CA1148976A - Bimetallic soaps and processes therefor - Google Patents
Bimetallic soaps and processes thereforInfo
- Publication number
- CA1148976A CA1148976A CA000337052A CA337052A CA1148976A CA 1148976 A CA1148976 A CA 1148976A CA 000337052 A CA000337052 A CA 000337052A CA 337052 A CA337052 A CA 337052A CA 1148976 A CA1148976 A CA 1148976A
- Authority
- CA
- Canada
- Prior art keywords
- zinc
- calcium
- bimetallic
- soap
- soaps
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Lubricants (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
BIMETALLIC SOAPS AND PROCESSES THEREFOR
ABSTRACT OF THE DISCLOSURE
Uniformly coformed soaps of calcium and zinc at zinc/
calcium atomic ratios of about 2/3 to about 3/1 are provided having unexpectedly low melting points and outstanding lubricant and anti-stick properties.
Suitable methods of preparing same are disclosed based upon the simultaneous reaction of both calcium and zinc supplied in intimate association in correct proportions in a source material which is intensively dispersed in a liquid mass containing avail-able fatty acid groups and maintained at a suitable reaction temp-erature so as to form a finely divided pulverulent bimetallic soap of the uniform composition desired.
ABSTRACT OF THE DISCLOSURE
Uniformly coformed soaps of calcium and zinc at zinc/
calcium atomic ratios of about 2/3 to about 3/1 are provided having unexpectedly low melting points and outstanding lubricant and anti-stick properties.
Suitable methods of preparing same are disclosed based upon the simultaneous reaction of both calcium and zinc supplied in intimate association in correct proportions in a source material which is intensively dispersed in a liquid mass containing avail-able fatty acid groups and maintained at a suitable reaction temp-erature so as to form a finely divided pulverulent bimetallic soap of the uniform composition desired.
Description
~1~8976 BACKGROUND OF THE INVENTION
This invention relates to uniquely alloyed mixed metal soaps of calcium and zinc having outstanding lubricant qualities, partic:ularly for polymeric resins and plastics, and which melt sharply at surprisingly low temperatures.
Several metallic soaps of substantially saturated fatty acids such as stearic acid, notably calcium strearate and zinc stearate, have achieved commerical status as lubricants and/or anti-tack agents (abherents) in the plastics and metal working fields. However, to date mixed metal soaps have not received any special acclaim for such functions or exhibited any unexpected advantages therewith. Instead, the use of combined metal lubri-cants has evidently provided only expected levels of performance pretty much in direct proportion to the amounts of the individual components and their relative contributions when used separately.
It i8 a major objective of this invention to provide pulverulent metallic soaps, e.g. stearates, with superior lubri-cant and abherent properties. A related object is to provide mixed metal soaps of exceptional uniformity, homogeneity and suitability for lubricant type uses.
A more specific goal of this invention is to provide mixed metal soaps of calcium and zinc in such intimate associa-tion that they are completely homogeneous even in their finest particulate state of subdivision. Another specific object is to provide such soaps which are easy to handle, free flowing powders at normal temperatures and yet melt quickly and uniformly under heat processing operations, such as the milling and thermo-forming of polymeric resins and similar plastic substances. Still . . .
., , ,, .. .
:: :
.
., .
-~897t;
other objectives and advantages will be obvious from the detailed descriptiOn of our invention which follows.
.
SUMMARY OF THE INVENTION
~ In accordance with the present invention such highly desirable lubricant soaps can be obtained by intensively mixing together a liquid mass containing fatty acid anionic groups and a metal bearing material the metal content of which consists essentially of zinc and calcium in an atomic ratio of zinc/cal- : .
cium of between 2/3 and 3/1, the consistency and uniformity of said metal bearing material being such that it is readily dispersed by said intensive mixing at a substantially constant Zn/Ca ratio throughout said liquid mass and maintaining the temperature of the resultant mixture at a level sufficient to effect simultaneous reaction of both zinc and calcium with said fatty acid groups but not substantially above 100C, thereby effecting simultaneous formation of zinc and calcium soaps which coprecipitate from the reaction mixture in intimate association as fine solid particulates of substantially uniform metallic ratio.
