NZ263394A - Cleaning composition; stable, concentrated and clear composition comprising at least one short chain surfactant, the composition not being in the form of a microemulsion - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £63394 New Zealand No. 263394 International No. PCT/US94/02748 Prior ity D«t»$s):.. \3\ lfeJUBS.

Complete Spaoffloatfon Fled: Qam: (fl) , Publication DWr. 2.1.SER.1997 P.O. Journal No: Ittr.QQ Title of Invention: Concentrated cleaning compositions Name, address and nationality of applicant(s) as in international application form: ft «**x*u a*. lam of oUio THE PROCTER & GAMBLE COMPANY,Aof One Procter & Gamble Plaza, Cincinnati, Ohio 45202, United States of America NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION 2 6 3 3 & 4 0 94/21768 g. «*• ^ A * PCT/US94/02748 lft CONCENTRATED CLEANING COMPOSITIONS Technical Field The present invention relates to concentrated cleaning 25 compositions. Although the present invention relates primarily to cleaning compositions for hard surfaces, it may also be of interest for other cleaning compositions including dishwashing and laundry detergent compositions.

Background of the Invention Concentrated cleaning compositions are well known in the art. Concentrated compositions are mainly characterized by 35 the fact that they comprise a higher concentration of active ingredients compared to a conventional cleaning composition, and a problem which is typically encountered SUBSTITUTE SHEET (RULE 261 WO 94/21768 PCT/US94/02748 when formulating concentrated cleaning compositions is therefore the physical stability of such compositions. Indeed, because such compositions comprise a high amount of active ingredients in a limited amount of water, stability 5 problems appear which lead, if not solved, to compositions which separate into several phases. This phenomenon affects the performance of the composition and is visually noticeable, thereby rendering such formulations unfit for commercialization.

Various solutions have been proposed to solve this problem which typically involve the use of specific stabilizing ingredients, or hydrotropes. Such ingredients have the sole function of stabilizing the composition. They thus 15 increase the cost of formulating such compositions without providing any cleaning performance benefits, and they furthermore require to free up parts in the formulation which could otherwise be used to formulate more actives.

For instance, EP 316 726 discloses concentrated compositions in the form of microemulsions which comprise water, perfume, a surfactant and a so-called co-surfactant. The co-surfactant is said to reduce the interfacial tension at interfaces between dispersed and continuous phases of an 25 emulsion of said surfactant, thereby creating a stable microemulsion. The so-called co-surfactants in the '726 publication are listed as specific glycol ethers, which are traditionally regarded as solvents in this field, or specific carboxylic acids. The co-surfactants in the '726 30 publication do not appear to participate to the overall cleaning performance of the product.

It is therefore an object of the present invention to formulate a stable concentrated cleaning composition 35 without using ingredients which are provided for the sole purpose of providing stability to the compositions herein, SUBSTITUTE SHEET (RULE 26) # 0 94/21768 PCT/US94/02748 3 26 3 39 (followed by page 3a) but which also participate significantly to the cleaning performance of said compositions.

It has now been found that this object can be met by 5 formulating a concentrated aqueous compositions comprising at least one short chain surfactant, i.e. with a hydrophobic group consisting of a Cg-Cio alkyl chain, said compositions not being in the form of microemulsions. Said short chain surfactants provide stability to the 10 compositions herein and, in the same time, significantly boost the overall cleaning performance, especially grease cleaning, both in neat and dilute usage.

Summary of the Invention The compositions herein are stable clear concentrated cleaning compositions comprising from 10 % to 80 % by weight of the total composition of water and at least one 20 short chain s^-factant comprising a Cg-Cio alkyl chain as its hydrophobic portion. The compositions herein are preferably not in the form of microemulsions.

In particular, the present invention consists of a stable and clear concentrated cleaning composition comprising by weight: from 5% to 30% of a short chain surfactant comprising a mixture of (a) a nonionic surfactant having the formula C6_10(EO).OH in which e is form 3 to 8 and (b) a C6_10 alkyl sulfonate; a long chain surfactant comprising a mixture of (a) a nonionic surfactant having the formula C12_16 (EO) nOH in which n is from about 2 to about 10 and (b) a nonionic surfactant having the formula C12.l6 (EO) nOH in which n is.. - f , . ^ from about 20 to about 60; \ V from 0.5% to 3% of a suds suppressant comprising a .. mixture of a Ce_22 fatty acid and a 2-alkyl alkanol; \ -3a- 2fi3 39 from about 1% to about 4% of potassium carbonate; and from about 30% to about 70% of water; wherein EO represents an ethoxy moiety. Optionally the composition further comprises a hydrophobic cleaning solvent having the formula C2_6 (EO)x (PO) yOH in which x and y are each from 0 to about 2, EO is as defined above and PO represents a propoxy moiety.

