SK5302000A3 - CLEANING COMPOSITION AND METHOD OF RETARDING THE DEPOSITION OFì (54) LIMESCALE ON SURFACE - Google Patents

Abstract

The invention provides 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. The invention also provides a cleaning composition which comprises: (a) 0.01-15 wt.% an alkoxylated aliphatic amine with 8-18 carbon ataoms 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. Cleaning compositions which comprise the amine show improved viscosity stability on storage. In the presence of the anionic surfactant at low pH the deposition of limescale on surfaces which have been treated with the composition is retarded.

Description

The invention relates to acidic cleaning compositions, and in particular to acidic antimicrobial cleaning compositions suitable for use on hard surfaces.

BACKGROUND OF THE INVENTION

Many preparations have been proposed in the literature for so-called "rust-off" compositions. These generally include enough acid to provide a low pH and may contain a thickening agent that causes the composition to retain on inclined surfaces, such as inside toilet bowls. As described in more detail below, known thickeners also include ethoxylated and non-ethoxylated tertiary amines, either alone or in conjunction with a hydrotrope. Known acids for use in such mixtures include sulfamic and phosphoric acids.

GB 1443244 relates to acid cleaners and scavengers which contain, as a thickening agent, an ethoxylated tertiary amine, wherein ETHOMEEN S12 (Λ /, Λ / dihydroxyethyloleylamine) is exemplified. The mixture also comprises acids that are selected from mineral acids and acid salts of strong inorganic acids such as sulfamic acids. An additional optional ingredient is bactericides.

FR 2459830 discloses compositions comprising unethoxylated and ethoxylated amines together with sulfamic acid. The composition may also contain disinfectants.

AU-A-57022/86 relates to cleaning systems comprising a mixture of sulfamic and phosphoric acids and an acid-stable surfactant. Bactericides are optional and formalin is listed as a bactericide that improves the antibacterial effect of acids.

EP-B-0276501 discloses a thickened aqueous cleaning composition comprising 0.1 to 50% by weight of a weak acid having a pK >

-2-sulfamic is given as an example), 0.1 to 20% by weight of an amine, which may include 2% by weight of oleyl-bis (2-hydroxyethyl) amine, and 0.01% to 5% by weight of hydrotrope (sodium xylene sulfonate is given as an example). Force disinfectants optional.

EP-A-0314232 relates to compositions which are subject to dilution viscosity and discloses that thickened liquid detergent compositions can be prepared with an amine oxide, an amine (such as ETHOMEEN S12), a betaine or quaternary ammoniums and sodium hydrotropes (xylene sulfonate) . It is stated in this application that amine oxides and quaternary ammonium compounds are known to have biocidal properties and that other microbiocides, including organic peroxyacids, are an optional component. These mixtures may be acidic, neutral or alkaline.

One problem with known compositions is that the viscosity of the compositions varies with time and specifically decreases when the product is stored.

SUMMARY OF THE INVENTION

These problems have been largely solved by a cleaning composition according to the invention comprising an alkoxylated aliphatic amine and an anionic surfactant which comprises:

(a) 0,01 to 15% by weight of an alkoxylated aliphatic amine of 8 to 18 carbon atoms and 1 to 8 moles of ethoxylation, the molar ratio of saturated to unsaturated aliphatic residues falling within the range of 40:60 to 80:20;

b) an anionic surfactant in an amount such that the molar ratio of ethoxylated amine to anionic surfactant is in the range of 3 to 3.5.

The invention also provides an alkoxylated aliphatic amine of 8 to 18 carbon atoms and 1 to 8 moles of ethoxylation, wherein the molar ratio of saturated to unsaturated aliphatic residues falls within the range of 40:60 to 80:20.

According to a second embodiment of the present invention there is provided a cleaning composition comprising:

-3a) 0.01 to 15% by weight of an alkoxylated aliphatic amine of 8 to 18 carbon atoms and 1 to 8 moles of ethoxylation, wherein the molar ratio of saturated to unsaturated aliphatic residues falls within the range of 40:60 to 80:20, and

b) 0.01 to 15% by weight of an anionic surfactant.

