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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:
______________________________________
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.
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