Washing or cleaning agent for reducing malodors

Abstract

A washing or cleaning agent that has MOFs (metal organic frameworks) in order to reduce offensive odor, a method for reducing malodors, and the use of MOFs to reduce malodors.

Claims

1. A washing or cleaning agent, wherein said washing or cleaning agent contains a metal organic framework (MOF) comprising organic ligands having the general formula (IV), ##STR00003## wherein R.sup.1 to R.sup.4 in general formula (IV) represent, independently of each other, H, COOH, COO.sup.?, OH, or NH.sub.2; wherein the washing or cleaning agent further comprises: a) 5 to 40 wt % anionic surfactants selected from the group consisting of alkylbenzene sulfonates, alkyl sulfates and mixtures thereof, b) 0.5 to 25 wt % nonionic surfactants selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglucosides, fatty acid glucamides and mixtures thereof; and wherein the metal organic framework is free of copper.

2. The washing or cleaning agent according to claim 1, wherein the organic ligand of the metal organic framework is obtained from 1,4-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid, fumaric acid, mono-, di-, or trivalent anions thereof, or mixtures thereof.

3. The washing or cleaning agent according to claim 1, wherein the metal organic framework comprises aluminum, titanium, zirconium, iron, zinc, bismuth, or oxoclusters, hydroxoclusters, hydroxyoxoclusters, or mixtures thereof as a metal component.

4. The washing or cleaning agent according to claim 1, comprising 0.001 to 10 wt % of the metal organic framework.

5. A method for reducing malodors, wherein a washing or cleaning agent, according to claim 1 is brought in contact with a surface.

6. The method for reducing malodors according to claim 5, wherein the metal organic framework is applied to a textile or a hard surface during an automated method.

7. The method for reducing malodors according to claim 5, wherein the malodor is caused by the presence of acids, thiols, amines, (hetero)aromatics, and/or alcohols.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates a nitrogen adsorption isotherm;

(2) FIG. 2 is an x-ray powder diffractogram showing the reflections of NH.sub.2-MIL-125(Ti);

(3) FIG. 3 shows a nitrogen adsorption isotherm without further activation of the material;

(4) FIG. 4 is an x-ray powder diffractogram showing the reflections of MIL-100(Al);

(5) FIG. 5 is a nitrogen adsorption isotherm after activation of a sample of the obtained material; and

(6) FIG. 6 is an x-ray powder diffractogram showing the reflections of NH.sub.2-MIL-101(Al).

DETAILED DESCRIPTION OF THE INVENTION

(7) After the activation of a sample of the obtained material at 120? C. and 10.sup.?3 mbar, a nitrogen adsorption isotherm (FIG. 1) was recorded at 77 K. At p/p.sub.0=0.3, a specific surface area of 1,134 m.sup.2/g could be determined from said isotherm by means of the single-point BET method (DIN ISO 9277:2014).

(8) The x-ray powder diffractogram (FIG. 2) of the sample shows the reflections of NH.sub.2-MIL-125(Ti) at the expected positions.

(9) Synthesis of MIL-100(Al)

(10) On the basis of the following literature: Volkrieger et al., Chem. Mater. 2009, 21, 5695-5697.

(11) A mixture of 11.2 mmol of Al(NO.sub.3).sub.3.9 H.sub.2O (Gr?ssing, 99%), 9.1 mmol of trimesic acid trimethyl ester (self-synthesized), 14 mL of 1 M HNO.sub.3, and 50.4 mL of deionized H.sub.2O was transferred to a 250-mL steel autoclave (DAB-3 from Berghof) having a PTFE insert. The autoclave was heated at 210? C. for 3 h 30 min in a drying oven.

(12) After cool-down to room temperature, the product was separated from the yellow mother liquor by means of a laboratory centrifuge at 4,000 rpm. To wash the precipitate, the precipitate was resuspended in 50 mL of ethanol and centrifuged again under the same conditions and the washing solution was discarded. This washing process was then repeated two more times. After the solid thus obtained was dried at room temperature at finally 10.sup.?3 mbar for 16 h, 6.3 g of raw product were obtained.

(13) Said raw product contained contaminants encapsulated in the pores, and said contaminants reduce the porosity. To remove said contaminants, the product was resuspended in 400 mL of N,N-dimethyl formamide and the suspension was held at 150? C. for 4 h in a 1-liter Schott flask inside a drying oven. Then the solid was centrifuged off, put into 50 mL of deionized water, and centrifuged again and the washing water was discarded.

