AU644791B2 - Film-forming emulsion polish compositions containing copolymeric siloxanes - Google Patents

Description

npI DATE 77/11/91 APPLN. ID 56307 AOJP DATE 02/01/92 PCT NUMBER PCT/IIS90/02542 PTr INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 (11) International Publication Number: WO 91/17223 CO9G 1/00 Al (43) International Publication Date: 14 November 1991 (14.11.91) (21) International Application Number: PCT/US90/02542 (81) Designated States: AT (European patent), AU, BE (European patent), CA, CH (European patent), DE (Euro- (22) International Filing Date: 3 May 1990 (03.05.90) pean patent)*, DK (European patent), ES (European patent), Fk (European patent), GB (European patent), IT (European patent), JP, LU (European patent), NL (Eu- (71) Applicant: S.C. JOHNSON SON, INC. [US/US]; Patent ropean patent), SE (European patent).

Section, M.S. 077, 1525 Howe Street, Racine, WI 53403-5011 (US).

Published (72) Inventors: HURLEY, Steve, M. 200 Echo Lane, Racine, With international search report.

WI 53406 MILLER, Eric, J. 5031 South Green Bay Road, Racine, WI 53403 RASOUL, Husam, A. 1812 Autumn Drive, Racine, WI 53402 (US).

(74) Agents: DRABIAK, Jerome, D. et al.; Patent Section, M.S.

077, S.C. Johnson Son, Inc., 1525 Howe Street, Racine, WI 53403-5011 1 (54)Title: FILM-FORMING EMULSION POLISH COMPOSITIONS CONTAINING COPOLYMERIC SILOXANES CH3 Cli A CH 3 I I I I

CH

3 -Si-O-f Si-]O)WfC-Si0 X-Si-CH 3 I I I

CH

3 Cfl CH 3

CH

3

CH

3

CH

3 B CH 3 II I I CH3-Si-0-HSi-O]yt(-Si-o0 zSiCH3 I I I I CH3 CH 3

CH

3

CH

3

(I)

(II)

(57) Abstract Disclosed are emulsion polish compositions comprisir3 a copolymeric siloxane selected from the group consisting of a poly(dimetyl)-co-poly(methylalkyl) siloxane polymer, a poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane polymer, and combinations thereof. The poly(dimethyl)-co-poly(methylalkyl) siloxane copolymer has formula wherein is an alkyl radical having 10-20 carbon atoms, and wherein is 70-91 mole percent and is 9-30 mole percent. The poly(dimethyl)-co-poly(mthyl, oxygen-containing) siloxane copolymer has formula (II) wherein is (CH 2 )i(L)(CH 2 CH20)nR, wherein is an integer from 3 to 10 inclusive, wherein is either or -COO-, wherein is either zero or an integer from 1 to 3 inclusive, wherein is -CH 3 or -C2H 5 and wherein is 62-92 mole percent and is 8-38 mole percent.

See back of page FILM-FORMING EMULSION POLISH COMPOSITIONS CONTAINING COPOLYMERIC SILOXANES Technical Field The present invernion is generally directed to filmforming emulsion polish compositions for furniture and similar household items. Depending upon the composition makeup, the emulsion can either be a water-in-oil emulsion or an oil-in-water emulsion. The emulsion polish compositions of the present invention, which are specifically formulated to provide rapid smear recovery, contain certain specified copolymeric siloxanes, briefly described below.

Those copolymeric siloxanes of the present invention, in particular, are briefly described as poly(dimethyl)-copoly(methylalkyl) siloxane copolymers and poly(dimethyl)-copoly(methyl, oxygen-containing) siloxane copolymers.

The present invention is thus more particularly directed to polish compositions, for furniture and similar household goods, wherein such compositions contain either poly(dimethyl)-co-poly(methylalkyl) siloxane polymer, poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane polymer, or combinations thereof.

Emulsion polish compositions containing these copolymeric siloxanes have been observed to possess rapid smear-recovery properties while exhibiting desirable depthof-gloss properties as well as certain other desirable film properties.

Background Art The ability of a polished surface to return to its original appearance after being smeared and the amount of time required to do so are two factors which tend to be rather important in the evaluation of the performance of a furniture polish composition.

Upon application onto a particular substrate surface, the polish compositions of the present invention have been observed to form a rather thin (approximately 1000 to 4000 Angstroms) generally uniform film on the substrate surface.

Due to the liquid nature of the resultant films of the surface-applied emulsion polish compositions of the present WO 91/17223 PCT/US90/02542 -2invention, such films typically exhibit, to a degree, visible physical evidence of surface disturbances, otherwise referred to as surface "smears", when'the surface-applied film is subjected to a rubbing action.

The term "smear recovery", as used herein, denotes not only the rate-of-recovery but also the ability of a thus "smeared" surface-applied polish film to return to its original surface appearance.

Polish compositions possessing superior smear recovery .properties have long been desired. Conventional polishes, however, and in particular the surface-applied films they produce, lack this quality. For example, commercial polishes that use conventional silicone-containing or conventional silicone-based fluids, as well as certain conventional waxes, and certain low molecular weight organic oils as glossing agents seemingly initially tend to provide certain desirable surface-appearance values but, in fact, ultimately suffer from certain inherent disadvantages. Such conventional polishes, in particular, readily tend to show certain surface disturbances such as fingerprints and otherwise readily tend to smear.

Certain investigations discussed in the prior-art references reviewed by us have attacked these and other surface "smear" problems by attempting to produce specific smear-resistant polishes which are said to provide treated surfaces that have relatively permanent finishes. Such socalled "permanent" finishes are said to require the application of significant force before their surface properties are disturbed. While such finishes tend to provide both high gloss and smear resistant properties, it is generally more difficult to remove these so-called "permanent" finishes; and such finishes thus have the tendency to build up with multiple applications.

Smear resistant films of this type are described e.g. in U.S. Pat. No. 3,847,622 to Brandl et al. The disclosed compositions of Brandl et al. contain water, wax, a mixture of organopolysiloxanes, a solvent, and a water-in-oil emulsifier. Such compositions, furthermore, are said to be substantially devoid of any tendency to smear or streak and WO 91/17223 PCT/US90/02542 3 are further said to be easily applied with a minimum of physical effort. Brandl et al. teach, however, that the use of silicones of diverse types, i.e. organopolysiloxanes, while beneficial from the standpoint of luster, gloss and durability, nevertheless fail to provide appreciable mitigation of the smear problem as they view it. The emulsion polish compositions disclosed by Brandl et al. are thus said to possess a "particularly high resistance to smearing." In U.S. P-t. No. 3,856,533, Schnurrbusch et al. disclose certain wax-containing surface-polish compositions which are said to be resistant to "finger-marking". Such compositions are disclosed as containing an organopolysiloxane (such as dimethylsiloxane), a wax, and a specified so-called "organosiloxane" containing an alkyl, an alkenyl, or a monocyclic aryl radical.

The present invention, in contradistinction to the prior art briefly discussed hereinabove, approaches the so-called "smear problem" in a manner which is markedly different from the approach set forth either in U.S. Pat. No. 3,847,622 to Brandl et al. or in U.S. Pat. No. 3,856,533 to Schnurrbusch et al. The present invention, in particular, enhances the smear-recovery properties of the emulsion polish compositions disclosed herein. Indeed, the unexpected and significant increase in smear recovery, which is attributable to the polysiloxane copolymers of our present invention, is shown in the comparative-example data presented hereinbelow. In particular, the smear-recovery properties of the novel emulsion polish compositions disclosed herein were not recognized by any of the prior-art polish formulators whose work we reviewed.

The prior-art references which we reviewed, while disclosing numerous furniture polishes using polysiloxanes, thus do not teach, disclose or even suggest the novel polysiloxane copolymers of our present invention. In particular, and as mentioned above, the novel polysiloxane copolymers of our invention have been demonstrated, by comparative example, as being unexpectedly superior over prior-art polysiloxanes such as polydimethylsiloxane.

