Process for treatment of vinyl and rubber

A stable composition and process for cleaning, protecting, preserving, and renewing surfaces, especially rubber and other polymers is disclosed. The treatment chemical is formulated to clean, protect, renew and preserve the polymer surface being treated. The inclusion of an alkanolamine selected from the group consisting of mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-isopropanolamine, di-isopropanolamine and tri-isopropanolamine which causes provide outstanding detergency to the formulation without adversely affecting the emulsion stability. Each component contributes to the performance of the composition and facilitates the proper deposition of treatment chemical.

This invention relates to improved polymer treatment compositions for 
cleaning, preserving, renewing, protecting and enhancing the appearance of 
rubber, vinyl, and polymer surfaces. This is achieved by incorporation 
into the treatment emulsion, at least one member of each of class a-d. The 
classes are; (a) dimethylpolysiloxane, (b) emulsification agents which 
facilitates the production of a stable emulsion, (c) an alkanolamine 
selected from the group consisting of mono-ethanolamine, di-ethanolamine, 
tri-ethanolamine, mono-isopropanolamine, di-isopropanolamine and 
tri-isopropanolamine which provides outstanding detergency to the 
formulation without adversely affecting the emulsion stability, and (d) 
water. 
One of the objects of the invention is to provide cleaning properties to a 
protectant formulation so that in addition to a superior preservation 
cleaning can be affected without affecting the emulsion stability. 
Heretofore, any attempt to incorporation detergents into a treatment 
emulsion used for treating vinyl and plastic resulted in a breaking of the 
emulsion and a product which did not function. As will become clear, the 
stability of the emulsion is based, in part on the choice of proper HLB. 
The HLB (or hydrophilic/liphophyllic balance) needs to be maintained in a 
narrow range or the silicone oil will split out of the emulsion. 
Unfortunately, most commonly used detergents have high HLB values and 
incorporating them into a stable emulsion is not possible. We have 
unexpectedly discovered that certain alkanolamine compounds will provide 
outstanding detergency without adversely affecting the emulsion stability. 
This allows for a truly multi-functional protectant. 
While not limited thereto, a major application for the invention lies in 
protecting and improving the appearance and useful life of rubber parts of 
automobiles auto tires, rubber sealing strips, and vinyl tops. 
Preservatives made according to the invention will not only protect and 
enhance the appearance of plastics, particularly vinyls and acrylics, but 
will also clean them. 
All percentages specified are % based upon total composition. All 
temperatures are in degrees centigrade. 
DESCRIPTION OF THE ARTS AND PRACTICES 
The oldest materials used for the preservation of rubber were based on lamp 
black and included materials highly corrosive to metal and painted 
surfaces commonly found on automobiles. These rubber treatment materials 
were applied like paint to the rubber surfaces. The rubber treated in this 
manner had an unnatural "painted" appearance. Re-application required 
removal of old coatings, and were difficult and inefficient. Not only were 
such materials ineffective in protecting rubber surfaces from 
deterioration caused by environmental stresses, but they were also quite 
messy and difficult to use. In addition, the corrosive and toxic 
ingredients were harmful to the adjacent surfaces and to the user. 
It is also known that dimethylpolysiloxane polymers can be applied to the 
surface of rubber to give a surface protecting and sealing film. One such 
method of application is direct application of the dimethylpolysiloxane to 
the polymer surface. While resulting in some surface protection the method 
of application is cost ineffective and results in a nonuniform greasy 
film. Another method is to dissolve the dimethylpolysiloxane in a solvent 
like mineral spirits and apply the solution to the tire. In addition to 
the environmental liabilities of using a polluting flammable solvent, the 
solvent often has a deleterious effect upon the rubber. The last and most 
accepted application method is the preparation of an aqueous emulsion 
using a surface active agent and high pressure processes like 
homogenization to get a milky white liquid. 