The first reactant, namely the liquid mass containing fatty acid anionic groups can be either of two general types as follows:
1) Molten fatty acids per se or fatty acids liquified `~ ~ with the aid of hot, chemically inert miscible di-: luents or solvents such as paraffinic oils like kerosene; and
This invention relates to uniquely alloyed mixed metal soaps of calcium and zinc having outstanding lubricant qualities, partic:ularly for polymeric resins and plastics, and which melt sharply at surprisingly low temperatures.
Several metallic soaps of substantially saturated fatty acids such as stearic acid, notably calcium strearate and zinc stearate, have achieved commerical status as lubricants and/or anti-tack agents (abherents) in the plastics and metal working fields. However, to date mixed metal soaps have not received any special acclaim for such functions or exhibited any unexpected advantages therewith. Instead, the use of combined metal lubri-cants has evidently provided only expected levels of performance pretty much in direct proportion to the amounts of the individual components and their relative contributions when used separately.
It i8 a major objective of this invention to provide pulverulent metallic soaps, e.g. stearates, with superior lubri-cant and abherent properties. A related object is to provide mixed metal soaps of exceptional uniformity, homogeneity and suitability for lubricant type uses.
A more specific goal of this invention is to provide mixed metal soaps of calcium and zinc in such intimate associa-tion that they are completely homogeneous even in their finest particulate state of subdivision. Another specific object is to provide such soaps which are easy to handle, free flowing powders at normal temperatures and yet melt quickly and uniformly under heat processing operations, such as the milling and thermo-forming of polymeric resins and similar plastic substances. Still . . .
., , ,, .. .
:: :
.
., .
-~897t;
other objectives and advantages will be obvious from the detailed descriptiOn of our invention which follows.
.
SUMMARY OF THE INVENTION
~ In accordance with the present invention such highly desirable lubricant soaps can be obtained by intensively mixing together a liquid mass containing fatty acid anionic groups and a metal bearing material the metal content of which consists essentially of zinc and calcium in an atomic ratio of zinc/cal- : .
cium of between 2/3 and 3/1, the consistency and uniformity of said metal bearing material being such that it is readily dispersed by said intensive mixing at a substantially constant Zn/Ca ratio throughout said liquid mass and maintaining the temperature of the resultant mixture at a level sufficient to effect simultaneous reaction of both zinc and calcium with said fatty acid groups but not substantially above 100C, thereby effecting simultaneous formation of zinc and calcium soaps which coprecipitate from the reaction mixture in intimate association as fine solid particulates of substantially uniform metallic ratio.
The first reactant, namely the liquid mass containing fatty acid anionic groups can be either of two general types as follows:
1) Molten fatty acids per se or fatty acids liquified `~ ~ with the aid of hot, chemically inert miscible di-: luents or solvents such as paraffinic oils like kerosene; and
2) Aqueous solutions of water soluble soaps, usually of alkali metals like sodium and pot~ssium, but : 2 . . , - ' .'~ ' ~ ' -~ : . ..
397~;
including ammonium soaps or certain organic amine soaps, e.g. those formed by triethanol amine.
DETAILED DESCRIPTION OF INVENTION
Said second type of liquid mass, i.e. an aqueous solution of water soluble soap, is preferred because of the handling convenience of same as well as the simplicity of pro-viding a suitably homogeneous, easily dispersible metal bearing coreactant. Thus, aqueous solutions of water soluble salts of calcium and zinc can be readily prepared of almost any desirable metals content and with very uniform and precise control of the atomic ratio of zinc/calcium therein. On the other hand, when the fatty acid reactant is supplied as the first type of liquid mass, i.e. in the free acid form, the coreactant metal bearing material will generally be derived from either the free metals or their oxides or hydroxides, Special attention is then required to provide such materials in a sufficiently fine state of sub-division to render same readily dispersible in said liquid mass while simultaneously insuring a correct, uniform ratio of calcium and zinc throughout said subdivided material.
