AU1229899A

AU1229899A - Alkoxylated amines and their use in cleaning compositions

Info

Publication number: AU1229899A
Application number: AU12298/99A
Authority: AU
Inventors: Marcella Margherita Leda Bartoletti; Giuseppe Vincenzo Bolzoni; Emanuela Ferro; Marco Galli; Ronald Meredith Morris
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1997-10-13
Filing date: 1998-10-09
Publication date: 1999-05-03
Anticipated expiration: 2018-10-09
Also published as: HUP0004913A3; JP2001520259A; DE69821636D1; SK5302000A3; EP1023423A1; GB9721691D0; PL188434B1; HUP0004913A2; HU224521B1; WO1999019431A1; AR017315A1; CA2305193C; TR200000972T2; DE69821636T2; ZA989144B; JP4323093B2; ES2214747T3; KR20010015748A; PL339808A1; CA2305193A1

Description

WO 99/19431 PCT/EP98/06633 ALKOXYLATED AMINES AND THEIR USE IN CLEANING COMPOSITIONS Technical Field 5 The present invention relates to acidic cleaning compositions, and in particular to acidic antimicrobial cleaning composition suitable for use on hard surfaces. 10 Background to the Invention Many formulations have been proposed in the literature for so-called 'descaler' compositions. These generally 15 comprise sufficient acid to give a low pH and may comprise a thickening agent to as to cause the composition to be retained on sloping surfaces, such as the inside of toilet bowls. As described in more detail below, known thickeners include both ethoxylated and unethoxylated tertiary amines, 20 either alone or in combination with a hydrotrope. Known acids for use in such compositions include sulphamic and phosphoric acids. GB 1443244 relates to acid cleaners and descalers which 25 comprise as a thickening agent an ethoxylated tertiary amine of which ETHOMEEN S12 (N,N-dihydroxyethyl-oleylamine) is given as an example. The composition also comprises acids which are selected from mineral acids and acid salts of strong inorganic acids such as sulphamic acid. 30 Bacteriocides are an additional, optional component.

WO 99/19431 PCTIEP98/06633 - 2 FR 2459830 discloses compositions which comprise non ethoxylated and ethoxylated amines together with sulphamic acid. The composition may also comprise disinfectants. 5 AU-A-57022/86 relates to cleaning systems which comprise a mixture of sulphamic and phosphoric acids and an acid stable surfactant. Bacteriocides are optional and formalin is disclosed as a bacteriocide which improves the 10 antibacterial effect of the acids. EP-B-0276501 discloses thickened aqueous cleaning compositions which comprise 0.1-50%wt of a weak acid having a pK >2 (of which sulphamic acid is given as an example), 15 0.1-20%wt of an amine which can include 2% of oleyl-bis(2 hydroxyethyl)amine and 0.01%-5%wt hydrotrope (sodium xylene-sulphonate is given as an example). Disinfecting agents are optional. 20 EP-A-0314232 relates to compositions which undergo a viscosity increase on dilution and discloses that thickened liquid detergent compositions can be prepared with an amine oxide, amine (such as ETHOMEEN S12), betaine or quaternary ammonium compound and hydrotrope (sodium xylene 25 sulphonate). It is stated in the specification that amine oxides and quaternary ammonium compounds are known to have biocidal properties and that further microbiocides including organic peracids are optional. These compositions can be of acidic, neutral or alkaline pH. 30 WO99/19431 PCT/EP98/06633 - 3 One problem with the known compositions is that the viscosity of the compositions drifts with time, and, in particular falls when the product is stored. 5 Brief Description of the Invention We have determined that compositions which comprise a specific mixture of both saturated and unsaturated 10 alkoxylated aliphatic amines in the presence of an anionic surfactant show an improved stability of viscosity on storage. Surprisingly, we have found that the addition of a anionic sulphonate surfactant hydrotrope to these formulations has the additional benefit that the surface 15 energy of surfaces treated with the composition is reduced and the subsequent deposition of limescale is retarded. Detailed Description of the Invention 20 According to a first aspect of the present invention there is provided an alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the 25 range 40:60 to 80:20. According to a second aspect of the present invention there is provided a cleaning composition which comprises WO 99/19431 PCT/EP98/06633 - 4 a) 0.01-15%wt an alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and 5 b) 0.01-15%wt of an anionic surfactant. According to a third aspect of the present invention there is provided a process for retarding the deposition of 10 limescale on a surface which comprises the step of treating said surface with a cleaning composition having a pH of less than 1 which comprises: a) 0.01-15%wt an alkoxylated aliphatic amine with 8-18 15 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and, b) 0.01-15%wt of an anionic surfactant. 20 Amines Typically, the alkoxylated aliphatic amine is an 25 ethoxylated tertiary amine of the general formula: H (A)x-N (R)- (A)yH WO 99/19431 PCT/EP98/06633 - 5 wherein R is an alkyl or alkenyl group comprising 8-18 carbon atoms, A is an ethoxy or propoxy group and x and y may be the same or different and are integers from 1-3. 5 The preferred materials are ethoxylated amines wherein A is -OCH2 2 Preferably x and y are both 1. In preferred embodiments of the invention R is mixed saturated and unsaturated C14-C18 10 alkyl and is most preferably derived from fatty acids residues of which the majority correspond to oleic and/or stearic acids. Preferably the mole ratio of saturated to unsaturated fatty 15 acids falls into the range 50:50 to 66:33. A particularly suitable alkoxylated aliphatic amine is a material known as ETHOMEEN BTB/12