WO 91/17223 PCr/US90/02542 4 Indeed, it was only through our present discovery that the surprising smear-recovery properties of the emulsion polish compositions of the present invention came to light.

In U.S. Pat. No. 2,698,805 to Currie et al., for example, there are disclosed certain conventional polishes which are said to be easy to apply. Such conventional emulsion polish compositions contain a hydrocarbon-soluble organopolysiloxane having from 1 to 3 aryl, alkyl, or arylkyl radicals per silicon atom. Such emulsion polish compositions further include a hydrocarbon solvent, a specified aluminum stearate compound, and water. The alkyl radicals which Currie et al. disclose are methyl, ethyl, propyl and octadecyl. The polish compositions disclosed by Currie et al., furthermore, are said to be smear-free. In contradistinction, the polish compositions of our present invention do indeed smear; but, upon being smeared, recover more rapidly than conventional compositions containing conventional polydimethylsiloxane polymers of comparable viscosity and/or weight-average molecular weight relative to the above-mentioned polymeric siloxanes disclosed herein.

Indeed, the concept of rapid smear recovery is not disclosed or even suggested by Currie et al. Moreover, the preferred organopolysiloxane disclosed in the Currie '805 patent, namely dimethylpolysiloxane fluid, is shown hereinbelow as being inferior to the siloxane-containing compositions of the present invention with regard to smearrecovery properties.

Further, U.S. Pat. No. 2,523,281 to Currie, is directed to automobile polishes containing an organopolysiloxane having from 1 to 3 aryl, alkyl or alkaryl radicals per silicon atom. Such automobile polishes also include a hydrocarbon solvent, finely-divided silica of a specified particle size, an emulsifying agent, and water. The disclosed alkyl radicals include methyl, ethyl, propyl, and octadecyl. Disclosed in this patent, furthermore, as the preferred organo polysiloxanes, are certain dimethylpolysiloxanes, which are shown hereinbelow as possessing inferior smear-recovery properties as compared to WO 91/17223 PCT/US90/02542 5 those siloxanes utilized in accordance with the principles of the present invention.

Still other patents, disclosing the use of polysiloxanes in furniture-care compositions, do not disclose the novel emulsion polish compositions of the present invention. In particular, U.S. Pat. No. 4,163,673 to Dechert; U.S. Pat. No.

4,354,871 to Sutton; and U.S. Pat. No. 4,613,646 to Sandvick, all disclose that dimethyl polysiloxane or polydimethyl siloxane is an especially-preferred polysiloxane for use in furniture polish compositions. Such siloxanes, however, form no part of the novel emulsion polish compositions of the present invention.

Indeed, the prior art does not disclose or even suggest the specific poly(dimethyl)-co-poly(methylalkyl) siloxane and poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymers of the present invention; nor does the prior art disclose or even suggest the unexpected smear-recovery properties of compositions containing the siloxane copolymers of the present invention.

For example, U.S. Pat. No. 4,404,035 to Ona et al.

discloses wax compositions comprising certain hydrocarbon ester-containing organopolysiloxanes, i.e. specified organopolysiloxanes containing at least one silicon-bonded hydrocarbon-ester group. The Ona et al. patent does not, however, teach or even suggest the usefulness of alkylene oxide polysiloxanes. Ona et al., in particular, teach away from using alkylene oxide polysiloxanes, as is shown by way of their so-called "solution as presented in their Example 2. That is, Ona et al., in their Example 2, specifically report that a polysiloxane having a side chain containing an alkylene oxide having the following formula

(CH

2 3 0(C 2

H

4 0) 20

(C

3

H

6 0) 20

H

produced a coating on a metal panel which, after being subjected to a 20-hou: water shower, was deemed to be unacceptable in luster, water-repellency and durability.

In U.S. Pat. No. 4,218,250 to Kasprzak, there is disclosed a wax-containing and/or abrasive-containing formulation which includes a cyclodimethyl siloxane fluid and a polydiorgano siloxane polyoxyalkylene copolymer. The WO 91/17223 PCT/US90/02542 6 disclosed polish formulation may also include a specific silicon-glycol copolymer having the following formula

(CH

3 3 SiO[(CH3) 2 SiO]x[G(CH 3 )SiO]ySi(CH 3 3 wherein x has an average value of 0 to 10, y has an average value of 1 to 10, G has the formula, -D-(OC 2

H

4 )zOH, with D being an alkylene radical containing from 2 to 10 carbon atoms and z having an average value of from 6 to 20. This patent, however, does not mention smear resistance or smear recovery; nor does this patent otherwise disclose either the specific poly(dimethyl)-co-poly(methylalkyl) siloxane or poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymers of the present invention.

Additionally, U.S. Pat. No. 3,306,869 to Lahr et al.

discloses floor polishes which are said to possess desirable so-called "leveling" properties as well as acceptable "scuffresistance" properties. Such floor polishes comprise a wax, a modified rosin, an emulsifying agent, and a polysiloxaneoxyalkylene block copolymer having a molecular weight below about 25,000 and a polysiloxane content in the range of from about 30 to about 60 percent by weight. U.S. Pat. No.

3,341,338 to Pater also discloses a polish formulation comprising a polysiloxane-oxyalkylene block copolymer and a wax. Neither patent, however, discloses or even suggests "smear recovery", or otherwise discloses the specific poly(dimethyl)-co-poly(methylalkyl) siloxane or poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymers of our present invention.

From the above discussion, it can either be implied that the smear-recovery problems associated with certain prior-art polish compositions are not appreciated or, if such problems have become recognized by those skilled in the art, it can be implied that an acceptable solution to the smear-recovery problem is still generally unknown to those skilled in the art.

Accordingly, there is presently a need for polish compositions which possess rapid smear-recovery properties.

Industrial Applicability One object of our invention, therefore, is to provide polish compositions for furniture and other similar household 7 items, wherein such polish compositions exhibit rapid smear-recovery qualities.

It is yet another object of our invention to provide furniture polish compositions which may be applied and removed with a minimum of effort, and which possess not only rapid smear-recovery properties but also acceptable so-called "depth-of-gloss" characteristics as well.

The foregoing, as well as other objects, features and advantages of our invention will become more readily clear to those skilled in the art upon reference to the following summary and detailed description.

Summary Disclosure of Invention In an embodiment of this inventon there is provided a surface-treating emulsion polish composition for furniture and imilar household items comprising water, at least one hydrocarbon solvent, at least one surfactant, and at least one copolymeric siloxane selected from the group consisting of a poly(dimethyl)-co-poly(methylalkyl) siloxane polymer, a poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane polymer, and combinations thereof, wherein the poly(dimethyl)-co-poly(methylalkyl) siloxane polymer has a weight-average molecular weight of about 2,500 to about 4,000 and the general formula

CH

3

CH

3 A CH 3

CH

3 -S i-O]x- i-CH 3

CH

3

CH

3

CH

3

CH

3 wherein A is an alkyl radical having 10 to 20 carbon atoms, w is about 70 to about 91 mole percent and x is about 9 to about 30 mole percent of the poly(dimethyl)-copoly(methylalkyl) siloxane polymer, and wherein the poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymer has a weight-average molecular weight of about 1,000 to about 4,000 and the general formula

CH

3

CH

3 B €H 3 i i- ]z-Si--CH3

CH

3

CH

3

CH

3

CH

3 wherein B is (CH2)i(L)(CH 2

CH

2 O)nR, wherein i is an integer from 3 to 10 inclusive, wherein L is or -COO-, wherein n is either zero or an integer from 1 to 3 inclusive, wherein R is -CH 3 or -C 2

H

5 and wherein y is about 62 to about 92 mole percent and z is about 8 to about 38 mole percent of the poly(dimethyl)-co-poly(methyl, oxygencontaining) siloxane copolymer.

