GB2180847A

GB2180847A - Liquid scouring cleansers

Info

Publication number: GB2180847A
Application number: GB08622761A
Authority: GB
Inventors: Stephen Henry Iding
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1985-09-24
Filing date: 1986-09-22
Publication date: 1987-04-08
Also published as: AU6305386A; DK456486A; DK456486D0; AU604648B2; FI863854A0; CA1272658A; GR862393B; EP0216416A3; GB2180847B; EP0216416A2; MA20773A1; FI863854A; GB8622761D0; SG47992G; HK48092A

Abstract

Phase-stable liquid compositions, for use as hard surface cleansers, comprise a mixture of sodium C12-C18 paraffin sulfonate and sodium salt of linear alkyl benzene sulfonate, terpenes, polar solvents, acrylic acid polymeric thickeners, abrasives and viscosity enhancer compounds. The compositions are viscous, and provide cleaning of both greasy and particulate soils from hard surfaces without streaking or filming.

Description

1 GB2180847A 1

SPECIFICATION

Liquid scouring cleansers v TECHNICAL FIELD

Thie invention relates to liquid scouring cleansers. In particular, it relates to viscous, aqueous scouring cleansers containing an abrasive and a binary solvent system. These cleansers are suitable for use as general purpose household cleaning compositions.

& 50 BACKGROUND

General purpose household cleaning compositions for hard surfaces such as metal, glass, ceramic plastic and linoleum surfaces, are commercially available in both powdered and liquid form. Powdered cleaning compositions consist mainly of builder or buffering salts such as phosphates, carbonates, silicates, etc., and although such compositions may display good inor ganic soil removal, they are generally deficient in cleaning ability on organic soils such as the grease/fatty/oily soils typically found in the domestic environment.

Liquid cleaning compositions, on the other hand, have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relatively high level of surfactant material is delivered directly to the soil. Moreover, it is a rather more straightforward task to incorporate high concentrations of anionic or nonionic surfactant in a liquid rather than a granular 20 composition. For both these reasons, therefore, liquid cleaning compositions have the potential to provide superior grease and oily soil removal over powdered cleaning compositions.

Nevertheless, liquid cleaning compositions still suffer a number of drawbacks which can limit their consumer acceptability. Thus, they generally contain little or no detergency builder salts and consequently they tend to have poor cleaning performance on particulate soil and also lack 25 11 robustness- under varying water hardness levels. In addition, they can suffer problems of product form, in particular, phase instability, inhomogeneity, lack of clarity, or inadequate visco sity characteristics for consumer use. Moreover, the higher in-product and in-use surfactant concentration necessary for improved grease handling raises problems of extensive suds forma tion requiring frequent rinsing and wiping on behalf of the consumer. Although oversudsing may 30 be controlled to some extent by incorporating a suds-regulating material such as hydrophobic silica and/or silicone or soap, this in itself can raise problems of poor product stability and homogeneity and also problems associated with deposition of insoluble particulate or soap residues on the items or surfaces being cleaned, leading to filming, streaking and spotting.

Importantly, liquid cleaners suffer from the disadvantage that they do not contain abrasives, which contribute substantially to the cleaning performance of many dry- powder household and industrial cleaning compositions. Liquid cleansers that do contain abrasives can suffer from phase instability including layering and abrasive settling. This phase instability problem is aggravated when solvents are present in the cleanser compositions.

Terpenes are, per se, well-known components of perfume compositions and are often incor- 40 porated into detergent compositions at low levels via the perfume. Certain terpenes have also been included in detergene compositions at higher levels; for instance, German Patent Applica tion 21 13732 discloses the use of aliphatic and alicyclic terpenes as antimicrobial agents in washing compositions; British Pat. No. 1,308,190 teaches the use of dipentenes in a thixotropic liquid detergent suspension base composition. German Patent Application 29 09 690 teaches the 45 use of pine oil (a mixture mainly of terpene alcohols) in liquid hard surface cleaning compo sitions.