Detailed Description of the Invention The compositions of the present invention are concentrated aqueous compositions. By concentrated, it is meant herein that the compositions comprise from 10 % to 90 % by weight of the total composition of water, preferably from 15 % to 75 %, most preferably from 30 % to 80 %.

The compositions according to the present invention are clear and stable. By clear and stable, it is meant herein that the compositions of the present invention are macroscopically substantially transparent, in the absence of any opacifier, and that said compositions do not - V\ WO 94/21768 PCT/US94/02748 macroscopically separate into separate phases during at least 1 month, at temperatures ranging from 4°C to 50°C, upon standing.

The compositions according to the present invention further comprise at least one short chain surfactant, or mixtures thereof. All surfactants have in common that they comprise a hydrophobic portion and a hydrophilic portion. By short chain surfactant, it is meant herein surfactants which 10 comprise a Cg-Cio alkyl chain as their hydrophobic portion. Such short chain surfactants are accordingly those conventionally used in this field, but with a shorter alkyl chain, and can be of any type. Accordingly, suitable short chain surfactants for use herein include C6~C10 15 sulfates (C6-C10SO4), alkyl ether sulfates (C5-C10 (OCH2CH2) eSC>4), alkyl sulfonates (C5-C10SO3) , alkyl succinates (C6-C1QOOCCH2CH2COOZ) , alkyl carboxylates (C5-CiqCOOM), alkyl ether carboxylates (Cg-Cio(OCH2CH2)eCOOM), alkyl sarcosinates (C6-CioCON(CH3)R) / alkyl sulfo 20 succinates (Cg-CioOOCCH(SO3M)CH2COOZ), amine oxides (C5-CiqRR'NO), glucose amides (Cg-CioCONR''x)/ alkyl pyrrolidones (Cg-C^o(C4H6ON), alkylpolysaccharides (Cg-CioOGg), alkyl alkoxylates (Cg_ C10(OCH2CH2)e(0CH2CH2CH2)p0H) and betaines (C5- Cio1^ (CH3) 2CH2COO-) . In the formulae in brackets, e and p are independently from 0 to 20 and e+p>0, Z is M or R, M is H or any counterion such as those known in the art, including Na, K, Li, NH4, amine, X is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain 30 with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof, R, R and R' '' are Ci~ C5 alkyl groups, possibly functionalized with hydroxyl groups, R and R' are preferably C1-C3, most preferably methyl, R'' is preferably 2-hydroxyethyl or 2 35 hydroxypropyl, G is a saccharide, preferably glucose, and g is of from 1.5 to 8. All these surfactants are well known in the art. A more complete disclosure of conventional SUBSTITUTE SHEET (RULE 26) 0 94/21768 glucose amides can be found for instance in WO 92-06154 and a more complete disclosure of conventional alkyl polysaccharides can be found for instance in US 4,536,319. The compositions according to the present invention may 5 comprise any of the above surfactants alone, or any combination thereof, depending on the end use envisioned.

Preferred short chain nonionic surfactants for use herein are alkyl alkoxylates according to the formula Cg-10 Cio(OCH2CH2)e(OCH2CH2CH2)pOH, where e and p representing respectively the degree of ethoxylation and propoxylation, are independently of from 0 to 20, and that e+p>0. Most preferred short chain nonionic surfactants for use herein are those where e and p are such that e+p is from 3 to 10, 15 particularly those where p is 0 and e is from 3 to 8. Also, most preferred short chain nonionic surfactants for use herein are those where said short chain is a hydrocarbon chain comprising from 7 to 10 carbon atoms.