We have found that the reaction between the free fatty acid type medium and the appropriate metal bearing coreactant materials therefor can best be carried out at temperatures between about 80 and llo& and preferably at temperatures between about 90 and 105&. H~wever, when the reaction is betw~en aqueous soap solution and an aqueous solution of metal salts, soE~at lower reaction tempera-tures are generally in order with the range of prim~ry interest being from about 50C to about loo& and most preferably from about 60 to 90C.
_3_ :
, .. .
' . .
~1~8~76 The coformed calcium and zinc soaps of this invention having zinc/calcium atomic ratios of between 2/3 and 3/1 are ex-ceptionally effective as lubricating and processing aids for plastics or metal working, molding and like operations. This perforrnance appears to be attributable to the intimate associa-tion of zinc and calcium soaps therein, somewhat analogous to the amalgamation of metals in alloys, as shown by the sharp and surprisinglylow melting points possessed by the present soaps. Thus, although the melting point of calcium stearate is about 155C, the melting points of coformed zinc-calcium stearates prepared in accordance with this invention at zinc/
calcium atomic ratios of between 2/3 and 3/1 are actually signi-ficantly below even the 122C melting point of zinc stearate its~elf. The eutectic among these mixed zinc-calcium stearates appears to occur at a Zn/Ca atomic ratio of about 3/2, exhibiting a melting point of only 180C as well as peak abherent properties.
In fact, with soap forming fatty acids of greatest interest, i.e. those formed from substantially saturated fatty acids containing from about 12 to 24 carbon atoms, the optimum propor-tions of Zn/Ca in the coformed soaps of this invention appearsto lie between atomic ratios of about 1/1 and about 2/1.
Futher details of our invention are illustrated by the specific examples and embodiments which follow.
Into a jacketed ~tainless steel reactor equipped with a variable speed stirrer, eight liters of a dilute aqueous solution of sodium stearate (0.125 molar) is charged and heated .~ .
:' ..: ''' ' ' '' ' - ' ' ~ , ' . , : ' . ~ :
- .~ . .
to about 80C while stirring slowly. The stirrer speed is then increased and 325 milliliters of a uniform aqueous solutLon containing 74 grams CaC12 and 127g ZnC12 per liter is added to the so~ium stearate solution while mixing rapidly and maintaining the ternperature of the mixture at about 80C during addition of said solution of metal chlorides and for an additional 30 minutes thereafter. The resulting fine white powdery precipi-tate is collected in a filter, washed several times with warm water and dried to constant weight in shallow trays in a forced air oven operated at a temperature of 75 to 85C. About 300 grams of fluffy white product are obtained having a uniform sharp melting point of 108C + 1 and possessing the following analytical properties:
Moisture Content 0.5~ by wt.
Total ash content 11.8% " "
Zinc content 6.5% " "
Calcium content 2.7% " "
Atomic Ratio (Zn/Ca) 1.48 A series of runs was made using the equipment described in Example 1 and substantially the same reaction conditions ex-cept that the proportions of CaC12 and ZnC12 in the uniform aqueous solution added to the sodium stearate solution was varied from run to run. In each run a fine, fluffy, white powdered soap was obtained, the melting points of which varied from run to run as shown in the following table:
V
.
~ '' ' ~1~8976 ZnC12 CaCl2 Zn/Ca Example Conc Conc Atomic Melting Pt.