One aspect of our present invention is thus directed to a surface-treating emulsion t composition for furniture and similar household items. The emulsion composition, in [G:\WPUSERUJBAAM0021 :TCW 7A particular, comprises water, at least one hydrocarbon solvent, at least one surfactant, and at least one copolymeric siloxane, herein referred to as a poly(dimethyl)-copoly(methylalkyl) siloxane copolymer having the general formula

CH

3

OH

3 A CH 3 CH3-S i--O--Si--CH3 I I I

CH

3

CH

3

CH

3

CH

3 s wherein A is an alkyl radical having 10 to 20 carbon atoms, wherein the above-presented copolymeric siloxane has a weight-average molecular weight of about 2,500 to about 4,000 and a viscosity of preferably about 20 to about 200 centipoise, and wherein the "w" value is about 70 to about 91 mole percent and the value is about 9 to about 30 mole percent of the above-presented copolymeric siloxane.

Yet another aspect of our present invention is directed to yet another surface-treating emulsion composition for furniture and similar household items. Such an emulsion composition, in contradistinction to what was briefly disclosed above, comprises water, at least one hydrocarbon solvent, at least one surfactant, and at least one other copolymerc siloxane, herein referred to as a poly(dimethyl)- 11:TCW WO 91/17223 PC/US90/02542 8 co-poly(methyl, oxygen-containing) siloxane copolymer having the general formula

CH

3

CH

3 B CH 3 I I I I CH3-Si-O-[-Si-0]y-[-Si-O]z-Si-CH 3 I I I I

CH

3

CH

3

CH

3

CH

3 wherein B is (CH 2 )i(L)(CH 2 CH20)nR, wherein i is an integer from 3 to 10 inclusive, wherein L is or -COO-, wherein n is either zero or an integer from 1 to 3 inclusive, wherein R is -CH 3 or -C 2

H

5 wherein the copolymeric siloxane has a weight-average molecular weight of about 1,000 to about 4,000 and a viscosity ofoaboutl10 to about 250 centipoise, and wherein the value is about 62 to about 92 mole percent and the value is about 8 to about 38 mole percent of the second above-presented copolymeric siloxane.

The second above-presented copolymeric siloxane is thus characterized as a poly(dimethyl)-co-poly(methyl, oxygencontaining) siloxane copolymer because the latter portion thereof contains at least one methyl group and at least one oxygen group.

In accordance with the above, still other surfacetreating emulsion compositions for furniture and similar household items comprise combinations of the copolymeric siloxanes briefly summarized above.

We observed that the above-summarized copolymeric siloxanes possess surprising and unexpected smear-recovery properties, as compared to the above-described siloxane copolymers which we investigated in connection with the prior-art references mentioned above.

Best Mode For Carrying Out The Invention Thus, one embodiment of the polish composition of our invention comprises water, at least one hydrocarbon solvent, at least one surfactant, and at least one copolymeric siloxane.

The copolymeric siloxanes of our present invention are selected from the group consisting of poly(dimethyl)-copoly(methylalkyl) siloxane copolymer, poly(dimethyl)-co- WO 91/17223 PCT/bS90/02542 -9poly(methyl, oxygen-containing) siloxane copolymer, and combinations thereof.

The poly(dimethyl)-co-poly(methylalkyl) siloxane copolymer of our invention, more particularly, has the general formula

CH

3

CH

3 A CH 3 I I I I

CH

3 -Si-0-[-Si-O]w-[-SS--Si-CH 3 I I I I

CH

3

CH

3

CH

3

CH

3 wherein A is an alkyl radical having 10 to 20 carbon atoms, wherein the copolymeric siloxane has a weight-average molecular weight of about 2,500 to about 4,000 and a viscosity of about 20 to about 200 centipoise, and wherein the value is about 70 to about 91 mole percent and the value is about 9 to about 30 mole percent of the copolymeric siloxane. (The above-mentioned and molepercentage values, when added together, thus equal 100%.) A more preferred poly(dimethyl)-co-poly(methylalkyl) siloxane copolymer has a value (the mole percent of silicon atoms having dimethyl groups attached) of about 85 to about 95 mole percent of the copolymeric siloxane and an "x" value (the mole percent of silicon atoms having at least one

C

10

-C

2 0 alkyl group attached) of about 5 to about 15 mole percent of the copolymeric siloxane.

A still more preferred poly(dimethyl)-copoly(methylalkyl) siloxane copolymer has a weight-average molecular weight of about 2,500 to about 3,500, a viscosity of about 25 to about 250 centipoise, a value of about mole percent, and an value of about 10 mole percent.

The alkyl radicals (depicted as in the abovepresented formula) of these preferred poly(dimethyl)-copoly(methylalkyl) siloxane copolymers include only evennumbered alkyl radicals; and such siloxane copolymers thus only have either 10, 12, 14, 16, 18, or 20 carbon atoms.

The poly(dimethyl)-co-poly(methyl, oxygen-containing)' siloxane copolymer of this invention has the general formula WO 91/17223 PC/US90/02542 10

CH

3

CH

3 B CH3 I I I I

CH

3 -Si-0-[-Si-O]y-[-Si-i--Si-CH 3 I I I I

CH

3

CH

3

CH

3 CH3 wherein B is (CH 2 )i(L)(CH2CH 2 0)nR, wherein i is an integer from 3 to 10 inclusive, wherein L is or -COO-, wherein n is either zero or an integer from 1 to 3 inclusive, wherein R is -CH 3 or -C 2

H

5 wherein the copolymeric siloxane has a weight-average molecular weight of about 1,000 to about 4,000 and a viscosity ofvabout 0 to about 250 centipoise, wherein the value is about 62 to about 92 mole percent, and the value is about 8 to about 38 mole percent of the copolymeric siloxane. [The above-mentioned and molepercentage values of a particular poly(dimethyl)-copoly(methyl, oxygen-containing) siloxane copolymer, when added together, thus equal 100%.] It is further contemplated, within the scope of our present invention, that the CH 2 CH20 group shown in the side chain can be substituted by CH 2

CH

2 CH20 or CH 2

CH(CH

3

)O.

A more preferred poly(dimethyl)-co-poly(methyl, oxyge containing) siloxane copolymer has a viscosity of about 20 to about 110 centipoise, a value (the mole percent of silicon atoms having dimethyl groups attached) of about 85 to 95 mole percent of the copolymeric siloxane, and a value (the mole percent of silicon atoms having a methyl and an oxygen-containing group attached) of about 5 to 15 mole percent of the copolymeric siloxane.

A still more preferred poly(dimethyl)-co-poly(me-ryl, oxygen-containing) siloxane copolymer has a weight-average molecular weight of about 3,000 to about 3,500, and a viscosity of about 20 to about 100 centipoise. Such preferred copolymeric siloxanes, moreover, have an value of either -CH 3 or -C 2

H

5 Specific examples of still other, particularly preferred poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymers are described in the below-discussed examples.

Typically, the copolymeric siloxanes of the present N invention are employed in amounts ranging from about 0.5 to 4A,^.

WO 91/17223 PCT/US90/02542 11 about 50 weight percent, based upon the total weight of a specified composition (exclusive of any propellant), with concentrations of about 1 to about 10 weight percent being preferred, and with concentrations of ab~ut 1 to about weight percent being even more preferre The concentration of copolymeric siloxane, utilized in such a specified composition, is not critical. Indeed, those skilled in the art can well appreciate that specific copolymeric siloxane amounts will generally be dictated in accordance with the relative proportions of certain other ingredients which are included in a particular composition.

Such is also true of each of the other ingredients of the compositions of our present invention. That is, the concentrations of other ingredients, described in greater detai- hereinbelow, are not critical and are given only to exemplify the present invention.

The emulsion polish compositions of the present invention can be either oil-in-water so-called "water out") emulsions or water-in-oil so-called "oil out") emulsions. Those skilled in the art can readily choose an appropriate surfactant (or emulsifier), or combination of surfactants (or emulsifiers), to produced the desired type of emulsion.

