AU668919B2

AU668919B2 - Aqueous hard surface detergent compositions containing calcium ions

Info

Publication number: AU668919B2
Application number: AU36157/93A
Authority: AU
Inventors: Mayumi Daiki; Nakamura (Okabe), Yuko; Ryohei Ohtani
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1992-02-19
Filing date: 1993-02-08
Publication date: 1996-05-23
Anticipated expiration: 2013-02-08
Also published as: TR27773A; DE69320794D1; EP0626995B1; CN1076477A; AU3615793A; FI943800A0; HUT68839A; FI943800A; HU9402400D0; NZ249400A; CZ197494A3; RU94040384A; CA2130466C; DE69320794T2; EP0626995A1; CA2130466A1; CN1052505C; ES2119890T3; MA22805A1; MY109586A

Description

1,eeP -lcl OPI DATE 13/09/93 AOJP DATE 25/11/93 APPLN. ID 36157/93 PCT NUMBER PCT/US93/01156 II IlHIIIIIHI li l AU9336157 INTERNATIONAL AFPLIAIIUIN runL1nLr unLJucr- 1r11.; 1rnl (PCT) (51) International Patent Classification 5 (11) International Publication Number: WO 93/17084 CUD 1/29, 1/86 Al (43) International Publication Date: 2 September 1993 (02.09.93) (21) International Application Number: PCT/US93/01156 (74) Agents: REED, David et al.; The Procter Gamble Company, 5299 Spring Grove Avenue, Cincinnati, OH (22) International Filing Date: 8 February 1993 (08.02.93) 45202 (US).

Priority data: (81) Designated States: AU, BB, BG, BR, CA, CZ, FI, HU, JP, 4/69607 19 February 1992 (19.02.92) JP KP, KR, LK, MG, MN, MW, NO, NZ, PL, RO, RU, 4/74509 30 March 1992 (30.03.92) JP SD, SK, UA, US, European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OAPI patent (BF, BJ, CF, CG, CI, CM, GA, GN, ML, (71) Applicant (for all designated States except US): THE PROC- MR, SN, TD, TG).

TER GAMBLE COMPANY [US/US]; One Procter Gamble Plaza, Cincinnati, OH 45202 (US).

Published (72) Inventors; and /V'/kpmu*9R (Oak e) With international search report.

Inventors/Applicants (for US only) :4**AB Yuko [JP/JPI; Before the expiration of the time limit for amending the 4-10, Shigino-Nishi, Joto-ku, Osaka DAIKI, Mayu- claims and to be republished in the event of the receipt of mi [JP/JP]; 17-1-503, Shimizu-cho, Kisshoin Minami-ku, amendments.

Kyoto OHTANI, Ryohei [JP/JP]; 1-5, Arujiharacho, Ibaraki-shi, Osaka (JP).

(54) Title: AQUEOUS HARD SURFACE DETERGENT COMPOSITIONS CONTAINING CALCIUM IONS (57) Abstract An aqueous hard surface detergent composition which provides improved solution feel comprising 3-35 by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof and 0.01-0.5 by weight calcium ion.

WO 93/17084 PCT/US93/01156 AQUEOUS HARD SURFACE DETERGENT COMPOSITIONS CONTAINING CALCIUM IONS TECHNICAL FIELD The present invention relates to an aqueous hard surface detergent composition containing calcium ion which provides improved solution feel without deteriorating storage stability of the composition. The composition is particularly useful for dishwashing liquids, more particularly under soft water conditions.

BACKGROUND

Anionic surfactants such as alkyl ethoxy sulfates with short ethylene oxide chains, alkyl sulfates, alkyl benzene sulfonates, a-olefin sulfonates, and alkyl ethoxy carboxylates are known to be very effective for hard surface cleaning, but are also known to have more or less unfavorable "slippery" feel in use. This undesirable attribute is a problem to hard surface cleaning compositions, especially for dishwashing purposes.

