US 3756835 A
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United States Patent 3,756,835 PROTECTIVE POLISH Roy J. Betty, Jr., and Harold C. Nemeth, Chicago, IlL, assignors to Akzona Incorporated, Asheville, N.C. No Drawing. Filed Apr. 5, 1971, Ser. No. 131,543 Int. Cl. C08h 9/00; C09f; C09g US. Cl. 106-11 4 Claims ABSTRACT OF THE DISCLOSURE A protective polish composition for use in auto laundries comprising a di(long chain aliphatic) quaternary ammonium nitrite, a di(long chain aliphatic) diethoxylated quaternary ammonium compound or a di(long chain alkyl) quaternary ammonium compound; an ethoxylated tertiary amine cationic emulsifier; and an emulsifiable mineral oil.
This invention relates to a protective polish composition especially useful in auto laundries to obtain rapid drying of the vehicles, and more particularly to a polish composition which is substantive and therefore particularly useful in very dilute form in the rinse liquids of auto laundries to eifect a highly substantive, protective polish on the surface of the vehicle being washed.
Protective polish compositions are not generally new; see for example, Soap and Chemical Specialties, February 1962, page 72 et seq. Most of the presently used compositions have some undesirable properties or are difficult to mix or store. Some require relatively expensive ingredients, some are difficult to formulate, some require uneconomical amounts for proper polish effect, some are not sufliciently substantive, some are unstable, some possess salt which is corrosive, and some do not mix readily with the wash or rinse liquid. U.S. Pats. Nos. 3,497,365 and 3,551,168 teach protective polish compositions which generally overcome meny of the above disadvantages. The applicants, however, have discovered that specific desired properties may be unexpectedly improved by use of the quaternary ammonium compounds called for by their invention. For example, use of a di(long chain aliphatic) quaternary ammonium nitrite greatly increases corrosion protection and use of a di(long chain aliphatic) diethoxylated quaternary ammonium compound decreases the time for water run-off.
An object of this invention is to provide a protective polish composition which overcomes the above disadvantages.
Another object is to provide a protective polish composition, of the above character, which is highly substantive.
Still another object is to provide a protective polish composition, of the above character, which can be substantially diluted in rinse waters.
A further object is to provide a composition which imparts improved water shedding properties allowing rapid drying of washed articles.
A still further object is to provide a protective polish composition which provides improved corrosion protection.
Another object is to provide a protective polish composition which has freeze-thaw stability.
Other objects of the invention will in part be obvious and will in part appear hereinafter.
In accordance with the objects enumerated above, the novel protective polish composition of this invention comprises at least one di(long chain aliphatic) quaternary ammonium nitrite, a di(long chain aliphatic) diethoxylated quaternary ammonium compound, or a di(long chain alkyl) quaternary ammonium compound, said aliphatic hydrocarbon groups having about 8 to 18 carbon atoms, at least one ethoxylated cationic emulsifier having an average of about 4 to about 12 moles of ethylene oxide moieties therein, and an emulsifiable oil. More specifically, a nominally 100% active, containing some water and solvent, protective polish concentrate according to this invention comprises about 25 to 62 wt. percent of a quaternary ammonium compound as described above; 7.5 to 17.5 wt. percent of an ethoxylated tertiary amine cationic emulsifier, and 38 to 75 wt. percent of an emulsifiable mineral oil such as mineral seal oil. Waxes and/or silicone may be added.
Preferred compositions according to this invention comprise about 25 to 54.5 wt. percent quaternary ammonium compound, about 7.5 to 17.5 wt. percent of an ethoxylated tertiary amine cationic emulsifier, and about 38 to 67.5 wt. percent of an emulsifiable mineral oil.
Quaternary ammonium compounds useful in the composition of our invention are selected from the group consisting of:
a [Brig-R4] N02 wherein R and R are selected from alkyl and alkenyl groups of about 8 to 18 carbon atoms and mixtures thereof, R is selected from methyl and -(CH CH O),,H and R is selected from methyl and -(CH CH O) H wherein at and y are positive integers having a sum of l to about 5;
wherein R and R are as defined above, R is (CH2CH2O)XH,
R is (CH CH O) H wherein x and y are as defined above and A is an anion; and
7 alkyl and alkenyl groups. R, and R may be the same or different, straight chain or branched chain. Suitable groups include octyl, nonyl, decyl, hendecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octenyl, nonenyl, decenyl, hendecenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, octadecenyl, and their branched chain derivatives such as N-sec-alkyl (C as obtained by amidation of olefins followed by hydrolysis, or they may be mixtures of alkyl and alkenyl groups as obtained from natural fats and oils. R and R may be the same or diiferent, straight chain or branched chain.