As those skilled in the art can well appreciate, the term "emulsion" is generally recognized as connoting a stable mixture of two or more mutually immiscible liquids held in suspension by small percentages of substances called emulsifiers (or surfactants). All emulsions, moreover, are characterized as comprising a continuous phase and a discontinuous phase which is dispersed throughout the continuous phase.

In the emulsion polish compositions of our present invention, the hydrocarbon solvents and surfactants described below are typically those conventionally used in furniture polish compositions. The critical component, insofar as the present invention is concerned, thus is either the poly(dimethyl)-co-poly(methylalkyl) siloxane copolymer, the poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane WO 91/17223 PCT/US90/02542 12 copolymer, or both such siloxane copolymers (for certain polish compositions containing both).

In general, solvents are typically utilized in conventional polish compositions for purposes of removing solvent-soluble residues from substrate surfaces. For optimum results, therefore, any solvents that are utilized in preparing the emulsion polish compositions of this invention should be sufficiently volatile so as to bring about rapid drying after the composition has been applied to a substrate surface, and yet, not so volatile as to prematurely dry up before desired spreading of the composition onto the substrate surface (for purposes of providing a desired film) has taken place.

Accordingly, those solvents deemed particularly useful, in accordance with the principles of our present invention, have so-called "kauri-butanol" values of from about 20 to about 50, and have boiling-point ranges of from about 600 to about 210 0 C, and preferably from about 950 to about 150 0

C.

A wide variety of commercially-available isoparaffinic hydrocarbon solvents, such as those commercially available from the Exxon Corporation under the "Isopar" brand as well as the isoparaffinic-type hydrocarbon solvents commercially available from the Phillips Petroleum Corporation under the "Soltrols" brand, are moreover presently preferred because they are substantially odor-free.

Other suitable hydrocarbon solvents, in accordance with the principles of the present invention, include hexane, heptane and the so-called "Stoddard" solvents.

The various above-described hydrocarbon solvents, furthermore, can be utilized individually or in combination.

The hydrocarbon solvent can be present in amounts of from about 0.15 to about 90 weight percent, based on the total weight of the emulsion polish composition (excluding any propellant, if present). Preferably, however, the hydrocarbon solvent will be present in an amount of from about 1.0 to about 25 percent, with about 5 to about weight percent being even more preferred.

As was briefly mentioned above, all emulsions comprise a continuous phase and a discontinuous phase. While the amount WO 91/17223 PCr/US90/02542 13 of surfactant (or emulsifier) present in the emulsion polish compositions of our present invention is not critical, it is to be understood that such emulsion polish compositions must include an amount of surfactant (or emulsifier), or an amount of combinations of surfactants (or emulsifiers), for effectively dispersing the discontinuous phase throughout the continuous phase.

Accordingly, surfactants (or emulsifiers) useful for purposes of our present invention include conventional nonionic, cationic, and anionic surfactants (or emulsifiers) commonly employed in commercial polishes for application to furniture surfaces. Such conventional surfactants can be used alone or in combination.

In preferred embodiments of our present invention, certain conventional non-ionic surfactants, as well as certain combinations of conventional non-ionic surfactants, are utilized because they provide desirable emulsionstability properties. Conventional non-ionic surfactants (or emulsifiers), suitable for purposes of the present invention, include, but are not limited to, the so-called "sorbitan" esters of oleic and lauric acids; those polyethoxylated sorbitan esters having up to 20 ethoxy units; the monoglycerides and diglycerides of the fat-forming fatty acids; and combinations thereof.

Additional examples of preferred, commercially-available non-ionic surfactants (or emulsifiers) include certain "Span" brand and "Tween" brand emulsifiers, both presently available from ICI Americas, Inc.; and the "Monamid" brand emulsifiers, presently available from Mona Industries, Inc. Particular examples of such emulsifiers include sorbitan monooleate, sold by ICI Americas, Inc., under the "SPAN 80" brand; sorbitan monolaurate, sold by ICI Americas, Inc., under the "SPAN 20" brand; and sorbitan monopalmitate, sold by ICI Americas, Inc., under the "SPAN 40" brand. Mixtures of the various above-mentioned surfactants (or emulsifiers) can also be utilized, if desired, in accordance with the principles of our present invention.

It is further contemplated or expected that the following conventional cationic surfactants or emulsifiers WO 91/17223 PCr/US90/02542 14 would be suitable for purposes of our present invention.

These include certain quaternary ammonium compounds such as the quaternary ammonium halides, the quaternary ammonium sulfates, those so-called "fatty" amines which are ethoxylated and have about 2 to about 10 moles of ethylene oxide, and the chloride salts or acetate salts of amines, as well as those amines which are ethoxylated and have 2 or more moles of ethylene oxide. Mixtures of the above surfactants (or emulsifiers) can also be utilized by those skilled in the art, in accordance with the principles of our invention, if desired.

Conventional anionic surfactants or emulsifiers, suitable for purposes of our present invention, include certain sulfates (such as sodium lauryl sulfate and the sodium alkyl ether sulfates), those sulfosuccinates containing polyethylene glycol moieties attached thereto, and the alkyl aryl sulfonates. Mixtures of the above surfactants (or emulsifiers) can also be utilized, in accordance with the principles of our present invention, if desired.

The surfactants (or emulsifiers), mentioned above, while not critical, can thus be present in the compositions of our present invention in amounts ranging from about 0.1 to about weight percent, based on the total weight of our emulsion polish composition (exclusive of any propellant, if present), with from about 0.2 to about 1.2 weight percent being preferred.

The emulsion polish compositions of this invention also contain water as the principal constituent of the emult;ion.

The presence of water in the emulsion polish composition of our invention has been observed to assist in the "leveling" of the resultant film of the emulsion polish composition, upon application of such a film to a substrate surface. The presence of water, moreover, tends to remove any watersoluble soil particles that may be present on the thustreated substrate surface. Generally, watei, will therefore make up the balance of the emulsion polish composition, taking into account the active ingredients noted above; and such balance amount of water is accordingly present in an amount ranging from about 2 to about 99 weight percent, based WO 91/17223 PC~/US90/02542 15 upon the total weight of the composition (exclusive of any propellant, if present), with concentrations of about 66 to about 93 weight percent being preferred.

As was briefly implied above, the most preferred emulsion polish compositions of this invention are totally wax-free. However, it may be desirable, in certain situations, to utilize a relatively minor amount of wax in specific formulations. Thus, from about 0.1 to about weight-percent wax, based upon total weight of the emulsion polish composition, may be employed in the furniture polish compositions of the present invention. Conventional waxes, suitable for purposes of our invention, accordingly include, but are not limited to, certain synthetic waxes such as the microcrystalline waxes and the petroleum waxes as well as certain natural waxes such as the candellila and the carnauba waxes.

Still other well-known additives, including but not limited to perfumes and preservatives, may be added to the emulsion polish compositions of our present invention.

Perfumes are typically added, for example, to impart a desired fragrance. Conventional perfumes, suitable for purposes of the present invention, are well known to those skilled in the art and accordir-jly need not be described in detail here. The amount of perfume which is included is typically present in an amount that is effective for imparting a desired fragrance intensity. Such an amount of perfume can range, for example, from about 0.05 to about 1 weight percent, based upon the total weight of the emulsion polish composition (exclusive of any propellant, if present).

Preservatives, typically formaldehyde, are generally utilized to retard or otherwise thwart undesired bacterial activity within packages containing certain formulations of the emulsion polish compositions of the present invention.

As those skilled in the art can well appreciate, the presence of such preservatives is for prolonging the shelf life of the thus-formulated emulsion polish composition product. A variety of well-known conventional quaternary compounds can moreover be utilized for such a purpose.