European Application 81-200540.3 teaches the use of terpenes with solvents such as benzyl alcohol and ethylene glycol dibutyl ether in liquid cleanser compositions. European Application 82-201396.7 teaches the use of terpenes and butyl carbitol (a trademark for 2-(2-butoxyethoxy)ethanol) in a liquid cleanser, optionally with particulate zeolite builders.

However, the use of the combination of selected terpenes, polar solvents, selected surfactant mixture, abrasive with polymeric acrylic acid thickeners and viscosity enhancers disclosed herein does not appear to have been considered, heretofore.

SUMMARY OF THE INVENTION

The compositions herein may be succinctly described as viscous, phase stable liquid scouring cleansers which comprise 1-10% of a surfactant mixture of paraffin sulfonate (NaPS) and alkyl benzene sulfonate (LAS), 0.5-10% of a terpene or a terpene derivative, or mixtures thereof; 0.5-3% of a polar solvent (benzyi alcohol); 0.4-1% of a high molecular weight acrylic polymeric 60 thickener; and from 1-50% of a water-insoluble abrasive of the type described hereinafter; and 0.03-0.5% of selected viscosity enhancing compounds.

DETAILED DESCRIPTION OF THE INVENTION

The essential terpene, benzyl alcohol, abrasive, thickener, selected surfactant components, and 65 2 GB2180847A 2 other ingredients used in the practice of the present invention are described in more detail, hereinafter. All percentages and ratios mentioned in this specification are by weight, unless otherwise stated.

It has now been discovered, however, that the defects of prior art liquid cleansers can be minimized or overcome through the incorporation therein of a specified mixture of surfactants, 5 acrylic acid polymeric thickeners, and selected terpenes, viscosity enhancers of the alcohol, nitrile, ketone and aldehyde classes as defined herein, in combination with benzyl alcohol, and with an abrasive.

The present invention provides abrasive-containing liquid cleaning and scouring compositions which have excellent phase stability and suds control across a broad range of usage and water 10 hardness conditions and which provide excellent shine performance together with improved cleaning characteristics both on greasy/oily soils and on inorganic particulate soils, with little tendency to cause filming or streaking on washer surfaces. Importantly, the abrasives used herein are soft, preferably having a Mohs hardness of 3 or less.

Terpenes-Terpenes, as a solvent class, have limited water-solubility. They can be incorporated 15 into liquid cleaning compositions in homogeneous form, even under---cold- processing condi tions, with the ability to provide excellent cleaning characteristics across the range of water hardness on grease/oily soils and inorganic particulate soils, as well as on shoe polish, marker ink, bath tub soil, etc., and excellent shine performance with low soil redeposition and little or no propensity to cause filming, streaking or spotting on surfaces washed therewith. Moreover, 20 the terpenes herein specified, and in particular those of the hydrocarbon class, are valuable in regulating the sudsing behavior of the instant compositions in both hard and soft water and under both diluted and neat or concentrated usage.

Preferred terpenes for odor impact are mono-and bicyclic monoterpenes, especially those of the hydrocarbon class, which include the terpinenes, terpinolenes, limonenes and pinenes, and 25 mixtures thereof. Highly preferred materials of this type are d-limonene, dipentene, alpha-pinene, beta-pinene and the mixture of terpene hydrocarbons obtained from the essence of citrus (e.g., cold-pressed orange terpenes and orange terpene oil phase ex fruit juice). These terpenes are used at concentrations of at least 0. 1 %, preferably 0.5%-5%, most preferably 1-3%, in the compositions for fragrance and cleaning effects. The weight ratio of surfactant:terpene preferably 30 is between 20:1 and 32, more preferably 4:1 to 1.5A.

