CA1098041A

CA1098041A - Aerosol propellant from chlorinated alkane, alkane and carbon dioxide for antiperspirant

Info

Publication number: CA1098041A
Application number: CA286,590A
Authority: CA
Inventors: William G. Kiffel; Daniel Grosse
Original assignee: SC Johnson and Son Inc
Current assignee: SC Johnson and Son Inc
Priority date: 1976-09-15
Filing date: 1977-09-13
Publication date: 1981-03-24
Also published as: NL7710068A; DE2741882A1; FR2365621B3; GB1544157A; FR2365621A1; PH17493A

Abstract

ABSTRACT OF THE DISCLOSURE
An improved, substantially non-flammable, non-fluoro-carbon containing propellant system comprising from about 65-85% by weight of a compound selected from 1,1,1-trichloro-ethane, dichloromethane, and mixture thereof, from about 14-32% by weight of a hydrocarbon propellant selected from normal butane, isobutane, propane, and mixtures thereof, and from about 0.5-3.3% by weight carbon dioxide. A substantially non-flammable antiperspirant composition comprising a propellant intermediate comprising 65-85% by weight of propellant inter-mediate of a compund selected from 1,1,1-trichloroethane, di-chloromethane, and mixtures thereof, from about 14-32% by weight of propellant intermediate of a hydrocarbon propellant selected from the group consisting of normal butane, isobutane, propane, and mixtures thereof, from about 0.5-3.3% by weight of propellant intermediate carbon dioxide, and an antiperspir-ant intermediate comprising from about 20-60% by weight of an antiperspirant intermediate astringent salt, from about 20-79%
by weight of an antiperspirant intermediate of an emollient, from about 0-10% by weight of a powder talc, starch, baking soda and mixtures thereof, and from 1-10% by weight of an antiperspirant intermediate of a bulking agent wherein the ratio of propellant intermediate to antiperspirant intermediate is from 33:1 to 2:1.

Description

This invention relates to an improved, substantially non-flammable, non-~luorocarbon containing propellant system and two antiperspirant compositions util~zing the same. More particularly, this invention relates to a carbon dioxide, hy-drocarbon propellant, chloroethane propellant system for use in dispensing antiperspirant compositions having aluminum chlorhydroxide mixed with emollients, bulking agent and per fume.
Recent events have caused concern among a number o~ -manu~acturers o~ antiperspirant compositions. Most antiper-spirant compositions currently sold today are similar to those disclosed in Spitzer British Patent 1,167,173. These composi~
tions are ~luorocarbon type propellants as solvent and propel-lant ~or the active ingredients in the composition. These compositions typically include ~rom 0.2-10~ aluminum chlorhy-droxidej from 2-50~ of an emollienk material, ~rom 0.05-1~ o~
a bulking agent, and f'rom 50-98~ o~ a ~luorinated propellant or mixtures of fluorinated propellants.
Antiperspirant composit~ons of the type disclosed in the above Britlsh patent have ~ound widespread acceptance as the same are both cosmetically acceptable and perceived as e~-~ectîve. HoweverJ since the fluorocarbon propellants act both as the solvent and propellant in these systems, the formulation or preparation o~ a non-fluorina~ed~ hydrocarbon propellant system ~or these type compositions has been most difficult be-cause the hydrocarbon propellants have different density and solubility characteristiçs than the fluorocarbons.
There are currentl~ two general types of formulations sold embodying the disclosure o~ the above British patent: the regular type and the dry powder type. The prime di~ference between these compositions is the dry powder type has a sig~

