroxyl and amino groups are separated by at least two carbon atoms.

[0070] Step (b) can be carried out in bulk or in a polar solvent capable of dissolving the unsaturated ester obtained from step (a). Bulk synthesis is preferred.

[0071] In one embodiment of the present invention, step (b) is carried out at a temperature in the range of 20-80°C, preferably 40-70°C.

[0072] The pressure conditions of step (b) are not critical. It is possible to operate under a significant reduced pressure, for example from 10 to 500 mbar. Step (b) of the present invention can also be carried out at pressures above 500 mbar. To simplify step (b), it is preferred to carry it out at atmospheric pressure, but it is also possible to carry it out at slightly higher pressures, for example up to 1200 mbar (abs). A further option is to increase the pressure significantly, for example to work up to 10 bar. It is preferred to carry out step (b) at atmospheric pressure.

[0073] In one embodiment of the present invention, the duration of step (b) is from 10 minutes to 48 hours, preferably from 1 hour to 30 hours.

[0074] Step (b) is preferably carried out without the addition of a catalyst.

[0075] It is also possible to deactivate the catalyst from step (a) before carrying out step (b). In another embodiment, the catalyst is not deactivated.

[0076] In step (c), the product obtained from step (b) is reacted with HOOC-CH2-O-(AO) x -X 1 The variable elements x and X 1 and AO are as defined above. In the context of the present invention, HOOC-CH2-O-(AO) x -X 1 can also be referred to as the monoacid of the polyalkylene oxide.

[0077] In one embodiment of the invention, the compound of formula: HOOC-CH2-O-(AO) x -X 1 (In the formula, X 1 =H) contain, as impurities, both the respective diacid and the unoxidized diol, for example in a total amount of up to 50 mol %, preferably 10 to 30 mol %.

[0078] In one embodiment of the present invention, the formula HOOC-CH2-O-(AO) x -X1 (In the formula, X 1 =CH3) contains, as impurities, unoxidized alcohols, for example in a total amount of up to 30 mol %, preferably 0.5 to 15 mol %.

[0079] In the above embodiment, such unoxidized species react with the product resulting from step (b) via transesterification rather than reacting to form the desired ester.

[0080] Step (c) may be carried out in the presence of a moisture remover, which is added at the beginning of step (c). Suitable examples include molecular sieves, in particular molecular sieves 4Å, MgSO4 and Na2SO4. It is also possible to add additional moisture remover during the reaction or to replace the moisture remover with fresh moisture remover. It is also possible to distill off the water or alcohol formed during the reaction and to use, for example, a Dean-Stark apparatus.

[0081] Step (c) may be carried out in the absence of an acid catalyst. It is preferred to operate in the presence of an acid inorganic catalyst, an acid organometallic catalyst or an acid organic catalyst or a mixture of two or more acid catalysts.

[0082] Generally, any of the catalysts used in step (a) can also be used in step (c). In a preferred embodiment, the process of the invention is carried out as a one-pot reaction, and the same catalyst from step (a) is used in step (c).

[0083] Step (c) can be carried out in bulk or in the presence of a solvent. Examples of suitable solvents include hydrocarbons such as paraffins or aromatics. The choice of solvent is similar to that of step (a).

[0084] In one embodiment of the present invention, the duration of step (a) is from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours, more preferably from 1 hour to 20 hours.

[0085] Step (c) is preferably carried out under an inert gas atmosphere, such as carbon dioxide, nitrogen or a noble gas, among which mention may be made especially of argon.

[0086] In one embodiment of the present invention, step (c) is carried out at a temperature between 80° C. and 200° C. It is preferred to operate at temperatures between 130° C. and 180° C., in particular between 140° C. and 170° C. or less. Particularly preferred is a maximum temperature of up to 165° C., very preferably up to 160° C.

[0087] After carrying out step (c), the polyester of the present invention is obtained, for example, as a waxy solid. In many embodiments, the polyester of the present invention contains some unreacted acid HOOC-CH2-O-(AO) x -X 1 or its manufacturing by-products (see above). However, said unreacted acid is not a problem when the polyesters of the present invention are used in cleaning compositions.

[0088] In an exemplary step (a) of the process of the present invention, activated maleic acid and a diol (HO-A 2 -OH) and triol (A 3 (OH)3), a branched unsaturated polyester is formed (a few maleic acid units are converted to the trans configuration): [ka]

[0089] In an exemplary step (b), the branched unsaturated polyester from step (a) is reacted with a primary monoamine R 1 -NH2 by aza-Michael addition: [ka]

[0090] Another aspect of the present invention relates to the use of the polyesters of the present invention in cleaning compositions, particularly laundry detergent compositions. Such compositions may also be referred to as laundry detergent compositions of the present invention, or simply as compositions of the present invention. The laundry detergent compositions of the present invention may be in solid or liquid or gel form at ambient temperature, with liquid or gel form being preferred.

[0091] The polyesters of the present invention can be added in cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions. Preferably, the polyesters of the present invention can be added (used) in cleaning or cleaning compositions.