There have been several practical limitations on the use of such an aqueous 
product. Most of which result from two problems (a) the inability to lay 
down a uniform film without several applications, and (b) the sealing of 
the polymer surface. Several inventors have addressed the problems. Most 
notably, U.S. Pat. No. 3,956,174 issued May 1976, to Palcher discloses 
that a dimethylpolysiloxane emulsion can be improved by addition of from 
about 15% to about 65% by weight of one or more polyol compounds, 
preferably diethylene glycol and glycerin. The patent teaches that the 
preservative disclosed is compounded of nontoxic materials which are safe 
for the user as well as for surfaces adjacent to rubber parts on 
automobiles. The Palcher invention attempts to seal up the tire pores by 
inclusion of these polyols. This may be cosmetically appealing, but is not 
the preferred way to treat the polymer surface. Polymers are porous 
materials through which pass small amounts of water, environmental gases, 
ozone and other materials. The degradation of the polymer which starts on 
the surface, also occurs within the porous polymer matrix. While sealing 
up the porous structures with the Palcher compositions, minimizes surface 
degradation, little protection is given to the internal polymer structure. 
Until the compositions of this invention, surface treatments were all that 
was available. 
Palcher states "An object of the invention is to provide a substantial 
degree of protection and preservation over a substantial period of time. 
To this end, it has been further discovered that a significantly greater 
measure of protection can be imparted, especially to natural and synthetic 
polymer surfaces, if at least one polyol compound is added to the emulsion 
of the organopolysiloxane and water. Not only is a greater degree of 
protection and longevity thereof provided by this composition, but also 
the appearance is greatly improved. These constituents appear not to 
combine chemically but they do combine mechanically to a homogeneous 
mixture. Combination is accomplished by emulsifying the silicone in water 
and then adding the other constituents to that emulsion. The result 
achieved by treatment with the mixture is different, and better than the 
result that is achieved if the material is treated with the constituents 
individually." Clearly, the Palcher patent requires cleaning first and 
therefore the glycols included in the formulations were not used for 
cleaning. In practice, multiple applications of a treatment product after 
cleaning is impractical and rarely done. It was not until the present 
invention that a truly one step product has been possible. The 
compositions clean, protect, restore and provide ozone protection to 
polymer surfaces in one application. 
U.S. Pat. No. 5,183,845 issued February 1993 to Parkinson et al, which is 
incorporated herein by reference, teaches "emulsions of the present 
invention are applied to the polymer surfaces and by virtue of the 
composition, once applied, the emulsion will break causing the deposition 
of a uniform coating of treatment chemical. The treatment chemical is 
formulated to protect, renew and preserve the polymer surface being 
treated." It was not until the present invention that a truly one step 
product has been possible. The compositions clean, protect, restore and 
provide ozone protection to polymer surfaces in one application. 
SUMMARY OF THE INVENTION 
The compositions of the current invention are treatment emulsions 
containing at least one component from the following classes (a) 
dimethylpolysiloxanes (b) emulsification agents which facilitate the 
production of a stable emulsion, and most importantly, (c) an alkanolamine 
selected from the group consisting of mono-ethanolamine, di-ethanolamine, 
tri-ethanolamine, mono-isopropanolamine, di-isopropanolamine and 
tri-isopropanolamine which provides outstanding detergency to the 
formulation without adversely affecting the emulsion stability, and (d) 
water. 
In order to clean, preserve and renew surfaces the treatment composition of 
the invention are applied to the polymer surface to be treated. One 
preferred method is spraying. The compounds of this invention can be 
applied to the polymer surface, wet or dry. Previous compositions were 
applicable only to wet surfaces. We believe that penetration of the 
polymer surface by the dimethylpolysiloxane occurs by capillary action 
whereby the molecules of the preservative composition, and especially the 
polysiloxane fluid, are drawn into the surface. There, the molecules can 
hook or wrap around the molecules of the material to be protected to 
physically attach themselves thereto.

