Wax formulations

This invention relates to liquid poly(alpha-olefins) in wax solutions or emulsions which when applied to surfaces (such as by way of illustration and not of limitation vinyl, leather, rubber, elastomers, natural and synthetic polymers, sealed and finished wood, painted or enameled metal such as automobile finishes, etc.) are capable of cleaning, preserving, renewing, restoring and improving the appearance, etc., thereof so as to yield a high gloss finish which is durable and has high resistance to water and detergent wash-off. The preferred embodiment contains the liquid poly(alpha-olefins) in conjunction with silicones and most preferably with metal salts such as zinc salts.

Heretofore, various formulations have been used to clean, preserve, 
restore, renew, improve, etc., the appearance of surfaces including vinyl, 
leather, rubber, elastomers, natural and synthetic polymers, sealed and 
finished wood, painted metal, such as automobile finishes, etc. These 
formulations generally contain the following: 
a. Wax or blend of waxes such as carnauba, synthetic waxes, etc., in a 
solvent system, 
b. Aqueous emulsions of waxes with some solvents, 
c. Aqueous emulsions of waxes and silicones with some solvents, 
d. Silicones, e.g., unsubstituted or substituted dimethylpolysiloxane 
fluids or mixtures of these in aqueous emulsions, 
e. As above but featuring some additives, such as polyols, like glycerine, 
diethyleneglycol, etc. 
Formulations of the type a, b, and c which require generally cumbersome 
application procedures (buffing), are overall inefficient in producing 
high gloss, and are subject to build-up. Formulations of the type d and e 
show little of the above mentioned problems and are capable of producing 
very high gloss and demonstrable improvements in general appearance. None 
of the above formulations are durable and generally show little resistance 
to wash off when exposed to water or detergents. However, it is highly 
desirable that formulations should not only retain the initial efficiency 
in terms of gloss and appearance improvements but also feature durability 
and resistance to water and detergent wash-off. 
The following are examples of formulations which have been employed to 
solve this problem. 
1. U.S. Pat. No. 3,956,174 has attempted to solve the problem by 
incorporating polyols in their formulation Armour--All.RTM.. Testing of 
such modified formulation failed to show durability and resistance to 
wash-off by water or detergents. 
2. Others have attempted to improve the resistance of their formulations to 
wash-off by water or detergents through the use of silicone resins like 
General Electric's SR131 resin or by employing specialty waxes such as 
American Hoecht's E and F waxes in a solvent system. Some definite 
improvement can be confirmed in testing these systems on automotive 
finishes. However, these formulations offer no distinct advantages when 
used on vinyl, leather, rubber and elastomers. 
3. Others attempted to improve the resistance to wash-off of such a product 
by water and detergents through the incorporation of amino functional 
silicones, such as Dow Corning's DC531 or DC536 fluids. These water 
emulsion formulations generally resulted in products subject to 
instability and were generally found to offer little improvement, if any. 
We have now discovered that liquid hydrocarbon polymers in wax solutions or 
emulsions which when applied to surfaces (such as by way of illustration 
and not of limitation vinyl, leather, rubber, elastomers, natural and 
synthetic polymers, sealed and finished wood, painted or enameled metal 
such as automobile finishes, etc.) are capable of cleaning, preserving, 
renewing, restoring and improving the appearance thereof, etc., so as to 
yield a high gloss finish which is durable and has high resistance to 
water and detergent wash-off. The preferred embodiment employs the liquid 
hydrocarbon polymer in conjunction with silicones and most preferably in 
conjunction with metal salts such as zinc salts. 
The liquid hydrocarbon polymers of this invention are prepared in the 
manner of U.S. Pat. No. 2,937,129 which is, by reference, incorporated 
into the present application as if part hereof. 
Thus, the hydrocarbon starting material comprising primarily alpha-olefins 
is polymerized in the presence of a free radical catalyst at low pressure 
but sufficient to keep the reactants and product from vaporizing. In 
practice, one employs temperatures of from about 40.degree. to 250.degree. 
C. and pressures of less than about 500 psi for a period of 7 to 20 
half-lives of the free radical catalyst, and a molar ratio of free radical 
catalyst to hydrocarbon of about 0.005 to 0.35. 
Alpha-olefins may be polymerized to obtain the hydrocarbon polymers of this 
invention. These include alpha-olefins of the formula RCH.dbd.CH.sub.2 
where R is a hydrocarbon group, such as where R has 3-18 carbons, for 
example 5 to 15 carbons, but preferably 8 to 12 carbons. Typical 
alpha-olefins include the following: hexene-1, heptene-1, octene-1, 
decene-1, undecene-1, dodecene-1, tetradecene-1, etc. 
A typical liquid poly(alpha-olefin) is prepared according to U.S. Pat. No. 