[0092] Another subject of the present invention is therefore cleaning compositions, in particular for fabrics, which comprise at least one polyester of the present invention, preferably cleaning compositions and / or fabric care and home care products, in particular cleaning compositions which remove, disperse and / or emulsify soils and / or modify the treated surfaces and / or maintain the whiteness of the treated surfaces, preferably exhibiting at least two of these advantages, more preferably at least three of these advantages and even more preferably four or more of these advantages.

[0093] Selected advantages of the cleaning compositions of the present invention are as follows: i) Good clay removal; ii) good removal of particulate stains; iii) good dispersion and / or emulsification of the dirt; iv) modification of the treated surface to improve removal of subsequent recontamination; v) Increased whiteness; vi) in embodiments in which at least one enzyme selected from lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases is present, as well as combinations of at least two of the aforementioned types, additionally improves the removal of oily / greasy stains, food stains and / or combination stains; and / or vii) In the presence of at least one enzyme according to vii), additionally oily / greasy stain removal, food stain removal and / or combination stain removal.

[0094] In one embodiment of the present invention, the composition of the present invention contains the polyester of the present invention in a concentration of 0.05 to 20% by weight, preferably 0.1 to 15% by weight, and more preferably 0.5 to 5% by weight.

[0095] In one embodiment of the invention, the polyesters of the invention are added to a composition comprising from about 1% to about 70% by weight of a surfactant combination. In such an embodiment, the polyesters of the invention may be present at a concentration of from about 0.1% to about 5% by weight of the composition, or from about 0.5% to about 2% by weight of each of the compositions of the invention.

[0096] Preferably, the compositions of the present invention are laundry detergents, cleaning compositions and / or fabric care and home care products, preferably laundry detergent compositions. Such compositions of the present invention improve soil removal, dispersion and / or emulsification and / or modify treated surfaces and / or maintain the whiteness of treated surfaces.

[0097] In one embodiment of the present invention, the composition of the present invention has a dynamic viscosity, measured by Brookfield, for example, with a Brookfield viscometer LVT-II at 25° C. with a spindle 3 at 20 rpm, in the range of 20 to 20,000 mPa s.

[0098] In one embodiment of the present invention, the composition of the present invention has a water content in the range of 50-98% by weight, preferably up to 95% by weight.

[0099] The composition of the present invention is preferably phosphate-free, in other words does not contain phosphate. "Phosphate-free" should be understood in the context of the present invention to mean that the content of phosphates and polyphosphates is in the range of 10 ppm to 1% by weight, preferably 10 ppm to 0.2% by weight or less, in total, based on the total non-volatile content, measured gravimetrically.

[0100] In one embodiment of the present invention, the compositions of the present invention may have a non-volatile content in the range of 10-30% by weight, preferably 15-30% by weight, as measured by evaporating under reduced pressure ("vacuum") at 105°C until the residue is constant, but for at least 2 hours.

[0101] In one embodiment of the invention, the compositions of the invention may contain a solvent other than water, such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, and phenoxyethanol, with ethanol, isopropanol, or propylene glycol being preferred.

[0102] In one embodiment of the present invention, the compositions of the present invention contain 0.5 to 12% by weight of the organic solvent based on the total weight of each composition. In an embodiment in which the compositions of the present invention are provided as a unit dose, for example in the form of a pouch, the content of the organic solvent may be in the range of 8 to 25% by weight based on the total weight of each composition.

[0103] In one embodiment of the present invention, the composition of the present invention has a pH value in the range of 7-11, preferably 7.5-9.5, more preferably 8-9.

[0104] The compositions of the present invention may contain one or more surfactants selected from nonionic, anionic, cationic and zwitterionic surfactants, with nonionic and anionic surfactants being preferred.

[0105] In one embodiment of the present invention, the laundry detergent composition of the present invention further comprises at least one anionic surfactant selected from linear alkylbenzene sulfonates and alkoxylated sulfonated fatty alcohols.

[0106] In one embodiment, the polyester of the present invention is a surfactant based on C 10 ~C 15 It may be used in cleaning compositions that include a surfactant system that includes an alkylbenzene sulfonate (LAS) and one or more additional surfactants selected from nonionic, cationic, anionic surfactants other than LAS, and mixtures thereof.

[0107] Preferred examples of alkoxylated sulfonated fatty alcohols are those represented by the general formula (II): C n H 2n+1 -O(CH2CH2O) a -SO3M (II) is a compound according to The variable definitions are as follows: n is a number ranging from 10 to 18, preferably 12 to 14, and more preferably n=12; a is a number ranging from 1 to 5, preferably from 2 to 4, and more preferably 3. M is selected from alkali metals, preferably potassium, more preferably sodium or ethanolammonium.

[0108] In a compound according to formula (II), the variables n and a may be average numbers and therefore are not necessarily integers, but in an individual molecule according to formula (II), n and a both represent integers.

[0109] In one embodiment of the invention, the composition of the invention contains an additional anionic surfactant, hereinafter also referred to as linear alkylbenzene sulfonate.

[0110] In one embodiment of the present invention, the composition of the present invention contains, as an anionic surfactant, nC 10 ~C 18 Alkylbenzenesulfonic acid alkali metal or amine salts, especially sodium n-dodecylbenzenesulfonate or ethanolammonium n-dodecylbenzenesulfonate, such as mixtures obtained from the sodium salts of linear 4-dodecylbenzenesulfonic acid and linear 5-dodecylbenzenesulfonic acid, may be used in amounts ranging from 10 to 40% by weight based on the total non-volatile content of the liquid detergent composition.