DETAILED DESCRIPTION OF THE INVENTION 
It has been found that detergency can be incorporated into protectant 
compositions by including an alkanolamine selected from the group 
consisting of mono-ethanolamine, di-ethanolamine, tri-ethanolamine, 
mono-isopropanolamine, di-isopropanolamine and tri-isopropanolamine which 
causes provide outstanding detergency to the formulation without adversely 
affecting the emulsion stability. This allows for a truly multi-functional 
product. 
The emulsion composition comprises; 
(a) a dimethylpolysiloxane conforming to the following structure; 
##STR1## 
wherein: Me is methyl; 
n is an integer ranging from 49-1575; 
(b) an emulsification agent having an HLB of between 8 and 11; 
(c) an alkanolamine selected from the group consisting of 
mono-ethanolamine, di-ethanolamine, tri-ethanolamine, 
mono-isopropanolamine, di-isopropanolamine and tri-isopropanolamine; 
and (d) water. 
In a preferred embodiment the emulsion composition which comprises; 
(a) 5-30% of a dimethylpolysiloxane conforming to the following structure; 
##STR2## 
wherein: Me is methyl; 
n is an integer ranging from 49-1575; 
(b) 0.5-5.0% of emulsification agent having an HLB of between 8 and 11; 
(c) 0.5 and 5.0% of an alkanolamine selected from the group consisting of 
mono-ethanolamine, di-ethanolamine, tri-ethanolamine, 
mono-isopropanolamine, di-isopropanolamine and tri-isopropanolamine. 
and 
(d) 60-94% water. 
In a more preferred embodiment the emulsion composition comprises; 
(a) 15-30% of a dimethylpolysiloxane conforming to the following structure; 
##STR3## 
wherein: Me is methyl; 
n is an integer ranging from 49-1575; 
(b) 1.0-5.0% of emulsification agent having an HLB of between 8 and 11; 
(c) 1.0 and 5.0% of an alkanolamine selected from the group consisting of 
mono-ethanolamine, di-ethanolamine, tri-ethanolamine, 
mono-isopropanolamine, di-isopropanolamine and tri-isopropanolamine. 
and 
(d) 60-93% water. 
In a preferred embodiment the alkanolamine is di-ethanolamine. 
The classes of materials which make up the composition are; 
(a) Dimethylpolysiloxane 
In order to fully define the structure of the dimethylpolysiloxanes, the 
following information is taken from the Siltech Inc. bulletin on fluids; 
Siltech Fluids conform to the following generic structure; 
##STR4## 
wherein Me is methyl; 
n is an integer ranging from 49-1575. 
Silicone fluids are sold by their viscosity. The viscosity, expressed in 
centistokes measured at 25C, defines the value of "n"and consequently the 
molecular weight. 
Siltech Inc. markets the following fluids; 
______________________________________ 
Regular Viscosity Fluids 
Viscosity 25 C. 
Siltech Name (Centistokes) 
Molecular Weight 
______________________________________ 
Siltech F-50 50 3,780 
Siltech F-100 
100 5,970 
Siltech F-200 
200 9,430 
Siltech F-350 
350 13,650 
Siltech F-500 
500 17,250 
Siltech F-1,000 
1,000 28,000 
______________________________________ 
______________________________________ 
High Viscosity Fluids 
Viscosity 25 C. 
Siltech Name (Centistokes) 
Molecular Weight 
______________________________________ 
Siltech F-10,000 
10,000 62,700 
Siltech F-12,500 
12,500 67,700 
Siltech F-60,000 
60,000 116,500 
______________________________________ 
Knowing the molecular weight and the structure allows for calculation of 
"n", which will range from 49 (F-50), to 1575 (F-60,000). 
The dimethylpolysiloxane fluid or liquid silicone in the composition 
functions as lubricant for the polymer molecules and as waterproofing the 
rubber. Both mechanisms impede scission. Scission is promoted by the 
presence of ozone and other environmental chemicals. A thin film of 
silicone applied to the polymer being treated both at the surface and 
within the matrix is most effective in helping to exclude deleterious 
materials. 