Viscosity Enhancers-As mentioned hereinbefore, a special problem for thickened liquid scour ing cleansers is achieving a stable, high viscosity product. It has been surprisingly discovered that certain alcohol, aldehyde, nitrile, acetate and ketone compounds having VE empirical formulas Of CAR where n= 10 or 12; m= 14, 16, 17, 18 or 20 and R=O, 02 or N, are viscosity 35 enhancers (VE) when used in conjunction with the high molecular weight acrylic acid polymeric thickeneres. Some preferred VE compounds are selected from citronellol, geraniol, linalool, nerol, rhodinal, alpha-terpineol, beta-citronellol, rhodinol, citronella nitrile, carvone, fenchone, menthol, isoborneol and mixtures thereof. These preferred VE compounds are commercially available.

These VE compounds are used in the compositions of this invention at concentrations of from 40 about 0.03% to about 0.5%, more preferably from about 0.05% to about 0. 25%.

Polar Solvent-The polar solvent of this invention has a water solubility at 2WC in the range of from about 0.2% to about 10% and is used at a level of from about 0.5% to about 3%. Benzyl alcohol (C6HCH2OH), the preferred polar solvent, is used in the compositions at concentrations of at least 0.1%, preferably 0.5-3%, most preferably 1-2%. This polar solvent increases the 45 cleaning power of the compositions.

The weight ratio of terpenes to benzyi alcohol is preferably in the range from 5:1 to 1:5, most preferably 2:1 to 1:2.

Abrasive-The abrasive is used at a level of 1-50% (preferably 5-40%; most preferably 10-35%). The abrasives employed herein are selected from water-insoluble, mild abrasive materials. It is highly preferred that the abrasives used herein' not be undesirably -scratchy.Abrasive materials having a Mohs hardness in the range of about 7, or below, are typically used; abrasives having a Mohs hardness of 3, or below, can be used to avoid scratches on aluminum or stainless steel finishes. Suitable abrasives herein include inorganic materials, especially such preferred materials as calcium carbonate and diatomaceous earth, as well as materials such as Fuller's earth, magnesium carbonate, China clay, attapulgite, calcium hydroxyapatite, calcium orthophosphate, dolomite and the like. Organic abrasives such as urea-formaldehyde, polyvinyl chloride, methyl methacrylate and melamine-formaldehyde resins can also be used, preferably at a level of 5-15%. The organic abrasives are more compatible with detergency builders and sequestrants.

It is preferred that the abrasives herein have a particle size range in the 100-600 U.S. Sieve Series Mesh, preferably 200-400 U.S. Sieve Series Mesh, size. Diatomaceous earth and calcium carbonate are commercially available in the 5-150 micron particle size range, and, as will be seen hereinafter, give excellent cleaning performance. The preferred abrasive is commercially available as Georgia Marble RO-4 Ground Calcium Carbonate.

t 1 1 A 3 GB2180847A 3 p 4 50 Surfactants-The selected combination of NaPS and LAS has been found to provide superior phase stability in the cleansers of this invention. The selected water- soluble detersive surfactant useful herein is a mixture of linear alkyl benzene sulfonates (LAS) and paraffin sulfonates (NaPS).

In general, such detersive surfactants contain an alkyl group in the Cl,Cl. range; the selected surfactants are most commonly used in the form of their sodium, potassium or triethanolammon- 5 ium salts. The C11-C16 alkyl benzene sulfonates and the C12-ClI paraffin sulfonates are selected for the compositions of the present invention. As used herein, the abbreviations---LAS-and ---NaPS-include these broader surfactant definitions, unless otherwise specified.

The compositions herein generally will contain about 1% to about 10%, preferably 2% to about 8%, more preferably 2.5-5%, of the surfactant mixture. The mixture has a ratio of NaPS 10 to LAS of from 20:1 to 2A, preferably 10:1 to 2A, and more preferably from 7:1 to 4A.

Thickeners-The selected thickeners of this invention are the high molecular weight polyacry lates which have molecular weights of about 0.5-1.5 million with preferably some crosslinking of about 1-4%. Examples of suitable thickeners are (1) Sokalan PHC-25 ex BASF; (2) Acrysof ICS-1 ex Rohm and Haas (works best at high pH 11.9); and (3) Carbopol 941 ex B.F. Goodrich. 15 Carbopol 941 works well but leaves a film when rinsed after product use. The thickeners of this invention are employed at 0.4-1%, preferably 0.45-0.75% by weight of the composition.