WO 91i/'17223 PCr/US90/02542 16 The emulsion polish compositions of the present invention can be applied directly onto a substrate surface, utilizing e.g. a wide variety of well-known conventional pressurized systems containing an appropriate amount of a liquid or_gaseous propellant. In particular, the emulsion polish compositions can be applied directly onto a substrate surface, utilizing well-known spray means such as conventional pump sprayers. Additionally, the emulsion polish compositions can be applied to furniture surfaces, utilizing a polishing cloth, or other suitable means.

Furthermore, the emulsion polish compositions of our present invention can be provided in aerosol form, depending upon the particular copolymeric siloxane compound or compound mixture which is utilized in the emulsion polish composition.

To produce such an aerosol form, the emulsion polish composition (containing such an appropriate copolymeric siloxane compound or compound mixture) is introduced into a conventional aerosol container which is then capped with an aerosol valve. Thereafter, an effective amount of a suitable, conventional propellant is introduced into the aerosol container, in a known manner, for achieving a desired pressure in the container. Such propellant pressure should therefore be sufficient for enabling substantially complete expulsion of the aerosol container-contained ingredients, in the form of a spray in the desired manner, through the aerosol valve. Any of a wide variety of suitable conventional propellants which may be used include such wellknown liquified hydrocarbons propellant gases as isobutane, n-butane and propane, and sucn well-known halogenated hydrocarbons as difluoroethane and the "Freon" brand of propellants, sold by E. I. Du Pont de Nemours Co. Mixtures of halogenated hydrocarbons and other hydrocarbons may also be used in accordance with the principles of the present invention, if desired.

The aerosol emulsion polish compositions of this invention typically contain between about 5 and about weight percent of .propellaat, based upon the total weight of the aerosol-containing emulsion polish composition of the present invention. The weight percentage or concentration of WO 91/17223 PCr/ US90/02542 17 propellant is not critical and thus can vary widely depending on the desired end use.

Moreover, the precise method of manufacturing the polish compositions of this invention is not critical. The order and/or manner of addition of the various emulsion polish composition ingredients, mentioned above, may accordingly generally be varied and typically will not affect the quality of a particular emulsion polish composition which is thus being formulated or produced. Conventional techniques for forming water-in-oil and oil-in-water emulsion polishes are typically used to produce the various embodiments of the emulsion polish compositions of the present invention.

The so-called "wax-free" emulsion polish composition embodiments of the present invention are prepared utilizing a known, so-called "cold-blend" process. One conventional cold-blend processing method, suitable for purposes of the present invention, comprises charging the oil-phase ingredients (namely, the hydrocarbon solvent, the polysiloxane, the surfactant, and fragrance, if present) into a vessel of suitable dimension, preferably equipped with agitation means, and thereafter mixing the oil-phase ingredients until a homogeneous blend is achieved. Water and any other aqueous-phase ingredients preservative) are next slowly added to the vessel, while maintaining a moderate degree or amount of agitation, to thereby produce the emulsion polish composition. If it is necessary to stabilize the thus-produced emulsion polish composition, the resulting composition can then e.g. be homogenized by passing such emulsion polish composition through a 3/64 inch diameter orifice, utilizing a 60 to 80 psig pressure drop across the orifice.

Wax, if a component of the emulsion polish composition of the present invention, is added with the initial oil-phase ingredients; and the resultant mixture is then heated to a 3F temperature sufficient to melt the wax and achieve a homogeneous mixture. After the addition of water and any other ingredients, the wax-containing composition is either cooled or allowed to cool to room temperature 25 0 C) and is preferably thereafter homogenized.

WO 91/17223 PC/US0/02542 18 Still other aspects, advantages and features of the present invention will become apparent upon reviewing the following examples, which are illustrative and not intended to limit the scope of the present invention except as defined in the appended claims.

All percentages set forth herein are by weight of the total composition, unless otherwise indicated.

In the following examples, certain preferred embodiments of the emulsion polish compositions of our invention are presented. Also presented are certain comparative examples, documenting comparative testing of the copolymeric siloxanes of the present invention with respect to several prior-art polysiloxanes.

Typical emulsion polish compositions of the present invention include: Formulation Ingredients Preferred More Preferred Wt.-% copolymeric 0.5-50 1-10 siloxane hydrocarbon 0.15-90 5-20 solvent surfactant 0.1-10 0.2-1.2 water 2-99 67-94 additives 0-50 0-2 Preferred and exemplary embodiments of the present invention are set forth in Tables 1-5, below. The numerical values shown below represent weight concentrations percent by weight of the total composition) of the various ingredients included therein.

Table 1: Poly(dimethyl)-co-poly(methylalkyl) Siloxane Emulsion Polish Composition Ingredients Wt.-% poly(dimethyl)-co-poly(methylalkyl) siloxane a 4.6 sorbitan monooleateb 0.45 polyoxyethylene 20 sorbitan monooleatec 0.02 fragrance 0.4 isoparaffinic hydrocarbond 19.2 formaldehyde 0.20 water 75.13 WO 91/17223 PCr/US90/02542 19 Footnotes: a. The poly(dimethyl)-co-poly(methylalkyl) siloxane was poly (90 mole-%) dimethyl-co-poly (10 mole-%) methylhexadecyl siloxane, having a weight-average molecular weight of 2852.

b. One surfactant utilized, the sorbitan monooleate, was SPAN 80 brand surfactant.

c. The other surfactant utilized, the polyoxyethylene sorbitan monooleate, was TWEEN 80 brand surfactant.

d. The isoparaffinic hydrocarbon utilized, Isopar C brand isoparaffinic hydrocarbon, has a flash point of 40 0

F.

The copolymeric siloxanes that can be utilized in the formulation presented in Table 1 include poly(dimethyl)-copoly(methylalkyl) siloxanes having a weight-average molecular weight of about 2,500 to about 4,000, a viscosity of about to about 200 centipoise, and an value (the mole percentage of silicon at)ms having at least one C 10

-C

20 alkyl group attached thereto) of about 9 to about 30 mole percent.

Table 2: Poly(dimethyl)-co-poly(methyl, oxygencontaining) Siloxane Emulsion Polish Composition InQredients Wt.-% poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxanee 5.00 sorbitan monooleate f 0.50 polyoxyethylene 20 sorbitan monooleate g 0.02 fragrance 0.30 isoparaffinic hydrocarbonh 12.00 formaldehyde 0.20 water 81.98 Footnotes: e. The poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane utilized was a poly (91 mole-percent) dimethylco-poly (9 mole-percent) methylethoxyethyoxyethylundecanoatyl siloxane, having a weight-average molecular weight of 3224.

f. One surfactant utilized, the sorbitan monooleate, was SPAN 80 brand surfactant.

WO 91/17223 PCT/US90/02542 20 g. The other surfactant utilized, the polyoxyethylene sorbitan monooleate, was TWEEN 80 brand surfactant.

h. The isoparaffinic hydrocarbon utilized was Isopar C brand isoparaffinic hydrocarbon, having a flash point of 40 0

F.

The copolymeric siloxanes that can be utilized in the formulation presented in Table 2 include poly(dimethyl)-copoly(methyl, oxygen-containing) siloxane copolymers having weight-average molecular weights of about 1,000 to about 4,000, viscosities of about 10 to about 250 centipoise, and a value (the mole percentage of silicon atoms having at least one methyl and oxygen-containing group attached thereto) of about 8 to 38 mole percent.

Comparative-Testing Examples To demonstrate the superior smear-recovery properties of emulsion polish compositions obtained from utilizing the copolymeric siloxanes of the present invention, certain comparative smear-recovery tests were performed. The results of these comparative smear-recovery tests clearly show the relative decrease in smear recovery time provided by the copolymeric siloxanes of the present invention, as compared to conventional siloxanes.

The comparative smear-recovery tests were conducted utilizing a Murakami brand Goniophotometer, specially outfitted with a solenoid-driven, spring-loaded swing arm.