Suitable groups for R and R include octyl, nonyl, decyl, hendecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and their branched chain derivatives such as N-sec-alkyl (C as obtained by amidation of olefins followed by hydrolysis.
It is well known in the art that ethylene oxide may replace an active hydrogen atom or a nitrogen atom and form linear adducts having ether linkages. The length of such adduct depends upon the molar ratio of the ethylene oxide to nitrogen groups. The addition of ethylene oxide to an amino nitrogen atom having more than one active hydrogen does not necessarily take place uniformly and therefore, the extent of ethoxylation of a nitrogen containing molecule is expressed by the molar ratio of ethylene oxide to the nitrogen containing compound.
Referring to the ethoxylated tertiary amine, it is preferred to utilize a compound containing one alkyl or alkenyl group having from 8 to 18 carbon atoms, or mixtures thereof. Suitable groups are those set forth above for R and R having from 8 to 18 carbon atoms. Especially preferred are mixtures such as are derived from tallow and coco. Mixtures of compounds ethoxylated to various degrees may be utilized provided that the average degree of ethoxylation, on the basis of all the tertiary amine, is about 4 to about 12 moles. A preferred average degree of ethoxylation is about 4.1 to 9.0 moles, and an especially suitable average is about 4.3 to 6.7 moles. For example, a 2 mole and 15 mole adduct may be mixed in proportions to give average of 4 to 12 moles.
Emulsifiable mineral oils suitable for the formulations of this invention have a viscosity in the range of from about 20 to 200 SUS at 100 F. We prefer to use mineral seal oil having a viscosity of about 40 SUS at 100 F.
While the above proportions have been set forth illustrating a nominally 100% active concentrate, a lesser active, such as nominally 70% and 40%, concentrate may be formulated and satisfactorily stored. The diluent most advantageously utilized is water.
The composition may be applied to the vehicle by diluting a 40% active concentrate 50 to 200 fold with water and spraying it onto the vehicle after it has been washed and rinsed or even while it is being rinsed. The composition is so substantive that it may be used during or after rinsing. In fact, visual observation of the vehicle so treated will immediately reveal that the remaining water, after application, will quickly run off in droplets and a glossy finish appears. Such treatment greatly aids drying, either by air blast or by wiping.
It might also be noted that when the protective polish composition of this invention is compared to prior art compositions, a substantial improvement in water run-off occurs. Such occurs even with the use of substantially less composition than heretofore used, the explanation apparently being because of the use of the particular quaternary and emulsifier in the composition. Other quaternaries, such as the imidazolinium salts and mono-long chain fatty amine quaternaries do not provide similar results. Some of the data that follows illustrates such comparison.
In formulating the polish composition, care must be taken to effect a ready-mix type solution. Car wash operation generally involves dilution of the polish composition by adding it to a tank of water prior to application, or by bleeding the concentrated composition into the rinse water as it is fed to the spray nozzles of the automatic machinery. Such requires a formulation which dilutes easily. It has been found that the cationic emulsifier has a direct influence on such ease of dilution. If the average number of ethylene oxide moieties in the cationic emulsifier is greater than about 12, the formulation clouds (emulsion breakage), and if the average number is less than about 4, it gels when in the concentrate form.
For a fuller understanding of the nature and objects of this invention, reference should be had to the following EXAMPLE I The following ingredients were formulated:
Weight percent N,N-dicoco 1 N,N-dimethyl quaternary ammonium nitrite active in a mixture of water, methanol and isopropanol (Arquad 2C-NO 40 N-tallow ethoxylated tertiary amineethoxylated with 15 moles ethylene oxide (Ethomeen T/ 25 6.5 N-coco ethoxylated tertiary amineethoxylated with 5 moles ethylene oxide (Ethomeen C/ 15) 2.5 Mineral seal oil 51 1 Coco is a mixture of saturated and unsaturated hydrocarbon groups of 8 to 18 carbon atoms, predominately dodccyl derived from coconut oil fatty acids.
Tallow is a mixture of saturated and unsaturated hydrocarbon groups of 12 to 18 carbon atoms, predominately octadgicgsnyl, hcxadccyl and octadecyl, derived from tallow fatty The above formulation, nominally a concentrate, may be diluted to a 40% active water dilution and continuously added (about 2 ounces per gallon of water) to the rinse water of an existing quick wash auto laundry. The laundering technique employed involves washing of the auto body, rinsing with fresh water, followed by a second rinse, in which the above formulation has been added. Then, for test purposes, a third rinse of fresh water, without additives, is sprayed on the auto body, blown dry, and the result visually observed and compared against polish compositions presently used. The rinse water runs off faster than with other prior art polish compositions, and a glossier finish appears on the auto body surface. This formulation has good freeze-thaw stability.