(14) The product thus obtained was finally cleaned by means of a Soxhlet apparatus by using 0.5 L of deionized water for 12 h and then desolvated at 220? C. and 10.sup.?3 mbar for 4 h.

(15) In this way, 2.0 g of a white, light solid were obtained.

(16) Without further activation of the material, a nitrogen adsorption isotherm (FIG. 3) was recorded at 77 K. At p/p.sub.0=0.3, a specific surface area of 1,637 m.sup.2/g could be determined from said isotherm by means of the single-point BET method (DIN ISO 9277:2014).

(17) The x-ray powder diffractogram (FIG. 4) of the sample shows the reflections of MIL-100(Al) at the expected positions.

(18) Synthesis of NH.sub.2-MIL-101(Al)

(19) On the basis of the following literature: M. Hartmann, M. Fischer, Microporous Mesoporous Mater. 2012, 164, 38-43.

(20) 30 mmol of 2-aminoterephthalic acid (Aldrich, 99%) were dissolved in 1.1 L of N,N-dimethyl formamide and heated in a 2-liter three-neck flask to 110? C. with reflux.

(21) 60 mmol of AlCl.sub.3.6 H.sub.2O (Fluka, 99%) were divided into seven portions of equal size. Each portion was dissolved in 14 mL of N,N-dimethyl formamide while heating was performed and was stored sealed for further use.

(22) At a time interval of 15 min and while magnetic stirring was performed, the individual aluminum chloride solutions were added to the hot solution of 2-aminoterephthalic acid. After the last addition, the solution was held at 110? C. for 3 h with stirring and then for 16 h without stirring.

(23) After cool-down to room temperature, the formulation was filtered by means of a G4 fit and washed there with 1?200 mL of N,N-dimethyl formamide and with 5?200 mL of ethanol.

(24) The product thus obtained was extracted by means of a Soxhlet apparatus by using 1 L of ethanol for 12 h and then dried at 90? C. for 24 h in a drying oven.

(25) 6.95 g of product were obtained.

(26) After the activation of a sample of the obtained material at 120? C. and 10.sup.?3 mbar, a nitrogen adsorption isotherm (FIG. 5) was recorded at 77 K. At p/p.sub.0=0.3, a specific surface area of 2,839 m.sup.2/g could be determined from said isotherm by means of the single-point BET method (DIN ISO 9277:2014).

(27) The x-ray powder diffractogram (FIG. 6) of the sample shows the reflections of NH.sub.2-MIL-101(Al) at the expected positions.

Example 2: Odor Test

(28) The performance with regard to reduction of offensive odor was determined as follows. The MOF powders were suspended in a solvent (aqueous or non-aqueous, such as ethanol, deionized water, or washing-agent solution (produced by dissolving 4 g of a liquid washing agent in 1 L of water of 16? dH)) by means of an ultrasonic bath. Nonwovens (various materials, such as polypropylene (PP) or viscose) were uniformly wetted with suspension on a permeable base. The filter function of the nonwoven material causes immobilization of the MOF solid particles. A (2 cm?2 cm) nonwoven equipped with the particular MOF was placed in a screw-top glass jar of defined size. A defined amount of a sweat offensive-odor mixture was introduced into said jar. The jar was immediately closed. After a holding time of 5 min, the jar was opened and the odor intensity was determined olfactorily (scale of 0-10; 0=no offensive odor, 10=strong offensive odor). In addition to compounds according to the invention, comparison compounds and untreated nonwoven as a standard were also examined. Each examination was performed twice by two persons independently of each other.

(29) The sweat offensive-odor mixture contained the following components:

(30) 20 wt % octanoic acid

(31) 20 wt % nonanoic acid

(32) 20 wt % 3-methylbutanoic acid

(33) 20 wt % 2-ethyl-2-hexenoic acid

(34) 20 wt % 3-mercapto-1-hexanol

(35) The following table summarizes the results as mean values of a double determination. The MOF was applied to the nonwoven from ethanolic suspension. The nonwovens were then dried at 120? C. The untreated PP nonwoven (standard) has an odor intensity of 8.5.

