CA1127038A - Composition capable of removing hydrophilic and hydrophobic contaminants from surfaces - Google Patents
Composition capable of removing hydrophilic and hydrophobic contaminants from surfacesInfo
- Publication number
- CA1127038A CA1127038A CA333,202A CA333202A CA1127038A CA 1127038 A CA1127038 A CA 1127038A CA 333202 A CA333202 A CA 333202A CA 1127038 A CA1127038 A CA 1127038A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- methylene chloride
- trichloroethane
- ethanol
- cleaning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000000356 contaminant Substances 0.000 title abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 title abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 36
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011368 organic material Substances 0.000 claims abstract description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 7
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 4
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000001704 evaporation Methods 0.000 abstract description 7
- 230000008020 evaporation Effects 0.000 abstract description 7
- 230000000007 visual effect Effects 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000009877 rendering Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 18
- 239000002904 solvent Substances 0.000 description 5
- 239000003398 denaturant Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
COMPOSITION CAPABLE OF REMOVING HYDROPHILIC
AND HYDROPHOBIC CONTAMINANTS FROM SURFACES
Abstract of the Disclosure A novel cleaning and drying composition is disclosed which has a number of unique proper-ties rendering the composition particularly useful for cleaning and refinishing electrical equipment and tools. The composition preferably comprises about 30% ethanol, 50% methylene chloride, 15%
1,1,1-trichloroethane and 5% perchloroethylene;
this combination of ingredients gives a final product that dissolves water and many organic materials while at the same time having a high evaporation rate and flame resistance (flash point greater than 100°F.). The composition also gives a visual indication of the need for recleaning and replacement thereof by becoming cloudy when ex-cessive moisture has been absorbed.
(Docket No. 16752)
AND HYDROPHOBIC CONTAMINANTS FROM SURFACES
Abstract of the Disclosure A novel cleaning and drying composition is disclosed which has a number of unique proper-ties rendering the composition particularly useful for cleaning and refinishing electrical equipment and tools. The composition preferably comprises about 30% ethanol, 50% methylene chloride, 15%
1,1,1-trichloroethane and 5% perchloroethylene;
this combination of ingredients gives a final product that dissolves water and many organic materials while at the same time having a high evaporation rate and flame resistance (flash point greater than 100°F.). The composition also gives a visual indication of the need for recleaning and replacement thereof by becoming cloudy when ex-cessive moisture has been absorbed.
(Docket No. 16752)
Description
7~3~
COMPOSITION CAPABLE OF REMOVING HYDROPHILIC
AND HYDROPHOBIC CONT~MIN~NTS_FROM SURFACES
Back~round of the Invention 1. Field of the Invention The present invention is concerned with novel compositions which are capable of removing both hydrophilic and hydrophobic contaminants from surfaces. More particularly, it is concerned with compositions which are especially suited for cleaning and refinishing electrical equipment and tools, and to this end the compositions have a number of unique properties. Principal among these properties are the ahility to dissolve water and organic materials, coupled with high evaporation rates and resistance to flaming.
COMPOSITION CAPABLE OF REMOVING HYDROPHILIC
AND HYDROPHOBIC CONT~MIN~NTS_FROM SURFACES
Back~round of the Invention 1. Field of the Invention The present invention is concerned with novel compositions which are capable of removing both hydrophilic and hydrophobic contaminants from surfaces. More particularly, it is concerned with compositions which are especially suited for cleaning and refinishing electrical equipment and tools, and to this end the compositions have a number of unique properties. Principal among these properties are the ahility to dissolve water and organic materials, coupled with high evaporation rates and resistance to flaming.
2. Description of the Prior Art Equipment and tools used by electrical utilities of*en ~ecome contaminated with a large variety of materials such as grease, dirt, salt and water. Such equipment and tools thus need to be cleaned and refinished periodically, in order to maintain safe operating conditions. Popular cleaners hereto-fore used for this purpose have generally included chlorinated - solvents such as perchloroethylene and trichloroethane. These sol~ents do not, however, remove water or wet contamination that may be tightly held onthe surface of a well-used tool.
,. i .
- . ~ -:~' , ' , . .
Removal of such water is important not only to maxlmize the electrical integrity of the tool, but also to ensure a good bond when the tool is recoated.
There are of course solvents that can readil~ remove water, such as alcohol or acetone. These solvents are highly flammable however, havin~ flash points well below 100F., and thereby present a danger during use. Heretofore known solvents which dissolve water and have flash points greater than 100F.
evaporate far too slowly for practical use as a cleaner dryer.
Prior patents describing various types of cleaning compositions include: U.S. Patents Nos. 3,592,691, 3,625,763,
,. i .
- . ~ -:~' , ' , . .
Removal of such water is important not only to maxlmize the electrical integrity of the tool, but also to ensure a good bond when the tool is recoated.