Parallel strands of either 220 micron or 320-325 micron diameter commercially-available monofilament fibers were utilized as the smear-causing medium. Fifteen-degree incident-specular reflectance of each substrate-applied film was monitored as a function of time-after-smearing. The films were cast on conventional 2.25 inch square nitrocellulose lacquer-coated glass slides. The backs of the glass slides were cc :ed with black lacquer to prevent reflection from the back face of these glass slides. Percent smear recovery was measured as the percent specular reflectance, as compared to the specular reflectance before the film was smeared.

WO 91/17223 PCr/US90/02542 21 Procedure for Determining Smear Recovery The procedure for determining the smear recovery of transparent thin films is as follows.

A Murakami brand, model GP-1R, commercially-available Goniophotometer, specifically outfitted wi.h a solenoiddriven swing arm was utilized. Attached to the swing arm was a 3/4 inch-wide smear medium. The smear medium consisted of a plurality of contacting, parallel strands of either 220 or 300-to-325 micron-diameter commercially-available monofilament line. Each such strand comprised an elongated, generally linear portion and a unitary, generally "C"-shaped portion at one end of the linear strand. Each such monofilament line strand was generally disposed, relative to a test substrate coupon, such that the generally linear strand portion was generally perpendicular to the test substrate while the curved portion of t e monofilament strand rested on the surface of the test substrate.

Thus, the curved portion of each such strand of the plurality was disposed such that the curved portion of each such filament came into contact with the substrate, thereby to assure substantially complete contact of the plural strands over the test substrate area being smeared.

Each test substrate consisted of a 2.25 inch by 2.25 inch square of 1/8 inch-thick pieces of clear glass having a refractive index of about 1.50 to 1.52. It is important, for this procedure, that the lacquer and the glass have refractive index values that are about the same. Each such clear piece of glass, moreover, was coated with 1.25 grams of high-gloss nitrocellulose-containing furniture lacquer. Such lacquer included about 21.3 non-volatile material. The glass-applied lacquer was cured slowly under a watch glass on a level surface, thereby to assure a smooth uniform finish on the piece of glass. The back of each such glass test slide was thus coated with a black lacquer to eliminate reflection from that surface. The lacquer-applied side of each such piece of glass had a refractive index of between 1.50 and 1.53.

Each such glass slide, thus-coated, was weighed on a conventional analytical balance capable of weighing to 0.01 WO 91/17223 PCT/US90/02542 22 milligrams. Each glass slide was thereafter placed onto a conventional spin coater. A 5 non-volatile solution of the test copolymer composition was then caused to flow over the test slide. The solution-applied test slide was then immediately spun at 500 to 2500 revolutions per minute, until the solvent evaporated therefrom. The weight of each such thus-treated glass slide was thereafter noted, to thereby determine by difference the weight of the amount of copolymeric siloxane that was thus deposited thereon. The thickness of the thus-deposited residual film was then determined mathematically.

Thus treated, each test slide was inserted into the specimen holder of the Goniophotometer; and the 15 degree incident specular reflectance of the test surface was then measured directly. The solenoid-driven arm was activated to smear the test film. Such smearing resulted in a decrease in specular reflection of the test film. The specular reflectance of the film was monitored as a function of time to determine the amount of time that it took for the thusdisturbed film to recover to 95% of its original reflection.

Table 3, below, presents the time for 95% recovery of specular reflection for specific poly(dimethyl)-copoly(methylalkyl) siloxane copolymers of the subject invention as well as for certain prior-art polydimethyl siloxanes which are being compared to the copolymeric siloxanes of the present invention.

WO 91/17223 PCT/US90/02542 23 Table 3: Smear Recovery, Comparative Data: Polv(dimethyl)-co-polv(methvlalkvl) Siloxanes Siloxane Polymer Siloxane No. 1 Siloxane No. 2 Siloxane No. 3 Siloxane No. 4 Siloxane No. 5 Siloxane No. 6 Siloxane No. 7 Siloxane "A" 3 Siloxane "B" 3 Copolymer Molecular Weight 2737 2834 2932 2951 3127 3224 3900 2000 3780 Copolymer Viscosity Centipoise 68 67 57 68 78 >119 182 19 48 x/A Values S0%/C 10 10%/C 12 10%/C 14 10%/C 16 10%/C 18 10%/C 20 30%/C 14 Smear Recovery, in sec.

2 2 1 1 1 2 Footnotes: i. Smear recovery is the amount of time, expressed in seconds, that is needed to recover to 95% of the original reflectance value. The specular reflectance determination procedure, utilizing a 320 micron diameter smear pattern, is more particularly set forth in the above-noted procedure.

j. The prior-art polysiloxanes identified in Table 3 are similar to those polysiloxanes disclosed in Examples 1 nnd 4 of U.S. Pat. No. 2,523,281 to Currie and in Examples 5 through 7 of U.S. Pat. No. 2,698,805 to Currie et al. In such prior-art polysiloxanes, the "x" and values listed in Table 3 are nonexistent.

Siloxane No. 1 is polydimethyl-co-polymethyldecyl siloxane copolymer. Siloxane No. 2 is polydimethyl-copolymethyldodecyl siloxane copolymer. Siloxane No. 3 is polydimethyl-co-polymethyl tetradecyl siloxane copolymer.

Siloxane No. 4 is polydimethyl-co-polymethylhexadecyl siloxane copolymer. Siloxane No. 5 is polydimethyl-copolymethyloctadecyl siloxane copolymer. Siloxane No. 6 is polydimethyl-co-polymethyleicosenyl silcxane copolymer.

Siloxane No. 7 is polydiTethyl-co-polymethyltetradecyl siloxane copolymer. Siloxanes and both prior-art compounds, are polydimethyl siloxane polymers.

lI, i .ril tlli WO 91/17223 PCT/US90/02542 24 The results, as shown in Table 3 above demonstrate that, at comparable molecular weights, the smear-recovery properties of the poly(dimethyl)-co-poly(methylalkyl) siloxane copolymers of this invention are superior to the prior-art polydimethyl siloxanes. All of the compositions of the present invention recover to 95% of their initial specular reflectance in 5 seconds or less, as compared to the prior-art dimethyl siloxane-containing compositions which require 20 to 30 seconds.

The poly(dimethyl)-co-poly(methylalkyl) siloxane copolymers listed in Table 3 were prepared from commerciallyavailable polydimethyl-co-polymethylhydrosiloxane precursors and commercially-available alpha-olefins, utilizing a wellknown hydrosilylation reaction.

More specifically, synthesis of the siloxane copolymers was performed by the well-known hydrosilylation reaction of polydimethyl-co-polymethylhydrosiloxan (available either from Petrarch System, Inc., Dow Corning, or General Electric) and alpha-olefins of varying lengths (available from Aldrich). A round-bottomed flask equipped with magnetic stirring bar, condenser and calcium-chloride tube was charged with a 50 solution of the reactants (up to 10% molar excess alpha-olefin) in dry toluene. A solution of hydrogen hexachloroplatinate (IV) in diglyme/isopropanol was then added to the reaction mixture (150 ppm Pt). The reaction mixture was then stirred at 60 0 C for three hours. At the en of this reaction period, the resultant mixture was refluxed with activated charcoal for 1 hour, and filtered hot.

Finally, the solvent and excess alpha-olefins were removed under reduced pressure of 0.5 mm. Hg at 100 0 C. The reaction proceeded to completion as evidenced by the absence of the Si-H absorption at about 2160 cm-1 in the infrared spectra.

Residual alpha-olefin in the purified polymers was determined by gas-liquid chromatography. In all siloxane copolymers thus produced, residual alpha-olefin was less than 4 Still more particularly, the reactants that were utilized to prepare the siloxanes presented in Table 3 are as follows.