The compositions of the invention contain at least one viscosity 
dimethylpolysiloxane fluid. In a preferred embodiment there are two 
different viscosity fluids. 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. 
Dimethylpolysiloxane 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 from 50 
centistokes up to about 60,000 centistokes. 
In a preferred embodiment a mixture of two fluids, one having a low 
viscosity fluid (Siltech F-50 to Siltech F-100) (50-100 centistokes), and 
the other a higher viscosity fluid Siltech F 1,000 to Siltech F 60,000 
(1,000 to 60,000 centistokes) results in the best performance attributes. 
We believe that the increased performance obtained by using two different 
viscosity fluids is based upon penetration. The high viscosity 
dimethylpolysiloxane has some difficulty penetrating the surface to be 
protected. It remains on or close to the surface of the polymer being 
treated and provides a protective surface barrier. It also provides added 
gloss. The low viscosity dimethylpolysiloxane on the other hand, if 
prepared in a composition of this invention, rapidly penetrates the 
surface. This low viscosity fluid acts as a polymeric lubricant in the 
polymer matrix. It also coats the polymer molecules and provides 
protection within the matrix. 
(b) Emulsification Agent 
The emulsification agent facilitates the production of a stable emulsion. 
In short it allows for the oil soluble dimethylpolysiloxanes and other 
oils to remain suspended in a milky white emulsion, until they can be 
applied to the surface of the polymer being protected. 
Many types of emulsifiers can be used in the preparation of the compounds 
of this invention. The materials useful in this application have an HLB of 
between 8.0 and 11. 
HLB is the measure of the amount of water soluble component on an 
emulsification agent. Typically for a nonionic surfactant it is calculated 
as 
HLB=(% water soluble component in the surface active agent)/5 
Therefore emulsification agents useful in the practice of this invention 
will have between 40 and 50% water soluble component present in the 
compound. Most commonly, a pair of emulsifiers are blended to get an HLB 
with a numerical average of 8 to 11. Emulsifier pairs generally result in 
a more stable emulsion. 
Examples of various emulsifiers were evaluated to show the affect of HLB 
the formula tested for this section was; 
______________________________________ 
Material % Weight 
______________________________________ 
(a) dimethylpolysiloxane 
1,000 visc Siltech F 1,000 
16.0 
100 visc Siltech F 100 
9.0 
(b) emulsification agent 
Various (Above) 3.0 
(c) di-ethanolamine 5.0 
(d) water 67.0 
______________________________________ 
The specified emulsifier was added and an emulsion prepared. Each example 
represents a repeat preparation of the formula substituting the specified 
emulsifier into the formula. 
______________________________________ 
Example Material HLB Result 
______________________________________ 
1 C.sub.12 H.sub.25 --O--(CH.sub.2 CH.sub.2 O).sub.3 H 
8 Stable 
2 C.sub.10 H.sub.22 --O--(CH.sub.2 CH.sub.2 O).sub.3 H 
9 Stable 
3 C.sub.10 H.sub.22 --O--(CH.sub.2 CH.sub.2 O).sub.6 H 
12.5 Split 
(Unstable) 
4 Nonylphenol with 10.0 Stable 
5 moles of E.O. 
5 Nonylphenol with 11.0 Stable 
6 moles of E.O. 
______________________________________ 
This evaluation shows that the HLB is a key to making the emulsion stable. 
The range from 8 to 11 is critical. 
Despite the stability, the products so prepared failed to provide any 
detergency. Tests were re-run evaluating various additives aimed at 
providing the desired detergency. Tires soiled with mud were tested with 
modifications of the above formulations. 