EXAMPLE II In similar fashion to 'Example I the following ingredients were formulated:
Weight percent The above formulation, nominally a 100% concentrate, may be satisfactorily diluted and added to the rinse water of auto wash laundries in the same manner as the composition described in Example I.
EXAMPLE III A nominally 100% active concentrated was formulated using the following components:
Composition 1: Weight percent Arquad 2C-NO 37.5 N-tallow tertiary amine ethoxylated with 5 moles ethylene oxide (Ethomeen T/15) 3.0 'Eth'omeen T/25 6.5 Ethomeen C/15 2.5 Mineral seal oil 50.5
Similarly a nominally 100% active concentrate was prepared using the following components:
Composition 2: Weight percent N,N dicoco N,N dimethyl quaternary ammonium chloride 75% active in aqueous isopropanol 39.5 Mineral seal oil 5'1.5 Ethomeen T/15 9.0
1% and 10% active aqueous solutions were prepared of each of the above compositions for corrosion tests. One inch by three inch mild steel coupons were cleaned and then one series of coupons were dipped in Coinposition 1, one series in Composition 2, and one series of coupons dipped in water as a control. Following dipping, the coupons were suspended above water. All of the corrusion testing was performed at room temperature.
The coupons as treated above were observed at various The above tests were also conducted with three inch square pieces of steel wool with very similar results.
EXAMPLE IV Additional formulations were prepared using 51.5 wt. percent mineral seal oil, 7.5 percent N-tallow tertiary amine containing 5 moles ethylene oxide, 1.5 percent tertiary amine ethoxylated with 15 moles ethylene oxide and 39.5 percent of the quaternary ammonium compound indicated in Table II. The concentrate COIIIPOSltions containing some aqueous isopropanol, denoted as nominally 100% active compositions were noted for clearness. Then the compositions were diluted, on the basis of the concentrate compositions, to 40 percent active with tap water and noted for clearness. Then the compositions were diluted to 1 percent active with tap water and noted for clearness. The results are shown in Table II.
The water repellency of the formulations noted 1n Table II was tested by washing a 7" x 8" panel of vinyl coated aluminum siding with detergent and hot water; air drying the panel, dipping the panel into a 1% active solution of the noted formulation for 15 seconds; air drying the panel; spraying the panel with cold tap water for 1 minute; timing in seconds the run-0E time from the surface of the vertical held panel following stopping of the spray. The results are noted in Table II with an untreated control panel subjected to the same tests as the panels dipped into the 1% active composition. The faster the water run-ofl? observed, the better the coating. The results are shown in Table 11.
TABLE II Water repellency, seconds (painted aluminum) Clear... Clear-.. Clear--. 6
Appearance Nominal activity- 100% 40% 1% active active active Quaternary ammonium compound -....do... Cloudy ....do-.- 7
....d0 ..do-.. Cloudy 8 ..-.do-.. Clear... Clear-.. 14
:...do-.- Cloudy. Cloudy- 40 1 Rumofi after 1 minute cold water spray.
It is seen from the above examples that an especially suitable protective polish composition for inclusion into rinse water during laundering of vehicles comprises about 30 to 40 wt. percent of the above identified specific quaternary ammonium compound, about 8.5 to 15 wt. percent tertiary ethoxylated amine having an alkyl or alkenyl of about 8 to 18 carbon atoms and an average degree of ethoxylation of 4 to 12 moles, and about 45 to 60 wt. percent mineral seal oil.
The above examples show that the di(long chain aliphatic) quaternary ammonium nitrite exhibits surprisingly effective corrosion inhibition when compared to the di- (long chain aliphatic) quaternary ammonium chloride. The corrosion inhibition is clearly an important aspect of providing the most satisfactory protective polish.
As is seen from the above examples, when a di(long chain aliphatic) diethoxylated quaternary ammonium compound is used, it provides solutions which are clear from to 1% active. Table H shows that the composition containing a di(long chain aliphatic) diethoxylated quaternary ammonium compound provides the fastest runoff of any of the compositions tested. The composition containing N,N-di(hydrogenated tallow) 'N,-N-(ethoxylated 3.5 moles ethylene oxide) quaternary ammonium chloride may be compared with the composition containing N,N-di(hydrogenated tallow) N,N-dimethyl quaternary ammonium chloride, and it is seen that the composition containing the ethoxylated quaternary ammonium compound provides a clear solution from 100 to 1% activity, while the solution containing the dimethyl quaternary ammonium chloride is cloudy at 40 and 1% activity. Also, it is seen from Table II that the composition containing the dimethyl quaternary ammonium compound has a run-off time of about 67% longer than the composition containing the ethoxylated quaternary ammonium compound.