In preparing Siloyane No. 1, the hydrosiloxane precursor was poly(90%)dimethyl-co-poly(10%)methylhydrosiloxane, and WO 91/17223 PC/US90/02542 25 the alpha-olefin was 1-decene. In preparing Siloxane No. 2, the hydrosiloxane precursor was and the alpha-olefin was 1dodecene. In preparing Siloxane No. 3, the hydrosiloxane precursor was and the alpha-olefin was 1tetradecene. In preparing Siloxane No. 4, the hydrosiloxane precursor was and the alpha-olefin was 1hexadecene. In pre, iring Siloxane No. 5, the hydrosiloxane precursor was and the alpha-olefin was 1octadecene. In preparing Siloxane No. 6, the hydrosiloxane precursor was poly(10%)methylhydrosiloxane, and the alpha-olefin was 1eicosene. In preparing Siloxane No. 7, the hydrosiloxane precursor was and the alpha-olefin was 1tetradecene.

Table 4, below, presents the amount of time that is necessary to achieve a 95% recovery of specular reflection, for those emulsion polish compositions made from specified poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymers of the present invention, in comparison to specular reflection recovery times of certain emulsion polish compositions made from specific prior-art polydimethyl siloxanes.

The poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxanes, listed in Table 4 as Siloxane Nos. 8 through each had the -COO- moiety as its value and the -C 2

H

radical as its value.

WO 91/17223 PC/ US90/0O542 26 Table 4: Smear Recovery, Comparative Tests: Poly(dimethyl)co-poly(methyl, oxygen-containing) Siloxanes Copolymer Copolymer Smear Molecular Viscosity z/n/i Recovery,k Siloxane Polymer Weight Centipoise Values in sec.

Siloxane No. 8 3968 30 8%/0/10 6 Siloxane No. 9 4142 28 8%/1/10 4 Siloxane No. 10 4316 35 8%/2/10 4 Siloxane No. 11 4490 71 8%/3/10 Siloxane No. 12 2914 37 10%/0/10 0.2 Siloxane No. 13 3051 78 10%/1/10 0.4 Siloxane No. 14 3189 110 10%/2/10 1 Siloxane No. 15 3327 100 10%/3/10 1 Siloxane 3780 48 24.9 Footnotes: k. Smear recovery is the amount of time, expressed in seconds, that is needed to recover to 95% of the original reflectance value. The specular reflectance determination procedure, utilizing a 220 micron diameter smear pattern, is more particularly set forth in the above-noted procedure.

1. The prior-art polysiloxane identified in Table 4 is similar to those polysiloxanes disclosed in Examples 1 and 4 of U.S. Pat. No. 2,523,281 to Currie and in Examples 5 through 7 of U.S. Pat. No. 2,698,805 to Currie et al. In such prior-art polysiloxanes, and in that prior-art siloxane presented in Table 4, the L and values are nonexistent.

Siloxane No. 8 is polydimethyl-copolymethylethylundecanoatyl siloxane copolymer. Siloxane No.

9 is polydimethyl-co-polymethylmethoxyethylundecanoatyl siloxane copolymer. Siloxane No. 10 is polydimethyl-copolymethyl ethoxyethoxyethylundecanoatyl siloxane copolymer.

Siloxane No. 11 is polydimethyl-copolymethylethoxyethoxyethoxyethylundecanoatyl siloxane copolymer. Siloxane No. 12 is polydimethyl-copolymethylethylundecanoatyl siloxane copolymer. Siloxane No.

WO 91/17223 PC'/US90/02542 27 13 is polydimethyl-co-polymethylmethoxyethylundecanoatyl siloxane copolymer. Siloxane No. 14 is polydimethyl-copolymethylethoxyethoxyethylundecanoatyl siloxane copolymer.

Siloxane No. 15 is polydimethyl-copolymethylethoxyethoxyethoxyethylundecanoaty1 siloxane copolymer. Siloxane a prior-art compound, is polydimethyl siloxane polymer.

The procedure that was utilized to produce those abovediscussed Siloxanes numbered 1 through 7 was also utilized to produce those Siloxanes numbered 8 through 15, with the following exceptions.

Siloxane No. 8 was produced from poly(92%)dimethyl-copoly(8%)methylhydrosiloxane and the oxygen-containing compound referred to as ethyl undecenoate, where one wellknown procedure for producing this type of oxygen-containing compound is set forth in Vogel's Textbook of Practical Organic Chemistry, 4th ed,, published 1981, at page 512.

Siloxane No. 9 was produced from poly(92%)dimethyl-copoly(8%)methylhydrosiloxane and the o);rgen-containing compound referred to as methoxyethylundecenoate, where one well-known procedure for producing this type of oxygencontaining compound is set forth in the above-cited Vogel text. Siloxane No. 10 was produced from poly(92%)dimethylco-poly(8%)methyihydrosiloxane and the oxygen-containing compound referred to as ethoxyethoxyethylundecenoate, where one well-known procedure for producing this type of oxygencontaining compound is set forth in the above-cited Vogel text. Siloxane No. 11 was produced from poly(92%)dimethylco-poly(8%)methylhydrosiloxane and the oxygen-containing compound referred to as ethoxyethoxyethoxyethylundecenoate, where one well-known procedure for producing this type of oxygen-containing compound is set forth in the above-cited Vogel text. Siloxane No. 12 was produced from poly(90%)dimethyl-co-poly(10%)methylhydrosiloxane and ethylundecenoate. Siloxane No. 13 was produced from poly(90%)dimethyl-co-poly(10%)methylhydrosiloxane and methoxyethylundecenoate. Siloxane No. 14 was produced from orly(90%)dimethyl-co-poly(10%)methylhydrosiloxane and ethoxyethoxyethylundecenoate. Siloxane No. 15 was produced WO 91/17223 US90/02542 28 from poly(90%)dimethyl-co-poly(10%)methylhydrosiloxane and ethoxyethoxyethoxyethylundecenoate.

The results, as shown in Table 4 above, demonstrate that, at comparable molecular weights, the smear-recovery properties of the poly(dimethyl)-co-poly(methyl, oxygencontaining) siloxane copolymers of this invention are superior to the prior-art polydimethyl siloxane presented.

All of our Siloxanes numbered 8 through 15 in Table 4 recover to 95% of their initial specular reflectance in 6 seconds or less, as compared to the prior-art dimethyl siloxane which requires about 25 seconds.

Table 5, below, presents the amount of time that is necessary to achieve a 95% recovery of specular reflection, for those emulsion polish compositions made from other specified poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymers of the present invention, in comparison to specular reflection recovery times of certain emulsion polish compositions made from specific prior-art polydimethyl siloxanes.

The poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxanes, listed in Table 5 as Siloxane Nos. 16 and 17, each had the moiety as its value and the -CH 3 radical as its value.

Table 5: Smear Recovery, Comparative Tests: Poly(dimethyl)-co-poly(methyl, oxygen-containing) Siloxanes Copolymer Copolymer Smear Molecular Viscosity z/n/i Recovery, m Siloxane Polymer Weiht Centipoise Values in sec.

Siloxane "D n 2000 19 11 Siloxane No. 16 2734 22 12%/2/3 3 Siloxane No. 17 3443 18 12%/3/3 2 Siloxane -'E n 3780 48 Footnotes: m. Smear recovery is the amount of time, expressed in seconds, that is needed to recover to 95% of the original reflectance value. The specular reflectance determination procedure, utilizing a 320 micron diameter smear pattern, is more particularly set forth in the above-noted procedure.

WO 91/17223 PC/US90/02542 29 n. The prior-art polysiloxanes identified in Table 5 are similar to those polysiloxanes disclosed in Examples 1 and 4 of U.S. Pat. No. 2,523,281 to Currie and in Examples 5 through 7 of U.S. Pat. No. 2,698,805 to Currie et al. In such prior-art polysiloxanes, and in those prior-art compounds presented in Table 5 as Siloxanes and the and "i" values are nonexistent.

The procedure utilized to produce those Siloxanes numbered 1 through 7 was utilized to produce those Siloxanes numbered 16 and 17 in Table 5, with the following exceptions.