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nificantly higher percentage of powder components, i.e., the bulking agent, astringent salt, and powder) than the oils in the system. This gives the compositions a dryer or more pow-dery feel on application. The regular type are somewhat wet and oily on application. The propellant systems of the pres-ent invention are ef~ective with either the dry powder type or the regular type antiperspirants.
There have been numerous attempts to formulate pro-pellant systems using l,l,l-trichloroethane or dichloromethane.
Most of these propellant systems have included fluorinated hy-drocarbons and/or non-condensable gases such as nitrous oxide or carbon dioxide. Examples of such disclosures are U.S.
Patent 3,342,672, an article in SOAP ~ CHEMICAL ENGINEERI~G, February 1957 issue at page 99 entitled "Chlorothene in Aerosols1', and an article in AEROSOL AGE, June 1963, page 29, entitled "Blend of Nitrous Oxide and Fluorocarbons". None of the above'articles or patents disclose the concept of utiliz-ing l,l,l-trichloroethane or dichloromethane in combination with a carbon dioxide and a hydrocar'bon propellant to produce a ~ubstantially non-~lammable aerosol spray and more particu-larly to produce a substantially non-flammable antiperspirant composition of the type similar to that disclosed in the above British patent.
Unexpectedly, it has been found that a substantially non-~lammable fluorocarbon-free propellant syctem can be pro-duced comprising from about 65-85~ by weight of a compound se-lected from l,1,1-trichloroethane, dichloromethane, and mix-kures thereof, from about 14-32% by weight of a hydrocarbon propellant, and from about 0.5-3~3% by weight carbon dioxideO
Also, it has been unexpectedly found that an effective and cosmetically acceptable antiperspirant composition can be pre

-2-pared by mixing the above propellant with an antiperspirantintermediate comprising rrom about 20-60% by ~eight based on antiperspirant intermediate astrlngent salt, from about 20-79 by weight based on antiperspirant intermediate emollients, ~rom about 0-10~ by weight o~ a powder selected ~rom talc~
starch, baking soda and mixtures thereo~, and from about 1-10%
by weight based on antiperspirant intermediate bulking agent in a ratio of propellant to antiperspirant intermediate o~
~rom 33 1 to 2:1.
It is, therefore, the primary ob~ect of the present invention to provide a substantially non-~lammable, ~luoro-carbon-free propellant system.
It is a ~urther object of the present invention to provide a substantially non-flammable, fluorocarbon~free anti-perspirant composition.
It is a still further object o~ the present inven-tion to provide a substantially non-~lammable, fluorocarbon-~ree propellant system utilizing conventional antiperspirant intermediate compositions.
It is a ~urther obJect o~ the present`invention to provide a substantlally non-flammable propellant system includ-ing hydrocarbon and carbon dioxide.
Stlll further objects and advantages of the propel-; lant system and antiperspirant composition o~ the invention will become more apparent ~rom the ~ollowing more detailed de-scription.
This invention relates to a substantially non-flam-mable, non-fluorocarbon propellant system comprising from about 55-85% by weight of a compound selected from the group consisting of 1~13 l-trichloroethane, dichloromethane, and mixW
tures thereof, ~rom about 14 32~ by weight o~ a hydrocarbon ~(~9~

propellant selected from normal butane, isobutane, propane, and mixtures thereof, and ~rom about 0.5-3.3~ by weight of carbon dioxide.
The invention further resides in a substantially non-flammable antiperspirant composition comprising a propel-lant intermediate comprising from about 65-85~ by weight based on propellant intermediate of a compound selected from the group consisting of l,l,l-trichloroethane, dichloromethane, and mixtures thereof, from about 14-32% by weight based on ; 10 propellant intermediate of a hydrocarbon propellant selected : from the group consisting of normal butane, isobutane, propane, and mixtures thereof, from about 0.~5-3.3~ by weight based on propellant intermediate of carbon dioxide, and an antiper-spirant intermediate )comprising from about 20-60% by weight based on antiperspirant intermediate astringent salt, from about 20-79% by weight based on antiperspirant intermediate emollient, up to about 10~ of a powder selected ~rom talc~
starch3 sodium bicarbonate, and mixtures thereof, and from ~ about 1-10% by weight based on antiperspirant intermediate of a bulking agent, wherein the ratio of propellant intermediate to antiperspirant intermediate is within the.range of from .
.
about 3~:1 to 2:1. :
The propellant compositlons o~ the present invention ~: comprises a first ingredient from about 65-85~ by weight of a .
compound selected ~rom the group consisting o~ l,l,l-trichloro-ethane, dichloromethane, and mixtures thereof, pre~erably from about 70-80% by weight the compound,~ and most preferably from about 74-76.5% by weight the compound... The preferred compound - .
is l,l,l-trichloroethane. The compounds are most important ln the composltion o~ the present invention since they have a solubilizing e~fect on the carbon dioxide which enables the 8ai~