There is therefore a considerable demand for a hard surface detergent composition which has good detergency and good storage stability while having good solution feel when cleaning and rinsing, particularly for dishwashing purposes. As defined herein, good solution feel is best defined as the absence of "slippery" or "slimy" feel, or a "draggy" kind of feel which one feels when the composition is in use. "Good solution feel" is an important attribute for commercial liquid detergent products. Those wash solutions which have good solution feel on hands and objects to be cleaned allow easy handling of the objects, and provide good rinsing characters. Such benefits are most appreciated for dishwashing purposes.

Many attempts have been made to improve solution feel using various technology. These attempts are usually directed towards the use of nonionictype surfactants, and other suds enhancing-type and solvent-type components.

i WO 93/17084 PCT/US93/01156 2 Generally, these compositions have sacrificed detergency to obtain the improved solution feel.

Kokoku 46-43550 (Kao Corporation) teaches a liquid detergent composition which is mild to skin and has good detergency comprising alkaline earth metal salts of certain alkyl alkylene-oxy sulfate and certain alkyl alkyleneoxy carboxylates.

Kokai 51-125405 (The Procter Gamble Company) teaches compositions comprising calcium and magnesium salts of anionic surfactants including alkyl ether sulfates and amine oxides, C1-5 alkanols and water, wherein the weight ratio of amine oxide to anionic surfactant is 1:100 to 1:2.

Up to about 25% of the anionic surfactants can be monovalent salts.

U.S. Patent 2,766,212 (General Aniline and Film Corporation) teaches compositions which comprise alkyl ether alkoxy sulfate salts and water soluble polyvalent salts of magnesium, c~dcium, iron, or aluminum of 5 50% by weight of the surfactant. Examples show compositions comprising at least of the anionic surfactant in which magnesium and calcium ions help detergency.

U.S. Patent 4,681,704 (The Procter Gamble Company) teaches a detergent composition with effective grease removal comprising 10 alkaline earth metal salt, preferably magnesium, of anionic surfactants, 0.5 amine oxides, and 0.5 15% betaines.

However, the above mentioned disclosures use alkaline earth metals I mainly for their cleaning benefits, and do not disclose or suggest the improvement to solution feel benefits contributed by calcium ions. Further, the compositions of the above mentioned disclosures have high divalent ion levels, so that they would be unstable upon storage in the context of the present invention, namely, would form undesirable precipitates of calcium. Preferred compositions and examples shown in the above disclosures also have high surfactant levels, and thus the amount of calcium needed to reduce or eliminate II: I -I WO 93/17084 PCT/US93/01156 -3the "slippery feel" of the composition would place the composition into a phase where calcium is believed to easily precipitate.

Here, it has been found that by using calcium ions at a certain low level, a composition which provides improved solution feel without deteriorating storage stability is obtained.

OBJECT OF INVENTION It is an object of the present invention to provide a clear aqueous hard surface detergent composition which has improved solution feel in use without deteriorating storage stability of the composition.

It is also an object of the present invention to provide a liquid hard surface detergent composition which has balanced good quality in detergency, solution feel, and storage stability.

It is further an object of the present invention to provide a method of improving the solution feel of an aqueous hard surface detergent composition or a wash solution of an aqueous hard surface detergent composition.by-addin DETAIL DESCRIPTION The present invention relates to an aqueous hard surface detergent composition which provides improved solution feel comprising: 3 35% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising: a. at least 3% by weight of the composition and at least 20% by weight of the surfactant system alkyl ethoxy sulfate with an alkyl group of

C

1 0-16 and an average of 1 10 moles of ethylene oxide per molecule; 6.

m I V9ii, a ii i i.; oao a re or a or oo a e r s I, on a o or ooo or no a a a no o a o a

)I

I or a L o 0

O

a or a o 2,i r a Ir o ,I 1 oo II oo Ir an a o b. other anionic surfactants selected from the group consisting of alkyl benzene sulphonates, a-olefin sulphonates, alkyl ethoxy carboxylates, and mixtures thereof; c. diethanol amide with an alkyl chain of C8- 20 present in an amount of up to 9% by weight; d. 0-10% by weight of the composition amine oxide with an alkyl chain of

C

8 16 and 0.1-0.5% by weight calcium ion.