[0111] The ethanol ammonium may be selected from monoethanol ammonium, N,N-diethanol ammonium and N,N,N-triethanol ammonium, with monoethanol ammonium being preferred.

[0112] Further examples of anionic surfactants include C8-C 12 Alkyl sulfate, C 12 ~C 18 Fatty alcohol ether sulfate, ethoxylated C4-C 12 Sulfuric acid half esters of alkylphenols (ethoxylated: 3-50 mol ethylene oxide / mol), C 12 ~C 18 Alkyl sulfonic acid, C 12 ~C 18 Sulfofatty acid alkyl esters, e.g., C 12 ~C 18 Sulfo fatty acid methyl esters, C 10 ~C 18 Alkylarylsulfonic acid, preferably nC 10 ~C 18 Alkylbenzene sulfonic acid, C 10 ~C 18Alkyl alkoxy carboxylates and e.g. C8-C 24 Alkali metal and ammonium salts of soaps such as carboxylic acids. The alkali metal salts of the aforementioned compounds are preferred, with the sodium salts being particularly preferred.

[0113] In one embodiment of the invention, the composition according to the invention contains at least one non-ionic surfactant, such as a polyglycoside, an alkoxylated fatty amine or an alkoxylated fatty alcohol, more preferably at least one compound according to formula (III), (IV) or (V).

[0114] In one embodiment of the invention, the polyglycoside has formula (III): (G) u -OR 3 (III) and R 3 is a linear or branched chain, preferably linear C8-C 18 alkyl, u is in the range of 1.1 to 4, G is selected from monosaccharides having 4 to 6 carbon atoms, preferably glucose and xylose.

[0115] More preferred polyglycosides are linear C4-C 16 alkyl polyglycosides having the average general formula (III.1): [ka] (In the formula, R 4 is C1-C4 alkyl, in particular ethyl, n-propyl or isopropyl; R 5 is -(CH2)2-R 4 and G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, u is in the range of 1.1 to 4, the average number of branched C8 to C 14Alkyl polyglycosides are likewise suitable.

[0116] In one embodiment of the present invention, the alkoxylated fatty amine has the general formula (IV): C m H 2m+1 -N[(AO) r H]2(IV) and m is a number ranging from 10 to 18; r is different or the same and ranges from 1 to 12; AO are different or the same and are selected from ethylene oxide or a combination of ethylene oxide with at least one of propylene oxide and butylene oxide.

[0117] In one embodiment of the present invention, the polyalkoxylated fatty alcohol has the general formula (V): C m H 2m+1 -O[(AO) r H] (V) and The variables are as above: M is selected from alkali metals, preferably potassium, more preferably sodium; AO are different or identical and are selected from ethylene oxide, propylene oxide and butylene oxide, and combinations of at least two of the foregoing, in particular ethylene oxide CH2CH2O, r is different or the same and is selected from the range of 1 to 12, preferably 5 to 10.

[0118] In the above surfactants, the variables m and y may be average numbers, so they are not necessarily integers, but in individual molecules according to formula (II), m and y both represent integers.

[0119] In one embodiment of the present invention, the composition of the present invention contains at least one sequestering agent.Preference is given to phosphate-free sequestering agents.Examples thereof are citric acid and aminopolycarboxylic acids and their corresponding alkali metal salts, especially sodium salts.Preferred aminocarboxylic acids are methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA).

[0120] MGDA and its corresponding salts can be selected from racemic mixtures, D- and L-isomers, and non-racemic mixtures of D- and L-isomers. Preferably, MGDA and its corresponding salts are selected from racemic mixtures and mixtures containing 55-85 mol% of L-isomer with the remainder being D-isomer. Particularly preferred are mixtures containing 60-80 mol% of L-isomer with the remainder being D-isomer.

[0121] The distribution of L- and D-enantiomers can be measured by optical rotation measurements (polarimetry) or, preferably, by chromatography, e.g., HPLC using a chiral column, e.g., HPLC using one or more cyclodextrins as stationary phase. Preferably, the ee is measured by HPLC with immobilized optically active ammonium salts, such as D-penicillamine.

[0122] GLDA and its corresponding salts can be selected from racemic mixtures, D- and L-isomers, and non-racemic mixtures of D- and L-isomers. Preferably, GLDA and its corresponding salts are selected from mixtures containing 75-99 mol% of the L-isomer, the remainder being the D-isomer. Particularly preferred are mixtures containing 80-97.5 mol% of the L-isomer, the remainder being the D-isomer.

[0123] In one embodiment of the present invention, the composition of the present invention does not contain bleaching agent.Bleaching agent in the context of the present invention refers to organic peroxides, inorganic peroxides and chlorine bleaching agents.Examples of organic and inorganic peroxides are sodium perborate, anhydrous or for example as monohydrate or tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or for example as monohydrate, hydrogen peroxide, in each case as free acid or alkali metal salt, especially sodium salt, persulfate, organic peroxyacids, such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, as well as sulfonylperoxyacids and cationic peroxyacids. Chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

[0124] "Free" in the context of bleach means less than 0.5% by weight based on total nonvolatile content.