(C) Alkanolamine 
Alkanolamines are items of commerce and confirm to the following structure; 
______________________________________ 
Alkanolamine Structure 
______________________________________ 
mono-ethanolamine 
H.sub.2 N--CH.sub.2 CH.sub.2 --OH 
di-ethanolamine HN--(CH.sub.2 CH.sub.2 --OH).sub.2 
tri-ethanolamine N--(CH.sub.2 CH.sub.2 --OH).sub.3 
mono-isopropanolamine 
H.sub.2 N--CH.sub.2 CH(CH.sub.3)--OH 
di-isopropanolamine 
HN--(CH.sub.2 CH(CH.sub.3)--OH).sub.2 
tri-isopropanolamine 
N--(CH.sub.2 CH(CH.sub.3)--OH).sub.3 
______________________________________ 
In order to evaluate the detergency affects, the alkanolamine compounds of 
the present invention were added at 5% solids to the specified emulsion. 
The stability and detergency were then evaluated. Detergency was evaluated 
on a scale of 1-5 (1 worst (no detergency) to 5 best). 
EXAMPLE 6 
______________________________________ 
Material % Weight 
______________________________________ 
(a) dimethylpolysiloxane 
1,000 visc Siltech F 1,000 
16.0 
350 visc Siltech F 350 
9.0 
(b) Emulsifier 3.0 
(Example 2) 
(c) Di-ethanolamine 3.0 
(d) water 69.0 
______________________________________ 
The above formula was found to be stable and have exceptional detergency. 
EXAMPLES 7-14 
Example 6 was repeated only this time the specified alkanolamine was 
substituted for the di-ethanolamine; 
______________________________________ 
Additive Emulsion 
Example @ 5% Weight Stability Detergency 
______________________________________ 
7 mono-ethanolamine 
Stable 5 
8 tri-ethanolamine Stable 4 
9 mono-isopropanolamine 
Stable 3 
10 di-isopropanolamine 
Stable 5 
11 tri-isopropanolamine 
Stable 4 
12 Sodium Dodecyl Benzene 
Split * 
Sulfonic Acid 
13 Sodium Lauryl Sulfate 
Split * 
14 Alpha olefin Sulfonate 
Split * 
______________________________________ 
*products which were split could not be evaluated for detergency. 
EXAMPLE 15 
______________________________________ 
Material % Weight 
______________________________________ 
(i) dimethylpolysiloxane 
1,000 visc Siltech F 1,000 
16.0 
350 visc Siltech F 350 
9.0 
(ii) Emulsifier 3.0 
(Example 4) 
(iii) Di-ethanolamine 
3.0 
(iii) water 69.0 
______________________________________ 
The above formula was found to be stable and have exceptional detergency. 
EXAMPLES 16-23 
Example 15 was repeated only this time the specified alkanolamine was 
substituted for the di-ethanolamine; 
______________________________________ 
Additive Emulsion 
Example @ 5% Weight Stability Detergency 
______________________________________ 
16 mono-ethanolamine 
Stable 4 
17 tri-ethanolamine Stable 4 
18 mono-isopropanolamine 
Stable 3 
19 di-isopropanolamine 
Stable 5 
20 tri-isopropanolamine 
Stable 5 
21 Sodium Dodecyl Benzene 
Split * 
Sulfonic Acid 
22 Sodium Lauryl Sulfate 
Split * 
23 Alpha olefin Sulfonate 
Split * 
______________________________________ 
*products which were split could not be evaluated for detergency. 
As is clearly seen, the alkanolamine selected from the group consisting of 
mono-ethanolamine, di-ethanolamine, tri-ethanolamine, 
mono-isopropanolamine, di-isopropanolamine and tri-isopropanolamine 
provides outstanding detergency to the formulation without adversely 
affecting the emulsion stability. The alkanolamines, while not normally 
considered detergents by themselves, unexpectedly function as detergents 
in our emulsion systems. 
The more commonly used detergents all destroy the emulsion by altering the 
HLB of the system. They cannot be used in producing commercially viable 
compositions. The use of alkanolamines (a) provides detergency; (b) has no 
affect upon HLB; (c) has no affect upon emulsion stability; and (d) 
provides a commercially viable system for a multi-purpose treatment 
product.