There are of course solvents that can readil~ remove water, such as alcohol or acetone. These solvents are highly flammable however, havin~ flash points well below 100F., and thereby present a danger during use. Heretofore known solvents which dissolve water and have flash points greater than 100F.
evaporate far too slowly for practical use as a cleaner dryer.
Prior patents describing various types of cleaning compositions include: U.S. Patents Nos. 3,592,691, 3,625,763,
3,743,542, 3,546,304, 3,574,123, 3,789,007 and 4,023,984.
Summary of the Invention Greatly improved cleaning and drying compositions which overcome the problems noted above have now been discovered.
Broadly speaking, the compositions comprise, wherein all percentages are by weight, based upon the total weight of the composition taken as 100~, a basic mixture having therein from about 25 to 35~ ethanol and ~rom about 40 to 70% of a compound selected from the group consisting of methylene chloride, *
"Freon 11" and mixtures thereof. In addition, from about 0 to 35% of an adjunct admixed with the basic mixture can be included which has one or more chlorinated hydrocarbons therein. The adjunct should be such as to not substantially lower the flame resistance of the basic mixture, however.
In more preferred forms r the ethanol should be present at a level of about 30% and the adjunct should include 1,1,1-trichloroethane and perchloroethylene, in order to increase *Trademark for trichlorofluoromethane the solveIIt properties of the o~erall composition.
Compositions in accordance with the invention have flash points of greater than 100 F., can remove w~ter and various other materials such as organic contaminants, and give a visual indication of when the composition should he replaced. This unique combination of properties has here~o-fore not been available in any known composition.
Description of the Preferred Embodiments __ The compositions of the present invention are in liquid form and are particularly adapted for cleaning and drying surfaces such as those on electrical equipment and tools. The compositions are capable of removing both hydrophilic and hydrophobic contaminants from surfaces, and have a variety of desirable properties. The basic mixture of the compositions of the invention have therein from about 25 to 35% ethanol and from about 40 to 70~ of a compound selected from the group consisting of methylene chloride, "Freon ll" and mixtures thereof. ~rom about 0 to 35% of an adjunct can be admixed with the basic mixture and includes one or more chlorinated hydrocarbons; the adjuncts should be such as to not substantially lower the flame resistance of the basic mixture (i.e., flash point should be higher than about 100F.) and should not evaporate at an excessi~ely slow rate (the rate should be less than about 2, with the evaporation rate of butyl acetate taken as l). ~hroughout the instant specification and claims, all percentages are given on a weight bas~s, based upon the total weight of the composition taken as 100%.
The ethanol component of the compositions of the invention is most preferably present at a le~el of about 30%.
~ *Trademark for trichlorofluoromethane : - ' ~LZ~Q3~
The function of the alcohol is believed to be as a dryer and water remover. Below about 25~, the overall compositions have been found to be inefficient at removing water; on ~he other hand, above about 35~ ethanol, the flame resistance of S the compositions is excessively lowered. Therefore, a cerkain degree of criticality exists with respect to the use o ethanol, and the percentages of use.
It will also be understood that denatured ethyl alcohol has actually been used in the invention. The de-naturant in the alcohol is a combination of methyl isobutyl ketone and heptane, and the alcohol is 95~ ethanol and 5% denaturant. Although the specific chemical identity of the denaturant is not critical, it is preferred that the denaturants have relatively rapid evaporation rates, i.e., greater than about 1.5, with n-butyl acetate being taken as 1. For example, kerosene or gasoline as denaturants ~lould not evaporate with sufficient rapidity and should not be used for this purpose. Of course, pure ethanol could also be used in the invention if available.
The other component of the basic mixture is selected 2~ from the group consisting of meth~lene chloride and "Freon 11"
and mixtures thereof. This component serves as a vapor phase flame retardant for the ethanol, and in effect raises the flash point of the latter. Here again, the amount of this component used in the basic mixture is of some importance in order to obtain adequate flame protection. Methylene chloride is the preferred component and not only functions as a flame retardant because of its high relative evaporation rate but because it itself is not flammable. "Freon 11" has these ; *Trademark for trichlorofluoromethane.
~Z7038 properties as well, but methylene chloride is nevertheless preferred because of its higher boiling point. The most preferred level of use o~ methylene chloride is about 50~.
The adjunct can be used at a level o from abou~ 0 ~o 35%, most preferably about 20%. The ad]unct includes a chloxinated hydrocarbon selected ~rom the group consistiny o l,l,l-trichloroethane, perchloroethylene, 1,1,2-tri-chloroethane and propylene dichloride. In particularly preferred forms, the ad~unct consists essentially of about 15% l,l,l-trichloroethane and about 5% perchloroethylene.