[0125] In one embodiment of the invention, the composition of the invention contains at least one alkali metal or ethanolammonium salt of a fatty acid, preferably at least one potassium or ethanolammonium salt of a fatty acid. Examples are the sodium and especially potassium salts of lauric, myristic, palmitic, stearic, (hydrogenated) erucic and behenic acids, as well as soap mixtures derived from natural fatty acids, in particular coconut, palm kernel, olive or tallow fatty acids. Preferred examples are potassium coconut soap, potassium stearate, potassium oleate, nC 12 H 25 More preferred are potassium cocoate soaps having the average formula of COOK.The amount of potassium salt of fatty acid may range from 10 to 25% by weight based on the total non-volatile content of the liquid detergent composition.

[0126] The compositions of the present invention are liquid laundry detergent compositions. The liquid laundry detergent compositions may contain ingredients other than those mentioned above. Examples of these are surfactants other than those mentioned above, especially zwitterionic surfactants, as well as fragrances, dyes, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers and corrosion inhibitors.

[0127] Examples of fragrances are benzyl salicylate, 2-(4-tert-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.

[0128] Examples of dyes are Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101, Acid Green 1, Solvent Green 7 and Acid Green 25.

[0129] The detergent compositions of the present invention may contain one or more preservatives or biocides. Biocides and preservatives prevent deterioration of the liquid detergent compositions of the present invention due to attack from microorganisms. Examples of biocides and preservatives are BTA (1,2,3-benzotriazole), benzalkonium chloride, 1,2-benzisothiazolinone-3-one ("BIT"), 2-methyl-2H-isothiazol-3-one ("MIT"), 2-butyl-benzo[d]isothiazol-3-one ("BBIT"), 2-octyl-2H-isothiazol-3-one ("OIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("OIT"). Sothiazol-3-one ("CIT"), benzoic acid, lactic acid, salicylic acid, sorbic acid and their sodium, cxalcium and MEA salts, iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoin ("DCDMH"), bromochlorodimethylhydantoin ("BCDMH") and dibromodimethylhydantoin ("DBDMH"). Further examples of biocides and preservatives are 4,4'-dichloro 2-hydroxydiphenyl ether, also known as 5-chloro-2-(4-chlorophenoxy)phenol, Diclosan, DCPP (commercially available as a 30% by weight solution of 4,4'-dichloro 2-hydroxydiphenyl ether in 1,2-propylene glycol), 2-bromo-2-nitropropane-1,3-diol, also known as 2-bromo-2-nitro-1,3-propanediol; glutaraldehyde, also known as 1-5-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde; glyoxal, also known as ethanedial, oxylaldehyde, 1,2-ethanedial, as well as benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate, saccharinate, didecyldimethylammonium chloride, N-(3-aminopropyl)-N-dodecylpropane, peracetic acid, or H2O2.

[0130] The detergent composition of the present invention may contain a total of 0.001 to 2% by weight of preservatives or biocides, for example, 0.1 to 2% by weight of 2-phenoxyethanol or 0.005 to 0.6% by weight of DCPP.

[0131] For example, the following antimicrobial agents and / or preservatives are of particular interest: 4,4'-Dichloro-2-hydroxydiphenyl ether (CAS number 3380-30-1), also known as 5-chloro-2-(4-chlorophenoxy)phenol, Diclosan, DCPP (commercially available under the trade name Tinosan® HP100 as a 30% by weight solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propylene glycol): and 2-Phenoxyethanol (CAS number 122-99-6, also known as: phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, Protectol® PE); 2-Bromo-2-nitropropane-1,3-diol (CAS number 52-51-7, alias: 2-Bromo-2-nitro-1,3-propanediol, Bronopol®, Protectol® BN, Myacide AS); Glutaraldehyde (CAS number 111-30-8, also known as: 1-5-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA); Glyoxal (CAS number 107-22-2; synonyms: ethanedial, oxylaldehyde 1,2-ethanedial, Protectol® GL); 2-Butyl-benzo[d]isothiazol-3-one (BBIT, CAS number 4299-07-4); 2-Methyl-2H-isothiazol-3-one (MIT, CAS number 2682-20-4); 2-Octyl-2H-isothiazol-3-one (OIT, CAS number 26530-20-1); 5-Chloro-2-methyl-2H-isothiazol-3-one (CIT, CMIT, CAS number 26172 -55-4);5-chloro-2-methyl-2H-isothiazol-3-one (CMIT, EINECS 247-500-7) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) mixture (CMIT / MIT mixture, CAS number 55965-84-9);1,2-benzisothiazol-3(2H)-one (BIT, CAS number 2634-33-5); Hexa-2,4-dienoic acid (sorbic acid, CAS number 110-44-1) and its salts, such as calcium sorbate, sodium sorbate, potassium (E,E)-hexa-2,4-dienoate (potassium sorbate, CAS number 24634-61-5); Lactic acid and its salts; in particular sodium lactate; L-(+)-lactic acid (CAS number 79-33-4); Benzoic acid (CAS No. 65-85-0, CAS No. 532-32-1) and salts of benzoic acid, such as sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate; Salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate (CAS numbers 8001-54-5, 63449-41-2, 91080-29-4, 68989-01-5, 68424-85-1, 68391-01-5, 61789-y71-7, 85409-22-9); Didecyldimethylammonium chloride (DDAC, CAS number 68424-95-3 and CAS number 7173-51-5); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine, CAS number 2372-82-9); Peracetic acid (CAS number 79-21-0); Hydrogen peroxide (CAS number 7722-84-1).

