WO2000020545A1

WO2000020545A1 - Hard surface cleaning bar

Info

Publication number: WO2000020545A1
Application number: PCT/EP1999/006095
Authority: WO
Inventors: Vinodkumar Ramniranjan Dhanuka; Kamsu Venkata Sathyanarayana Murthy; Suresh Ramamurthi; Devadatta Shivaji Sankholkar
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 1998-10-06
Filing date: 1999-08-18
Publication date: 2000-04-13
Also published as: GB9821781D0; AU5517999A; AR020703A1

Abstract

The present invention provides a synergistic abrasive bar cleaning composition, which comprises: a) 30-85 %wt of at least one particulate abrasive; b) at least 0.5 %wt of a particulate with a minimum water absorptive capacity of 200 %; c) 0.5-15 %wt of a C2-C6 alkanolamine; d) at least 0.1 %wt of an electrolyte base other than alkanolamine; e) 0.5-35 %wt of at least one surfactant; f) and optionally, 0.1-20 %wt of a solvent other than water or alkanolamine.

Description

Hard Surface Cleaning Bar

Technical field:

The invention relates to synergistic abrasive bar cleaning compositions, containing particulate abrasives for cleaning hard surfaces and a process for preparing the same.

Background and Prior art :

Commercial hard surface cleaning compositions typically comprise, one or more surfactants selected from amongst primary alcohol sulphates, alkyl benzene sulphonates, alcohol ethoxylates, alkyl ether sulphates, fatty acid soaps and secondary alkyl sulphonates, and a plurality of abrasives dispersed in. Combinations of these together with electrolytes are generally used to form a suspending system as is well known in the art.

Solvents are well known components of non-abrasive cleaning compositions. Typical solvents used in cleaning compositions include, alcohols (such as ethanol) , ethers (such as Butyl Cellosolve [TM] ) , paraffins (such as Isopar L [TM] ) , esters and terpenes (such as d-limonene) . Another known class of solvents are the alkanolamines . EP503219A (P&G) relates to a cleaning composition containing 0.1-10% of an alkanolamine.

Non-liquid abrasive cleaning compositions in the form of pastes, gels and powders are also known. Typical abrasives used in these compositions include calcites and dolomites.

Cleaning compositions in the bar form are economically superior as compared to other product forms . The product dosage per swipe from the bar is highly controlled in comparison to the other forms such as paste, gel or powder. The bar also does not get easily sogged in the presence of water and the active ingredients are not lost.

It is the basic objective of the present invention to provide a synergistic abrasive bar cleaning composition which would effectively clean and will be storage stable. Another object of the present invention is to provide for synergistic abrasive bar cleaning composition having alkanolamine and an electrolyte base other than alkanolamine for removal of difficult soils.

Yet another object of the present invention is directed to provide an improved synergistic abrasive bar cleaning composition with significant levels of a C2-C6 alkanolamine and an electrolyte base other than alkanolamine.

Thus according to one aspect of the present invention there is provided a synergistic abrasive bar cleaning composition comprising:

a) 30-85%wt of at least one particulate abrasive ; b) at least 0.5%wt of a particulate with a minimum water absorptive capacity of 200% ; c) 0.5-15%wt of a C2-C6 alkanolamine ; d) at least 0.1%wt of an electrolyte base other than alkanolamine ; e) 0.5-35%wt of at least one surfactant ; and f) optionally, 0.1-20%wt of a solvent other than water or alkanolamine .

According to another aspect the invention provides a process for the preparation of the synergistic abrasive cleaning composition in the bar form comprising the steps of: a) in-situ generation of alkaline alumino silicate and making a dough containing surfactants and other particulate abrasives;

b) addition of alkanolamine and the electrolyte base ; and

c) structuring the composition by mixing with the particulate having a minimum water absorptive capacity of 200% followed by addition of other optional ingredients, mixing, extruding into bars following a conventional method.

Particulates :

An essential feature of compositions according to the present invention is 30 to 85 %wt of the total composition of a particulate abrasive and at least 0.5%wt of the total composition of a second particulate having a minimum water absorptive capacity of 200%

Preferably, the particulate abrasive is insoluble in water. In the alternative, the abrasive may be soluble and present in such excess to any water present in the composition that the solubility of the abrasive in the aqueous phase is exceeded and consequently solid abrasive exists in the composition.