M

, available from AKZO. BTB/12 is believed to be a mixture of material derived from 20 fully hardened tallow and the oleyl derivative in a 65/35 ratio. Such a mixed material can be prepared by synethesis using an appropriate ratio of mixed starting materials or obtained by mixing an alkoxylated aliphatic amine such as ETHOMEEN HT12 T M (ex AKZO) with an unsaturated material such 25 as ETHOMEEN S12. ETHOMEEN S 12 TM (ex AKZO) is N,N (dihydroxyethyl)-oleylamine. In embodiments of the invention as cleaning products, the preferred levels of the alkoxylated aliphatic amine are WO99/19431 PCT/EP98/06633 -6 1-10%wt on product with levels of 2-6%wt on product being particularly preferred. 5 Anionic Surfactants In particularly preferred embodiments of the invention the alkoxylated aliphatic amine is present together with an anionic surfactant. Preferably, the levels of these 10 materials are such that they interact so as to thicken the composition Suitable anionic surfactants include the sulphonate hydrotropes. Preferred surfactants are alkylarylsulphonates 15 such as salts, particularly alkali metal salts, of toluene, cumene or xylene sulphonate. The preferred anionic surfactant is sodium cumenesulphonate. A suitable material is ELTESOL SC 40T M (ex. Albright and Wilson). Typical levels of anionic surfactant range from 0.05-2%wt on 20 product. Preferably, formulations comprising the alkylaryl sulphonates are formulated at a pH below 1. Without wishing to limit the invention by reference to any theory of 25 operation, it is believed that at a pH below 1, the ethoxylated amine behaves as a cationic surfactant and interacts with the alkylaryl sulphonate to form a water insoluble gel which deposits as a monolayer on surfaces. It is believed that this monolayer lowers the surface WO 99/19431 PCTIEP98/06633 - 7 energy of the surface and retards or prevents the deposition of further limescale. The preferred mole ratio of the ethoxylated amine and the 5 anionic surfactant is 3-3.5, more preferably 3.25-3.5. The preferred viscosity of the cleaning compositions according to the present invention is between 50 mPas and -i 1000 mPas when measured at 11.7 sec shear and at 25 0 C 10 using Haake RV2 rotoviscometer (RTM) and an MV1 bob Acids 15 Typically, cleaning compositions which embody the present invention comprise 0.01-15%wt of a limescale removing acid, preferably an organic acid and more preferably sulphamic acid. In such embodiments, typical levels of the acid (for instance the amino sulphonic acid) range from 1-10%wt on 20 product with levels of 2-6% on product being particularly preferred. It is preferred that the pH of the compositions according to the invention should have a pH of <2.0, more preferably 25 a pH <1.0. 30 WO99/19431 PCT/EP98/06633 - 8 Peroxygen Sources Preferred embodiments of the invention are cleaning and/or hygiene compositions which comprises a peroxygen compound. 5 Where present, typical sources of peroxygen species include one or more of hydrogen peroxide, peracetic acid and/or other organic or inorganic peroxygen sources. Hydrogen peroxide is a preferred source of peroxygen species. 10 Typical levels of hydrogen peroxide range from 1-10%wt on product with levels of 3-8% being particularly preferred. 15 Nonionic Surfactants Preferred compositions according to the invention additionally comprise nonionic surfactant. 20 Suitable nonionic surfactants include alkoxylated alcohols, preferably ethoxylated alcohols. Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic 25 hydrophobic compound which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group 30 can be readily adjusted to yield a water-soluble compound WO99/19431 PCT/EP98/06633 - 9 having the desired degree of balance between hydrophilic and hydrophobic elements. The preferred alkoxylated alcohols are selected from the 5 group comprising ethoxylated alcohols of the general formula:

R

I

-(OCH

2

CH

2 )m-OH 10 wherein R i is straight or branched, C 8 to C 18 alkyl or hydroxyalkyl and m is, on average, 1-14. Ethoxylated alcohols suitable for use in the present invention include LIAL 111.10EO [TM] available in the marketplace from DAC. Typical levels of nonionic surfactant in products according 15 to the present invention range from 0-5%. Particularly preferred compositions according to the present invention comprise: a) 1-10%wt, preferably 3-5%wt sulphamic acid, 20 b) 1-10%wt, preferably 2-5%wt ethoxylated amine, c) 0-5%wt, preferably 0.05-1%wt, nonionic surfactant, d) 0.05-2%wt, preferably 0.4-1.1%wt, anionic surfactant hydrotrope, e) 1-10%wt, preferably 4-6%wt, hydrogen peroxide 25 Minors While the combination of the surfactants in the 30 compositions of the invention provide a thickening effect WO99/19431 PCT/EP98/06633 - 10 it is possible to add other thickeners. Gums, particularly xanthan gums are suitable thickeners. Preferred xanthan gums are the Kelzan m series (available from Kelco Corp). Typical levels of xanthan gum range from 0.05-1wt%. The 5 resulting viscosity of the composition, as measured on a Haake RV2 rotoviscometer) is preferably in the range 10-200 -i mPas at 20 sec shear and 25 0 C, using an MV1 bob. More preferably the viscosity is 10-100 mPas under the conditions mentioned above. 10 Metal ion sequestrants such as ethylene diamine tetraacetates, amino-poly phosphonates (such as those in the DEQUEST Tm range ex. Monsanto) and phosphates and a wide variety of other poly-functional organic acids and salts, 15 can also optionally be employed. Preferred metal ion complexing agents are selected from dipicolinic acid, ethylene diamine tetra acetic acid (EDTA) and its salts, hydroxy-ethylidene diphosphonic acid (Dequest 2010), ethylenediamine-tetra(methylene phosphonic acid) (Dequest 20 2040), diethylene-triamine-penta(methylene phosphonic acid) (Dequest 2060). Optional, minor components also include those typically found in cleaning compositions and are selected from 25 opacifiers, colours perfumes and fluorescers. Preferred levels of perfume range from 0.05-2%wt. Acid stable perfumes are available from a variety of sources. A particularly preferred composition according to the 30 present invention comprises: WO99/19431 PCT/EP98/06633 - 11 ETHOMEEN BTB/12 ex AKZO 2-5% Ethoxylated amine SULPHAMIC ACID 4% HYDROGEN PEROXIDE 5% LIAL 111.10EO ex DAC 0.1% Nonionic surfactant ELTESOL SC40 ex Albright 0.4-1.1%* Sodium Cumene Sulphonate BRILLIANT BLUE 9 ex WJE 0.0021% CI 307047/colour PERFUME ex IFF 0.12% Othello 39 DEQUEST 2066 ex Monsanto 0-0.3% WATER to 100% *variable to adjust viscosity 5 Typical products having the above formulation made with 3.0%wt of the amine and around 0.56%wt of the SCS are preferably clear, have a specific gravity of 1.040 g/ml, an -initial viscosity at 106 sec1 (at 25C) of 120mPas, an initial viscosity at 11.06 sec (at 25 0 C) of 2300-600 mPas initial viscosity at 11.7 sec' (at 25°C) of 300-600 mPas 10 and pH 0.9 (at 25 0 C). In order that the present invention may be further understood it will be illustrated hereafter with reference to the following non-limiting examples and with reference 15 to the accompanying figures wherein: Figure 1 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 WO99/19431 PCT/EP98/06633 - 12 -1 sec as measured using on a Haake RV2 rotoviscometer and an MVI bob after storage at room temperature. Figure 2 shows the viscosity of materials according to the 5 present invention and comparative examples in mPas at 106 s-1, as measured using on a Haake RV2 rotoviscometer (RTM) and an MV1 bob after storage at room temperature. Figure 3 shows the viscosity of materials according to the 10 present invention and comparative examples in mPas at 106 s-1, as measured using on a Haake RV2 rotoviscometer and an MV1 bob after storage at 37 0 C. Figure 4 shows the viscosity of materials according to the 15 present invention and comparative examples in mPas at 11.7 sec measured on a Haake RV2 rotoviscometer and an MVI bob after storage at 37 0

C.

