AU617356B2 - Cleaning paste with soluble abrasive - Google Patents

Description

i COMMONWEALTH OF AUSTRALIA Patent Act 1952 E SPECIFIC T 3 6

(ORIGINAL)

C O M P L E T Class Int. Class Application Number Lodged Complete Specification Lodged Accepted Priority S**"Related Art *Name of Applicant of Applicant ."'.Address of Applicant 9* Published 14 December 1987 :COLGATE-PALMOLIVE COMPANY S300 Park Avenue, New York New York 10022, United States of America Actual Inventor/s :Albert Jay Lancz RICE CO., Patent Attorneys, 28A Montague Street, BALMAIN 2041.

s Address for Service Complete Specification for the invention entitled: CLEANING PASTE WITH SOLUBLE ABRASIVE The following statement is a full description of this invention including the best method of performing it known to us/me:-

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BACKGROUND AND PRIOR ART I "f The present invention relates to the formulation of a stable, hard i ii surface detergent composition in the form of a non-pourable viscous cleaning composition, substantially free of water, having a maximum water content of 6% by weight, comprising a gelled mixture of an organic liquid I vehicle consisting essentially of organic solvents and nonionic surfactants including an ethoxylated fatty acid as the essential component in the in situ'gelation of said liquid vehicle, upon the addition of a small amount of about 0.7-1.5% by weight sodium hydroxide. The addition of gel-insoluble ingredients, particularly a water-soluble inorganic builder-abrasive, to the *I ieeee: S gel mixture forms a viscous paste product containing a stable suspension of the relatively large particles of said abrasive.

The abrasive is insoluble in the gel product, but soluble in water.

Thus, after using this paste product to clean a hard surface, the water applied to rinse off the cleaning product- dissolves both the gel and the abrasives, and leaves no gritty residue on or around the cleaned surfaces.

la he prior art is replete with hard surface cleansers containing abrasives both ,in the form of scouring powders and in liquid form. Water insoluble abrasives as the major and primary cleaning component in scouring powder cleansers is well known, as disclosed in U.S. Patent No. 3,850,833.

However, the use of said water-insoluble abrasives in hard surface scouring powder cleansers has been found to leave an unpleasant gritty residue on the cleaned surface. This problem has been addressed in the prior art by substituting a water soluble abrasive for all or part of the insoluble abrasive, resulting in a composition wherein the water soluble components 19 rinse away with the wash water, leaving substantially no residue on the cleaned surface, as disclosed in U.S. Patent No. 3,577,347. Another method 1 of addressing the abrasive residue problem is the use of a powdered or I particulate water-insoluble abrasive having a maximum particle size under j 0.15 mm., and about 87 by weight of the abrasive particle having a diameter of about 0.037 mm or larger for effective cleaning, and a small amount of an organic hydrotrope sodium cumene sulfonate) to improve grease Sremoval, as disclosed in U.S. Patent No. 4,289,640.

S Likewise, hard surface liquid detergent composition containing waterinsoluble abrasives suspended in an aqueous medium encounter the problems of I *Ii S'i stability as well as the difficulty of complete removal of the insoluble abrasive particles from the cleaned surface. These problems have been addressed in the prior art by preparing a heavy duty liquid detergent composition containing a water soluble builder salt having colloidal-size particles (below 1 micron and usually below 0.1 micron), dispersed in an aqueous medium containing a fatty acid amide emulsifying agent as disclosed i in U.S. Patent No. 4,057,506. Other means of addressing the stability problem is disclosed in U.S. Patent No. 3,522,186 wherein is disclosed a water-insoluble abrasive dispersed in an aqueous medium containing tetrapotassium pyrophosphate, sodium soap, diethanolamide and about 0.25methanol or ethanol, to prevent the separation of the aqueous liquid 2 into two layers. Another means of addressing the stability problei i disclosed in U.S. Patent No. 4,051,055 wherein an aqueous hard surface Icleaning composition containing water insoluble abrasive is suspended in a thickened aqueous medium with at least 1% clay as the thickening agent, said Ithickened system preventing separation of the abrasive from the liqiuid medium. The presence of fluoride salts enhances the ability of the Clay- I V thickened system to hold the abrasive particles in suspension.