No. g./l g./l Ratio of Product _ _ 2 66 124 0.43 120C
S 3 87 107 0.67 115C
4 109 89 1.0 113C
153 53 2.3 113C
6 164 44 3.0 116C
7 175 36 4.0 119C
It will be seen from the above results that simultaneously formed and coprecipitated zinc-calcium stearates in which the Zn/Ca ratio is between about 2/3 and 3/1 have surprisingly low melting points, i.e. significantly lower than the melting point of pure zinc stearate even though the melting point of pure calcium stearate is far higher.
Obviously, many substitutions and variations are possible in the above examples within the general guidelines and operating limits already specified for the present invention.
For example, potassium stearate or any other sufficiently soluble stearate can be used as the fatty acid group source and other water soluble salts of zinc and calcium, such as the nitrates, can be used in forming the uniform aqueous coreactant solution with substantially the same results provided that the zinc and calcium are simultaneously reacted to form particulate bimetallic stearates having uniform atomic metal ratios within the ranges specified.
.
.~, . .. .
.. . '', . , ' . ' ' .' , ' ~ ~ ~
', ' . ' ' ' ,- , . - '' .
- . . . ~ . ., :
~1~8976 The coprecipitated bimetallic stearate produced in Example 1 was teasted as an internal lubricant and anti-stick additive in heat curable polyester resin in direct comparison with pure zinc stearate and pure calcium stearate. The testing was carried out with thermosetting syrups prepared from an unsaturated polyester resin sold under the Trade Name of "Hatco Polyester Resin GR 13037" using the following basic formulation recipe in parts by weight:
Resin syrup - 100 pts.
Para-t-butyl perbenzoate - 0.6 pts.
Metal stearate powder - "X" pts.
The concentration t"X") of each of the metal stearate additives in the above recipe Was varied from 1 part to 3 parts by welght and casts of the well-mixed syrups were cured on shiny aluminum foils for 5 minutes at 163C. The cured films con-taining the coprecipitated zinc-calcium stearate of Example 1 at concentrations of 2 parts and above released readily from the foil whereas about 3 parts by weight of the pure metal stearates was required for successful parting of the cured sample from the metal support. Furthermore, the parted surfaces of the resin films containing the coprecipitated stearates were noticeably smoother and glossier than those containing the pure metal stearate additives.
Because of the intimate state of association of the calcium and zinc species in the coformed bimetallic soaps of .
. : . - .
1~8976 this invention and the resulting ease of melting and fusion thereof, these products should prove compatible with a wide variety of resins and serve as versatile processing aids and viscosity control agents as well as abherent additives in many environments.
~a , ... . .. . . . . . .
.
397~;
including ammonium soaps or certain organic amine soaps, e.g. those formed by triethanol amine.
DETAILED DESCRIPTION OF INVENTION
Said second type of liquid mass, i.e. an aqueous solution of water soluble soap, is preferred because of the handling convenience of same as well as the simplicity of pro-viding a suitably homogeneous, easily dispersible metal bearing coreactant. Thus, aqueous solutions of water soluble salts of calcium and zinc can be readily prepared of almost any desirable metals content and with very uniform and precise control of the atomic ratio of zinc/calcium therein. On the other hand, when the fatty acid reactant is supplied as the first type of liquid mass, i.e. in the free acid form, the coreactant metal bearing material will generally be derived from either the free metals or their oxides or hydroxides, Special attention is then required to provide such materials in a sufficiently fine state of sub-division to render same readily dispersible in said liquid mass while simultaneously insuring a correct, uniform ratio of calcium and zinc throughout said subdivided material.
We have found that the reaction between the free fatty acid type medium and the appropriate metal bearing coreactant materials therefor can best be carried out at temperatures between about 80 and llo& and preferably at temperatures between about 90 and 105&. H~wever, when the reaction is betw~en aqueous soap solution and an aqueous solution of metal salts, soE~at lower reaction tempera-tures are generally in order with the range of prim~ry interest being from about 50C to about loo& and most preferably from about 60 to 90C.