carbon dioxide to be used without high loss of vapor pressureduring the use of the aerosol product. Also the propellant compositions can be used in con;junction with a vapor tap valve. This is not possible with normal carbon dioxide sys-tems. Furthermore~ the above compounds have a density and physical properties similar to those of the fluorinated hydro-carbon propellants previously widely used in antiperspirant type compositions. E'or this reason the above compounds de-press the effective vapor pressure o~ the composition and sol-ubilizes the propellants in the active ingredient oils.
The hydrocarbon propellants used in the present in-vention are the conventional~hydrocarbon propellant materials such as normal butane, isobutane~ and propane. Mixtures o~
these materials also may be used and are advantageously used to obtain the desired pressure in combination w~th the carbon dioxide compressed gas material. The hydrocarbon propellants are present in the propellant system in an amount o~ ~rom about 14-32% by weight and pre~erably from about 14-26~ by weight and most pre~erably from ~rom 21-24% by weight. The pre~erred hy~
drocarbon propellant is a blend ~rom 70-90% isobutane and 10-30% propane which gives a vapor pressure ln the range o~ 40-52 psig and the most preferred is a blend of 80% isobutane and 20%
propane which glves a vapor pressure o~ 46 psig.
The third ingredient in the propellant composition of the present invention is carbon dioxide. Carbon dioxide is present in an amount of from about 0.5-3.3% and preferably from about 1.0-2.5~ and most pre~erably ~rom about 1.5-2.5~ by weight. The carbon dioxide adds a vapor pressure to the compo-sitions o~ the present invention while at the same time not appreciably adding to the ~lammability o~ the same.
The compositions utilizing the propellant system o~

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the present invention are substantially non-rlammableO To be classed as "substantially non flammable" as these words are used in the instant speci~ication or claims, the composition must be non-flammable when tested by either the flame exten-sion test or the c105 ed drum test as published in the Test Proceedings of the Chemical Specialties Manu~acturing Associa-tion. To be considered non-~lammable in the flame extension test, a spray of the antiperspirant across an open flame of a plumber's candle should not extend the flame more than 18 inches. With regard to the closed drum test~ the aerosol can should be able to be sprayed into a closed drum ~or a period of greater than 60 seconds before the candle contained in the drum causes an explosion. Some of the compositions included within the claims of the present invention may be classed as flammable by one or the other o~ the~e"~s~. However, the pre~erred compositions are not Plammable when tested by both o~ these methods.
Generally, it is most desirable that the initial pressure in pounds per square inch gauge at 70F. be within the range of 25-75 psi. Within this pressure range, the com-positions will be adequately dispensed ~rom the container while insuring a margin oP saPety against expLosion in the vent the containers are subjected to extreme temperature.
Also, an important ~actor in the ~lammabillty char-acteristics oP antiperspirant and aerosol compositions is the discharge rate o~ the composition. The discharge rate can be varied greatly depending on the particular valve orifices used in the aerosol valve. However, for most conventional aerosol valves of the type commonly used in antiperspirant compositions having a vapor tap orifice of from 0.010-0.050 -in.~ a stem ori~ice oP from 0.10-0.50 in., a button ori~ice o~ from 0.010-0.050 in., and any conventional dip tube, the compositionswithin the range of the present invention will be considered substantially non-~lammable. The pre~erred valve has a vapor tap o~ 0.135 in., a stem orifice o~ 0.020 in.~ a button ori~ice of 0.018 in. J and uses a capillary type dip tube having a di-ameter of 0.040 in. Generally, these compositions have an initial discharge rate o~ from 0.55 gram per second ko 1.0 grams per second.
The propellant composition of the present invention can be used with substantially any a;erosol intermediate in a ;2 : I
ratio of propellant to intermediate o~ from 33:1 to 1-:~, al-, :
- ~ though a non-aqueous intermediate is pre~erred. The propellant composition is speci~ically adapted to be used with antiper-spirant type compositions wherein the ratio of propellant to antiperspirant intermediate which comprises astringent, emol-lient, and bulking agent in a ratio of propellant to antiper-spirant intermediate of from 33:1 to 2:1 and preferably ~rom 20:I~to 4:1, and most pre~erably 15:1 to 7:1 and optimally ~rom about 10:1 to 8:1.
These antiperspirant compositions, as described in the above-noted ~ritish patent, include an astringent salt selected from ~inc chloride, zinc su1fate, zinc sul~ocarbo1ate, aluminum sul~ate,~aluminum chloride, aluminum sul~ocarbo1ate, aluminum chlorhydrate~ zirconium chloride~ zirconium tetra chloride, and ~irConium sulfate. These astringent salts are generally found in the ankiperspirant intermediate of the corn-position o~ the present invention in an amount ~rom about 20~
60~ by ~Aeight based on antiperspirant intermediate, and pre~er-ably from about 25-40% by weight based on an antiperspirant intermediate and most preferably from about 30-35% by weight based on antiperspirant intermediate.