WO99/19431 PCTIEP98/06633 - 13 EXAMPLES: Example 1: Viscosity Stability 5 A composition was prepared as follows: ETHOMEEN BTB/12 ex AKZO 3% Ethoxylated amine SULPHAMIC ACID 4% HYDROGEN 5% PEROXIDE LIAL 111.10EO ex DAC 0.1% Nonionic surfactant ELTESOL SC 40 ex Albright 0.4-1.1%* Sodium Cumene Sulphonate BRILLIANT BLUE ex WJE 0.0021% CI 307047/colour PERFUME ex IFF 0.12% Othello 39 DEQUEST 2066 ex Monsanto 0.15% WATER to 100% In order to demonstrate the interaction of the ethoxylated 10 amine and the anionic surfactant, the other components were each under and over dosed at +/- 10%. Results are shown in Table 1 below, for an initial viscosity of 500 m.Pas at -11.7 sec1 shear. 11.7 sec shear.

WO99/19431 PCTIEP98/06633 - 14 TABLE 1 VISCOSITY Component -10% +10% ETHOMEEN BTB/12 950 190 SULPHAMIC ACID 530 600 HYDROGEN PEROXIDE 550 620 LIAL 111.10EO 560 460 ELTESOL SC 40 145 1330 PERFUME 510 600 DEQUEST 2066 470 560 5 From the above it can be seen that the greatest modification of viscosity occurs when the relative levels of the anionic surfactant and the ethoxylated amine are varied, and that variation in the levels of the other components has little effect. 10 As shown by the figures in Table 2 below, the molar ratio of the ethoxylated amine / anionic surfactant can be modified to give thickening at a range of viscosities. Again, a finished product similar to that described above 15 was used.

WO99/19431 PCT/EP98/06633 - 15 Table 2 (all with 3.0% Ethomeen BTB12) 4 Sodium Cumene Molar Ratio Viscosity mMas (11.7 sec - shear, 25 0 C) 0.69% 2.89 1500(non-flowing gel) 0.63% 3.03 1000 0.60% 3.18 700 0.59% 3.24 400 0.57% 3.35 300 0.56% 3.42 200 0.54% 3.51 75 0.50% 3.83 -10(water thin) 5 Compositions having a viscosity between 50 mPas and 1000 mPas (a molar ratio of from 3-3.5) were flowable compositions which were suitable for use as toilet cleaners. Compositions with a lower viscosity were too thin to stay on sloping surfaces, while those with a higher 10 viscosity could not be dispensed with ease. Compositions with a viscosity of from 200-700 mPas were particularly suited to this purpose. A range of compositions of the type described above were 15 prepared with differing degrees of saturation in the ethoxylated amine. The materials used were: 'S12' an N,N-dihydroxyethyl-oleylamine (ETHOMEEN S12), 'HT12' a fully hardened N,N-dihydroxyethyl-tallowylamine 20 (ETHOMEEN HT12), WO99/19431 PCT/EP98/06633 - 16 '50/50' an equal weight mixture of 'S12' and 'HT12', and '66/33' a mixture of 'HT12' and 'S12' in a 66:33 weight ratio (similar to BTB12) 5 The effect of storage on viscosity is shown in figures 1-4. Figure 1 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 -1 sec , as measured using on a Haake RV2 rotoviscometer and 10 an MVI bob after storage at room temperature. It can be seen that the viscosity of the 'HT12' sample rose with time until the product became a non-flowing gel. The viscosity of the 'S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The 15 viscosities of the products containing a mixture of hardened and unhardened tallow remained in the acceptable range on storage. Figure 2 shows the viscosity of materials according to the 20 present invention and comparative examples in mPas at 106 sec , as measured using on a Haake RV2 rotoviscometer and an MV1 bob after storage at room temperature. It can be seen that the viscosity of the 'HT12' sample first fell and then rose. The viscosity of the 'S12' sample fell, such 25 that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.