[0132] The biocide or preservative may be added to the composition of the present invention in a concentration of 0.001 to 10% relative to the total weight of the composition. Preferably, the composition of the present invention contains 2-phenoxyethanol in a concentration of 0.1 to 2% or 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%.

[0133] The present invention therefore further relates to a method for protecting the compositions of the invention from bacterial contamination or growth, comprising the addition of 2-phenoxyethanol.

[0134] The present invention therefore further relates to a method for imparting antimicrobial activity to textiles after treatment with a composition according to the invention containing 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP).

[0135] Examples of viscosity modifiers are agar, carrageenan, tragacanth, gum arabic, alginates, pectin, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, crosslinked poly(meth)acrylates, such as polyacrylic acid crosslinked with methylene bis(meth)acrylamide, as well as silicic acid, clays (including but not limited to montmorillonite, zeolites, dextrins, and casein).

[0136] A hydrotrope in the context of the present invention is a compound that promotes the dissolution of compounds with limited solubility in water. Examples of hydrotropes are, but are not limited to, organic solvents such as ethanol, isopropanol, ethylene glycol, 1,2-propylene glycol and glycerol, as well as further organic solvents that are miscible with water under normal conditions. Further examples of suitable hydrotropes are the sodium salts of toluenesulfonic acid, xylenesulfonic acid and cumenesulfonic acid.

[0137] Examples of useful enzymes are one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the foregoing classes. Particularly useful enzymes are selected from proteases, amylases and cellulases.

[0138] The preferred amount of the polyester of the invention in the composition of the invention is in the range of 0.001% to 5% by weight of the active enzyme in the detergent composition according to the invention. Together with the enzyme, enzyme stabilizing systems such as, for example, calcium ions, boric acid, boronic acid, propylene glycol and short chain carboxylic acids may also be used. In the context of the present invention, short chain carboxylic acids are selected from monocarboxylic acids having 1 to 3 carbon atoms per molecule and dicarboxylic acids having 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, glutamic acid (HOOC(CH2)3COOH), adipic acid and mixtures of at least two of the above, as well as the corresponding sodium and potassium salts.

[0139] Examples of polymers are especially polyacrylic acid and the respective alkali metal salts thereof, in particular the sodium salt thereof. A suitable polymer is especially polyacrylic acid, preferably having an average molecular weight M in the range from 2,000 to 40,000 g / mol, preferably from 2,000 to 10,000 g / mol, in particular from 3,000 to 8,000 g / mol. wand each is partially or completely neutralized with an alkali, in particular with sodium. Likewise suitable polycarboxylate copolymers are, in particular, copolymers of acrylic acid and methacrylic acid, and polycarboxylate copolymers of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid. Polyacrylic acid and its corresponding alkali metal salts can function as anti-redeposition agents.

[0140] Another class of useful copolymers are polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone ("NVP") and N-imidazole, copolymers of acrylic acid and NVP or N-imidazole, or copolymers of acrylic acid and both NVP and N-imidazole. The average molecular weight M of such (co)polymers as measured by gel permeation chromatography is w is in the range of 5,000 to 100,000 g / mol. Polyvinylpyrrolidone and copolymers of NVP and N-imidazole and copolymers of acrylic acid and NVP or N-imidazole can function as dye transfer inhibitors.

[0141] Further examples of polymers are polyethylene terephthalate, polyoxyethylene terephthalate and polyethylene terephthalate endcapped with one or two hydrophilic groups per molecule, the hydrophilic groups being selected from CH2CH2CH2-SONa, CH2CH(CH2-SONa)2 and CH2CH(CH2SONa)CH2-SONa.

[0142] Further examples of the polymer include polyfunctional polyethyleneimines and / or polyfunctional diamines. Such polyfunctional polyethyleneimines have a molecular weight M in the range of 3,000 to 250,000, preferably 5,000 to 200,000, more preferably 8,000 to 100,000, and even more preferably 10,000 to 20,000 g / mol. wSuitable polyfunctional polyethyleneimines have 80% to 99% by weight, preferably 85% to 99% by weight, more preferably 90% to 98% by weight, and most preferably 93% to 97% or 94% to 96% by weight of ethylene oxide side chains, based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core with polyethylene oxide side chains. Examples of suitable polyethyleneimines have molecular weights M in the range of 500 to 5000 g / mol, preferably 500 to 2000 g / mol. w , and more preferably 600 to 800 g / mol w In this case, the ethoxylated polyethyleneimine has an average of 5 to 50, preferably 10 to 35, and more preferably 20 to 35 ethylene oxide (EO) units per NH functional group.