2,937,129. Specifically, dodecene-1 was polymerized according to the 
procedure of Example 3 of U.S. Pat. No. 2,937,129 which is incorporated 
herein as if part hereof. 
VYBAR.RTM. 825 which is prepared in the manner of Example 3 of U.S. Pat. 
No. 2,937,129 is a commercial poly(alpha-olefin) polymer of the Bareco 
Division of Petrolite Corporation, having the following properties. 
__________________________________________________________________________ 
Property Test Method 
Units VYBAR.RTM. 825 
__________________________________________________________________________ 
Melting Point ASTM D-36 Mod. 
.degree.F. (.degree.C.) 
N/A 
Pour Point ASTM D-97 .degree.F. (.degree.C.) 
-30 (-34.4) 
Viscosity 
@ 32.degree. F. 
(0.degree. C.) 
ASTM D-2669 
Centipoise 
6400 
@ 50.degree. F. 
(10.degree. C.) 2800 
@ 100.degree. F. 
(37.8.degree. C.) 
ASTM D-3236 530 
@150.degree. F. 
(65.6.degree. C.) 157 
@ 210.degree. F. 
(98.9.degree. C.) 54 
@ 250.degree. F. 
(121.degree. C.) 31 
@ 300.degree. F. 
(149.degree. C.) 18 
Penetra- 
tion @ 77.degree. F. 
(25.degree. C.) 
ASTM D-1321 
0.1 mn N/A 
@ 110.degree. F. 
(43.degree. C.) 
@ 130.degree. F. 
(54.degree. C.) 
@ 140.degree. F. 
(60.degree. C.) 
Density 
@ 75.degree. F. 
(24.degree. C.) 
ASTM D-1168 
grams/cc 
0.86 
@ 200.degree. F. 
(93.degree. C.) -- 
Iodine 
Number ASTM D-1959 
cg 1.sub.2 /g sample 
30 
Color ASTM D-1500 0.0 
__________________________________________________________________________ 
N/A Not Applicable 
A wide variety of waxes can be employed in this invention. In general, an 
emulsifiable wax is preferred. These include waxes containing chemical 
groups which facilitate emulsification such as carboxylic or related 
groups. Examples of emulsifiable waxes include the following: 
(1) oxygen-containing wax or oxidized waxes as illustrated by those 
described in the following patents: 
natural waxes such as Candellila, carnauba, beeswax, Coconut wax, montan 
wax (i.e. Hoechst waxes), as well as oxidized petroleum waxes as 
illustrated by U.S. Pat. Nos. 2,879,237-241; 3,163,548; 4,004,932, etc. 
(2) carboxylic adducts such as maleic and related added to waxes such as 
those described in the following U.S. Pat. Nos.: 
3,933,511; 3,933,512, etc. Typical examples are esters, amides, 
ester-amides, etc. of compositions of one or more of the formulae 
disclosed in U.S. Pat. Nos. 3,933,511; 3,933,512 (which patents are, by 
reference, incorporated herein as if part hereof), such as where R is the 
wax moiety; i.e. esters, amides, ester-amides of the following formulae: 
##STR1## 
where n is, for example 1-5, or even 25 or more in certain instances. 
These are sold by Petrolite Corporation's Bareco Division under the 
CERAMER.RTM. trademark. 
This invention includes at least one organopolysiloxane fluid. These fluids 
are also referred to as silicone fluids and are distinguished from 
silicone elastomers and resins. They are basically dimethylpolysiloxane 
fluids, which are substantially linear in nature. The structure of the 
dimethylsilicone fluid is shown by the following general formula where n 
is the number of units: 
##STR2## 
By substitution of some of the methyl groups with other organic or organo 
functional groups, such as vinyl, phenyl, trifluoropropyl, and amino, 
other organopolysiloxane fluids can be produced. The table shown on the 
following page, shows the properties of various unsubstituted 
dimethylsilicone fluids as well as those dimethylsilicone fluids having 
between 10 mole percent to about 35 mole percent substitution of phenyl 
groups. 
TABLE I 
______________________________________ 
Substituted 
Dimethylsilicones 
Unsubstituted 10% 25% 45% 
Dimethyl- Phenyl Phenyl Phenyl 
silicones Methyl Methyl Methyl 
______________________________________ 
Viscosity, 
100 1,000 10,000 
100 100-150 
500 
Cstk. at 
25.degree. C. 
Specific 0.97 0.97 0.97 
##STR3## 
N.sub.n .sup.25 
1,403 1,404 
Flash pt. 
600 600 600 520 570 
Min. .degree.F. 
(Open) Cup 
Dielectric 
2.74 2.76 2.7 
Constant 
V.T.C.* 0.60 0.62 0.61 0.62 0.76 0.83 
Freezing -67 -58 -50 
Pt. .degree.F. 