The present invention also relates to a method of improving the solution feel of an aqueous hard surface detergent composition comprising component (1) described above or a wash solution of an aqueous hard surface detergent composition by adding calcium ion to said composition.

The composition has less of an unacceptable slippery feel, and is easy to handle when cleaning and rinsing. The compositions of the present invention 15 have good storage stability, that is, the composition is stable in ordinary use conditions, more specifically, it does not generate precipitation or gel in the temperature range of from -5 0 C to 40 0

C.

Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises", is 20 not intended to exclude other additives or components or integers.

Anionic Surfactant The compositions of the present invention preferably comprise 15-35%, more preferably 20-30% by weight surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof. At least 20%, preferably at least 40%, more preferably at least 60%, by weight of the surfactant system is the sum of anionic surfactants, diethanol amide, and amine oxide. Among the anionic surfactants, at least preferably at least more preferably at least 12%, of the composition is alkyl ethoxy sulfate 4 i i WO 93/17084 PC/US93/01156 with an alkyl group of C10-16 and an average of 1 10 moles, more preferably 2 5 moles, of ethylene oxide per molecule, The anionic surfactants are selected from said alkyl ethoxy sulfates, alkyl sulfates, alkyl benzene sulfonates, a-olefin sulfonates, alkyl ethoxy carboxylates, and mixtures thereof.

Alkyl ethoxy sulfate, particularly having an alkyl group of C 10 16 and an average of 1 10 moles, preferably 2 5 moles, more preferably 2.5 moles, of ethylene oxide per molecule, provides good detergency and less negative effect on solution feel. Furthermore, compositions including a considerable amount of such alkyl ethoxy sulfates are susceptible to the effect of improved solution feel due to calcium ions. The average number of moles of ethylene oxide per molecule of the alkyl ethoxy sulfates can change the character of the surfactant. Here, alkyl sulfate is dealt as an alkyl ethoxy sulfate having 0 moles of ethylene oxide per molecule. Generally, it is known that the longer the ethylene oxide chain contribute less to poor solution feel, but have poorer detergency performance. Those which have less than an average ethylene oxide chain of 1 moles per molecule by themselves will contribute to poor solution feel.

The salts for the anionic surfactant component can be alkali metal, alkali earth metal, amines, or ammonium salts, preferably sodium or ammonium salts. Alkali earth metal salts of these surfactants are known for good detergency and sudsing. Some or all of the calcium ion of the present composition can be introduced as calcium salts of the anionic surfactant.

Other Surfactants The compositions of the present invention comprise, for the balance of the surfactant system, other anionic surfactants, nonionic surfactant and amphoteric surfactants. These surfactants are formulated in the compositions of the present invention to enhance detergency, and to enhance and stabilize suds. The species and levels of the other anionic, nonionic and amphoteric i i WO 93/17084 PCT/US93/01156 -6surfactants are chosen in order to obtain optimum balance of detergency, solution feel, and storage stability.

The compositicas of the present invention can contain nonionic surfactants such as diethanol amides and amine oxides. 4* preferably 4 7% by weight of diethanol amide and 0 10% preferably 2 5% by weight of amine oxide is contained in the composition. These two surfactants are known to provide good detergency and good storage stability, but can negatively effect solution feel. The use of calcium ion to improve solution feel is particularly useful in composition comprising diethanol amide and/or amine oxide.