Said preferred short chain nonionic surfactants for use 20 herein can be manufactured by the processes well known to the man skilled in the art, such as condensation of the corresponding alcohol and alkylene oxide, but such short chain surfactants are more conveniently commercially available for instance from Sidobre under the trade name 25 Mergital@C4 (C8E04), from Kolb under the trade names Imbentin® AG/810/050 and AG/810/080 (respectively C8-10E05 and C8-IOEO8)• Preferred short chain anionic surfactants for uje herein 30 are Cg-C^o alkyl sulfates (Cg-CioS04) anci alkyl sulfonates (Cg-Cios03) • Most preferred are the C6-C8 alkyl sulfates and sulfonates. The alkyl sulfonates can provide products with less filming/streaking, as demonstrated hereinafter, as compared to other anionics such as alkyl sulfates. Such 35 short chain anionic surfactants can be made by well known sulphation or sulphonation processes followed by neutralization, but said anionic short chain surfactants SUBSTITUTE SHEET (RULE 26) # are ^ore conveniently commercially available, for instance from Rhone Poulenc under the trade name Rhodapon® OLS, or from Witco under the trade name Witconate@.

The compositions according to the present invention may comprise from 0.1 % to 50 % by weight of the total composition, preferably from 1% to 40%, most preferably from 1.5% to 30% of said short chain surfactants. It has been found that said short chain surfactants allowed the 10 formulation of concentrated compositions without the need for any stabilizing systems, or certain formulation type such as microemulsions. Said short chain surfactants are also particularly effective in cleaning, especially grease cleaning.

The compositions according to the present invention may comprise short chain surfactants only, or combinations of short chain surfactants with conventional longer chain surfactants. Accordingly, suitable long chain surfactants 20 for use herein include those listed herein above in the description of short chain surfactants, but with a longer alkyl chain, of from Cn-C24- Preferred long chain surfactants for use herein are long chain alkyl sulfonates, e.g. paraffin sulfonates and alkyl ethoxylates, and 25 mixtures thereof.

If combinations of short chain and long chains are used, it is preferred to observe certain ratios: if short chain anionic surfactants are used, it is preferred to observe a 30 minimum weight ratio of short chain anionic surfactant to longer chain surfactant of 1:10. If short chain nonionic surfactants are used, it is preferred to observe a minimum weight ratio of short chain nonionic to longer chain surfactant of 1:5.

Depending on the end use envisioned, the compositions herein may further comprise a variety of other optional SUBSTITUTE SHEET (RULE 26) wo 94/21768 7 263 394 ingredients including builders, alkanolamines, pH adjusting agents, perfumes, dyes, bleaches, enzymes and the like. When an alkalinity source is present, it is desirable that the potassium cation be used, E.g., when 5 potassium carbonate is used instead of sodium carbonate, as demonstrated hereinafter, there is less filming/streaking. As used herein, potassium carbonate comprises potassium bicarbonate.

In some instances, it may be appropriate to include a suds suppressing system in the compositions herein. Said suds suppressing system can advantageously be a mixture of 2- alkyl alkanols, — or mixtures thereof/ with a C9 to C22 fatty acid, or 15 mixtures thereof. Such a system is particularly advantageous as both ingredients appear to act in synergy. Thus even a very low amount of said system is enough to control suds efficiently. Accordingly/ said system is present in amounts of from 0.1% to 5% by weight of the 20 total composition, preferably 0.5% to 3%.

The compositions herein do not require the presence of a stabilizing compound. By stabilizing compound, it is meant herein a compound whose sole function is to enhance the 25 physical stability of the composition. Such compounds are typically xylene or toluene sulphonate salts, and glycol ethers, including ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol methyl ether, propylene 30 glycol methyl ether, tripropylene glycol methyl ether, propylene glycol monobutyl ether and other various solvents such as ethanol and butanol. Accordingly, the compositions of the present invention are preferably substantially free of such stabilizing compounds.

The present invention further encompasses a method of cleaning a hard surface which comprises the steps of ! i' I h - "J!. 1397 ! 8 diluting a composition according to the preceding claims in water, then applying it to said hard surface. Depending on the exact formulation, the compositions herein may be used both neat and diluted from 10 to 500 times.