U.S. Patent No. 4,657,692 also discloses a thickened aqueous scouring cleanser, free of syneresis (separation of solids from liquid), containing a wae inoul abrasive suspended in an aqueous medium conta±ining a colloidal aluminum oxide thickener, water soluble alkali metal inorganic isalts such as the phosphates, polyphosphates, carbonates, etc., and about fl0.5-3% of a surfactant and a halogen bleach. European Patent Application lNo. 0,193,375 resorts to the use of a water soluble salt, which functions iboth as an abrasive and detergency builder, such as sodium bicarbonate, 0 tripolyphosphate, and the like, in a pourable, homogenous abrasivecontaining aqueous detergent composition for cleaning hard surfaces, and 00 also containing a mixture of anionic and nontonic surfactants in the weight ratio of 1:1 to 9:1 anionic to nonionic surfactant, A 'hard surface, water-based cleanser in paste form comprising 50-65% sodium bicarbonate and 50-35% by weight water containing sodium chloride and a fatty acid (C1 2 diethanolamide is disclosed in U.S. Patent No.

0 0 4,179,414.

Water-based gels containing at least 40% nonionic surfactant and 2-10% water soluble builder salts is disclosed in U.S. Patent 4,107,067 as a flowable gel laundry detergent composition.

U.S. Patent No. 4,257,908 also discloses a laundry detergent composition in a stable f lovable form, containing 25-55% of a phosphate builder salt, 5-40% of an anionic surfactant in 30-50% of an aqueous medium containing alcohol in the weight ratio of 5:1 to 20:1 water to alcohol.

Also, non-aqueous liquid pasty or gelatinous detergent compositions having scouring properties is disclosed in U.S. Patent No. 3,981,826, Scomprising a dispersion of a normally solid water soluble anionic surfactant and a solid particulate water soluble inorganic salt (a builder salt) and a Ssuspending agent such as highly-voluminous oxides (silica, magnesia, alumina or clay) in about 19-79% of a water-miscible organic liquid solvent such as a polyhydric alcohol (glycerol, ethylene glycol, and the like), and Soptionally a lower monohydric alcohol (ethanol, methanol, etc.). Another Sorganic solvent-based gelled or thickened hard surface cleaning composition Soi which is flowable and pourable is disclosed in U.S. Patent 3,865,756 jcomprising a gelling agent which functions as an abrasive such as colloidal silica, an alkaline builder salt such as water soluble phosphates and silicates, a surfactant, a water insoluble abrasive, calcium silicate, and about 55-90% of an organic cleaning solvent such as a major amount of an S!I aliphatic hydrocarbon mineral spirit mixed with 4-7% ethylene glycol ii II monobutyl ether. U.S. Patent No. 2,864,770 also discloses a pourable non-

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aqueous water-soluble organic solvent-based thixotropic liquid detergent i composition containing glycols and glycerol as the organic solvent, an

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anionic surfactant, and a phosphate builder in suspension.

2 However, none of the above mentioned patents disclose a hard surface non-pourable viscous cleaning composition, substantially free of water, comprising a gelled mixture of an organic liquid vehicle consisting S* essentially of water-soluble organic solvents and nonionic surfactants Sincluding an ethoxylated fatty acid as one of the surfactants, and a small Samount of sodium hydroxide which reacts in situ with the ethoxylated fatty acid to form a clear organic, non-flowable gel, and about 10-25% of a water soluble builder-abrasive suspended in said gelled vehicle.

SUMMARY OF THE INVENTION It has now been found that the formulation of present novel organic cleaning composition is based on the ability of ethoxylated fatty acid, ethoxylated lauric acid, to react with sodium hydroxide in organic fmedia and form:a.gel with the media. Another feature of present novel formulation is the incorporation of a water-soluble abrasive material into Hthe organic gelling mixture. This enables the preparation of viscous products containing inorganic solids suspended in a gelled organic vehicle.

