COPOLYMERS AND THEIR USE IN DETERGENT COMPOSITIONS

Abstract

What are described are copolymers containing cationic structural units and macromonomeric structural units. The copolymers can be used advantageously in laundry detergent compositions and are advantageously suitable therein especially for cleaning of cotton-containing textiles or for reducing the resoiling of cotton-containing textiles on which the copolymers or the laundry detergent compositions have been employed.

Claims

1. A copolymer containing a) 0.1 to 15.4 mol % of at least one cationic structural unit (A) and b) 0.1 to 99.9 mol % of at least one macromonomeric structural unit (B), wherein the at least one cationic structural unit (A) is represented by the following formulae (I) and/or (II): ##STR00016## in which R.sup.1 and R.sup.1a are each the same or different and are each independently hydrogen and/or a methyl radical, R.sup.1b, R.sup.3, R.sup.4 and R.sup.5 are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbyl radical having 5 to 20 carbon atoms, an aryl radical having 6 to 14 carbon atoms and/or polyethylene glycol (PEG), Y is the same or different and is represented by oxygen, NH and/or NR.sup.3, V is the same or different and is represented by (CH.sub.2).sub.x, ##STR00017## x is the same or different and is represented by an integer from 1 to 6, X and X.sub.1 are each the same or different and are each independently represented by a halogen atom, C.sub.1- to C.sub.4-alkylsulfate and/or C.sub.1- to C.sub.4-alkylsulfonate, and the at least one macromonomeric structural unit (B) is represented by the formula (III): ##STR00018## in which R.sup.x is same or different and is represented by H and/or methyl, Z is the same or different and is represented by CO and/or O(CH.sub.2).sub.4, I on molar average is a number from 0 to 6, and p on molar average is a number from 1 to 150.

2. The copolymer as claimed in claim 1, wherein the at least one cationic structural unit (A) is/are the polymerization product of at least one monomer species selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium chloride, [2-(acryloylamino)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methosulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or methosulfate, [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride (DADMAC).

3. The copolymer as claimed in claim 1, wherein the at least one macromonomeric structural unit (B) of the formula (III) is/are the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether (in which I on molar average is a number from 1 to 6), polyethylene glycol (meth)acrylate and polyethylene glycol-co-polypropylene glycol (meth)acrylate (in which I on molar average is a number from 1 to 6).

4. The copolymer as claimed in claim 1 wherein, in the at least one macromonomeric structural unit (B) of the formula (III), i) R.sup.x is H, I=0 and p on molar average is a number from 1 to 150, when Z is O(CH.sub.2).sub.4 or ii) R.sup.x is the same or different and is represented by H and/or methyl, I on molar average is a number from 1 to 6, and p on molar average is a number from 1 to 150 when Z is CO.

5. The copolymer as claimed in claim 1, which, in addition to the structural units (A) and (B), contains at least one structural unit (C) other than the structural units (A) and (B), and which contains 0.1 to 15.4 mol % of the at least one structural units (A), 0.1 to 99.8 mol % of the at least one structural unit (B) and 0.1 to 99.8 mol % of the at least one structural unit (C).

6. The copolymer as claimed in claim 5, wherein the at least one structural unit (C) is/are the polymerization product of at least one monomer species selected from the group consisting of noncationic acrylamides, noncationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms.

7. The copolymer as claimed in claim 5, wherein the at least one structural unit (C) is selected from the group consisting of the polymerization product of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and the structural units of the following formulae (IV) and (V): ##STR00019## in which R.sup.1 is the same or different and is hydrogen and/or methyl, and R.sup.3 and R.sup.4 are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbyl radical having 5 to 20 carbon atoms, an aryl radical having 6 to 14 carbon atoms, an alkylaryl radical having 7 to 14 carbon atoms, a branched or unbranched C.sub.1-C.sub.5-monohydroxyalkyl group and/or polyethylene glycol (PEG), ##STR00020## in which R.sup.11 is the same or different and is represented by H and/or methyl; X is the same or different and is represented by NH(C.sub.nH.sub.2n) with n=1, 2, 3 or 4; and R.sup.13 is the same or different and is represented by OH, N(CH.sub.3).sub.2, SO.sub.3H, PO.sub.3H.sub.2, OPO.sub.3H.sub.2 and/or para-substituted C.sub.6H.sub.4SO.sub.3H.

8. The copolymer as claimed in claim 7, wherein the at least one structural unit (C) is selected from the group consisting of structural units of the formula (IV).