Thermal .00037 .00038 
Conduct- 
ivity** 
Surface 21 21 21 
Tension, 
Dynes 
Per CM. 
at 25.degree. C. 
Specific Heat 
0.35 0.35 
Gal/G.degree. C. 
______________________________________ 
##STR4## 
where V.sub.100 is the viscosity 
##STR5## 
- 
Generally organopolysiloxane fluids are available as mixtures of polymers 
of varying chain length. It has been found for purposes of the invention 
that the viscosity of the silicone fluids is a measure of the 
effectiveness. Silicone fluids can be used which have a viscosity range up 
to about 100,000 centistokes up to about 10,000 centistokes. Most 
preferably, the viscosity is in the range of about 300-400 centistokes. 
Apparently, as the viscosity becomes too great, there is difficulty in 
penetration of the silicone fluids into the surface to be protected. When 
the viscosity becomes too low, the average chain length of polymer is 
apparently too small to provide adequate protection. 
The exact choice of an organopolysiloxane fluid or fluid mixture as 
described above, will depend upon the identify of the surface to be 
protected. It has been found that for most applications, the standard 
unsubstituted dimethylpolysiloxane fluid is an excellent choice. In other 
instances, it has been found that the inclusion of up to about 10% by 
weight, based on the weight of the dimethylpolysiloxane fluid, of a 
commercially available amino-substituted dimethylpolysiloxane fluid 
provides increased adherence to the surface to be protected. This 
combination is particularly advantageous for treatment of metal surfaces. 
The use of the phenyl and other substituted dimethylpolysiloxane fluids is 
a matter of choice, depending upon the material to be treated and/or the 
environmental stress to which the surface will be exposed. 
The silicone fluid or mixture of fluids is used in the form of a water 
emulsion. The amount of water which can be used is preferably from about 
65% to about 660% by weight, based on the weight of the silicone fluid. 
However, the amount of water can be as high as about 5000% by weight if 
desired. 
It is believed that the small particle size of the silicone in the emulsion 
(usually less than about 1/2 micron) greatly facilitates penetration of 
the silicone into the surface to be protected. 
Emulsions of silicone fluids in water are available from several major 
chemical companies, including for example, General Electric Company; 
Silicone Products Department of Waterford, New York; Union Carbide 
Corporation; Silicones Division of West Virginia; and Dow Corning 
Corporation of Midland, Michigan. The silicone emulsions usually contain 
from about 35% to about 50% by weight of a silicone fluid or fluid 
mixture, with the remainder being mostly water and small amounts of 
emulsifier and adjuvant materials such as a rust inhibitor. A typical 
emulsion contains 35 parts by weight dimethylpolysiloxane, 10 parts by 
weight of an emulsifier, such as nonylphenol, 5 parts by weight of a rust 
inhibitor, such as sodium nitrite, and 65 parts by weight of water. 
A wide variety of metal salts such as zinc salts can be employed in the 
composition of this invention. In general, the preferred form of metal 
salts added comprises zinc salts, preferably zinc carbonates and 
carboxylates, as illustrated by zinc octoate and zinc ammonium carbonate.

The following examples are presented for purposes of illustration and not 
of limitation. 
EXAMPLE 1 
A high viscosity emulsion dressing of about 20-40 poises was prepared 
according to the present invention as follows: 
Part A 
Molten wax (4.25 parts of CERAMER.RTM. 67) was added to: 
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Component Parts by Weight 
______________________________________ 
Zinc octoate at 18% Zn 
0.12 
Diethanolamine 0.35 
______________________________________ 
When the addition was complete the temperature of the mixture was raised 
above 113.degree. C. for about 5 minutes. 
In Part B deionized water was added at 15 parts to a separate, master 
vessel and then preheated to about 96.degree. C. Next, ammonium hydroxide 
at 0.17 parts was added to the hot water with the necessary precautions 
against its loss. Part A was slowly added with vigorous agitation to Part 
B which was subsequently cooled to room temperature by mixing in 10 parts 
of deionized water at 15.degree.-26.degree. C. 
In Part C and to a separate vessel were added: 
______________________________________ 
Component Parts by Weight 
______________________________________ 
An emulsion of dimethyl poly- 
siloxane having a viscosity of 
about 1000 cps and solids at 50% 
3.80 
An emulsion of dimethyl poly- 
siloxane having a viscosity of 
about 60,000 cps and solids at 35% 
5.00 
Rohm & Hass' Triton X-45 
1.50 
Deionized water 27.00 
______________________________________ 
The blend of the above silicone emulsions and Triton X-45 was premixed for 
10 minutes. Mixing was maintained with deionized water being added and 
then continued for 10-15 minutes prior to adding Part C (with mixing) to 
combined Parts A and B. 