While this abrasive is insoluble in th~e gelled vehicle, it becomes soluble upon dilution of the product with water. Cleaning with the undiluted product is aided by the mild abrasive action of the abrasive, sodium pyrophosphate. The entire product dissolves in water leaving no gritty on or around the cleaned surfaces. Furthermore, this abrasive becomes a "surfactant builder" when the produq't is used diluted. Household surfaces such as ceramic and formica surfaces can be cleaned with present novel products in the absence or presence of 1'later without scratching the surface. This product, both undiluted &nd diluted, has significantly improved cleaning efficiency provided by the triple action of the organic solvent, the nonionic detergent and the abrasive. In the diluted product, the abrasive dissolves in the Water and becomes a detergency buil.Aer.. The hard surface organic viscous product in accordance with this invention can function as a spray cleaner, a scouring cre~am and a floor and wall all purpose cleanser. Simulated floor cleaning tests show that at 3 g/l of present novel cleaning product performed better than "Mr. Clean" at 15 this translates to 5 bottles of Mr. Clean being equal to 1 bottle of present cleaning product.

Accordingly, the primary object of this invention is to provide a novel hard surface viscous organic cleaning product comprising an ethoxylated fatty acid and sodium hydroxide dissolved in an organic vehicle which react in situ to form a gelled vehicle.

Another object of this invention is to provide a novel viscous organic cleaning composition containing inorganic water-soluble particulate abrasive ~O suspended in the gelled organic vehicle.

i; j I Still another object of this invention is to provide an abrasive- Scontaining organic gel which dissolves in water leaving no gritty residue on Sor around the cleaned surfaces.

S Still another object of this invention is to provide an all purpose Sorganic cleanser having threefold cleansing action.

i'I S Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent upon examination of the following specification or may be learned by practice of this invention.

0 To achieve the foregqing and other objects in accordance with the present invention as embodied and broadly described herein, the novel, S stable, hard surface non-pourable organic cleaning gel composition of this invention comprises about 65-80% by weight of an organic liquid vehicle i basc on he weight oF -re. compo'lor consisting essentially ofAabout 15-35% by weight of a water miscible organic 0 solvent, about 35-70% of a nonionic surfactant mixture containing an ethoxylated fatty acid as one of the surfactants, and a small amount of about 0.7-1.5% by weight of sodium hydroxide, which reacts in situ with the j ethoxylated fatty acid to form a clear, nonflowable gelled vehicle, j substantially free of water, capable of suspending water-soluble inorganic S particulate abrasive.

More specifically, the organic gel composition of present invention comprises about 65-80% by weight of a substantially water-free organic vehicle consisting essentially of about 15-35% by wight of a water soluble organic solvent and about 35-70% by weight of a nonionic surfactant mixture containing an ethoxylated fatty acid as one of the surfactants, about 0.7by weight of sodium hydroxide, gelled by the in situ reaction of the ethoxylated fatty acid with the sodium hydroxide; and about 10-25% by weight of an inorganic water soluble particulate abrasive (builder salt) uniformly suspended in the gelled vehicle.

A4'C^ S The water miscible organic solvent, is selected from the group consisting of..lower alkyl glycol ethers, lower alkyl monohydric alcohols, Slower alkyl dihydric alcohols, and mixtures thereof.

The described hard surface cleaning products of present invention are Sstable, non-pourable, clear, thick (viscous) pastes, having a minimum Sviscosity of about 14,000-15,000 cps units measured on Brookfield HATD viscometer. The viscosity of the gel product provides a stable suspension Sof relatively large particles of water-soluble abrasives, larger than Scolloidal sized particles. The product of present invention has many Sapplications as an all purpose cleaner. Undiluted with water, the product ,can be used as a scouring cleaner for sinks and tubs, and as a spot cleaner for soiled hard surfaces, providing triple cleaning action due to the I coaction of the organic solvent, the nonionic detergent and the abrasive, S i without leaving a gritty residue conventional with abrasive cleansers.