The compositions also include an amolli.ent type material which is generally non-volatile, non-hydroscopic liquid. These materials may be selected from a wide range of materials such as organic esters including isopropyl myristate, isopropyl palmitate, 2-ethylhexyl laurate, the various esters as disclosed in U.S. Patent 3,833,720, including Cl-C4 alkyl lactate, diCl-C4 alkyl succinate, diethyl malate, diethyl maleate, diC2-C4 alkyl tartarate, diCl-C4 alkyl glutarate, dimethyl adipate, and diethyl adipate; certain polyalkylene glycols such as the Ucon fluids supplied by Union Carbide and disclosed in U.S. Patent 2,425,755, such as the monohydro~y . .
o~yethylene, oxy 1,2-propylene aliphatic monoethers wherein the aliphatic monoether group has from 1 to lO carbon atoms, the ratio of oxy-1,2-propylene to o~yethylene being at least 0.33:1 and having a molecular weight of at least 500, alcohols such as lauryl alcohol, carboxylic acids such as maleic acids, and silicone oils such as dimethyl polysiloxanes and various volatile silicone oils. These emol.lient materials may be present in the antiperspirant intermediate of the compositions of the present invention from about 20~79% by weight based on -: antiperspirant intermediate, preferably from about 56-72.5% by : weight based on antiperspirant intermediate, and most prefer-ably from about 61.5-67.5% by weight based on antiperspirant intermediate. ~ .
A maior optional component is a powder added to the dry powder type to enhance the cosmetic properties of the com-position. These powders are present in amounts of up to about lO~ by weight of the antlperspirant intermediate, and prefer~
ably from about l-5~ by weight. Suitable powders include talc, starch, including starch derivatives, baking soda or sodium bicarbonate) and mixtures of these materials.
Lastly, it is desirable to include a small amount of a bulking agent in the compositions of the present invention.
3xamples of such materials are hydrophoblc treated clays which swell in organic solvents such as hydrophobic bentonite includ-ing the reaction products of bentonite and dimethyldistearyl ammonium chloride, colloidal silicas~ montmorillonite clays, and grease-forming soaps such as aluminum stearates. General-ly these materials are present in small amounts in the compo-sition of the present invention from about l-lO~ and preferably from about 2.5-4~ and most preferably about 2.5-3.5~ by weight based on antiperspirant intermediate.
~ he antlperspirant compositions also may include a variety of other optional ingredients including perfume in an amount from 0.1-2.0~ by weight based on the weight of the pro- '~
pellant and antiperspirant intermediate as well as small amounts of preservatlves and other conventional additives.
The compositlons o~ the present invention will now be lllustrated by way'of the following examples wherein all the part~ and percentages are by weight and all temper~tures in degrees F~hrenheit.
EXAMPL~ A
An antiperspirant intermediate ls prepared~having khe ~ollowing composition: ' Aluminum chlorhydroxide33.00 Isopropyl myristate 62.00 ,I Pumed silica (Cabosil M-5)3.00 Perfume r 2.00 100. 00 This intermediate is prepared by blending the ingre-, dients together at ~oom temperature to ~orm Antiperspirant Clen~es ILr~de ~nAI`fC~

Intermediate A.
EXAMPLES 1-4 and GOMPARATIVE EXAMPLE 1 A series of antiperspirant aerosol compositions are filled into 3-piece tinplate containers to a ~ill weight of 200 grams. The containers are fitted with a valve including a vapor tap valve. The compositions are shown in Table I.
TABLE I
1,1)1- 20~ Initial Flammability tri- Propane Discharge ' CO chloro- 80~ Rate Flame Closed Ex. Int. A. ~ 2 ethane' Isobutane g_sec. Ext. ~rum CE 1 10.0 -~ 67 23.00 0.50 No No 1 10.0 5 67 22.~0 o.65 No No 2 1Ø01.00 67 22.00 0.70 No