_3_ :
, .. .
' . .
~1~8~76 The coformed calcium and zinc soaps of this invention having zinc/calcium atomic ratios of between 2/3 and 3/1 are ex-ceptionally effective as lubricating and processing aids for plastics or metal working, molding and like operations. This perforrnance appears to be attributable to the intimate associa-tion of zinc and calcium soaps therein, somewhat analogous to the amalgamation of metals in alloys, as shown by the sharp and surprisinglylow melting points possessed by the present soaps. Thus, although the melting point of calcium stearate is about 155C, the melting points of coformed zinc-calcium stearates prepared in accordance with this invention at zinc/
calcium atomic ratios of between 2/3 and 3/1 are actually signi-ficantly below even the 122C melting point of zinc stearate its~elf. The eutectic among these mixed zinc-calcium stearates appears to occur at a Zn/Ca atomic ratio of about 3/2, exhibiting a melting point of only 180C as well as peak abherent properties.
In fact, with soap forming fatty acids of greatest interest, i.e. those formed from substantially saturated fatty acids containing from about 12 to 24 carbon atoms, the optimum propor-tions of Zn/Ca in the coformed soaps of this invention appearsto lie between atomic ratios of about 1/1 and about 2/1.
Futher details of our invention are illustrated by the specific examples and embodiments which follow.
Into a jacketed ~tainless steel reactor equipped with a variable speed stirrer, eight liters of a dilute aqueous solution of sodium stearate (0.125 molar) is charged and heated .~ .
:' ..: ''' ' ' '' ' - ' ' ~ , ' . , : ' . ~ :
- .~ . .
to about 80C while stirring slowly. The stirrer speed is then increased and 325 milliliters of a uniform aqueous solutLon containing 74 grams CaC12 and 127g ZnC12 per liter is added to the so~ium stearate solution while mixing rapidly and maintaining the ternperature of the mixture at about 80C during addition of said solution of metal chlorides and for an additional 30 minutes thereafter. The resulting fine white powdery precipi-tate is collected in a filter, washed several times with warm water and dried to constant weight in shallow trays in a forced air oven operated at a temperature of 75 to 85C. About 300 grams of fluffy white product are obtained having a uniform sharp melting point of 108C + 1 and possessing the following analytical properties:
Moisture Content 0.5~ by wt.
Total ash content 11.8% " "
Zinc content 6.5% " "
Calcium content 2.7% " "
Atomic Ratio (Zn/Ca) 1.48 A series of runs was made using the equipment described in Example 1 and substantially the same reaction conditions ex-cept that the proportions of CaC12 and ZnC12 in the uniform aqueous solution added to the sodium stearate solution was varied from run to run. In each run a fine, fluffy, white powdered soap was obtained, the melting points of which varied from run to run as shown in the following table:
V
.
~ '' ' ~1~8976 ZnC12 CaCl2 Zn/Ca Example Conc Conc Atomic Melting Pt.
No. g./l g./l Ratio of Product _ _ 2 66 124 0.43 120C
S 3 87 107 0.67 115C
4 109 89 1.0 113C
153 53 2.3 113C
6 164 44 3.0 116C
7 175 36 4.0 119C
It will be seen from the above results that simultaneously formed and coprecipitated zinc-calcium stearates in which the Zn/Ca ratio is between about 2/3 and 3/1 have surprisingly low melting points, i.e. significantly lower than the melting point of pure zinc stearate even though the melting point of pure calcium stearate is far higher.
Obviously, many substitutions and variations are possible in the above examples within the general guidelines and operating limits already specified for the present invention.
For example, potassium stearate or any other sufficiently soluble stearate can be used as the fatty acid group source and other water soluble salts of zinc and calcium, such as the nitrates, can be used in forming the uniform aqueous coreactant solution with substantially the same results provided that the zinc and calcium are simultaneously reacted to form particulate bimetallic stearates having uniform atomic metal ratios within the ranges specified.