Particularly preferred compositions contain: (1) from 5% to 30% of short chain surfactant, preferably a mixture of (a) short chain nonionic surfactant having the formula Cg_ 10(EO)c(PO)pOH wherein EO is an ethoxy moiety, PO is a 10 propoxy moiety with each c and p being from 0-20, preferably from 3 to 10, more preferably c being from 3 to 8 and p being 0 and (b) Cg-io alkyl sulfonate, (2) optional, but preferred, long chain nonionic surfactant, preferably nonionic C12-I6 (E°)n' preferably a mixture of 15 nonionic surfactants in which one has an n of from about 2 to about 10 and the other has an n of from about 20 to about 60; (3) optional hydrophobic cleaning solvent, preferably C2-6(E0)x(PO)yOH wherein x and y are each from 0 to about 2, and more preferably C4(EO)2OH; (4) optional, 20 but preferred, fatty acid suds suppressant at a level of from 0.1% to 1%, preferably from 0.2% to 0.8%; (5) optional, but preferred, Ci2_i0 fatty alcohol, more preferably branched chain fatty alcohols such as 2-butyl octanol and/or 2-hexyl decanol; and (6) optional, but 25 preferred, alkalinity source, more preferably potassium carbonate. The balance of each composition is preferably an aqueous solvent system.

The present invention will be further illustrated by the following examples.

Examples The following compositions are made by mixing the listed ingredients in the listed proportions.

SUBSTITUTE SHEET (RULE 26) WO 94/21768 PCT/US94/02748 # I II III IV C13/15 alkyl ethoxylate EO3 3 3 C12/15 alkyl ethoxylate EO30 5 5 Cg alkyl sulfate - 10 10 Cg alkyl sulfonate - 20 Cq alkyl ethoxylate EOg - 9 - - Cg/10 alkyl ethoxylate EO5 - 20 Citric acid 3 3 1- Monoethanolamine 3 3 11 Triethanolamine - 3 Water & minors up to 100% All compositions were evaluated for their physical stability at 4°C, at room temperature (20°C), and at 50°C. Composition I, which is not within the invention, was a gel at 4°C, and an emulsion at room temperature and at 50°C. All other compositions, within the invention, were clear 20 transparent liquids in the same conditions.

Other compositions were made by mixing the listed ingredients in the listed proportions.

V C13/15 alkyl ethoxylate E03 4 C13/15 alkyl ethoxylate E07 • -30 C7-9 alkyl sulfate 7.5 C8 alkyl sulfate C8 alkyl sulfonate C7-9 alkyl ethoxylate E06 C8-10 alkyl ethoxylate E05 10 35 C13/15 alkyl ethoxylate E030 6 Na Paraffin Sulfonate Citric acid 3 VI VII VIII 3 5 1 3-5 8-10 10 5 9-9 4 3 5 3 SUBSTITUTE SHEET (RULE 26) t Sodium carbonate 2-hexyl decanol Palm Kernel Fatty Acid Water & minors 1 0.4 3 0.6 1 0.4 1 up to 100%- The invention is illustrated by the following examples, All values in table are weight percentages.

Example No.: Ingredient 1 Wt% 2 Wt% 3 Wt% Sodium Octyl Sulfate Sodium Octyl Sulfonate 15 Alfonic R 810-65 (c8-10 eo6 average) Neodol R 23-3 <c12-13 eo3> Lutensol R A0-30 <c13-15 e°30) Sodium Carbonate Potassium Carbonate Palm Kernel Fatty Acid 2-Butyl Octanol 25 Hydrophobic Perfume* Deionized Water and Minors PH 7.0 .0 4.0 6.0 2.0 0.4 0.4 1.5 g.s. .8 7.0 10.0 4.0 6.0 2.0 0.4 0.4 1.5 g.s. .8 7.0 10.0 4.0 6.0 2.0 0.4 0.4 1.5 q. s. .8 Alfonic is a trade name used by Vista Chemical. Neodol is a trade name used by Shell Chemical Co. Lutensol is a trade name used by BASF Corp.

♦Hydrophobic perfume consists of terpenes, terpene alcohols, and other perfume materials which are typically insoluble in water.

SUBSTITUTE SHEET (RULE 26) ,V0 94/21768 PCT/US94/02748 11 The invention is also illustrated by the following Examples. All values in table are weight percentages.

Example No.: 4 5 Ingredient WtV. WtS.