Diethanol amide useful in the present invention has the formula 0 I II

(C

2

H

5

OH)

2 -N-C-R

I

wherein R I is selected from an alkyl chain of C 8 20 preferably C 12 14 Amine oxide useful in the present invention has the formula 0 4 II

R

2

N(OC

2

H

5 2 wherein R 2 is selected from an alkyl chain of C 8 2 0 preferably C 12-14- Calcium It has been found that by incorporating low levels of calcium ions, balanced benefits in solution feel and storage stability are obtained. The effect of the addition of low levels of calcium ion into dishwashing compositions is particularly beneficial under low hardness water conditions, where the amount of calcium introduced from tap water is low.

Calcium ions are added to the composition at :evels of 0.01 preferably 0 1 most preferably 0.1 At lower calcium levels, no effect on solution feel will be observed. At higher calcium levels, storage

R

0 1 "r o'0 i' WO 93/17084 PCr/US93/01156 -7stability will not be good. That is, it is known that calcium ions are relatively easily precipitated, at high temperature conditions, and thus are apt to deteriorate storage stability when added at high levels. Calcium ions are further known to contribute to detergency, particularly to grease removal. By selecting a calcium level in the above range, a composition having all three important benefits are obtained; good solution feel, good grease removal, and good storage stability.

The compositions of the present invention must have less than total surfactants to avoid precipitation of the calcium which is present at a level sufficient to improve solution feel. If the surfactant level is too high, the maximum amount of calcium that can be added without forming calcium precipitation would not be sufficient to improve solution feel to the composition.

The calcium ions can be incorporated in the composition in any convenient way, so long as the salts containing calcium ions are soluble in water and do not precipitate under ordinary use conditions. A suitable way of incorporating calcium ions is by adding them as salts selected from the group consisting of chloride, hydroxide, oxide, acetate, nitrate, formate, and mixtures thereof Chloride salts are most preferred.

Alternately, calcium ions can also be incorporated as counter-ions of anionic surfactants, such as by neutralizing the acid form of anionic surfactants with calcium oxide or calcium hydroxide, without affecting the benefits thereof. The preferred composition of the present invention comprises: 20 30% by weight of a surfactant system selected from the group f consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising: a. at least 35% by weight of the surfactant system alkyl ethoxy sulfate with an alkyl group of C10- 16 and an average of 2.5 3,5 ethylene oxide per molecule; WO 93/17084 PCT/US93/01156 -8b. 4 7% by weight of the composition diethanol amide with an alkyl chain of C 8 2 0 c. 2 5 by weight of the composition anfine oxide with an alkyl chain of C 8 16 0.1 0.3% by weight calcium ion; and 0.1 1% by weight magnesium ion.

Optional Components The compositions of the present invention can optionally contain components in addition to those already disclosed herein.

Optional surfactants useful in the composition of the present invention are those such as monoethanol amides, polyhydroxy fatty acid amides, alkyl polyglucosides, and alkyl ethoxylates.

Monoethanol amide is an optional surfactant in the present invention, having the formula

HO

I II

(C

2

H

5

OH),N-C-R

3 wherein R 3 is selected from an alkyl chain of C 8 2 0 preferably C12- 14 Polyhydroxy fatty acid amide is an optional surfactant in the present invention, having the formula O R 4

R

5

-C-N-Z

wherein R 4 is H, C 1 -4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1-4 alkyl, more preferably methyl; and R 5 is C 5 31 hydrocarbyl, preferably straight-chain C 10 16 alkyl; and Z is I. r WO 93/17084 PCT/US93/01156 -9polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.

Alkyl polyglucoside is an optional surfactant in the present invention, having the formula

R

6 0(CmH2mO)p(glucosyl)q wherein R 6 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups are C 10 18 preferably C 12 14 m is 2 or 3, preferably 2; p is from 0 to about 10, preferably 0; and q is 1.3 10, preferably 1.3 3, most preferably 1.3 2.7. To prepare these compounds the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 4and/or 6-position, preferably predominately the 2-position.

Alkyl ethoxylate is an optional surfactant in the present invention. Such alkyi ethoxylates are aliphatic alcohols with 1 25 moles of ethylene oxide.