Suitable abrasives are selected from, particulate zeolites, calcites, dolomites, feldspar, silicas, silicates, other carbonates, aluminas, bicarbonates, borates, sulphates and polymeric materials such as polyethylene. Preferred abrasives have a Moh hardness of 2-6 although higher hardness abrasives can be employed for specialist applications .

Preferred average particle sizes for the particulate abrasive fall in the range 0.5-400 microns preferably 10-200 microns .

Preferred levels of abrasive range from 35 to 60wt% of the composition.

The second particulate has minimum water absorptive capacity of 200%, however particulates having a water absorptive capacity of 200 to 300% are generally preferred and are generally selected from gel, precipitated or spray dried silica. The most preferred particulates with a water absorptive capacity being precipitated silica.

In the context of the present invention the term minimum water absorptive capacity of X% means that the particulate absorbs up to X% of it weight of water, thus minimum water absorptive capacity of 200% means that the particulate can absorb up to 200% of its weight of water.

The preferable levels at which the particulates with a water absorptive capacity are incorporated in the formulation range from 3 to 10 wt% of the total composition.

Alkano1amines

C2-C6 Alkanolamines for use in the compositions of the present invention can be mono- or poly-functional as regards the amine and hydroxy moieties. Preferred alkanolamines are generally of the formulation H2N- Ri-OH where Ri is a linear or branched alkyl chain having 2-6 carbons .

Preferred alkanolamines include 2-amino-2-methyl-l-propanol , mono- di- and tri- ethanolamine, mono- di- and tri - isopropanolamine, dimethyl-, diethyl or dibutyl ethanolamine, and mixtures thereof. It is envisaged that cyclic alkanolamines such as morpholine can also be employed.

Particularly preferred alkanolamine specially to clean tough or aged soil is 2-amino-2-methyl-l-propanol (AMP) .

The levels of alkanolamine in the compositions of the invention are from 0.5 to 15 %wt of the total composition. Typically the levels range from l-10%wt, it is particularly preferred to use 2-amino-2methyl-l-propanol at a level of 2- 6%wt .

Electrolyte base

Suitable electrolyte bases include soluble carbonates and bicarbonates, although use of hydroxides and other alkaline salts is not excluded. Alkali metal carbonates are particularly preferred, with potassium carbonate being the most preferred. The electrolyte is present at a level of at least 0.1 %wt of the total composition. Typical levels of electrolytes range from 0.5-5%wt, with l-2.5%wt being particularly preferred. The level of the electrolyte should be such that in use the pH of the composition is raised above the pKa of the alkanolamine, and preferably to a pH at least one unit above the pKa of the alkanolamine. Surfactants

The composition according to the invention comprises detergent active at a level from 0.5 to 35 %wt of the total composition. Generally the surfactants are chosen from anionic surfactants, nonionic surfactants or mixtures thereof .

Suitable anionic detergent active compounds are water soluble salts of organic sulphuric reaction products having in the molecular structure an alkyl radical containing from 8 to 22 carbon atoms, and a radical chosen from sulphonic acid or sulphur acid ester radicals and mixtures thereof.

Examples of suitable anionic detergents are sodium and potassium alcohol sulphates, especially those obtained by sulphating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl benzene sulphonates such as those in which the alkyl group contains from 9 to 15 carbon atoms; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphates ; sodium and potassium salts of sulphuric acid esters of the reaction product of one mole of a higher fatty alcohol and from 1 to 6 moles of ethylene oxide ; sodium and potassium salts of alkyl phenol ethylene oxide ether sulphate with from 1 to 8 units of ethylene oxide molecule and in which the alkyl radicals contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralised with sodium hydroxide where, for example, the fatty acids are derived from coconut oil and mixtures thereof. The preferred water-soluble synthetic anionic detergent active compounds are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of higher alkyl benzene sulphonates and mixtures with olefin sulphonates and higher alkyl sulphates, and the higher fatty acid monoglyceride sulphates . The most preferred anionic detergent active compounds are higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of higher alkyl benzene sulphonates or of higher-alkyl toluene, xylene or phenol sulphonates, alkyl naphthalene sulphonates, ammonium diamyl naphthalene sulphonate, and sodium dinonyl naphthalene sulphonate .

The amount of synthetic anionic detergent active to be employed in the detergent composition of this invention will preferably be up to 20% and most preferably from 2 to 15% by weight .