The compositions herein must be thickened for dispersion and phase stability at the 1800-400 cps viscosity range. The compositions of this invention preferably have a viscosity in the 2000-35000 cps range, as measured with a standard Brookfield Viscometer. Thickened 20 compositions tend to cling to vertical surfaces such as walls and windows, which makes them more convenient to use.

pH-The compositions herein are formulated in the alkaline pH range, generally in the range of pH 8-12, preferably about 10-11.5 to avoid hydrolysis of some perfume components. Caustics such as sodium hydroxide and sodium carbonate can be used to adjust and buffer the pH, as 25 desired. An alkaline pH is also essential in obtaining the specified viscosity.

Soaps-As mentioned hereinabove, one special problem associated with the use of liquid cleansers is their tendency to over-suds in use. It has been discovered that soaps, especially the alkali, ammonium and alkanolammonium salts of C12-C24 fatty acids, are especially useful as suds suppressors when conjointly present with terpenes and benzyi alcohol in the instant compo- 30 sitions. Soap concentrations of at least about 0.005%, preferably 0.05% to 0.4%, provide this important suds control function. Soap prepared from coconut oil fatty acids is preferred.

Other ingredients-The compositions herein can contain other ingredients which aid in their cleaning performance. Conventional additives such as detergency builders, water softeners, car rier liquids (especially water), perfumes, and the like can be used. For example, it is highly 35 preferred that the compositions with organic abrasives contain a detergent builder and/or metal ion sequestrant. Compounds classifiable and well known in the art as detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphos phate and sodium ortho- and pyrophosphates, silicates, and mixtures thereof. Metal ion seques trants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-poly- 40 phosphonates and phosphates (DEQUEST) and a wide variety of other poly- functional organic acids and salts too numerous to mention in detail herein. See U.S. Pat. No. 3,579,454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/sequestrant will comprise about 1% to about 25% of the composition. Colorants and perfumes can be used with all abrasives.

Moreover, the compositions herein can contain, in addition to ingredients already mentioned, various optional ingredients typically used in commercial products to provide aesthetic or addi tional product performance benefits. Typical ingredients include perfumes, dyes, optical brighten ers, soil suspending agents, detersive enzymes, gel-control agents, freeze-thaw stabilizers, bac tericides, preservatives, and the like. Nonionic surfactants at a level of 0.2-0.5% are excellent 50 freeze-thaw stabilizers.

The compositions herein typically contain up to about 90% water as a carrier. Water-alcohol (e.g., ethanol, isopropanol, butanol, etc.) mixtures can also be used.

Since the compositions herein are in liquid form, they can be prepared by simply blending the essential and optional ingredients in the aqueous carrier.

The following examples are given by way of illustrating the compositions herein, but are not intended to be limiting to the spirit and scope of the invention.

4 GB2180847A 4 EXA MPLE 1 Component Concentration in Cleanser Thickener Sokalan PHC-25 Surfactants 10 NaPS Las Neodo145-7 Solvent 15 Benzyl Alcohol Perfume Mix #1 Citrus Terpenes Citrus Phase Oil 20 Other Components Abrasive CaC03 (Avg. 50-60 microns) Other Na.C03 Dye NaOH Coconut/Lauric Fatty Acid 30 Water 0.67% 3.0% 0.6% 0.30% 1.30% 1.85% 0.15% 0.15% 30.0% 3.0% 0.005% 0.5% 0.2% To Balance Definitions NaPS Sodium CU-CII paraffin suffonate LAS Sodium salt of linear C,,_, alkyl benzene sulfonate Perfume Mix #1: The---OtherComponents- of the perfume mix #1 contain 50- 60% viscosity enhancing compounds of alcohol, nitrile and aldehyde of the C10H200, C10H17N and C,01-1,,0 formulas. A condensate of one mole of Cl,- Cl, fatty alcohol with 7 moles of ethylene oxide.