Siloxane No. 16, polydimethyl-copolymethylmethoxyethoxypropylsiloxane, was produced from poly(88%)dimethyl-co-poly(12%)methylhydrosiloxane and the oxygen-containing compound referred to as methoxyethoxyallyl, where one well-known procedure for producing this oxygencontaining compound is set forth in U.S. Pat. No. 4,260,725 to Keogh and Kinzler. Siloxane No. 17, polydimethyl-copolymethoxyethoxyethoxypropylsiloxane, was produced from poly(88%)dimethyl-co-poly(12%)methylhydrosiloxane and the oxygen-containing compound referred to as methoxyethoxyethoxyallyl, where one well-known procedure for producing this oxygen-containing compound is also set forth in U.S. Pat. No. 4,260,725. Siloxanes and both prior-art compounds, are polydimethyl siloxane polymer.

The results, as shown in Table 5 above, demonstrate that, at comparable molecular weights, the smear-recovery properties of the poly(dimethyl)-co-poly(methyl, oxygencontaining) siloxane copolymers of this invention are superior to the prior-art polydimethyl siloxanes presented.

Both of our Siloxanes, numbered 16 and 17 in Table 5, recover to 95% of their initial specular reflectance in 3 seconds or less, as compared to the prior-art dimethyl siloxanes which require 11 and 30 seconds.

The weight-average molecular weight determinations of these copolymeric siloxanes were calculated, based on supplier literature and determined mole percentages of Si-H.

The viscosities of these copolymeric siloxanes were WO 91/17223 iC~c /usQo/02542 30 determined at 25°C, utilizing a Brookfield, model HBT-200, c;ne-and-plate viscometer, a Brookfield model LVT viscometer, or a Bohlin Rheometer. Most viscosities were tetermined at rpm, when utilizing the Brookfield model H 200 viscometer.

The copolymeric siloxanes were applied onto substrate surfaces by spincoating 5 solutions of copolymeric siloxane in 2,2,4-trimethylpentane solvent, onto conventional 2.25 inch by 2.25 inch square nitrocellulose lacquer-coated test slides. The spin-coating procedure utilized was to flood the surface with solution, and then to spin the slide at 500-2500 rpm while the solution dried. Conditions were varied to attain a desired thickness for comparison purposes (2000-4000 Angstroms). Thickness was determined gravimetrically.

The above-mentioned, comparative smear-recovery data for the polymeric siloxanes of the present invention, namely the poly(dimethyl)-co-poly(methylalkyl) siloxane and poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymers, relative to certain prior-art polymeric siloxanes, are thus summarized in Tables What has been described herein are two copolymeric siloxanes that are particularly applicable for inclusion in an emulsion polish composition. While the novel polymeric siloxanes disclosed herein have been discussed with reference to particular emulsion polish compositions, the present invention is not limited to those particular emulsion polish compositions disclosed herein. Indeed, the foregoing specification is intended to be illustrative and is thus not to be taken as limiting. It is therefore anticipated that alternatives, changes or modifications will become apparent to those skilled in the art upon reference to the foregoing detailed description of the present invention. Accordingly, such alternatives, changes and modifications are to be considered as forming a part of our present invention insofar as they fall within the spirit and scope of the appended claims.

4

Claims (9)

1. A surface-treating emulsion polish composition for furniture and similar household items comprising water, at least one hydrocarbon solvent, at least one surfactant, and at least one copolymeric siloxane selected from the group consisting of a poly(dimethyl)-co-poly(methylalkyl) siloxane polymer, a poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane polymer, and combinations thereof, wherein the poly(dimethyl)-co-poly(methylalkyl) siloxane polymer has a weight-average molecular weight of about 2,500 to about 4,000 and the general formula CH 3 CH 3 A CH 3 C H I I CH 3 -S i-CH 3 CH 3 CH 3 CH 3 CH 3 to wherein A is an alkyl radical having 10 to 20 carbon atoms, w is about 70 to about 91 mole percent and x is about 9 to about 30 mole percent of the poly(dimethyl)-co- poly(methylalkyl) siloxane polymer, and wherein the poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymer has a weight-average molecular weight of about 1,000 to about 4,000 and thi. general formula CH 3 CH 3 B CH 3 I I I CH 3 -S i-O]y-[-'Si-O]Z--Si--CH 3 CH 3 CH 3 CH 3 CH 3 wherein B is (CH 2 )i(L)(CH 2 CH 2 0)nR, wherein i is an integer from 3 to 10 inclusive, wherein L is or -COO-, wherein n is either zero or an integer from 1 to 3 inclusive, wherein R is -CH 3 or -C 2 H 5 and wherein y is about 62 to about 92 mole percent and z is about 8 to about 38 mole percent of the poly(dimethyl)-co-poly(methyl, oxygen- containing) siloxane copolymer.

2. The emulsion polish composition of claim 1 wherein the copolymeric siloxane is the poly(dimethyl)-co-poly(methylalkyl) siloxane polymer.

3. The emulsion polish composition of claim 1 or claim 2 wherein x is 10 mole percent and A is selected from the group consisting of Clo, C 1 2 C 14 C 16 C 18 and C 20

4. The emulsion polish composition of claim 1 or claim 2 wherein x is 30 mole percent and A is C 14 The emulsion polish composition of claim 1 wherein the copolymeric siloxane is the poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane copolymer.

6. The emulsion polish composition of claim 5 wherein L is -COO-, R is -C 2 H 5 i is 10, and z is either 8 mole percent or 10 mole percent.

7. The emulsion polish composition of claim 5 wherein L is R is -CH 3 i is 3, z is 12 mole percent, and n is either 2 or 3. [G:\WPUSERJBAA)00021:TCW

8. A surface-treating emulsion polish composition for furniture and similar household items comprising water, at least one hydrocarbon solvent, at least one surfactant, and at least one copolymeric siloxane selected from the group consisting of a poly(dimethyl)-co-poly(methylalkyl) siloxane polymer, as defined in claim 1 and a poly(dimethyl)-co-poly(methyl, oxygen-containing) siloxane polymer as also defined in claim 1, said composition being substantially as hereinbefore described with reference to the Examples excluding any Comparative Examples.

9. The emulsion polish composition of any one of claims 1 to 8 further comprising an aerosol propellant.

10. An aerosol container containing the emulsion polish composition of claim 9. Dated 7 October, 1993 S. C. Johnson Son, Inc. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON I USERIBAA)00021 :TCW SN1 INTERNATIONAL SEARCH REPORT International Application No PCT/US90/02542 I. CLASSIFICATION OF SUBJECT MATTER (II several classification symbols pply, Indicate all) 3 According to International Patent Classification (IPC) or to both National Classifi -rt) n ani IPC IPC C09G 1/00 U.S 106/3 II. FIELDS SEARCHED Minimum Documentation Searched 4 Classification System I Classification Symbols U.S. 106/3, 287.13; 252/305 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Includel in the Fields Searched 6 III. DOCUMENTS CONSIDERED TO BE RELEVANT 14 Category Citation of Document, ir with indication, where appropriate, of the relevant passages It Relevant to Claim No. iu Y US, A, 2,953,047 (TERRY) 04 October 1960 1-7 see entire document Y US, A, 3,929,492 (CHAPMAN ET AL) 30 December 1975 1-9 see entire document Y US, A, 2,770,631 (MERKER) 13 November 1956 1-7 see entire document X CA, A, 746,973 (PATER) 22 November 1966 1-9 Y see entire document 1-9 Special categories of cited documents: i' later document published after the international filing date doment defining the general sate of the art which is not or priority date and not in conflict with the application but document dfining the gneral state of the art which is not cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published an or after the international document of particular relevance: the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance: the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing ts a0 1ot Ih Report 26 JUNE 1990- International Searching Authority I i e of Authorlfed 0 r so ISA/US C. MELISSA BONNER Form PCT/ISA/210 (second sheeti (May 1986)