The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains 8 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing 8 20 carbon atoms with 2 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols having an alkyl group containing 8 14 carbon atoms with 6 10 moles of ethylene oxide per mole of alcohol.

Amphoteric surfactants optionally included in the present invention are i WO 93/17084 PCT/US93/01156 betaines having the formula

R

8

(R

10 2

R

7

CO-N-R

9 -N+RI1 COOwherein R 7 is a C 7 2 1 alkyl group, or alkylaryl group, preferably C 9 17

R

8 is hydrogen or a C.-6 alkyl group, preferably C-.

3

R

9 is a C 1 10 alkylene group, preferably C2- 6 most preferably C 3 each R 10 is a C 1 -6 alkyl or hydroxy alkyl group, preferably C 1-3, most preferably methyl or an ethoxylated hydroxy alkyl containing from about 1 to about 10 ethylene oxide units; and

R

1 is an C 1-6 alkylene group, preferably methyl.

Magnesium ions at a level of 0.1 1% are preferably included in the composition of the present invention to improve detergency without affecting good solution feel and good storage stability of the composition.

The compositions of the present invention can also comprise 4 8% by weight of a hydrotrope selected from the group consisting of sodium and ammonium salts of cumene sulfonates, toluene sulfonates, xylene sulfonates, sulfo succinates, and mixtures thereof. Such components are utilized in the interests of achieving a desired product phase stability and viscosity.

Other desirable ingredients include solvents, preservatives, dyes, and perfumes.

Solvents useful in the present invention include water and lower molecular weight alcohols, such as ethanol. Ethanol is also known to reduce the viscosity of the product, if necessary for formulation. Solvents other than water are typically present at levels of 2 10% by weight.

Preservatives, dyes, and perfumes can be, and usually will be formulated in the composition of the present invention to make products attractive to the consumer. These components are typically present at levels not more than 1% respectively.

i r I 1 I WO 93/17084 PCT/US93/01156.

-11- Components which are preferably not included in the composition are those which generate precipitation upon binding with calcium ions. Examples are those which include sulfate, carboxylate, and fatty acid anions.

EXAMPI S The following examples illustrate the compositions of the present invention, but are not intended to be limiting thereof. All percentages and ratios are based on weight unless otherwise specified.

Preparation The liquid detergent compositions herein described can be made conveniently by one skilled in the art. Surfactants, hydrotropes, calcium salts, and optionally magnesium salts are added in an appropriate amount of water and are blended. In the present invention, the order of adding the components is not important. If necessary, the pH of the mixture is adjusted with HCI to a safe level for household products, and viscosity is adjusted with alcohol.

Perfume, dye, and preservatives are optionally added, and the composition is balanced with water. The standard product and examples 1 9 are all prepared according to this method.

Experimentation j 1. Solution feel 500g each of 6% solutions of the standard product and compositions of the present invention are prepared in a 1 liter beaker, and a porcelain crucible is soaked in the solution.

One hand is soaked in the sample solution and the other hand is soaked in the general standard product solution at the same time, and the feel of the crucible is evaluated according to the scale as shown below.

S- Evaluation is done by three special panelists, and the average score is i WO 93/17084 PC/US93/011 56 -12obtained.

Evaluation scale 0= There is no difference 1= I think there is a difference 2= I know there is a difference 3= I know there is a big difference 4= I know there is a very big difference the sample has a better feel (less slippery) the sample has a worse feel (more slippery) For those which have higher points than the composition with the same surfactant system without calcium, it is evaluated that the "solution feel was improved".

2. Storage Stability The sample is placed in a 100 ml glass container, and stored in rooms with established temperatures of-5oC and 40 0 C respectively. The condition of the product after 2 weeks is evaluated as follows.

clear and no change compared to before the test O precipitated, or cloudy X According to Table 1, it is understood that Examples 1, 3, 4, and 7 which are compositions of the present invention have both improved solution feel and good storage stability.