3 10.02.00 67 21.00 o.86 No No

4 10.03. do 67 20.00 0.95 No Yes The above examples show the effect of,increas,ing the C2 level. At abov~ 3.0% C02, the can pressure becomes exces-sive. With no C02, the discharge ra,te is too low to be e~fec-tive.
EXAMPLES 5-8 and COMPARATIVE EXAMPLE 2 A series o~ antiperspirant compositions as shown in Table II are prepared keeping the C02 constant.
As shown in Table II, as the hydrocarbon propellant ls increased, the flammability increases. HoweverJ composi-tions within the limits of the present invention are substan-tlally non-flammable. Further, the application properties of the above compositions are excellent ~3~ ' A series of antiperspirant compositions is prepared with the hydrocarbon propellant constant. The compositions are shown in Table II.

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TABLE II
1,1,1- 20S~ Initial Flammability tri- Propane Di~charge C0 chloro- 80~ Rate Flame Closed ~x. Int. 2 ethane Isobutane g/sec. Ext. Drum CE 2 10 2. 0 55. 0 33 0. 82 No Yes lo 2.0 60.0 28.0 o.80 No Yes 6 10 2.0 65.o 23.0 o.84 No Yes 7 10 2. 0 70. 0 18. 0 0.90 No l!~o 8 10 2. 0 75. 0 13. 0 0. 84 No No g 10 5 69. 5 20. o 0. 60 No No o lo l.o 6g.o 20. 0 0. 72 No No 11 10 2.0 68.o 20.0 0.87 No No EXAMP~E 12 A series of antiperspirant compositions was prepared with the following hydrocarbon propellants substituted for the 20~ propane~ 80~ isobutane:
A Normal butane B Isobutane C 45% n-butane, 55~ propane ' , D Propane ach o~ the above were tested for flammability. A
and B were non-flammable by both methods, while C and D were non-flammable by the ~lame extension test but were considered f'lammable by the closed drum.
~ : :
Examples 2 to ~ were repeated except,that methylene chloride was substituted for the l~ trichloroethane. The compositions and results o~ the flammability tests are shown in Table III.

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TABLE III
ao~ Flammability Pro~ane C0 Methylene ~0% Flame Closed xt. Int. A. _ 2 Chloride Isobutane Ext. Drum 13 10.0 1.0 67.o 22.0 No No 14 10.0 2.0 67~o 21.0 No No 10.0 3.0 67.o 20.0 No No The above shows the substantial equivalence between l,l,l-trichloroethane and methylene chloride.

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Claims

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A substantially non-flammable, non-fluorocarbon propellant system comprising from about 65-85% by weight of a compound selected from the group consisting of 1,1,1-trichloro-ethane, dichloromethane, and mixtures thereof, from about 14-32% by weight of a hydrocarbon propellant selected from normal butane, isobutane, propane, and mixtures thereof, and from about 0.5-3.3% by weight of carbon dioxide.

2. The system of claim 1 which comprises 70-80% by weight of said compound, 14-26% by weight of said , and 1.0-2.5% by weight carbon dioxide.

3. The system of claim 1 wherein said hydrocarbon is a blend of 80% isobutane and 20% propane.

4. The system of claim 3 which comprises 74-76.5%
by weight of said compound, 21-24% by weight of said hydro-carbon, and 1.5-2.5% by weight carbon dioxide.

5. The system of claim 1 wherein said compound is 1,1,1-trichloroethane.

6. The system of claim 2 wherein said compound is 1,1,1-trichloroethane.

7. The system of claim 4 wherein said compound is 1,1,1-trichloroethane.

8. A substantially non-flammable antiperspirant composition comprising a propellant intermediate comprising from about 65-85% by weight based on propellant intermediate of a compound selected from the group consisting of 1,1,1-tri-chloroethane, dichloromethane, and mixtures thereof, from about 14-32% by weight based on propellant intermediate of a hydro-carbon propellant selected from the group consisting of normal butane, isobutane, propane, and mixtures thereof from about 0.5-3.3% by weight based on propellant intermediate of carbon dioxide, and an antiperspirant intermediate comprising from about 20-60% by weight based on antiperspirant intermediate of astringent salt, from about 20-79% by weight based on anti-perspirant intermediate of emollient, up to about 10% by weight of the antiperspirant intermediate of a powder selected from talc, starch, sodium bicarbonate, and mixtures thereof, and from about 1-10% by weight based on antiperspirant intermediate of a bulking agent, wherein the ratio of propellant intermediate to antiperspirant intermediate is within the range of from about 33:1 to 2:1.