(36) TABLE-US-00001 MOF sample on Odor intensity Odor intensity PP nonwoven (nonwoven (nonwoven Color MOF type/ loading loading impression metal/linker 0.05 mg/cm.sup.2) 0.25 mg/cm.sup.2) of nonwoven MIL-100/Al/BTC 3 0 Acceptable MIL-101/Fe/BDC 4 2 Acceptable MIL-101/Fe/ABDC 5 0 Acceptable MIL-125/Ti/BDC 7 6 Acceptable MIL-125/Ti/ABDC 4 1 Acceptable MIL-101/Al/ABDC 2 0 Acceptable Al fumarate/Al/ 5.5 2 Acceptable fumaric acid CuBTC/Cu/BTC (not 6 2 Unacceptable according to the (blue) invention) BTC: 1,3,5-benzenetricarboxylic acid BDC: 1,4-benzenedicarboxylic acid ABDC: 2-amino-1,4-benzenedicarboxylic acid

(37) The following table comprises the results as mean values of a double determination. The MOF was applied to the nonwoven from suspension in deionized water (WT) or from the washing-agent-solution-based suspension (WASS). The nonwovens were then dried at 60? C. for 1 h.

(38) TABLE-US-00002 MOF sample on viscose Odor intensity, Odor intensity Odor intensity Color nonwoven untreated (nonwoven (nonwoven impression MOF type/metal/ viscose loading loading of linker nonwoven 0.05 mg/cm.sup.2) 0.25 mg/cm.sup.2) nonwoven MIL-100/Al/BTC 8 6 4 Acceptable via WT MIL-100/Al/BTC 8 2 1 Acceptable via WASS MIL-101/Al/ABDC 8 6 5 Acceptable via WT MIL-101/Al/ABDC 8 5 4 Acceptable via WASS MIL-53/Al/ABDC 7 6 6 Acceptable via WT MIL-53/Al/ABDC 7 4 4 Acceptable via WASS BTC: 1,3,5-benzenetricarboxylic acid BDC: 1,4-benzenedicarboxylic acid ABDC: 2-amino-1,4-benzenedicarboxylic acid

(39) Surprisingly, it has been found that MOFs according to the invention lead to a reduction in malodors. In addition, the color impression of the treated surface, for example of a textile, is not affected.

Example 3: Absorption

(40) A softener having the following composition was produced:

(41) TABLE-US-00003 wt % active Ingredient substance Dem. water 90.1669 MgCl*6 H.sub.2O 0.0595 Stepantex CHT 90 4.75 DC AC 8066 0.0190 Parmetol D11 0.0046 MIL-100(Al) 5.00

(42) Then the absorption behavior of the MOF according to the invention on textiles was determined, on the basis of the softener specified above, in comparison with an aqueous solution consisting of the same MOF as in the softener specified above and water.

(43) For this purpose, a 46-g cotton terry-cloth woven fabric was rinsed with 225 mL of liquid, containing 0.33 g of softener (for composition, see table above), in a launderometer for 30 minutes at 20? C. and then spin dried for 60 seconds (Thomas spin dryer, model 772 NEK286). After the drying, the aluminum content was determined.

(44) As a comparison, the same amount of the same MOF was applied to the terry-cloth woven fabric in a forced manner by dripping application and subsequent drying.

(45) To determine the adsorption behavior of the MOF according to the invention, the aluminum content was determined by means of ICP-OES (atomic emission spectroscopy) on the treated textiles.

(46) TABLE-US-00004 Amount of aluminum (mg (Al)/kg (textile)) Forced-application comparison example 89 Softener containing MIL-100(Al) 74

(47) One can see that the MOF according to the invention nearly completely adsorbs in the presence of softener.

Example 4: Odor Test

(48) To evaluate the reduction of malodors on textiles in the case of treatment from a softener liquid, the following was performed.

(49) Cotton terry cloth, polyester terry cloth, and Coroness cotton woven fabric pieces were each washed 10 times with a liquid, containing 1.5 g/L of the softener from example 3 (for composition, see table above in example 3) or 1.5 g/L of a softener identical to the softener from example 3 but without the MOF according to the invention, in a launderometer for 30 minutes at 20? C. and then spin dried for 60 seconds (Thomas spin dryer, model 772 NEK286) and dried in air.

(50) The treated textile pieces were then subjected to an odor test, wherein a very strong offensive odor was assessed as 10 and a very weak offensive odor was assessed as 1. The aluminum content was also determined by means of ICP-OES. As a further comparison, the untreated textile was examined.

(51) TABLE-US-00005 Amount of aluminum Intensity of offensive Cotton terry cloth (mg/kg) odor (1-10) Softener with MOF 510 2 Softener without MOF 10 4 Untreated 5 7

(52) TABLE-US-00006 Amount of aluminum Intensity of offensive Polyester terry cloth (mg/kg) odor (1-10) Softener with MOF 440 5 Softener without MOF 6 7 Untreated 2 9

(53) TABLE-US-00007 Coroness cotton woven Amount of aluminum Intensity of offensive fabric (mg/kg) odor (1-10) Softener with MOF 570 4 Softener without MOF 8 5 Untreated 4 8