Neodol 45-7 EXAMPLES 2 and 3 Impact of Terpenes on Product Viscosity Examples 2 and 3 were made in 2000 gram batches using a Lightening mixer. The ingredients 45 were added in the order in which they appear. A viscosity reading was recorded 5 minutes after each ingredient was added.

1 A GB2180847A 5 Example 2

Ingredient 1 Example 3

Formula Viscosity Formula Viscosity Soft water 59.00% - 58.00% Sokalan PHC-25 0.65% 100 cps - Acrysol ICS-1 - - 0.98% 25 cps Anionic surfactant 2.8% - 2.8% - Neodol45-7 0.5% 400 cps 0.5% 50 cps 10 Benzyl alcohol 1.5% 1.5% - Lauric fatty acid 0.10% - 0.10% - Coconut fatty acid 0.10% 25 cps 0.10% 25 cps NaOH 0.25% 550 cps 0.25% 225 cps NalC03 3.00% 250 cps 3.00% 150 cps 15 CaCO3 30.00% 1250 cps 30.00% 1500 cps Perfume mix 2.15% 2750 cps 2.15% 2700 cps NaPS/LAS ratio 5: 1.

The perfume mix #1 comprises organic compounds which contain about 3-4 parts citronello, 20 citronella nitrile and dihydro mercinol. This amount provides about 0.06- 0.09% of viscosity enhancers by weight of the total composition.

Note in Examples 2 and 3 that the addition of the viscosity enhancing perfume mix had a profound impact on product viscosity. Without the perfume mix, the formulations would experi- 25 ence abrasive settling and layering and have viscosities of only 1250 and 1500 cps vs. 2750 and 2700 cps, respectively.

EXAMPLES 4-14

Impact of Selected Compounds on Product Viscosity Base Formula 1 Ingredient Wt. % Soft water Balance 35 Sokalan PHC-25 0.65 Anionic surfactant 3.6 Neodo145-7 0.50 Benzyl alcohol 1.3 Lauric fatty acid 0.1 40 Coconut. fatty acid 0.1 NaOH 0.2 Na2C03 3.0 CaC03 30.00 Colorant 0.01 45 Citrus terpenes 2.00 NaPS/LAS ratio 5A.

Selected Compounds Example 4 0.15% Citronello 5350 cps 0.15% Dihydro Mercinol 4900 cps 6 0.15% Citronelial 3500 cps 55 7 0.15% Citronella Nitrile 3000 cps 8 0.15% Fenchyl Acetate 2300 cps 9 0.15% Linalyl Acetate 2250 cps 0.15% Camphene 1750 cps 11 0.15% Alpha-Pinene 1650 cps 60 12 0.15% Eucalyptol 2050 cps 13 0.15% Para Cymene 1700 cps 14 0.15% Terpinolene 1800 cps 6 GB2180847A 6 The base Formula 1 has a viscosity of 1900 cps. The selected compounds of Examples 4-14 were added separately to the base Formula 1 and the viscosity measured. The compounds of Examples 4-7 show profound impact on viscosity enhancement. The compounds of Examples 8 and 9 show marginal improvement. The compounds of Examples 10-14 show little or reduced 5 viscosity impact.

Other VE compounds of the empirical formulas, e.g., menthol, isoborneol, carvone and fenchone, were found to produce a profound inpact on viscosity of Base Formula 1.

EXAMPLES 15-20 10 impact of LAS on Viscosity Base Formula 11 Ingredient Wt. % Soft water Balance 15 Acrysol ICS-1 0.49 Surfactant:

NaPS Variable 1 see below LAS Variable f Benzyl alcohol 1.5 20 NaOH (50%) 0.25 Na,CO, 3.00 CaC03 (same as above) 30.00 Perfume mix #1 2.15 25 Examples: 15 16 17 18 19 20 NaPS concentration 2.8% 2.8% 2.8% 2.8% 2.8% 3.5% 30 LAS concentration 0.3 0.4 0.5 0.6 0.7 - Viscosity (cps) 1400 1900 2100 2500 3150 1500 Stability: Top OK OK OK OK Abrasive Layer at settles room 35 temp.