1 I u n .1K WO 93/17084 PCT/US93/O1 156 -13 TABLE 1 1 2 Standard product 3 4 5 6 7 8 Sodium C 12 14 alkyl ethoxy ave.) sulfate Ammonium

C

12 4 alkyl ethoxy (3 ave.) sulfate

C

12 14 alkyl dimethyl amine oxide C,2 alkyl diethanol amnide

C

12 4 alkyl Nmethyl glucoamide

C

12 alkyl ethoxy (3 ave.) alcohol

C

9 11 I alkyl ethoxy (8 ave.) alcohol Sodium toluene sulf onate Sodium cumene sulfonate Mg+ +(MgC1 ,*7H 2 0) Ca+ 4 {CaC1 2 Ethanol Water and other minors Solution feel(point) (comparison example) (improved points) (evaluation) bal balance 11.3 11.7 12.0 12.0 12.0 12.0 12.0 12.0 12.0 3.1 3.1 3.0 3.0 3.0 30 3.0 3.0 4.4 4.4 4.5 4.5 4.5 4.5 4.5 4.5 5.0 5.0 5.0 5.0 2.3 2.3 1.5 1.5 1.5 1.5 1.5 1.5 2.3 2.3 5.0 5.0 0.7 0.5 0.2 4.2 4.2 5.0 0.36 0.14 4.2 5.0 0.7 0.2 2.8 2.8 p

V

0.3 2.5 2.5 bal* bal Std 2.0 Std -+2.0 0 bal -1.38 bal -0.88 ex.2 +0.5 0 bal bal 0.75 +0.75 ex. 2 ex. 2 2.13 +2.13' 0 10 bal bal bal 1.38 -0.5 +0.13 ex.6 ex.6 +0.88+1.25 0 0 WO 93/17084 Storage stability 0

C)

0

C)

PCT/US93101 156 14 TABLE 1 (continued) Standard 1 product 2 3 4 5 6 7 8 o 0 0 0 0 X 0 C, x 0 o 0 0 0 X 0 0 x I t

Claims

1. An aqueous; hard surface detergent composition which provides improved solution feel comprising:

3-35% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising: a. at least 20% by weight alkyl ethoxy sulfate with an alkyl group of C 10 -1 6 and an average of 1-10 moles of ethylene oxide per molecule; b. other anionic surfactant selected from the group consisting of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl ethoxy carboxylate, and mixtures thereof; c. diethanol amide with an alkyl chain of C8 2 0 d. amine oxide with an alkyl chain of C 8 16 and 0.1-0.5% by weight calcium ion; wherein the composition contains at least 3% by weight the alkyl ethoxy sulfate, 0-10% by weight the amine oxide, and diethanol amide is present in an amount of up to 9% by weight. 2. A composition according to claim 1 comprising more preferably by weight calcium ion. 3. A composition according to claim 1 or 2 wherein said surfactant system comprises at least 35% by weight the alkyl ethoxy sulfate.

4. A composition according to claim 3 comprising 20-30% the surfactant system. A composition according to any of claims 1-4 wherein the alkyl ethoxy sulfate has an average of 2-5 moles, more preferably 2.5-3.5 moles, of ethylene oxide per molecule.

6. A composition according to any of claims 1-5 comprising 4-7% said diethanol amide.

7. A composition according to any of claims 1-6 comprising 2-5% said amine oxide.

8. A :omposition according to any of claim 1-7 comprising 0.1-1% by weight mag esium ion. (j IAi t: K LJ I- i

9. A method of improving the solution feel of an aqueous hard surface detergent composition or a wash solution of an aqueous hard surface detergent composition by adding from 0.1 0.5% by weight calcium ion, said aqueous hard surface detergent composition comprising 3 to 35% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants and mixtures thereof comprising: a. at least 20% by weight alkyl ethoxy sulfate with an alkyl group of C 10 1 6 and an average of 1-10 moles of ethylene oxide per molecule; b. other anionic surfactant selected from the group consisting of alkyl benzene sulphonate, alpha-olefin sulphonate, alkyl ethoxy carboxylate, and mixtures thereof; c. diethanol amide with an alkyl chain of C8- 20 d. amine oxide with an alkyl chain of C8- 1 6 and 0.1-0.5% by weight calcium ion; wherein the composition contains at least 3% by weight the alkyl ethoxy ,i 15 sulfate, 0-9% by weight the diethanol amide, and 0-10% by weight the amine oxide. 9