When a quaternary ammonium chloride containing two long chain alkyl groups is used in the composition of this invention, the composition may be tailored to obtain the desired results of water repellency or clear appearance. Good water repellency is obtained from ditetradecyl and dihexadecyl quaternary ammonium compounds, but the solutions will cloud at lower concentrations. 011 the other hand, the use of didodecyl quaternary ammonium compounds results in clear solutions at all activities, but shows increased run-oft" time. Thus, using the di(long chain alkyl) quaternary ammonium compositions can be suited to the most desirable requirement.
Table II compares a composition containing a N-monolong chain trimethyl quaternary ammonium chloride and shows that it does not impart any water repellency. It has been known in the art to use imidazolinium compounds for the purpose of rinsing formulations as taught by Pat. No. 3,222,213 which are shown in Table II to impart a much less degree of Water repellency than use of the compounds called for by our invention.
Use of the di(hydrogenated tallow) dimethyl quaternary ammonium chloride results in cloudy solutions at 40 and 1% activity and only fair run-oil".
The above indicated satisfactory formulations have good shelf life and act as protective polishes when applied to automobile bodies. The diluted form in which the formulations may be used make them extremely economical. Especially suitable formulations for commercial sale are those nominally 100% active and 40 and 70% water dilutions. When applied to the automobile in the rinse water, the concentration of active composition is from about 0.075, to 0.5%. Indeed, at this rate, a 10 gallon drum of a 40% active formulation will impart a uniform luster to about 1,000 to 3,000 automobiles. The dilution is readily accomplished and, if desired, a proportioning pump can be used for such purpose.
While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for 7 purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention.
1. A protective polish concentrate composition suitable for incorporation into rinse waters during laundering of vehicles comprising; as the substantive component of the composition about 25 to 54.5 Wt. percent of an ethoxylated quaternary ammonium compound having the structural formula t [B ia-Bil [A]- wherein R and R are selected from alkyl and alkenyl groups of about 8 to 18 carbon atoms and mixtures thereof; R is (CH CH O) H, R is (CH CH O) H wherein x and y are positive integers having a sum of 1 to about 5 and the average degree of ethoxylation is about 4.1 to about 9.0 moles and A is an anion selected from the group consisting of CH O S N0 N0 1 Cl, and Br-; as the emulsifying component of the composition about 7.5 to 17.5 wt. percent of bis-ethoxylated tertiary amine having a hydrocarbon group of 8 to 13 carbon atoms selected from alkyl and alkenyl, all of said tertiary amine having an average degree of ethoxylation of about 4 to about 12 moles; and about 38 to 67.5 wt. percent of mineral seal oil having a viscosity in the range of from about 20 to 200 SUS at 100 F.
2. The composition of claim 1 wherein said bisethoxylated tertiary amine is selected from the group consisting of bis-ethoxylated moles ethylene oxide) tallow amine, bis-ethoxylated moles ethylene oxide) tallow amine, bis-ethoxylated (5 moles ethylene oxide) coco amine.
3. The composition of claim 1 wherein the quaternary ammonium compound is N,N-di(hydrogenated tallow), N,N-(ethoxylated) quaternary ammonium chloride.
8 4. A protective polish composition comprising water and about 0.075 to 0.5 wt. percent of an active composition comprising; as the substantive component of the composition about 25 to 54.5 wt. percent, based upon said active composition, of an ethoxylated quaternary ammonium compound having the formula:
wherein R and R are selected from alkyl and alkenyl groups of about 8 to 18 carbon atoms and mixtures thereof, R5 is (CH CH O) H, R6 is wherein x and y are positive integers having a sum of l to about 5 and the average degree of ethoxylation is about 4.1 to about 9.0 moles and A is an anion selected from the group consisting of CH OSO N0 3 N0 1 Cl" and Br-; as the emulsifying component of the composition about 7.5 to 17.5 Wt. percent, based upon said active composition, of bis-ethoxylated tertiary amine having a hydrocarbon group of 8 to 18 carbon atoms selected from alkyl and alkenyl, all of said tertiary amine having an average degree of ethoxylation of about 4 to about 12 moles; and about 38 to 67.5 wt. percent, based upon said active composition, of mineral seal oil having a viscosity in the range of from about 20 to 200 SUS at F.
References Cited UNITED STATES PATENTS 3,497,365 2/1970 Atherton et al. l068 3,551,168 12/1970 Atherton et al l068 JOAN B. EVANS, Primary Examiner US. Cl. X.R. l06285