According to a third embodiment of the present invention, there is provided a method of retarding deposition of scale on a surface, comprising the step of treating said surface with a cleaning composition having a pH of less than 1, comprising:

(a) 0,01 to 15% by weight of an alkoxylated aliphatic amine of 8 to 18 carbon atoms and 1 to 8 moles of ethoxylation, the molar ratio of saturated to unsaturated aliphatic residues falling within the range of 40:60 to 80:20, and

b) 0.01 to 15% by weight of an anionic surfactant.

amines

Typically, an alkoxylated aliphatic amine is an ethoxylated tertiary amine of formula:

H (A) _x -N (R) - (A) _y H wherein R is an alkyl or alkenyl group having 8 to 18 carbon atoms, A is an ethoxy or propoxy group and the axes may be the same or different and are integers from 1 to third

Preferred materials are ethoxylated amines wherein A is -OCH ₂ CH ₂ -.

Preferably, x and y are both 1. In preferred embodiments of the invention, R is a mixed saturated and unsaturated C 14 -C 18 alkyl and is most preferably derived from fatty acid residues, most of which correspond to oleic and / or stearic acid residues.

Preferably, the molar ratio of saturated to unsaturated fatty acids falls within the range of 50:50 to 66:33.

A particularly suitable alkoxylated aliphatic amine is the material known as ETHOMEEN BTB / 12 ™, available from AKZO. BTB / 12 is considered to be a 65/35 blend of fully hardened tallow and oleyl derivatives. Such a mixed material can be prepared by synthesis using

The appropriate ratio of mixed starting materials or can be obtained by mixing alkoxylated aliphatic amines such as ETHOMEEN HT12 ™ (supplied by AKZO) with an unsaturated material such as ETHOMEEN S12. ETHOMEEN S12 ™ (supplied by AKZO) is N, N - (dihydroxyethyl) oleylamine.

In embodiments of the invention, levels of alkoxylated aliphatic amines of 1 to 10% by weight of the product are preferred as cleaning products, with a level of 2 to 6% by weight of the product being particularly preferred.

Anionic surfactants

In particularly preferred embodiments of the invention, an alkoxylated aliphatic amine is present together with an anionic surfactant. Preferably, the levels of these materials are such that they interact to thicken the mixture.

Suitable anionic surfactants include sulfonate hydrotropes. Preferred surfactants are alkylarylsulfonates such as salts, especially alkali metal salts, toluene, cumene or xylene sulfonate. A preferred anionic surfactant is sodium cumenesulfonate. A suitable material is ELTESOL SC 40 ™ (supplied by Albright and Wilson). Typical levels of anionic surfactants range from 0.05 to 2% by weight of the product.

Preferably, compositions containing alkylarylsulfonates are prepared with a pH of less than 1. Without wishing to limit the invention by reference to any theory of function, it is believed that at a pH of less than 1 ethoxylated amines behave as cationic surfactants and interact with alkylarylsulfonate to form water-insoluble a gel that is deposited as a monolayer on surfaces. It is believed that this monolayer reduces the surface energy of the surface and slows down or prevents the deposition of additional scale.

The preferred molar ratio of ethoxylated amine to anionic surfactant is 3 to 3.5, more preferably 3.25 to 3.5.

Preferably, the viscosity of the cleaning compositions of the invention is between 50 mPas and 1000 mPas when measured at shear 11.7 s ^-1 and at 25 ° C using Haake RV2

-5RTMs and MV1 probes.

acids

Typical cleaning compositions of the present invention comprise 0.01-15% by weight of a descaling acid, preferably an organic acid and more preferably a sulfamic acid. In such embodiments, typical levels of acid (e.g., aminosulfonic acid) are in the range of from 1 to 10% by weight of the product, with a level of 2 to 6% by weight of the product being particularly preferred.

It is preferred that the pH of the compositions of the invention have a pH < 2.0, more preferably a pH < 1.0.

Sources of peroxide

Preferred embodiments of the invention are cleaning and / or sanitary compositions containing peroxide forming agents.

If present, typical peroxide sources include one or more of hydrogen peroxide, peracetic acid and / or other organic or inorganic peroxide sources. Hydrogen peroxide is a preferred source of peroxide materials.

Typical levels of hydrogen peroxide range from 1 to 10% by weight of the product, with a level of 3 to 8% by weight being particularly preferred.

Non - ionic surfactants

Preferred compositions of the invention further comprise a nonionic surfactant.

Suitable nonionic surfactants include alkoxylated alcohols, preferably ethoxylated alcohols. Suitable nonionic detergent actives can be broadly described as being produced by condensation of alkylene oxide groups having a hydrophilic nature with organic hydrophobic substances, which may be aliphatic or alkylaromatic in nature.