[0143] Suitable polyfunctional diamines are typically ethoxylated C2-C 12 The alkylene diamines are preferably hexamethylene diamines, which are further quaternized and optionally sulfated. Typical polyfunctional diamines have molecular weights M in the range of 2,000 to 10,000, preferably 3000 to 8000, more preferably 4000 to 6000 g / mol. w In a preferred embodiment of the present invention, further quaternized and sulfated ethoxylated hexamethylenediamines may be used which contain an average of 10 to 50, preferably 15 to 40, more preferably 20 to 30 ethylene oxide (EO) groups per NH function, preferably having two cationic ammonium groups and two anionic sulfate groups.

[0144] In a preferred embodiment of the present invention, the cleaning composition of the present invention comprises at least one multifunctional polyethyleneimine and / or at least one multifunctional diamine. The multifunctional polyethyleneimine and multifunctional diamine or mixtures thereof can be added to the laundry detergent and cleaning composition of the present invention in small amounts, generally 0.05-15% by weight, preferably 0.1-10% by weight, more preferably 0.25-5% by weight, or even up to 2% by weight, based on the total weight of the specific composition including other components and water and / or solvent. In that case, such compositions show improved cleaning performance, such as improved soil removal ability, especially improved primary cleaning power for particulate stains on polyester fabrics.

[0145] Thus, one aspect of the present invention is a laundry detergent composition, particularly a liquid laundry detergent, comprising (i) at least one polyester of the present invention and (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional diamines, and mixtures thereof.

[0146] In one embodiment of the present invention, the ratio of at least one polymer of the present invention to (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional diamines, and mixtures thereof, is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3.

[0147] Examples of buffers are monoethanolamine / monoethanolammonium and N,N,N-triethanolamine / N,N,N triethanolammonium.

[0148] An example of a defoamer is silicone.

[0149] The compositions of the present invention are not only advantageous when used to clean soiled laundry of inorganic soils such as clay or organic greasy soils such as oil, or to remove non-bleachable stains from laundry, such as, but not limited to, stains from red wine, tea, coffee, various fruit juices such as vegetable and berry juices, yet the compositions of the present invention do not leave any residue on the fabric.

[0150] In one embodiment of the present invention, 50 to at least 85% by weight of the organic compounds contained in the composition of the present invention are biodegradable, preferably determined according to the 2016 OECD guidelines, as further described below.

[0151] To be suitable as a liquid laundry detergent, the compositions of the present invention may be in bulk form or in unit dose form, such as a sachet or pouch. Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol.

[0152] Another aspect of the present invention is the use of the composition of the present invention for washing laundry. In particular, an aspect of the present invention is the use of the composition of the present invention for washing laundry, especially laundry made of or containing polyester. Another aspect of the present invention is a process for washing laundry, hereinafter also referred to as the process of the present invention. The process of the present invention relates to washing laundry by applying at least one composition of the present invention, preferably in a washing machine. The process of the present invention can be carried out in an automatic laundry washing machine or manually. The detergent composition of the present invention is preferably diluted with water before application to soiled laundry.

[0153] In one embodiment of the present invention, the inventive process is characterized in that the respective inventive composition is applied to soiled laundry at a temperature in the range of 20-65°C.

[0154] By the washing process of the present invention, as well as by the use of the present invention, such clays can be removed very efficiently from soiled laundry.

[0155] A further aspect of the present invention is a process for making the liquid detergent composition of the present invention, hereinafter also referred to as the method of the present invention, which comprises mixing the polyester of the present invention and other ingredients, such as but not limited to sequestering agents, surfactants and optionally further ingredients as outlined above, with water in one or more steps.

[0156] The present invention is further illustrated by examples. EXAMPLES

[0157] I. Overview The hydroxyl numbers (HN) of the linear and branched unsaturated polyesters were determined according to DIN 53240 (2013).

[0158] Gel Permeation Chromatography (GPC) GPC measurements of the unsaturated polyesters and the polyesters of the invention were carried out at room temperature on a PSS Agilent 1200 Series or a Duratec Modell 840 in HFIP or DMAc (containing 0.5% LiBr). The nominal solvent flow rate was 1 mL / min. For fractionation, two SEC columns from PSS Polymer Standards were used, with pore sizes 100 and 1000 for HFIP and 2 x 1000 Å and 2 x 10000 Å for DMAc. For HFIP, a refractive index detector G136A and a UV / Vis detector G1314B from Agilent Technologies were used. Calibration was carried out with polystyrene as standard for the samples in HFIP and poly(methyl methacrylate) for the samples in DMAc. The results were evaluated using the WinGPC UniChrom V 8.20 software from Polymer Standards Service GmbH.

[0159] Abbreviations: MeHQ: 4-methoxyhydroquinone

[0160] [Table 1]

[0161] II.Synthesis Process (a.1)DEM / 1,6-HD / TMP;1.1:0.8:0.2 A 1 liter two-necked round bottom flask fitted with a mechanical stirrer with PTFE blades was charged with diethyl maleate (488 g, 2.83 mol), 1,6-hexanediol (243.1 g, 2.05 mol), 1,1,1-trimethylolpropane (69.0 g, 0.514 mol) and dibutyltin dilaurate (0.39 g, 1.61 mmol). The flask was fitted with a Liebig condenser fitted with a Claisen head and a stream of dry N2 was applied slowly through the head to keep the reaction under an inert atmosphere. The reaction mixture thus obtained was heated at 160 °C using an oil bath for 7 h. During the first 2 h, the reaction mixture was kept under N2 flow and then the pressure in the flask was gradually reduced to 90 mbar using a vacuum pump. After 7 h, an unsaturated polyester was obtained. MeHQ (660 mg) was dissolved in the unsaturated polyester, which was used in step (b.1) without further purification.