WO99/19431 PCT/EP98/06633 - 17 Figure 3 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 sec , as measured using on a Haake RV2 rotoviscometer and an MV1 bob after storage at 37 0 C. It can be seen that the 5 viscosity of the 'HT12' sample again first fell and then rose. The viscosity of the 'S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials 10 remained in the acceptable range on storage. Figure 4 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec , as measured using on a Haake RV2 rotoviscometer and 15 an MVI bob after storage at 37 0 C. It can be seen that the viscosity of the 'HT12' sample again rose. The viscosity of the 'S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of 20 hardened and unhardened materials remained in the acceptable range on storage. Example 2: Limescale Prevention 25 Hard water of -60 degrees French was prepared by flushing carbon dioxide through tap-water containing both calcite and dolomite overnight. Pairs of tiles were cleaned with a detergent composition and ethanol and rinsed with tap 30 water. One of the tile was treated with a composition WO99/19431 PCT/EP98/06633 - 18 according to the present invention (that of Example 1), with a contact time of 20 minutes: the tile was then rinsed with water. The hard water was then dripped onto the tiles for 24 hours, allowing one drop to fall onto each tile 5 every five minutes. Results for treated and untreated tiles were compared visually using a panel of ten people, scoring on a scale of 0=limescale absent and 5= more encrusted tile: results being presented in Table 3 below. In addition the limescale was titrated after dissolution 10 with dilute HCl. The results of titration are expressed in mg of calcium carbonate per tile in Table 3 below. Examples were performed in replicates A, B and C.

WO 99/19431 PCT/EP98/06633 - 19 Table 3 Treated Untreated Tile Tile Replicate Visual mg CaCo 3 visual mg CaCo 3 A 3.3 0.91 5.0 2.1 B 3.4 1.2 5.0 1.5 C 3.3 1.4 5.0 2.1 5 It can be seen from these results that the treatment of the tile had a measurable effect on the degree of limescale deposited on the tile in the test both as measured chemically and as seen on the surface.

Claims

1. An alkoxylated aliphatic amine with 8-18 carbon atoms 5 and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20.

2. A cleaning composition which comprises 10 a) 0.01-15%wt an alkoxylated aliphatic amine with 8 18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20. 15 b) 0.01-15%wt of an anionic surfactant.

3. A composition according to claim 1 or 2 wherein the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the general formula: 20 H(A)x-N(R) - (A)Y H wherein R is an alkyl or alkenyl group comprising 8-18 carbon atoms, A is an ethoxy or propoxy group and x 25 and y may be the same or different and are integers from 1-3.

4. A composition according to claim 3 wherein A is -OCH 2 CH 2 -. 30 WO99/19431 PCTIEP98/06633 - 21

5. A composition according to claim 3 wherein x and y are both 1.

6. A composition according to claim 3 wherein R is mixed 5 saturated and unsaturated C14-C18 alkyl.

7. A composition according to claim 1 wherein the mole ratio of saturated to unsaturated fatty acids in the alkoxylated aliphatic amine falls into the range 50:50 10 to 66:33.

8. A composition according to claim 2 wherein the pH of the composition is less than 1.0. 15

9. A composition according to claim 2 wherein the mole ratio of the ethoxylated amine and the anionic surfactant is 3-3.5, more preferably 3.25-3.5.

10. A composition according to claim 2 having a viscosity 20 between 50 mPas and 1000 mPas when measured at 11.7 -1 sec shear and at 25 0 C using Haake RV2 rotoviscometer and an MVI bob.

11. A composition according to claim 2 comprising 0.01 25 15%wt of a limescale removing acid.

12. A composition according to claim 2 which further comprises a peroxygen compound. 30 WO99/19431 PCTIEP98/06633 - 22

13. A composition according to claim 2 which comprises: a) 1-10%wt, preferably 3-5%wt sulphamic acid, b) 1-10%wt, preferably 2-5%wt ethoxylated amine, c) 0-5%wt, preferably 0.05-1%wt, nonionic 5 surfactant, d) 0.05-2%wt, preferably 0.4-1.1%wt, anionic surfactant hydrotrope, and, e) 1-10%wt, preferably 4-6%wt, hydrogen peroxide 10

14. A process for retarding the deposition of limescale on a surface which comprises the step of treating said surface with a cleaning composition according to any of claims 8-13 said composition having a pH of less than 1 and comprising: 15 a) 0.01-15%wt an alkoxylated aliphatic amine with 8 18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and, 20 b) 0.01-15%wt of an anionic surfactant.