S" Present novel organic pastes diluted with water can be used as a floor and wall cleaner. Present novel organic cleaning pastes can also be used as a Swaterless hand cleaner, particularly for mechanics and gardeners; for cleaning industrial and institutional cooking vessels, urns, etc, DETAILED DESCRIPTION OF THE INVENTION I I The major essential component of present nonpourable viscous cleaning composition is the nonionic surfactant system which constitutes about 35-70% b" y weight of a mixture of nonionit surfactants containing about 6-38% of an ethoxylated fatty acid, and /bout 10-64% of the other ethoxylated nonionic surfactants which may be a fatty alcohol, an alkyl phenol, a propylene q cny\ene aXt e-9<vopyleoe, o\ cor ckotv^TbAtnif oxide-propylene glycol condensation product,Aor a mixture thereof. More Sspecifically, the additional ethoxylated nonionic surfactant may be selected from the group consisting of a polyethylene oxide condensate of an alkyl aaphenol having an alkyl group containing about 6 to.J3 carbon atoms, a polyethylene oxide condensate of an aliphatic alcohol containing about 8 to 22 carbon atoms, a polyethylene oxide condensate of the condensation Ia -4

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Sproduct of propylene oxide with propylene glycol having a molecular weight i, Sof about 1500-to 1800, and mixtures thereof. Typical examples of Spolyethylene oxide condensates of alkyl phenol are nonyl phenol condensed Swith about 9.5 moles ethylene oxide per mole nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol. Typical examples of ethoxylated alcohols include about 6 moles ethylene oxide Scondensed with one mole of tridecanol, myristyl alcohol condensed with about moles ethylene oxide, Co-Ci, fatty alcohol condensed with about 6 moles i i ethylene oxide, Co-Ca, alcohol condensed with 5 moles ethylene oxide per Sjmole alcohol (Alfonic 1012-60). Examples of the polyethylene oxide I condensates of the condensation product of propylene oxide with propylene glycol are commercially available as Pluronic surfactants marketed by the ii Wyandotte Chemicals Corporation. The liquid character qf this product is retained up to the point where the polyoxyethylene content is about 50% of Sthe total weight of the condensation product. Examples of ethoxylated fatty Sacids include lauric, palmitic, stearic acid, etc., ethoxylated with about to 10 ethylene oxides per mole fatty acid. A preferred fatty acid S ethoxylate is lauric acid having 9 ethylene oxides (Alkasurf-L-9). The Ss presence of the ethoxylated fatty acid in the organic vehicle is essential in the formation of the gel, for the in situ reaction in the organic solvent with the sodium hydroxide to form a small amount of a soap which thickens and gels the organic liquid media. A small amount of sodium hydroxide evokes time-delayed hydrolysis followed by gelation of the vehicle holding the ethoxylated fatty acid.

Another essential component of present cleaning composition is the water miscible organic solvent in an amount of about 15-35% by weight of the total formulation. The organic solvent provides an organic media for the in situ reaction between the ethoxylated fatty acid and the sodium hydroxide in the gelling of the organic media. Suitable organic water miscible solvents 3S include the lower alkyl monohydric alcohol, lower alkyl dihydric alcohols 8 S(glycols), the lower alkyl glycol ethers, and mixtures thereof. Examples of Swater soluble lower monohydric alcohols are ethanol, iso-propanol, and Sbutanol. Examples of suitable glycols are ethylene glycol, diethylene glycol (Carbitol), and propylene glycol. Examples of lower alkyl glycol Sethers are the diethylene glycol monobutyl ether having the formula:

SC

4 HoOCH 2

CH

2

OCH

2 CH0OH also known as Butyl Carbitol (Union Carbide), ethylene j glycol monobutyl ether having the formula: CAH.OCEICH 2 0H and the like. It 0 is preferred to use a mixture of monohydric and dihydric alcohols, and most Spreferably a mixture of a monohydric alcohol, a dihydric alcohol and a glycol ether as the solvent for the nonionic surfactant mixture.

Another essential ingredient in present viscous cleaning composition is ii a water-soluble inorganic particulate abrasive, suspended in the gelled S" vehicle, in an amount of about 10-25% by weight of the total composition.

Sj The abrasive is insoluble in the gel, but soluble in water. The water soluble abrasive particles are relatively large particles of about 1/2 mm in diameter. The viscosity of the gelled vehicle which is a minimum of 14,000 to 15,000 cps units, is capable of maintaining the large particles in suspension. Suitable water soluble abrasives are selected from the group de consisting of alkali metal phosphates, polyphosphates and carbonates.