[0162] Process (b.1): A 250 mL round bottom flask equipped with a magnetic stir bar was charged with 457 g of the unsaturated polyester from step (a.1), corresponding to 1.92 mol of C-C double bonds. The flask was heated to 50° C. under a stream of dry N2 and H2N-CH2CH2-OH (117 g, 1.92 mol) was added slowly within 20 min. Once the addition was complete, the reaction mixture was stirred at 60° C. for 24 h. The reaction mixture thus obtained was allowed to cool to ambient temperature. The intermediate polyester IP.1 was obtained.

[0163] Process (c.1): In a 250 liter two-necked round bottom flask equipped with a mechanical stirrer with PTFE blades, 10.7 g of IP.1 were charged together with 63 g of (γ.1) (750 g / mol, calculated so that its COOH groups react with all the OH groups of IP.1) and Ti(OBu)4 (0.04 g, 500 ppm). The flask was fitted with a Liebig condenser equipped with a Claisen head and a slow stream of dry N2 was applied through the head to keep the reaction under an inert atmosphere. The reaction mixture thus obtained was heated at 150° C. for 24 hours using an oil bath until the acid number of the product reached 12 mg KOH / g. The reaction mixture was then allowed to cool and the product obtained was used without further purification. The polyester PE.1 of the invention was obtained. 1 Groups according to formula (I) were detected by 1 H NMR spectroscopy.

[0164] Process (c.2): A 250 liter two-neck round-bottom flask equipped with a mechanical stirrer with PTFE blades was charged with 20.0 g of IP.1 together with 78.4 g of (γ.2) (500 g / mol, calculated so that its COOH groups react with all the OH groups of IP.1) and Ti(OBu)4 (0.04 g, 500 ppm). The flask was fitted with a Liebig condenser equipped with a Claisen head and a slow stream of dry N2 was applied through the head to keep the reaction under an inert atmosphere. The reaction mixture thus obtained was heated at 150° C. for 24 hours using an oil bath until the acid number of the product reached 13 mg KOH / g. The reaction mixture was then allowed to cool and the product obtained was used without further purification. The polyester PE.2 of the invention was obtained.

[0165] III. Preparation and Testing of Liquid Laundry Detergent Compositions III.1 Overview A liquid base composition MC1 was prepared according to Table 2.

[0166] [Table 2]

[0167] III.2 Primary cleaning power in Linitest The samples were each tested in a liquid model formulation MC1 according to the composition shown in Table 2 above.

[0168] The polyesters of the invention were added to the model composition MC1 (additive dosage 3% owod of the liquid model detergent) together with commercially obtained soiled fabrics (P-H108: clay, ground soil, P-H115: standard clay; P-H144: red china clay; P-H145: tennis court soil, from the Center of Test Materials CFT Vlaardingen) and 5 g of a commercial soiled soil ballast sheet wfk SBL 2004 (from wfk Testgewebe GmbH Brueggen). The washing conditions were 3 g / L detergent, 250 mL liquor volume, 40° C. for 30 min, and measurements were carried out in quadruplicate. After washing, the fabrics were rinsed and dried. The fabrics before and after washing were evaluated instrumentally using a MACH5 multi area color meter from ColourConsult, which represents the laboratory measurements. The results are summarized in Table 3. From these laboratory measurements, the ΔE value between the unwashed stain and the washed stain was calculated. The higher the ΔE value, the better the performance. To better determine the pure cleaning effect of each polymer sample by itself, the obtained values ​​were further expressed as ΔΔE values ​​relative to a polymer-free reference material (baseline correction for the cleaning effect of the polymer-free (plain) detergent alone). Again, the higher the respective ΔΔE value, the better the performance.

[0169] [Table 3]

[0170] IV. Biodegradability Test Summary: Biodegradation tests are carried out according to OECD guidelines. According to the OECD guidelines, a test is valid if: 1. The reference material reaches 60% within 14 days. 2. The difference in extreme values ​​between replicate tests by the end of the study is less than 20%. 3. The oxygen uptake of the blank containing only the inoculum should be 20-30 mg O2 / l and should not exceed 60 mg O2 / l. 4. The pH value measured at the end of the test must be between 6 and 8.5.

[0171] Biodegradation in wastewater was tested in triplicate using the manometric respirometry method of OECD 301F, an aerobic test that measures the biodegradation of wastewater samples by measuring the consumption of oxygen. Measured amounts of wastewater were spiked with 100 mg / L of the test substance, nominally the only carbon source, together with an inoculum (aerated sludge taken from the municipal wastewater treatment plant in Mannheim, Germany). The sludge was stirred in a closed flask at constant temperature (25°C) for 28 days. Oxygen consumption is measured by measuring the change in pressure in a closed flask using an Oxi TopC. The released carbon dioxide was absorbed in a sodium hydroxide solution. A nitrification inhibitor was added to the flask to prevent oxygen consumption by nitrification. The amount of oxygen taken up by the microbial population during the biodegradation of the test substance (corrected for the amount taken up by a parallel blank inoculum) is expressed as a percentage of ThOD (theoretical oxygen demand measured by elemental analysis of the compound). A positive control glucose / glutamate is run along with the test samples as a reference material in each cabinet.