Sodium Octyl Sulfonate 7.0 7.0 Alfonic R 810-65 10.0 10.0 (Cg_io EOg average) Neodol R 23-3 4.0 4.0 (C12-13 E03) Lutensol R A0-30 6.0 6.0 (c13-15 EO30) Diethylene Glycol Monobutyl Ether 3.0 Potassium Carbonate 2.0 2.0 Palm Kernel Fatty Acid 0.4 0.6 2-Butyl Octanol 0.4 - Hydrophobic Perfume* 1.5 1.5 Deionized Water and Minors q.s. q.s. pH 10.5 10.5 Alfonic is a trade name used by Vista Chemical. Neodol is a trade name used by Shell Chemical Co. Lutensol is a trade name used by BASF Corp.

♦Hydrophobic perfume consists of terpenes, terpene alcohols, and other perfume materials which are typically insoluble in water.

Filming/Streaking data were obtained on the above Examples.

Filming/Streaking Test Method -Dilute (No Wax Floors) Materials SUBSTITUTE SHEET (RULE 26) PCT /US94/02748 12 1. Spontex cellulose sponges (cut to 2"x4"xl") 2. No wax floor tiles (12"xl2") 3. Test products - these are diluted with heated tap water that has been adjusted to a hardness of 7 grains and maintained at 110° F. Dilution is 1 part test product:128 parts water.

Procedure: 1. Clean the floor tiles with tap water using a sponge.

Then rinse with distilled water and dry with paper towels. Apply a small amount of isopropyl alcohol to each tile and dry thoroughly. 2. Clean sponges of all factory preservatives and rinse well. Use the same sponge for the entire test, rinsing well between change of products. Soak the sponge in the product being tested. 3. Transfer 15 mis of the diluted test product into an inverted sponge carrier. 4. Squeeze out excess product from the sponge and dip the sponge evenly on the flat surface of the carrier, gently squeezing down to soak up the product into the sponge. Tare the sponge on a 2-place balance, product side up.

. One tile is used per replicate. The sponge is wiped lighty over the tile surface by drawing an "M" pattern which covers the entire tile as much as possible. Then another "M" is drawn sideways. Place the sponge on the tared balance and record the amount of product applied to the tile. 6. Three replicates are used for each product tested.

SUBSTITUTE SHEET (RULE 26) O 94/21768 PCT/US94/02748 13 7. Tiles are air dried in air with 52% relative humidity at room temperature (about 24°C) for approximately one hour. 8. Three expert graders grade the panels on the following scale system: 0 = no filming/streaking 6 = very poor filming/streaking Grades are averages for each product.

Filming/Streaking Data Formula No. Filming/Streaking Mean Grade 3 1.4 2 1.8 1 2.1 The LSD for this test was 0.2 at the 95% Confidence Interval, therefore the Filming/Streaking mean values achieved for each formula are statistically distinct from 25 one another. The superior Filming/Streaking result was achieved through a combination of both the octyl sulfonate (3 vs 1) and the potassium carbonate (3 vs 2).

SUBSTITUTE SHEET (RULE 26) 263 394 14

Claims (5)

WHAT WE CLAIM IS:

1. A stable and clear concentrated cleaning composition comprising by weight: from 5% to 30% of a short chain surfactant comprising a mixture of (a) a nonionic surfactant having the formula CS_10(EO)8OH in which e is form 3 to 8 and (b) a Cs.10 alkyl sulfonate; a long chain surfactant comprising a mixture of (a) a nonionic surfactant having the formula C12_16 (EO)„OH in which n is from about 2 to about 10 and (b) a nonionic surfactant having the formula C12_16(EO)nOH in which n is from about 20 to about 60; from 0.5% to 3% of a suds suppressant comprising a mixture of a C8_22 fatty acid and a 2-alkyl alkanol; from about 1% to about 4% of potassium carbonate; and from about 30% to about 70% of water; wherein EO represents an ethoxy moiety.

2. The composition of Claim 1, further comprising a hydrophobic cleaning solvent having the formula C2_6 (EO) x (PO) yOH in which x and y are each from 0 to about 2, EO is as defined above and PO represents a propoxy moiety.

3. The composition of Claim 1 or 2, which is substantially free of stabilizing compounds.

4. A stable and clear concentrated cleaning composition according to Claim 1, 2 or 3, substantially as herein described.

5. The process of cleaning a hard surface comprising diluting a composition of any one of Claims 1 to 4 with water and applying it to said hard surface. .-as.. l:\libraryvact\clmms\3so214-c.wpd authorised agents A J PARK & SON Per ^ i.