In Part D, the following were added to a separate vessel: 
______________________________________ 
Component Parts by Weight 
______________________________________ 
Isopropyl Alcohol 1.00 
Methyl Paraben 0.05 
Propyl Paraben 0.05 
Hydrocarbon Solvent 15.00 
Poly(alpha-olefin) 
(VYBAR.RTM. 825 Petrolite Corporation, 
Bareco Division) 5.20 
______________________________________ 
The methyl and propyl parabens were predissolved in isopropyl alcohol. 
Hydrocarbon solvent and VYBAR.RTM. 825 were then added and mixed for 10 
minutes or until uniform. Following this, Part D was added (with mixing) 
to combined Parts A, B, and C. 
In Part E, a 2% solution of Carbopol 934 (which is carboxy vinyl polymer 
sold by B. F. Goodrich Co.) was prepared by mixing it with 98% of 
deionized water until homogeneous and having constant viscosity. 
Added with mixing were 10.93 parts of the 2% Carbopol 934 to the combined 
Parts A, B, C and D. The mixing was continued for 15 minutes. Following 
this a premixed blend of the following were added with mixing: 
Part F 
______________________________________ 
Component Parts by Weight 
______________________________________ 
Morpholine (Dow Chem. Co.) 
0.27 
Deionized water 0.31 
______________________________________ 
The completed batch was mixed until homogeneous. 
The process of example 1 was repeated to prepare the following emulsion 
dressings of various viscosities. The viscosity of the emulsion dressing 
was varied by changing the concentrations of (1) Carbopol 934, (2) 
VYBAR.RTM. 825, (3) Solvents, (4) Waxes and emulsifiers and adjusting the 
pH to 9.5 using ammonium hydroxide to yield the products of the following 
examples: 
(Ex. 2) a low viscosity emulsion dressing (about 1-9 poises) 
(Ex. 3) a medium viscosity emulsion dressing (about 10-19 poises), and 
(Ex. 4) a very high viscosity emulsion dressing (above 40 poises). 
The following are representative examples of the preferred ratios of 
ingredients which can be employed to yield suitable products. 
______________________________________ 
Component Parts by Weight 
______________________________________ 
Poly(alpha-olefin) (VYBAR.RTM. 825) 
0.60 to 8.00 
Wax 0.50 to 6.00 
Zinc Octoate at 18% Zn 
0.05 to 0.50 
Diethanolamine 0.10 to 0.80 
Deionized water 84.93 to 21.90 
silicone emulsion.sup.1 
2.00 to 10.00 
silicone emulsion.sup.2 
2.00 to 10.00 
Triton X-45 0.10 to 3.00 
Isopropyl alcohol 0.10 to 3.00 
Methyl Paraben 0.01 to 0.10 
Propyl Paraben 0.01 to 0.10 
Hydrocarbon Solvent 6.00 to 20.00 
Carbopol 2% solution 4.00 to 16.00 
Morpholine 0.10 to 0.60 
______________________________________ 
.sup.1 An emulsion of dimethyl polysiloxane having a viscosity of about 
1000 cps and solids at 50%. 
.sup.2 An emulsion of dimethyl polysiloxane having a viscosity of about 
60,000 cps and solids at 35%. 
The products of this invention are useful in 
--cleaning 
--restoring or improving the appearance in terms of gloss, uniformity and 
color 
--maintaining the appearance 
--protecting and preserving appearance and longevity of objects made from 
vinyl, leather, rubber, elastomers, natural and synthetic polymers, sealed 
and finished woods, painted metal such as automobile finishes, etc. 
Products of this invention are directed toward a wide scope of uses such as 
encountered in the household, sports, industrial, do-it-yourself 
maintenance or automobiles, recreational vehicles, boats, motorcycles, 
airplanes, etc. 
Specific illustration of products on which the products of this invention 
can be employed include the following: 
1. Automotive vinyl tops 
2. Automotive truck, recreational vehicles--tires 
3. Rubber and elastomeric gaskets used in the above 
4. Rubber and elastomeric hoses 
5. Rubber and elastomeric bumpers 
6. Snowmobiles--rubber and/or elastomeric belts 
7. Boats--rubber and/or elastomeric gaskets, vinyl appointments, etc. 
8. Water sports--under-the-water-swimsuits, fins, belts, water ski 
bindings, etc. 
9. Winter sports--ski boots (leather or vinyl) 
10. Outdoor recreation sports--hiking boots, leather gear, etc. 
11. Furniture featuring vinyl or leather, such as sofas, chairs, etc. 
12. Domestic objects made out of natural or synthetic polymers, such as 
Formica.RTM. 
13. Leather or vinyl objects such as gloves, belts, luggage, carrying 
cases, hand bags, accessories, etc. 
14. Furniture featuring sealed wood and simulated wood containing styrene 
or similar materials used to manufacture simulated wood articles.