[0172] Calculation: Theoretical oxygen demand: the amount of O2 required to oxidize a compound to its final oxidation products, e.g., H2O, CO2. This amount is determined using elemental analysis data.

[0173] Calculation of biodegradability (%): The experimentally obtained O2 uptake is taken as 100 and divided by the theoretical O2 demand.

[0174] The results of these biodegradation tests are shown in Table 4 below.

[0175] [Table 4]

[0176] In each test, the biodegradability of the reference material was greater than 60%.

Claims

1. A polyester comprising at least one diacid-based constitutional unit, at least one diol-based constitutional unit, and at least one polyol-based constitutional unit, the diacid-based constitutional unit being represented by formula (I): 【Chemistry 1】 (In the formula, R １ is the formula -A １ -O-(C=O)-CH ２ -O-(AO) ｘ -X １ where x is a number from 0 to 75, and X １ is hydrogen or methyl; AO is an alkylene oxide selected from ethylene oxide and combinations of ethylene oxide with at least one of propylene oxide and butylene oxide; A １ is a branched or linear C ２ ~C ６ -alkylene; the polyol building blocks are derived from a compound having y hydroxyl groups per molecule, where y is at least 3; The asterisk represents a bond to a diol or polyol building block through an ester oxygen atom; A polyester in which the molar ratio of diacid-based building blocks to the sum of diol and polyol building blocks (the latter multiplied by 2 / y) is in the range of 2:1 to 1:

2.

2. x is 0 or in the range of 1 to 30; R １ 2. The polyester of claim 1, wherein a majority of the AO in is ethylene oxide.

3. Average molecular weight M measured by gel permeation chromatography ｎ The polyester according to claim 1 or 2, wherein the molecular weight is in the range of 10000 to 50,000 g / mol.

4. N.H.R. １ C having no group ４ ~C ６ The polyester according to any one of claims 1 to 3, further comprising at least one constitutional unit selected from a dicarboxylic acid.

5. 5. Polyester according to any one of claims 1 to 4, wherein the diol building blocks are based on ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2,5-dimethyl-2,5-hexanediol or 2-ethyl-1,3-hexanediol or a mixture of at least two of the foregoing.

6. The polyester according to any one of claims 1 to 5, wherein the polyol component is selected from triols and tetrols.

7. 7. Polyester according to any one of claims 1 to 6, wherein the polyol building blocks are based on glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, n-hexane-1,3,6-triol, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane or trimethylolmethane or a mixture of at least two of the foregoing.

8. 8. The polyester of claim 1, wherein the molar ratio of diacid-based building blocks to the sum of diol and polyol building blocks is in the range of 1.5:1 to 1:1.

5.

9. A process for making the polyester of any one of claims 1 to 8, comprising the steps of: (a) reacting an activated α,β-ethylenically unsaturated dicarboxylic acid with a mixture of at least one diol and at least one polyol, said activated unsaturated dicarboxylic acid being selected from activated maleic acid, activated itaconic acid and activated fumaric acid; a molar ratio of carboxyl groups of the activated α,β-ethylenically unsaturated dicarboxylic acid to the sum of hydroxyl groups of the diol and polyol is in the range of 2:1 to 1:2; (b) The product obtained in step (a) is treated with HO-A １ -NH ２ and reacting (c) The product obtained in step (b) is reacted with HOOC-CH ２ -O-(AO) ｘ -X １ and converting using A process including.

10. 10. The process of claim 9, wherein the molar ratio of hydroxyl groups of the diol and polyol is in the range of 1:2 to 2:

1.

11. The activated α,β-ethylenically unsaturated dicarboxylic acid is a C ester of maleic acid and itaconic acid. １ ~C ４ Alkyl diesters, dichlorides and anhydrides and C of fumaric acid １ ~C ４ 11. The process according to claim 9 or 10, wherein the alkyl group is selected from alkyl diesters and dichlorides.

12. A laundry detergent comprising at least one polyester according to any one of claims 1 to 8.

13. 13. The laundry detergent of claim 12, further comprising at least one anionic surfactant selected from linear alkyl benzene sulfonates and alkoxylated sulfonated fatty alcohols.

14. 14. A laundry detergent composition according to claim 12 or 13, wherein the composition is in liquid or gel form at ambient temperature.

15. 15. The laundry detergent composition of any one of claims 12 to 14, further comprising at least one enzyme.

16. A method for protecting a laundry detergent composition according to any one of claims 12 to 15 from microbial contamination or growth, comprising adding 0.1 to 2% by weight of 2-phenoxyethanol.

17. A method for imparting antimicrobial activity to textile products after treatment with a laundry detergent composition according to any one of claims 12 to 15, comprising 4,4'-dichloro 2-hydroxydiphenyl ether.

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