A Examples of suitable water soluble abrasives include pyrophosphates such as tetrasodium or tetrapotassium pyrophosphates, tripolyphosphates, S:I tetrapolyphosphates, carbonates, etc. This abrasive becomes a surfactantbuilder when the product is used diluted and is readily removed from the cleaned surface, leaving no gritty residue. The preferred abrasives include tetrasodium pyrophosphate, and sodium carbonate.

The hard surace cleaning composition of this invention also may contain minor amounts of conventional additional components to impart any desired characteristic, which are compatible with the gel and do not adversely affect the gel structure. Suitable additives include coloring 9 Sagents, perfumes. preservatives, antiseptic agents and the like. These Sadditives constitute a maximum of 15% by weight of the composition.

The cleaning compositions of present invention are generally prepared Sby mixing the organic water miscible solvent components with an ethoxylated fatty acid and at least one additional nonionic surfactant component to form a clear, low viscosity liquid vehicle; adding a sodium hydroxide solution to Sthe clear liquid vehicle and mixing until the liquid gels, which may vary Sfrom a few minutes to several hours, depending on the amounts of the Scomponents; and lastly admixing the water soluble abrasive, color, perfume 1 i, and any other additional cnnventicnal ingredient with the gelled vehicle, until the abrasive is uniformly dispersed throughout the gelled vehicle and .1 a paste is formed. The cleaning composition is packaged in any suitable I geggee container, both flexible or rigid. The paste can also be extruded from a D collapsible container.

1 The final cleaning gel product is a stable thick (viscous) creamy, hard surface cleaner, substantially free of water, and has an alkaline pH within j: the range of about 8-11. It can be applied to the surface to be cleaned in Ij any suitable manner, with a sponge or a cloth, followed by rinsing the i .surface with water, leaving no gritty residue.

j I The following examples merely illustrate the invention, but it is g understood that the invention is not limited thereto. All amounts of S various ingredients in the examples and elsewhere in the specification are J by weight unless otherwise specified.

Example 1 Ingredients Lauric Acid Ethoxylate (9EO) 28.30 Tetrasodium Pyrophosphate 20.00 SDiethylene Glycol Monobutyl Ether 14.00 Ethanol C"-Cj Alcohol EO 5:1 10,00 Propylene Glycol 6,00 Deionized Water 4.00 !i Caustic Soda (507) 3,00 17 Graphtol Bluie 0.40 Perfume 0,30 SI pH 10.9 S S The vehicle ingredients, namely ethoxylated lauric acid ethoxylated S alcohol, butyl carbitol, ethanol and propylene glycol and the perfume are *b mixed to form a clear mobile liquid. The NaOH is mixed with the clear liquid until the vehicle is galled and forms a solid gel. After 5 minutes *0 S of gel ripening the Itetrasodium-pyrophosphate is mixed with the ripened gel to form a cream (paste). The blue pigment dispersion is admixed with the i j! cream.

This formulation produces a creamy blue cleaning product possessing .0.0 superior cleaning properties, leaving no gritty residue on the cleaned surface.

n_ E xampe 2 Ingredient's Lauric Acid Ethoxylate (9EO) 28.00 SSodium Carbonate 23.00 C Alcohol EO 5:1 21.00 Ethanol 12.50 Diethylene Glycol Monobutyl Ether 7.00 Propylene Glycol 5.00 387 Caustic Soda 3.00 Perfume 0.30 i: Ii Lemon/Lime Color Solution 0.20 This product is prepared in accordance with the process of Example 1.

L j This product is a viscous colored paste also having superior cleaning *properties.

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S. Examples I 3 4 i Alfonic 1012-60 48.0 10.0 14.0

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Alkssurf L-9' 6.0 28.3 21.0 Plurafac RA40' Pluxonic L-64 4 15.5 Butyl Carbitol 8.0 14.0 Ceqe Propylene Glycol 6.0 SEthanol 8.0 14.0 14.0 Water Color .9 5.9 5.9 NaOH .7 1.5 Tetrasodium pyraphosphate 12.0 20.0 23.0 Fragrance .5 .3 .3 12 ~3nCIQ~iq~;l:; i Ij 1. CaO-C, 4 alcohol EO 5:1 1i 2. Lauric acid EO 9:1 3. Low forming polyol propylene oxide and ethylene oxide poly-condensates i of propylene glycol S4. High foaming polyol: These compositions are prepared in accordance with the process of 1 Example 1.