The length of the hydrophilic or polyoxyalkylene radical that is

6-condensed with any particular hydrophobic group, can easily be adjusted to give rise to a water-soluble substance having the desired degree of equilibrium between hydrophilic and hydrophobic elements.

Preferred alkoxylated alcohols are selected from the group consisting of ethoxylated alcohols of formula:

R ¹ - (OCH ₂ CH ₂ ) _m -OH wherein R ¹ is straight or branched, C ₈ -C ₁₈ alkyl or hydroxyalkyl and _m is an average of 1 to 14. Ethoxylated alcohols suitable for use in the present invention include LIAL 111.10EO [TM] ] available on the market from DAC. Typical levels of nonionic surfactant in the products of the present invention range from 0 to 5% by weight.

Particularly preferred compositions of the invention include:

a) 1 to 10% by weight, preferably 3 to 5% by weight, of sulfamic acid,

b) 1 to 10% by weight, preferably 2 to 5% by weight, of ethoxylated amine,

c) 0 to 5% by weight, preferably 0.05 to 1% by weight, of a nonionic surfactant,

d) 0.05 to 2% by weight, preferably 0.4 to 1.1% by weight, of an anionic surfactant hydrotropic,

e) 1 to 10% by weight, preferably 4 to 6% by weight, of hydrogen peroxide.

Minority ingredients

Although the combination of surfactants in the compositions of the present invention provides a thickening effect, additional thickeners may be added. Gum, especially xanthan gum, is a suitable thickener. Preferred xanthan gums are Kelzan ™ materials (available from Kelco Corp). Typical levels of xanthan gum range from 0.05 to 1% by weight. The resulting viscosity of the mixture, as measured on a Haake RV2 rotoviscosimeter, is preferably in the range of 10 to 200 mPas at a shear of 20 s ^-1 and at 25 ° C, using an MV1 probe. More preferably, the viscosity is 10 to 100 mPas under the conditions mentioned above.

Metal ion sequestrants, such as ethylenediaminetetraacetates, aminopolyphosphonates (such as those of the DEQUEST ™ type available from Monsanto) and phosphates, and a wide range of other polyfunctional organic acids and salts can also optionally be used. Preferred metal ion complexing agents are selected from dipicolinic acid, ethylenediaminetetraacetic acid (EDTA) and salts thereof, hydroxyethylidene diphosphonic acid (Dequest 2010);

Optionally minor ingredients also include those typically found in cleaning compositions and are selected from opacifiers, dyes, perfumes, and fluorescent materials. Preferred perfume levels range from 0.05 to 2% by weight. Acid-stable perfumes are available from a variety of sources.

A particularly preferred composition of the invention comprises:

ETHOMEEN BTB / 12 ex AKZO 2 to 5% Ethoxylated amine Sulphamic acid 4% Hydrogen peroxide 5% LIAL 111.10EO ex DAC 0,1% Nonionic surfactant substance ELTESOL SC 40 ex Albright 0.4 to 1.1% * sodium cumenesulfonate BRILLIANT BLUE 9 exWJE 0.0021% Cl 307047 / color perfume exlFF 0,12% Othello 39 DEQUEST 2066 ex Monsanto 0 to 0,3% Water up to 100%

* Variable to adjust viscosity

Typical products having the above composition made with 3.0 wt% amine and about 0.56 wt% SCS are preferably clear, have a specific gravity of 1.040 g / ml, initial viscosity at 106 s ^-1 (at 25 ° C) 120 mPas, initial viscosity at 11.7 s ^-1 (at 25 ° C) 300-600 mPas and pH 0.9 (at 25 ° C).

It has been found that compositions containing a specific mixture of both saturated and unsaturated alkoxylated aliphatic amines in the presence of anionic surfactants exhibit improved storage viscosity stability. We have surprisingly found that the addition of anionic sulfonate surfactant hydrotropic to these formulations has the additional beneficial effect of reducing the surface energy of the surfaces treated with the composition and slowing the subsequent deposition of scale.

In order that the present invention may be further understood, it will be illustrated hereinbelow by means of the following non-limiting examples and the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the viscosity of the materials of the invention and comparative examples in mPas at 11.7 s ^-1 as measured using a Haake RV2 rotoviscometer and MV1 probe after storage at room temperature.