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 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 can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensate containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R3NO, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxyethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of structure R3PO, where one group R is an alkyl group of from 10 to 18 carbon atoms, and the others are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyldodecylphosphine oxide; and dialkyl sulphoxides of structure R2SO where the group R is an alkyl group of from 10 to 18 carbon atoms and the other is methyl or ethyl, for instance methyltetradecyl sulphoxide; fatty acid alkylolamides; alkylene oxide condensates of fatty acid alkylolamides and alkyl mercaptans .

The amount of nonionic detergent active to be employed in the detergent composition of the invention will generally be from 0.5 to 15% wt . , preferably from 5 to 10% by weight.

It is also possible optionally to include amphoteric, cationic or zwitterionic detergent actives in the compositions according to the invention.

Suitable amphoteric detergent-active compounds that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilizing group, for instance sodium 3- dodecylamino-propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyltaurate . Suitable cationic detergent-active compounds are quaternary ammonium salts having an aliphatic radical of from 8 to 18 carbon atoms, for instance cetyltrimethyl ammonium bromide.

Suitable zwitterionic detergent-active compounds that optionally can be employed are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic radical of from 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water- solubilising group, for instance 3- (N-N-dimethyl-N- hexadecylammonium) propane-1-sulphonate betaine, 3- (dodecylmethyl sulphonium) propane-1-sulphonate betaine and 3- (cetylmethylphosphonium) ethane sulphonate betaine.

Further examples of suitable detergent-active compounds are compounds commonly used as surface-active agents given in the well-known textbooks "Surface Active Agents", Volume I by Schwartz and Perry and "Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch.

The total amount of detergent active compound to be employed in the detergent composition of the invention will preferably be from 1.5 to 20%, preferably from 2 to 15% by weight .

Solvents

Solvents other than AMP or water can be present in the compositions of the invention. Suitable solvents include saturated and unsaturated, linear or branched hydrocarbons, and/or materials of the general formula :

wherein Ri and R2 are independently Cl-7 alkyl or H, but not both hydrogen, m and n are independently 0-5.

Preferred solvents are selected from the group comprising CioHie terpenes, Cio-Cie straight chain paraffins, and the glycol ethers .

Suitable glycol ethers include di-ethylene glycol mono n- butyl ether, mono-ethylene glycol mono n-butyl ether, propylene glycol n-butyl ether and mixtures thereof .

Suitable terpenes include d-limonene. Preferred paraffins include the material available in the marketplace as

^{^}Shellsol-T' (TM) .

Typical levels of solvent range from 1-15% wt . It is particularly preferred to use terpenes at levels 1-3% wt . Some of these terpene materials, such as limonene, have the further advantage that the exhibit insect-repellency. The straight chain paraffins can be used at higher levels than the terpenes, as these materials are less aggressive to plastics. The paraffins are believed to give better performance at in use pH ' s above 11.

The glycol ethers are preferred over the other solvents, at typical levels of 5-10% wt . on product with di-ethylene glycol mono n-butyl ether being particularly preferred. It is preferred that the ratio of the alkanolamine to the solvent falls in the range 3:1 - 1:3, with ratios of 1:1 to 1:3 being particularly preferred.

Advantageously, a portion of the solvent can be introduced as a perfume component, although the levels of solvent required would generally require the addition of higher levels of this component that would normally be present as a perfume ingredient in cleaning compositions. Preferably the terpenes are used in this manner as selected terpenes, such as limonene, have a pleasant citrus smell, whereas paraffins and glycol ethers are generally odourless.

Optional ingredients

The composition according to the invention can contain other ingredients, which aid in their cleaning performance. For example, the composition can contain detergent builders other than the special water-soluble salts such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates especially polyphosphates, mixtures of ortho- and pyrophosphates, zeolites and mixtures thereof. Such builders can additionally function as abrasives if present in an amount in excess of their solubility in water. In general the builder other than the special water-soluble salts when employed, preferably will form from 0.1 to 25% by weight of the composition.

Composition according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly hypohalites) , and preservatives . The invention will now be illustrated with respect to the following non-limiting examples.

Examples :

Process for preparation of the bar:

A batch of 25Kg was processed. 1250g of sodium carbonate was mixed with 3500g sodium salt of linear alkyl benzene sulphonate in a sigma mixer. 4750g of china clay was added followed by 2000g of butyl digol and mixed. To this 250g of aluminum sulphate, 7000g of feldspar and 250g of alkaline silicate was added and mixed thoroughly. 2000g of 2-amino-2- methyl- 1-propanol (AMP) , 250g of sodium bicarbonate followed by minor ingredients and 1500g of precipitated silica with water absorption capacity of 250% and water were added. The mixing was continued and followed by extrusion, billeting and stamping. The above process was employed for all the formulations presented in Table 1. The Examples 6 to 8, however were in the form of a solution.