10. An aqueous hard surface detergent composition which provides improved solution feel comprising: 3-35% by weight of a surfactant system selected from the group consisting 20 of anionic, nonionic, amphoteric surfpctants, and mixtures thereof, comprising: a. at least 20% by weight alkyl ethoxy sulfate with an alkyl group of C 1 0 16 and an average of 1-10 moles of ethylene oxide per molecule; b. other anionic surfactant selected from the group consisting of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl ethoxy carboxylate, and mixtures thereof; c. diethanol amide with an alkyl chain of C8- 20 d. amine oxide with an alkyl chain of C8-16; and 0.1-0.5% by weight calcium ion; wherein the composition contains at least 3% by weight of the alkyl ethoxy sulfate, 0-9% by weight of the diethanol amide, 0-10% by weight of the amine oxide and wherein the composition is substantially free of other sulfates, a carboxylates and fatty acid anions. ^=lI1 i6

11. A composition according to claim 1 substantially as herein described with reference to any one of the Examples. DATED: 22 February, 1996 THE PROCTER GAMBLE COMPANY By their Patent Attorneys PHILLIPS ORMVONDE FITZPATRICK IV ea17 F" II INTERNATIONAL SEARCH REPORT Interntional Application No PCT/US 93/01156 1. CASSIFICATION OF suijECir MArE (if several classfincation symabols apply, indicate all)6 According to International Patent aasslation (IFC ortto both National casifcation and IPC Int.Cl. 5 C1101/29; C1lDI/86 H. FIELDS SEARCHIED Mnflimum Documentation Searched 7 Classification System aessdicaiom symabols Int.C1. 5 C11D Documentation Searched other than Minimum Documentio to the Extent that such Documents ase Included in the Fields Searched$ M. DOCUMVENTS CONSIDERED TO BE RELEVANT 9 CaegryCitation of Documzent, 11 with indication, where appropriate, of the relevant pasuages Relevant to Cainm No.13 X US,A,4 507 219 HUGHES) 1,3-5,7 26 March 1985 see claims 1-6; examples X US,A,4 681 704 BERNARDINO ET AL.) 1,3-5,7 21 July 1987 cited in the application see the whole document X FR,A,2 296 688 (THE PROCTER GAMBLE CO.) 1,3-5,7 July 1976 cited in the application see claims V GB,A,2 058 823 (UNILEVER) 1,3-8' April 1981 see page 1, line 20 line 35; claims 1-4 *Special categories of ited documntft 10 late document published After the lnteratomal filing dat or piority date ad not in =fefl with the applcaton but document deilag the general ate of the art which Is no dtedto undertad the puiaciple or thory uadertytag the considered to be of pestimar releancenenio Er e@ile document but pulished en or after the latwratial or document orfetiai relevance; the claimed lnvatdon filing date cannet be cosdudnoe or cannot be considered to IV document which my throw doubts o uutydalm~el or involve a Inventive step which Is cited to establish tepbitonde fanother "r docment of p mr m lvace the cled Invention citation or other special runsm (as specified) cannot be coniidered to level"e a inventive step when the '0 dociumt oWe ll. to an oral diadneure uss eshibiton or document Is couableed with mee or more other such ica. other mun menu, such combination bing 3 obvious to a perso shliled PW document published pior to the Interaational flial dataet in the art. lateir thas the priority date dalmed W' document umber of the usme patent family 1IV. CERITIFICAION Date of the Actual Compltion of the lnwaieiSenrd Date of Malling of t~a Ineational Search Ripest 07 JUNE 1993 latarattiomtal Serching Authiority Signaftre of Authorud Officer EUROPEAN PATENT OFFCE SERBETSOGLOU A. I Form PKTILW2O (61 01 imium PCT/US 93/01156 Intertational AnmIIkIIin No C/S 9/15 Mn. DOCUMENTS CONSWDDED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Ct 0a tdom of Documet, with ldication, whom. pp r~iate, of the eleant pm a= Idel at to Clim N& GB,A,2 078 246 (THE PROCTER 6 January 1982 see the whole document GB,A,2 205 578 (KAG CORP.) 14 December 1988 see the whole document GB,A,2 123 847 (THE PROCTER 8 February 1984 see claims 1,3-5 GAMBLE CO.) GAMBLE CO.) EP,A,0 399 752 (THE PROCTER GAMBLE CO.) 28 November 1990 see page 3, line 9 page 6, line 22 see page 7, line 37 page 8, line 18 see claims EPA,0 062 371 (THE PROCTER GAMBLE CO.) 13 October 1982 see page 4, line 12 page 10, line 13; claim 1 WO,A,9 206 161 (THE PROCTER GAMBLE CO.) 16 April 1992 see claims 1,6,7; examples XI,XIII 1,3-8 1,3-8 1,5-7 1,4-8 1,4-8 1.'8 Fm Per/mA/nO 40M dwd OfJam I%* F- ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 9301156 SA 70403 This aenex if the patent family membrs relating to the patenat documents cited in the aboveamaloned naruatiomal searcripen. ThM membrs ameas contained in the European Patent Office EDP file on The European Patent Office in n way lishle for these particulars whack arm merely given for the pirpoe of infoemaijo.. 07/06/93 PatemPU ism tPblication Patent family PIlcto US-A-4507219 26-03-85 AU-B- AU-A- CA-A- LIE-A- EP-A, B GB-A, B JP-A- 561794 3182784 1231027 3471115 0151678 2144764 60106892