9. The composition of claim 8 wherein the propellant intermediate comprises from 70-80% by weight based on propel-lant intermediate of said compound, 14-26% by weight based on propellant intermediate of hydrocarbon, and 1.0-2.5% by weight based on propellant intermediate of carbon dioxide.

10. The composition of claim 8 wherein the propel-lant intermediate comprises from 74-76.5% by weight based on propellant intermediate of said compound, 21-24% by weight based on propellant intermediate of hydrocarbon, and 1.5-2.5%
by weight based on propellant intermediate of carbon dioxide.

11. The composition of claim 8 wherein the hydro-carbon is a mixture of from 70-90% by weight based on hydro-carbon of isobutane and 10-30% by weight based on hydrocarbon of propane.

12. The composition of claim 10 wherein the hydro-carbon is 80% by weight of hydrocarbon of isobutane and 20%
by weight of hydrocarbon of propane.

13. The composition of claim 8 wherein said compound is 1,1,1-trichloroethane.

14. The composition of claim 9 wherein said compound is 1,1,1-trichloroethane.

15. The composition of claim 10 wherein said com-pound is 1,1,1-trichloroethane.

16. The composition of claim 11 wherein said com-pound is 1,1,1-trichloroethane.

17. The composition of claim 9 wherein the antiper-spirant intermediate comprises from about 25-40% by weight based on antiperspirant intermediate of astringent salt, from about 56-72.5% by weight based on antiperspirant intermediate of emollient and from about 2.5-4% by weight based on antiper-spirant intermediate of the bulking agent.

18. The composition of claim 10 wherein the anti-perspirant intermediate comprises from about 30-35% by weight based on antiperspirant intermediate of astringent salt, from about 61.5-67.5% by weight based on antiperspirant intermediate of emollient, and from about 2.5-3.5% by weight based on anti-perspirant intermediate of bulking agent.

19. The composition of claim 8 wherein the astrin-gent salt is selected from the group consisting of zinc chlo-ride, zinc sulfate, zinc sulfocarbolate, aluminum sulfate, aluminum chloride, aluminum sulfocarbolate, aluminum chlorhy-drate, zirconium chloride, zirconium tetrachloride, zirconium sulfate, and mixtures thereof.

20. The composition of claim 8 wherein the emollient is selected from the group consisting of isopropyl myristate, isopropyl palmitate, 2-ethylhexyl laurate, C1-C4 alkyl lactate, diC1-C4 alkyl succinate, diethyl malate, diethyl maleate, diC2-C4 alkyl tartarate, diC1-C4 alkyl glutarate, dimethyl adipate, and diethyl adipate; monohydroxy oxyethylene, oxy-1,2-propylene aliphatic monoethers wherein the aliphatic monoether group has from 1 to 10 carbon atoms, the ratio of oxy-1,2-propylene to oxyethylene being at least 0.33:1 and having a molecular weight of at least 500, lauryl alcohol, maleic acid, and dimethyl polysiloxane, volatile silicone oils, and mixtures thereof.

21. The composition of claim 8 wherein the bulking agent is selected from the group consisting of hydrophobic bentonite, the reaction products of bentonite and dimethyldi-stearyl ammonium chloride, colloidal silica, montmorillonite clay, aluminum stearate, and mixtures thereof.

22. The composition of claim 8 wherein the ratio is 20:1 to 4:1.

23. The composition of claim 9 wherein the ratio is 15:1 to 7:1.

24. The composition of claim 10 wherein the ratio is 10:1 to 8:1.

25. The composition of claim 19 wherein the astrin-gent salt is aluminum chlorhydrate.

26. The composition of claim 20 wherein the emol-lient is selected from the group consisting of isopropyl my-ristate, isopropyl palmitate, 2-ethylhexyl laurate, and mix-tures thereof.

27. The composition of claim 21 wherein the bulking agent is selected from the group consisting of bentonite, colloidal silica, and mixtures thereof.