Table 1

In use properties of the bar:

a. Tough soil cleaning.

The oil that has been polymerised by heating at high temperature is known as tough soil. Vegetable oil is smeared uniformly on a stainless steel plate and heated to get a polymerised oil film on the plate.

0.12g of the product was uniformly rubbed on the soiled plate and then rinsed with water. The performance was assessed to determine percentage cleaning visually by trained personnel . The experiment was conducted with replicates and analysed statistically. The higher the figure the greater the cleaner the dishes Table 2

Claims

1. An abrasive bar cleaning composition comprising:

a) 30-85% wt of at least one particulate abrasive ;

b) at least 0.5%wt of a particulate with a minimum water absorptive capacity of 200%;

c) 0.5-15%wt. of a C∑-Ce alkanolamine

d) at least 0.1%wt of an electrolyte base other than alkanolamine ;

e) 0.5-35%wt of at least one surfactant ; and

f) optionally, 0.1-20%wt of a solvent other than water or alkanolamine.

2. An abrasive bar cleaning composition as claimed in claim 1 wherein said particulate abrasive comprise a particulate abrasive which is insoluble in water.

3. An abrasive bar cleaning composition as claimed in claim 1 or 2 wherein said particulate abrasive have a Moh hardness of 2-6.

4. An abrasive bar cleaning composition according to any previous claim wherein said particulate abrasive have average particle sizes in the range 0.5-400 microns preferably 10-200 microns.

5. An abrasive bar cleaning composition according to any previous claim wherein said particulate abrasive range from 35 to 60% by weight of the total composition.

6. A abrasive bar cleaning composition according to any previous claim wherein said particulate with water absorptive capacity comprise a particulate with a water absorptive capacity of 200 to 300%.

7. A synergistic abrasive bar cleaning composition according to any previous claims wherein said particulate with water absorptive capacity range from 3-10 % by weight of the total composition.

8. An abrasive bar cleaning composition according to any previous claim wherein said particulate with water absorptive capacity is selected from gel, precipitated or spray dried silica, preferably precipitated silica.

9. An abrasive bar cleaning according to any previous claim wherein said alkanolmine comprise 2-amino-2- methyl-1-propanol , mono-di and tri- ethanolamine, mono- di- and tri- isopropanolamine, dimethyl -diethyl or dibutyl ethanolamine, and mixtures thereof preferably 2 -amino-2 -methyl-1-propanol (AMP) .

10. An abrasive bar cleaning composition according to any previous claim wherein said alkanolamine range from 1- 10% wt . , preferably 2-6% by weight of the total composition.

11. An abrasive bar cleaning composition according to any previous claim wherein said electrolyte base is selected from soluble carbonates, bicarbonates, hydroxides or alkaline salt preferably alkali metal carbonates .

12. An abrasive bar cleaning composition according to any previous wherein said electrolyte base range from 0.5- 5% wt . , preferably 1-2.5% by weight of the total composition.

13. An abrasive bar cleaning composition according to any previous claim wherein the total amount of detergent active comprise from 1.5 to 20% preferably from 2 to 15% by weight of the total composition.

14. An abrasive bar cleaning composition as claimed in any previous claim wherein said solvent is selected from saturated and unsaturated, linear or branched hydrocarbons and materials of the general formula

15 A synergistic abrasive bar cleaning composition as claimed in any previous claim comprising:

a. 30-85%wt of said at least one particulate abrasive;

b. at least 0.5%wt silica as said particulate with said water absorptive capacity ; c. 0.5-15% wt . of said C2-C6 of alkanolamine ;

d. at least 0.1%wt of said electrolyte base other than alkanolamine ;

e. 0.5-35%wt of said at least one surfactant; and

f . Optionally, 0.1-20%wt of said solvent other than water or alkanolamine.

16. A process for the preparation of the abrasive cleaning composition in the bar form as claimed in anyone of claims 1 to 15 comprising the steps of: a) in-situ generation of alkaline alumino silicate and making a dough containing surfactants and other particulate abrasives;

b) addition of alkanolamine and the electrolyte base

c) and structuring the composition by mixing with the particulate having a minimum water absorptive capacity of 200% followed by addition of other optional ingredients, mixing, extruding into bars using a conventional method.