S The final products are viscous hard surface cleaning compositions, V easily removed by rinsing with water without having a gritty residue.

S All of the above undiluted cleaning pastes can be diluted with water ifor equally effective clean'ing of hard surfaces. The entire paste product dissolves in water leaving no gritty residue, abrasive particles, on or around the cleaned surfaces.

I It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention.

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Claims (16)

1. A hard::surface high viscosity organic cleaning composition comprising by weight, about 65-80% of an organic liquid vehicle consisting based on +he weight of +he c.ompoms'tor, essentially ohabout 15-35% of a water miscible organic solvent, about of a nonionic surfactant mixture containing an ethoxylated fatty acid as one of the surfactants, and about 0.7-1.5% sodium hydroxide, gelled by the in situ reaction of the ethoxylated fatty acid with the sodium hydroxide to form a clear, nonflowable gelled vehicle, substantially free of water; and about V1-1% by weight of an inorganic water solubl, particulate abrasive Sincorporated into the gelled vehicle.

2. The composition according to Claim 1, wherein the water miscible j* organic solvent is selected from the group consisting of a lower alkyl Sj glycol ether, lower alkyl monohydric alcohol, lower alkyl dihydric alcohol and mixtures thereof.

3. The composition according to Claim 2, wherein the water soluble particulate abrasives have larger than colloidal sized particles. S i

4. The composition according to Claim 1, wherein the cleaning pastes ij have a minimum viscosity of about 14,000 to 15,000 cps units, measured on fBrookfield HATD viscometer.

The comnosition according oe Claim 1, wherein the ethoxylated fatty acid constitutes about 6-3X 'by weight of the composition i

6. The composition according to Claim 1, wherein the nonionic surfactant in the mixture with the ethoxylated fatty acid may be selected I from the group consisting of a polyethylene oxide condensate of a C.-C 22 alkyl phenol, a polyethylene condensate of an aliphatic C-C 2 2 alcohol., a 1 polyethylene oxide condensate of the condensation product of propylene oxide (j with propylene glycol having a minlecular weight of about 1500 to 1800, and mixtures thereof.

7. The composition according to Claim 1, wherein the ethoxylated fatty R acid is lauric acid having 9 ethylene oxides per mole lauric acid. P

8. The composition according to Claim 2, wherein the water miscible organic solveit''is a mixture of a monohydric alcohol, a dihydric alcohol and ia glycol ether. I

9. The composition according to Claim 8, wherein the water miscible organic solvent is a mixture of ethanol, propylene glycol and diethylene Sglycol monobutyl ether.

The composition according to Claim 2, wherein the water miscible Sorganic solvent is a mixture of ethanol and diethylene glycol monobutyl ether.

11. The comptsition according to Claim 6, wherein the nonionic Ii i surfactant is polyethylene (5E0) CIo-Ci, alcohol

12. The composition according to Claim 3, wherein the water soluble I particulate abrasive is selected from the group consisting of alkali metal phosphates, polyphosphates, and carbonates. j

13. The composition according to Claim 12, wherein the water soluble abrasive is tetrasodium pyrophosphate.

14. The composition according to Claim 12, wherein the water soluble Iabrasive is sodium carbonate.

15. The composition according to Claim 14, wherein the water miscible Sorganic solvent is a mixture of ethanol, propylene glycol and diathylene glycol monobutyl ether, and the nonionic surfactant mixture is Co-C,. *alcohol EO 5:4 and ethoxylated 9EO lauric acid.

16. The composition according to Claim 13, wherein the water miscible organic solvent is a mixture of ethanol, propylene glycol and diethylene glycol monobutyl ether, and the nonionic surfactant mixture is an ethoxylated fatty acid and an ethoxylated fatty alcohol. Dated this 13th day of September 1988 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant F.B. RICE'& CO.