The adjunct serves to add variety of chemical types to the compositions so that they will be solvent for a greater variety o materials. Furthermore, the evaporation rates of the particular chlorinated hydrocarbons listed are closer to that of the preferred ethyl alcohol. These features increase the quality of the cleaner, but do not necessarily add to the properties of water solubility, rapid evaporation and flame retardancy. This unusual combination of properties can be obtained in a composition which includes only ethanol and methylene chloride (preferably 30% alcohol, 70% methylene chloride).
The chlorinated hydrocarbons used in the adjunct should all be of a so-called vapor degreasing ~rade, in order that catalytic decomposition does not occur during storage of the composition. However, this is not an absolute Pssential to the invention.
In preparative procedures, the selected ingredients are simply admixed at ambient temperatures to yield the final . .
~Z~
composition. No special steps or mixing procedures are required.
The most preferred composition of the invention as described above has a flash point of about 116~F., and a water solvency (ml.H2O per 100 grams of composition) of
Summary of the Invention Greatly improved cleaning and drying compositions which overcome the problems noted above have now been discovered.
Broadly speaking, the compositions comprise, wherein all percentages are by weight, based upon the total weight of the composition taken as 100~, a basic mixture having therein from about 25 to 35~ ethanol and ~rom about 40 to 70% of a compound selected from the group consisting of methylene chloride, *
"Freon 11" and mixtures thereof. In addition, from about 0 to 35% of an adjunct admixed with the basic mixture can be included which has one or more chlorinated hydrocarbons therein. The adjunct should be such as to not substantially lower the flame resistance of the basic mixture, however.
In more preferred forms r the ethanol should be present at a level of about 30% and the adjunct should include 1,1,1-trichloroethane and perchloroethylene, in order to increase *Trademark for trichlorofluoromethane the solveIIt properties of the o~erall composition.
Compositions in accordance with the invention have flash points of greater than 100 F., can remove w~ter and various other materials such as organic contaminants, and give a visual indication of when the composition should he replaced. This unique combination of properties has here~o-fore not been available in any known composition.
Description of the Preferred Embodiments __ The compositions of the present invention are in liquid form and are particularly adapted for cleaning and drying surfaces such as those on electrical equipment and tools. The compositions are capable of removing both hydrophilic and hydrophobic contaminants from surfaces, and have a variety of desirable properties. The basic mixture of the compositions of the invention have therein from about 25 to 35% ethanol and from about 40 to 70~ of a compound selected from the group consisting of methylene chloride, "Freon ll" and mixtures thereof. ~rom about 0 to 35% of an adjunct can be admixed with the basic mixture and includes one or more chlorinated hydrocarbons; the adjuncts should be such as to not substantially lower the flame resistance of the basic mixture (i.e., flash point should be higher than about 100F.) and should not evaporate at an excessi~ely slow rate (the rate should be less than about 2, with the evaporation rate of butyl acetate taken as l). ~hroughout the instant specification and claims, all percentages are given on a weight bas~s, based upon the total weight of the composition taken as 100%.
The ethanol component of the compositions of the invention is most preferably present at a le~el of about 30%.
~ *Trademark for trichlorofluoromethane : - ' ~LZ~Q3~
The function of the alcohol is believed to be as a dryer and water remover. Below about 25~, the overall compositions have been found to be inefficient at removing water; on ~he other hand, above about 35~ ethanol, the flame resistance of S the compositions is excessively lowered. Therefore, a cerkain degree of criticality exists with respect to the use o ethanol, and the percentages of use.
It will also be understood that denatured ethyl alcohol has actually been used in the invention. The de-naturant in the alcohol is a combination of methyl isobutyl ketone and heptane, and the alcohol is 95~ ethanol and 5% denaturant. Although the specific chemical identity of the denaturant is not critical, it is preferred that the denaturants have relatively rapid evaporation rates, i.e., greater than about 1.5, with n-butyl acetate being taken as 1. For example, kerosene or gasoline as denaturants ~lould not evaporate with sufficient rapidity and should not be used for this purpose. Of course, pure ethanol could also be used in the invention if available.
The other component of the basic mixture is selected 2~ from the group consisting of meth~lene chloride and "Freon 11"
and mixtures thereof. This component serves as a vapor phase flame retardant for the ethanol, and in effect raises the flash point of the latter. Here again, the amount of this component used in the basic mixture is of some importance in order to obtain adequate flame protection. Methylene chloride is the preferred component and not only functions as a flame retardant because of its high relative evaporation rate but because it itself is not flammable. "Freon 11" has these ; *Trademark for trichlorofluoromethane.
~Z7038 properties as well, but methylene chloride is nevertheless preferred because of its higher boiling point. The most preferred level of use o~ methylene chloride is about 50~.