only The above data show that combinations of NaPS and LAS have synergistic benefits for 40 viscosity enhancement, as well as phase stability,

Claims

1. An improved phase stable liquid scouring cleanser composition comprising:

(a) from about 1% to about 10% of synthetic surfactant mixture of paraffin sulfonate (NaPS) 45 and linear alkyl benzene sulfonate (LAS), said mixture of NaPS and LAS having a ratio of from 20:1 to 2:1; (b) from about 0.5% to about 5% of a mono- or sesquiterpene or mixtures thereof, the weight ratio of surfactant:terpene lying between 20:1 to 3:2; from about 0.5 to about 3% of a polar solvent having a water solubility at 25'C in the range of from about 0.2% to about 10%; from about 0.03% to about 0.5% of a compound selected from the group consisting of alcohols, aldehydes, acetates, ketones and nitriles of the formulas C',H. R where n=10 or 12; m= 14, 16, 17, 18 or 20 and R=O, 02 or N; from about 1% to about 50% of a water-insoluble abrasive; and from about 0.40% to about 1% of a high molecular weight acrylic acid polymeric thickener having a molecular weight range of about 0.5 million to about 1.5 million; and (c) (e) (f) k 1 Z wherein the viscosity of said composition is from about 1800 to about 4000 cps and wherein the pH of said composition is from 8 to 12.

2. The composition of Claim 1 wherein the ratio of said mixture of NaPS and LAS is from 60 10:1 to 2:1 and is present in said composition at a level of from 2% to 8%.

3. The composition of Claim 1 wherein the ratio of said mixture of NaPS and LAS is from 7:1 to 4:1 and is present at a level of about 2.5% to about 5%.

4. The composition in accordance with Claim 1 wherein the terpene is selected from d- limonene, dipentene, alpha-pinene and beta-pinene, and mixtures thereof, and is present at a 65 1 1 15 7 GB2180847A 7 concentration of 1% to 3% and wherein the weight ratio of surfactant mixture to terpene is 4:1 to 1.5: 1.

5. The composition in accordance with Claiml wherein said (d) is present at a concentration of 0.05 to 0.5%.

6. The composition in accordance with Claim 1 wherein said polar solvent is benzyl alcohol present at a concentration of from 0.5 to 3%.

7. The composition in accordance with Claim 1 wherein the weight ratio of terpgne to benzyl alcohol is in the range of from 5:1 to 1:5.

8. The composition in accordance with Claim -1 which in addition contains from 1% to 2% by weight of benzyl alcohol and wherein the ratio of terpene to benzyl alcohol is from about 2:1 to 10 about 1:2.

9. A composition in accordance with Claim 1 wherein (d) is selected from citronellol, geraniol, dihydro mercinol, linalool, nerol, rhodinal, alphaterpineol, beta-citronellol, rhodinol, citronella nitrile, carvone, fenchone, menthol, isoborneol and mixtures thereof.

10. A composition in accordance with Claim 1 wherein (d) is selected from citronellol, 15 dihydro mercinol, citronelial and citronella nitrile and mixtures thereof and is present at a level of 0.05% to 0.25% of said composition.

11. A composition in accordance with Claim 1 which comprises from 5% to 40% of an abrasive having a particle size range of 5-150 microns, said abrasive having a Mohs hardness of 7 and below.

12. A composition in accordance with Claim 11 wherein said abrasive is present at a level of 10% to 35%.

13. A composition in accordance with Claim 1 which comprises from 0.45% to 0.75% of said acrylic acid polymeric thickener and wherein said viscosity is from 200 to 3500 and wherein said pH is 10 to 11.5.

14. A composition in accordance with Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13 which comprises from 0.2% to 0.5% of a nonionic surfactant.

Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Ltd, Dd 8991685, 1987. Published at The Patent Office, 25 Southampton Buildings, London, WC2A 'I AY, from which copies may be obtained.