9. The copolymer as claimed in claim 5, wherein the at least one structural unit (C) is/are the polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tert-butylacrylamide.

10. The copolymer as claimed in claim 5, which, in addition to the structural units (A), (B) and (C), contains at least one structural unit (D) other than the structural units (A), (B) and (C), and which contains 0.1 to 15.4 mol % of the at least one structural unit (A), 0.1 to 99.7 mol % of the at least one structural unit (B), 0.1 to 99.7 mol % of the at least one structural unit (C) and 0.1 to 99.7 mol % of the at least one structural unit (D).

11. The copolymer as claimed in claim 10, which contains at least one structural unit (D) selected from the group consisting of the structural units of the following formula (VII): ##STR00021## in which S is the same or different and is represented by COOM.sub.k, R.sup.1 is the same or different and is represented by H and/or an unbranched or branched C.sub.1-C.sub.4-alkyl group; and M is a cation selected from the group consisting of hydrogen ion, alkali metal ion and alkaline earth metal ion, with k=valency.

12. The copolymer as claimed in claim 11, which contains at least one structural unit (D) that is the polymerization product of at least one monomer species selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid, sodium methacrylate and potassium methacrylate.

13. The copolymer as claimed in claim 10 wherein the structural units (A), (B) and optionally (C) and (D) are present in the copolymer in a random, blockwise, alternating or gradient distribution.

14. The copolymer as claimed in claim 1, having a weight-average molecular weight M.sub.w of from 10 000 to 400 000 g/mol.

15. A laundry detergent composition comprising at least one copolymer as claimed in claim 1.

16. A method for cleaning of a textile comprising the step of contacting the textile with at least one laundry detergent according to claim 15.

17. A method for reducing the resoiling of a textile comprising the step of contacting the textile with at least one laundry detergent according to claim 15.

Description

EXAMPLES

[0193] The following abbreviations are used:

TABLE-US-00001 AAPTAC [3-(acryloylamino)propyl]trimethylammonium chloride (75% by weight active in aqueous solution) DMAA N,N-dimethylacrylamide (100% active) DADMAC diallyldimethylammonium chloride (65% by weight active in aqueous solution) MAPTAC [3-(methacryloylamino)propyl]trimethylammonium chloride (50% by weight active in aqueous solution) NIPAM N-isopropylacrylamide (100% active) PEG MA polyethylene glycol-co-polypropylene glycol methacrylate 1000 1000 g/mol, 4-5 propylene glycol units (70% by weight active in aqueous solution) VA-44 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (100% active) V-PEG polyethylene glycol vinyloxybutyl ether, 1100 g/mol 1100 (100% active)

[0194] Preparation of Copolymers of the Invention

[0195] General Method for Preparation of Copolymers of the Invention

[0196] In a multineck flask equipped with a precision glass stirrer, reflux condenser and N.sub.2 connection, under nitrogen (5 liters/hour), for the examples cited in table 1 for preparation of copolymers of the invention, the stated amounts of chemicals (excluding the initiator) are dissolved in the stated amount of distilled water. It should be noted that some of the substances used for preparation of the copolymers are used in aqueous form (see the details given for the substances used for the preparation of the copolymers). The distilled water specified in table 1 is added in addition to the water introduced via these substances. In the case of acidic monomers, these are pre-neutralized with base, for example alkali metal carbonate, e.g. potassium carbonate. Subsequently, the aqueous solution is purged with nitrogen for 30 minutes and heated to 60 C. In the next step, the amount of initiator specified in table 1 (VA-44) is dissolved in 10 g of distilled water and metered in over a period of 90 minutes. After the metered addition has ended, stirring is continued at an internal temperature of 60 C. for a further hour. The conversion of the reaction is checked by a subsequent analysis of the solids, and any unconverted monomers, if necessary, are reacted via a small addition of a 10% by weight aqueous solution of the initiator already used beforehand until full conversion has been attained. Thereafter, the reaction mixture is cooled down to room temperature (20-23 C.).

[0197] Table 1 lists synthesis examples of copolymers of the invention.