The adjunct can be used at a level o from abou~ 0 ~o 35%, most preferably about 20%. The ad]unct includes a chloxinated hydrocarbon selected ~rom the group consistiny o l,l,l-trichloroethane, perchloroethylene, 1,1,2-tri-chloroethane and propylene dichloride. In particularly preferred forms, the ad~unct consists essentially of about 15% l,l,l-trichloroethane and about 5% perchloroethylene.
The adjunct serves to add variety of chemical types to the compositions so that they will be solvent for a greater variety o materials. Furthermore, the evaporation rates of the particular chlorinated hydrocarbons listed are closer to that of the preferred ethyl alcohol. These features increase the quality of the cleaner, but do not necessarily add to the properties of water solubility, rapid evaporation and flame retardancy. This unusual combination of properties can be obtained in a composition which includes only ethanol and methylene chloride (preferably 30% alcohol, 70% methylene chloride).
The chlorinated hydrocarbons used in the adjunct should all be of a so-called vapor degreasing ~rade, in order that catalytic decomposition does not occur during storage of the composition. However, this is not an absolute Pssential to the invention.
In preparative procedures, the selected ingredients are simply admixed at ambient temperatures to yield the final . .
~Z~
composition. No special steps or mixing procedures are required.
The most preferred composition of the invention as described above has a flash point of about 116~F., and a water solvency (ml.H2O per 100 grams of composition) of
4.5; however, if the composition is slightly altered, e.g., to 40~ methylene chloride, 20% ethyl alcohol, 30% 1,1,1-trichloroethane and 10% perchloroethylene, the flash point drops to 82F., and the water solvency power is reduced by more than half, to 2.2.
The compositions o the invention exhibit a number of unique properties in combination. As noted above, the compositions dissolve water and a wide variety of other contaminants; the 1ame resistance of the compositions is high (flash point of greater than about 100F); the compositions evaporate rapidly; and the compositions give a visual indication of the need for recleaning and recoating by becoming cloudy upon absorption of sufficient amounts of moisture. This combination of properties is highly advantageous and novel.
,~
The compositions o the invention exhibit a number of unique properties in combination. As noted above, the compositions dissolve water and a wide variety of other contaminants; the 1ame resistance of the compositions is high (flash point of greater than about 100F); the compositions evaporate rapidly; and the compositions give a visual indication of the need for recleaning and recoating by becoming cloudy upon absorption of sufficient amounts of moisture. This combination of properties is highly advantageous and novel.
,~
Claims (4)
1. A cleaning and drying composition consisting essential-ly of, wherein all percentages are by weight, based upon the total weight of the composition taken as 100%:
about 30% ethanol;
about 50% of a compound selected from the group consisting of methylene chloride, trichlorofluoromethane and mixtures thereof; and about 20% of additional material comprising a chlorinated hydrocarbon selected from the group consisting of 1,1,1-trichloroethane, perchloroethylene, 1,1,2-trichloroethane, propylene dichloride and mixtures thereof, said composition having a flash point of greater than about 100°F, the ability to absorb moisture and dissolve a variety of organic materials, and the property of becoming cloudy when excessive moisture has been absorbed thereby.
about 30% ethanol;
about 50% of a compound selected from the group consisting of methylene chloride, trichlorofluoromethane and mixtures thereof; and about 20% of additional material comprising a chlorinated hydrocarbon selected from the group consisting of 1,1,1-trichloroethane, perchloroethylene, 1,1,2-trichloroethane, propylene dichloride and mixtures thereof, said composition having a flash point of greater than about 100°F, the ability to absorb moisture and dissolve a variety of organic materials, and the property of becoming cloudy when excessive moisture has been absorbed thereby.
2. The composition as set forth in Claim l wherein the said compound is methylene chloride.
3. The composition as set forth in Claim l wherein said chlorinated hydrocarbon is of vapor degreasing grade.
4. A cleaning and drying composition, according to Claim l which consists essentially of, wherein all percentages are by weight, based upon the total weight of the composition taken as 100%:
about 30% ethanol;
about 50% methylene chloride;
about 15% 1,1,1-trichloroethane; and about 5% perchloroethylene.
about 30% ethanol;
about 50% methylene chloride;
about 15% 1,1,1-trichloroethane; and about 5% perchloroethylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3419579A | 1979-04-27 | 1979-04-27 | |
| US34,195 | 1979-04-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127038A true CA1127038A (en) | 1982-07-06 |
Family
ID=21874894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA333,202A Expired CA1127038A (en) | 1979-04-27 | 1979-08-03 | Composition capable of removing hydrophilic and hydrophobic contaminants from surfaces |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1127038A (en) |
-
1979
- 1979-08-03 CA CA333,202A patent/CA1127038A/en not_active Expired
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|---|---|---|---|
| MKEX | Expiry |