Figure 2 shows the viscosity of the materials of the invention and comparative examples in mPas at 10 6 s ^-1 as measured using a Haake RV2 rotoviscometer (RTM) and an MV1 probe after storage at room temperature.

Figure 3 shows the viscosity of the materials of the invention and comparative examples in mPas at 10 6 s ^-1 as measured using a Haake RV2 rotoviscometer MV1 probe after storage at 37 ° C.

Figure 4 shows the viscosity of the materials of the invention and comparative examples in mPas at 11.7 s ^-1 as measured on a Haake RV2 rotoviscometer and MV1 probe after storage at 37 ° C.

DETAILED DESCRIPTION OF THE INVENTION

Example 1 Viscosity stability

-9The following mixture was prepared:

ETHOMEEN BTB / 12 ex AKZO 3% Ethoxylated amine Sulphamic acid 4% Hydrogen peroxide 5% LIAL 111.10ΕΘ ex DAC 0,1% Nonionic surfactant substance ELTESOL SC40 ex Albright 0.4 to 1.1% * sodium cumenesulfonate BRILLIANT BLUE 9 exWJE 0.0021% Cl 307047 / color perfume exlFF 0,12% Othello 39 DEQUEST 2066 ex Monsanto 0,15% Water up to 100%

To demonstrate the interaction of ethoxylated amine and anionic surfactant, the other ingredients were all dosed at or below ± 10%. The results are shown in Table 1 below for an initial viscosity of 500 m.Pas at a shear of 11.7 s ^-1 .

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 SC40 145 1330 perfume 510 600 DEQUEST 2066 470 560

It can be seen from the above that the greatest change in viscosity occurs when the relative levels of anionic surfactant and ethoxylated amine change, and that the change in the level of the other components has little effect.

As shown in the figures in Table 2 below, the molar ratio of ethoxylated amine / anionic surfactant may be modified to provide concentration in the viscosity range. The end product similar to the product described above was used again.

Table 2 (all with 3.0% Ethomeen BTB12)

% cumene sodium Molar ratio Viscosity mPas (shear of 11.7 ^1, 25 ° C) 0.69% 2.89 1500 (non-liquid 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 about 10 (density as water)

Compositions having a viscosity between 50 mPas and 1000 mPas (molar ratio 3 to 3.5) were liquid compositions that were suitable for use as toilet cleaners. Lower viscosity compositions were too thin to remain on sloping surfaces, while higher viscosity compositions were not easy to remove. Compositions having a viscosity of 200 to 700 mPas were particularly suitable for these purposes.

Several mixtures of the type described above have been prepared with varying degrees of saturation in ethoxylated amine. The materials used were:

’S12 Ν, Ν-dihydroxyethyl-oleylamine (ETHOMEEN S12),

ΉΤ12 'fully hardened N, N-dihydroxyethyl-tallowamine (ETHOMEEN HT12),

-11 '50 / 50 'mixture of equal weight' S12 'and ΉΤ12', and '66 / 33 'mixture of ΉΤ12' and 'S12' in a weight ratio of 66:33 (similar to BTB12)

The effect of storage on viscosity is shown in Figures 1 to 4.

Figure 1 shows the viscosity of the materials of the invention and comparative examples in mPas at 11.7 s ^-1 as measured using a Haake RV2 rotoviscometer and MV1 probe after storage at room temperature. It can be seen that the viscosity of ΉΤ12 'of the sample increased with time until the product became a non-liquid gel. The viscosity of the 'S12' of the sample dropped so that the product eventually became too thin to remain on sloping surfaces. The viscosities of the products containing a mixture of hardened and non-hardened tallow remained within an acceptable range upon storage.

Figure 2 shows the viscosity of the materials of the invention and comparative examples in mPas at 10 6 s ^-1 as measured using a Haake RV2 rotoviscometer and an MV1 probe after storage at room temperature. It can be seen that the viscosity ΉΤ12 'of the sample first decreased and then increased. The viscosity of the 'S12' of the sample dropped so that the product eventually became too thin to remain on sloping surfaces. The viscosities of the products containing the mixture of hardened and non-hardened materials remained within acceptable storage limits.