.
.~, . .. .
.. . '', . , ' . ' ' .' , ' ~ ~ ~
', ' . ' ' ' ,- , . - '' .
- . . . ~ . ., :
~1~8976 The coprecipitated bimetallic stearate produced in Example 1 was teasted as an internal lubricant and anti-stick additive in heat curable polyester resin in direct comparison with pure zinc stearate and pure calcium stearate. The testing was carried out with thermosetting syrups prepared from an unsaturated polyester resin sold under the Trade Name of "Hatco Polyester Resin GR 13037" using the following basic formulation recipe in parts by weight:
Resin syrup - 100 pts.
Para-t-butyl perbenzoate - 0.6 pts.
Metal stearate powder - "X" pts.
The concentration t"X") of each of the metal stearate additives in the above recipe Was varied from 1 part to 3 parts by welght and casts of the well-mixed syrups were cured on shiny aluminum foils for 5 minutes at 163C. The cured films con-taining the coprecipitated zinc-calcium stearate of Example 1 at concentrations of 2 parts and above released readily from the foil whereas about 3 parts by weight of the pure metal stearates was required for successful parting of the cured sample from the metal support. Furthermore, the parted surfaces of the resin films containing the coprecipitated stearates were noticeably smoother and glossier than those containing the pure metal stearate additives.
Because of the intimate state of association of the calcium and zinc species in the coformed bimetallic soaps of .
. : . - .
1~8976 this invention and the resulting ease of melting and fusion thereof, these products should prove compatible with a wide variety of resins and serve as versatile processing aids and viscosity control agents as well as abherent additives in many environments.
~a , ... . .. . . . . . .
.
Claims (10)
1. A coformed bimetallic soap of calcium and zinc with substantially saturated fatty acids containing from 12 to 24 carbon atoms wherein the zinc/calcium atomic ratio is between about 2/3 and 3/1 and which melts at temperatures sub-stantially lower than pure zinc soap of the corresponding fatty acids.
2. A bimetallic soap as in claim 1 wherein stearic acid is the prevailing fatty acid.
3. A bimetallic soap as in claim 2 wherein the atomic ratio of zinc/calcium is between about 1/1 and about 2/1.
4. A bimetallic soap as in claim 3 wherein the atomic ratio of zinc/calcim is close to 1.5 to 1Ø
5. A process for preparing an intimately coformed, insoluble, bimetallic soap of calcium and zinc which comprises intensively mixing together (1) a liquid mass containing fatty acid groups and (2) a metal bearing material the metal content of which consists essentially of zinc and calcium in an atomic ratio of between about 2/3 and about 3/1, the consistency and uniformity of said metal bearing material being such that it is readily dispersed by said intensive mixing at a substantially constant Zn/Ca ratio throughout said liquid mass and maintaining the temperature of the resultant mixture at a level sufficient to effect simultaneous reaction of both zinc and calcium with said fatty acid groups but not substantially above 100°C, thereby effecting simultaneous formation of zinc and calcium soaps which coprecipitate from the reaction mixture in intimate association as fine solid particulates of substantially uniform composition.
6. The process of claim 5 wherein said liquid mass comprises free fatty acids containing 12 to 24 carbon atoms and said metal bearing material consists essentially of finely divided solid particles containing uniform proportions of zinc and calcium.
7. The process of claim 6 wherein said particles are chosen from the group consisting of metallic oxides, metal hydroxides and free metals.
8. The process of claim 5 wherein said liquid mass comprises an aqueous solution of soap formed from substantially saturated fatty acids containing 12 to 24 carbon atoms, said metal bearing material comprises an aqueous solution of calcium and zinc salts and said simultaneous reaction is carried out at a temperature of at least about 50°C.
9. The process of claim 8 wherein stearic acid is the prevailing fatty acid and said simultaneous reaction is carried out at a temperature of between about 60 and 90°C.