14-05-87 14-02-85 05-01-88

16-06-88

21-08-85 13-03-85 12-06-85 US-A-4681704 21-07-87 CA-A- 1239324 19-07m88 LIE-A- 3562781 23-06-88 EP-A,B 0157443 09-10-85 FR-A-2296688 30-07-76 AT-B- 346446 10-11-78 AU-Bm 497528 14-12-78 AU-A- 1000576 14-07-77 BE-A- 837342 06-07-76 CA-A- 1052223 10-04-79 CH-A- 603785 3 1-08-7 DE-A,C 2600022 10-02-77 GB-A- 1524441 13-09-78 JP-C- 1353205 11-12-86 JP-A- 51125405 01-11-76 JP- 61009354 22-03m86 NL-A- 7600072 08-07-76 SE-B- 418865 29-06-81 SE-A- 7600049 07-07-76 US-A- 4133779 09-01-79 GB-A-2058823 15-04-81 None GB-A-2078246 06-01-82 US-A- 4316824 23-02-82 CA-A- 1158518 13-12-83 CA-B- 1255992 20m06-89 JP-B- 4022960 20-04-92 JP-A- 57074398 10-05-82 GB-A-2205578 1412-88 JP-B- 4041718 09-07-92 JP-A- 63277300 15-11-88 GB-A-2 123847 08-02-84 CA-A- 1210299 26-08-86 SFror more details abouw "i ausx M Officia Journal of doe Earepe.. Patn Offlos, No. 12122 K i ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 9301156 SA 70403 This ae liets the patent family Menub relating to the patent documents cited in the aboveaioned inturuatiemd sMa repot. The members ae s coutaind in the European Patent Office EDP fie on The European Patent Office rn inayo wy liae for them particulars wich ae m y give for the pupms of infermsaL 07/06/93 Page 2 For ms darmJ nou shi a -es: ov Offidal Joual of doe Esropa PataM Offk, Ne. 12122