Figure 3 shows the viscosity of the materials of the invention and comparative examples in mPas at 10 6 s ^-1 as measured using a Haake RV2 rotoviscometer and MV1 probe after storage at 37 ° C. It can be seen that the viscosity ΉΤ12 'of the sample decreased again first and then increased. The viscosity of the 'S12' of the sample dropped so that the product eventually became too thin to remain on sloping surfaces. The viscosities of the products containing the mixture of hardened and non-hardened materials remained within acceptable storage limits.

Figure 4 shows the viscosity of the materials of the invention and comparative examples in mPas at 11.7 s ^-1 as measured using a Haake RV2 rotoviscometer and MV1 probe after storage at 37 ° C. It can be seen that the viscosity ΉΤ12 'of the sample increased again. The viscosity of the 'S12' sample decreased. The viscosity of the 'S12' of the sample dropped so that the product eventually became too thin to remain on sloping surfaces. The viscosities of the products containing the mixture of hardened and non-hardened materials remained within acceptable storage limits.

-12Example 2

Protection against limescale

60 degrees French hard water was prepared by passing carbon dioxide overnight through tap water containing both calcite and dolomite. The tile pairs were cleaned with detergent and ethanol and rinsed with tap water. One tile was treated with the composition of the invention (composition of Example 1), with a contact time of 20 minutes: the tile was then rinsed with water. Thereafter, hard water was dripped over the tiles for 24 hours, leaving one drop to hit the tile every five minutes. The results for the treated and untreated tiles were compared visually using a panel of ten people, with scores of 0 = limescale missing and 5 = more incremented tile: results are shown in Table 3 below. In addition, the scale was titrated after dilution with dilute HCl. The titration results are expressed in mg of calcium carbonate per tile in Table 3 below. Examples were performed in repetitions A, B and C.

Table 3

Treated tile Untreated tile repeat visually mg CaCO ₃ visually 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

From these results, it can be seen that the tile treatment had a measurable effect on the degree of limescale trapped on the tile both in tests and by measurement both chemically and as a visible effect on the surface.

Claims (12)

CLAIMS 1. A cleaning composition comprising an alkoxylated aliphatic amine and an anionic surfactant comprising: (a) 0,01 to 15% by weight of an alkoxylated aliphatic amine of 8 to 18 carbon atoms and 1 to 8 moles of ethoxylation, the molar ratio of saturated to unsaturated aliphatic residues falling within the range of 40:60 to 80:20; b) an anionic surfactant in an amount such that the molar ratio of ethoxylated amine to anionic surfactant is in the range of 3 to 3.5. The cleaning composition of claim 1, wherein the ethoxylated aliphatic amine has the general formula: H (A) _x -N (R) - (A) _y H wherein R is an alkyl or alkenyl group having 8 to 18 carbon atoms, A is an ethoxy group and the axes may be the same or different and are integers 1 to Third A cleaning composition according to claim 2, characterized in that both are 1. 4. A cleaning composition according to claim 1 wherein R is a mixed saturated and unsaturated C14-C18 alkyl. The cleaning composition of claim 1, wherein the molar ratio of saturated to unsaturated fatty acids in the alkoxylated aliphatic amine falls within the range of 50:50 to 66:33. A cleaning composition according to claim 1, wherein the pH of the composition is less than 1.0. -147. The cleaning composition according to claim 1, wherein the molar ratio of ethoxylated amine to anionic surfactant is 3.25 to 3.5. The cleaning composition of claim 1, wherein the anionic surfactant is an alkylarylsulfonate hydrotrope. The cleaning composition of claim 1 having a viscosity of between 50 mPas and 1000 mPas as measured at a shear of 11.7 s ^-1 and at 25 ° C using a Haake RV2 rotoviscometer and MV1 probe. A cleaning composition according to claim 1, characterized in that it contains 0.01 to 15% by weight of descaling acid. 11. A cleaning composition according to claim 1 comprising peroxide-producing substances. 12. A cleaning composition according to claim 1 comprising: a) 1 to 10% by weight, preferably 3 to 5% by weight of sulfamic acid, b) 1 to 10% by weight, preferably 2 to 5% by weight of ethoxylated amine, c) 0 to 5% by weight, preferably 0.05 to 1% by weight of a nonionic surfactant, d) anionic surfactant hydrotropy, e) 1 to 10% by weight, preferably 4 to 6% by weight, of hydrogen peroxide. A method of retarding deposition of scale on a surface, comprising the step of treating said surface with a cleaning composition according to any one of claims 1 to 12 having a pH of less than 1.