10. The process of claim 5 wherein the atomic ratio of zinc/calcium is between about 1/1 and about 2/1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US95329578A | 1978-10-20 | 1978-10-20 | |
| US953,295 | 1978-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148976A true CA1148976A (en) | 1983-06-28 |
Family
ID=25493792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000337052A Expired CA1148976A (en) | 1978-10-20 | 1979-10-04 | Bimetallic soaps and processes therefor |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5598299A (en) |
| BE (1) | BE878713A (en) |
| CA (1) | CA1148976A (en) |
| DE (1) | DE2942237A1 (en) |
| ES (1) | ES484437A1 (en) |
| FR (1) | FR2439231A1 (en) |
| GB (1) | GB2032428B (en) |
| IT (1) | IT1207272B (en) |
| NL (1) | NL7907647A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4296174A (en) * | 1980-08-08 | 1981-10-20 | E. I. Du Pont De Nemours And Company | Spandex filaments containing certain metallic soaps |
| DE3347532A1 (en) * | 1983-12-30 | 1985-07-11 | Basf Ag, 6700 Ludwigshafen | MAGNETIC RECORDING CARRIERS |
| DE3806192A1 (en) * | 1988-02-26 | 1989-09-07 | Neynaber Chemie Gmbh | METHOD FOR PRODUCING POWDERED BASIC METAL SOAPS |
| DE4305944A1 (en) * | 1993-02-26 | 1994-09-01 | Henkel Kgaa | Basic calcium / zinc mixed soaps |
| WO2013183161A1 (en) * | 2012-06-08 | 2013-12-12 | トヨタ自動車株式会社 | Liquid coolant composition for internal combustion engines and operating method for internal combustion engines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL132018C (en) * | 1965-06-14 | |||
| DE1300105C2 (en) * | 1966-03-29 | 1982-01-28 | Akzo Chemie GmbH, 5160 Düren | METHOD FOR PRODUCING NEUTRAL METAL SOAP MIXTURES |
| JPS565500B2 (en) * | 1971-09-03 | 1981-02-05 | ||
| JPS5289612A (en) * | 1976-01-22 | 1977-07-27 | Iwao Hishida | Granular composite of metallic soap |
| DE2823002B2 (en) * | 1978-05-26 | 1981-06-04 | Chemische Werke München Otto Bärlocher GmbH, 8000 München | Process for the production of metal soap granules |
-
1979
- 1979-09-11 BE BE0/197092A patent/BE878713A/en not_active IP Right Cessation
- 1979-09-11 GB GB7931543A patent/GB2032428B/en not_active Expired
- 1979-09-25 ES ES484437A patent/ES484437A1/en not_active Expired
- 1979-10-04 CA CA000337052A patent/CA1148976A/en not_active Expired
- 1979-10-10 FR FR7925262A patent/FR2439231A1/en active Granted
- 1979-10-16 NL NL7907647A patent/NL7907647A/en not_active Application Discontinuation
- 1979-10-18 DE DE19792942237 patent/DE2942237A1/en active Granted
- 1979-10-18 JP JP13366579A patent/JPS5598299A/en active Pending
- 1979-10-19 IT IT7926664A patent/IT1207272B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| NL7907647A (en) | 1980-04-22 |
| BE878713A (en) | 1979-12-31 |
| IT7926664A0 (en) | 1979-10-19 |
| GB2032428A (en) | 1980-05-08 |
| ES484437A1 (en) | 1980-05-16 |
| IT1207272B (en) | 1989-05-17 |
| DE2942237A1 (en) | 1980-04-24 |
| FR2439231A1 (en) | 1980-05-16 |
| DE2942237C2 (en) | 1987-06-25 |
| JPS5598299A (en) | 1980-07-26 |
| FR2439231B1 (en) | 1983-06-24 |
| GB2032428B (en) | 1983-01-12 |
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