TABLE-US-00002 TABLE 1 Substances used for preparation of copolymers of the invention V-PEG PEG MA Methacrylic Na hypo- dist. Copolymer 1100 1000 AAPTAC NIPAM MAPTAC DMAA DADMAC acid phosphite VA-44 H.sub.2O No. [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [g] [g] [g] 1 4.20 23.10 6.30 8.40 0.75 1.49 70.02 2 4.20 23.10 3.40 11.30 0.75 1.15 70.02 3 21.90 21.90 15.70 45.20 26.40 0.25 1.66 161.00 4 13.10 13.10 9.20 30.20 0.13 1.70 92.50 5 9.80 19.70 26.20 9.90 0.13 1.70 149.50

[0198] The amounts stated in table 1 are based on the active substance.

TABLE-US-00003 TABLE 1a Relative amounts according to table 1 Total amount Struc- Struc- Struc- Struc- Copol- of the mono- tural tural tural tural ymer mers used units (A) units (B) units (C) units (D) No. [mmol] [mol%] [mol%] [mol%] [mol%] 1 42.0 15.0 65.0 20.0 2 42.0 8.1 65.0 26.9 3 131.1 12.0 33.4 34.5 20.1 4 65.6 14.0 39.9 46.0 5 65.6 15.1 45.0 39.9

TABLE-US-00004 TABLE 2 Measured weight-average molecular weights M.sub.w: Copolymer Weight-average No. molecular weights M.sub.w 1 2.10 10.sup.5 g/mol 2 2.72 10.sup.5 g/mol 3 1.65 10.sup.5 g/mol 4 9.02 10.sup.4 g/mol 5 1.72 10.sup.5 g/mol

[0199] Adsorption Experiments on Cellulose-Coated Crystal Oscillators

[0200] The tests were effected with the QCM-D Quartz Crystal Microbalance with Dissipation Monitoring, Q-Sense, Vstra Frlinda, Sweden. The method is based on the change in the intrinsic frequency of a piezoelectric quartz crystal as soon as it is loaded with a mass. The surface of the crystal may be modified by spin-coating or vapor deposition. The crystal oscillator is within a test cell. The test cell used is a flow cell into which the solution to be examined is pumped from reservoir vessels. The pumping rate is kept constant during the measurement time. Typical pumping rates are between 50-250 L/minute. During the measurement, it should be ensured that the hoses and test cell are free of air bubbles. Each measurement begins with the recording of the baseline, which is set as the zero point for all frequency and dissipation measurements.

[0201] In this example, cellulose-coated crystal oscillators (low-charged nanofibrillar cellulose, thickness: 50-100 mm, adhesion promoter: any polycation) were used.

[0202] Aqueous solutions of the copolymers of the invention with an active content of 1000 ppm were examined. The water used was tapwater of 14 dH (German hardness). The pH was adjusted to pH 8.5 with NaOH or citric acid. The measurement data were used to calculate the mass of hydrated copolymer bound. The results are summarized in table 3 below.

TABLE-US-00005 TABLE 3 QCM-D adsorption characteristics Copolymer Mass adsorbed Mass adsorbed No. [ng/cm.sup.2] [mol/cm.sup.2] 1 323.0 1.5366 10.sup.12 2 183.9 6.7536 10.sup.13 3 283.9 1.7237 10.sup.12 4 144.2 1.5987 10.sup.12 5 153.7 8.9383 10.sup.13

[0203] The results in table 3 show that the copolymers of the invention are suitable for employment on cellulose-containing textiles, for example as soil release polymers, since they are adsorbed on the surface under examination.

[0204] Laundry Detergent Compositions with Illustrative Copolymers of the Invention

[0205] A number of illustrative laundry detergent compositions either with or without copolymer of the invention according to table 4 were produced. All the samples contain sodium hydroxide as a buffer system.

[0206] Key for the ingredients used in the compositions of table 4: [0207] LAS linear C12-14-alkylbenzenesulfonate, sodium salt [0208] SLES 2EO sodium lauryl ether sulfate with 2 mol EO (Genapol LRO, Clariant) [0209] NI 7EO nonionic C12-15-alcohol ethoxylate 7EO (Genapol LA070, Clariant) [0210] Fatty acid stripped C12-18 palm kernel fatty acid

TABLE-US-00006 TABLE 4 Laundry detergent compositions Ingredient % by weight of active substance LAS 5.20 SLES 2EO 6.50 NI 7EO 5.20 Fatty acid 2.80 Glycerol 2.40 Ethanol 1.20 Sodium citrate 1.70 Copolymer of the invention 1.00 Demineralized water and ad 100 NaOH for adjustment of pH pH 8.4
5 laundry detergent compositions comprising inventive copolymer no. 1, 2, 3, 4 or 5 are produced. All 5 laundry detergent compositions are clear at room temperature.