CA1231517A - Transparent iron oxide pigment - Google Patents
Transparent iron oxide pigmentInfo
- Publication number
- CA1231517A CA1231517A CA000491603A CA491603A CA1231517A CA 1231517 A CA1231517 A CA 1231517A CA 000491603 A CA000491603 A CA 000491603A CA 491603 A CA491603 A CA 491603A CA 1231517 A CA1231517 A CA 1231517A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- solvent
- iron
- amount
- percent
- 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
- 239000001034 iron oxide pigment Substances 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 239000000049 pigment Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- -1 ferrous compound Chemical class 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229960002089 ferrous chloride Drugs 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical group CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims 4
- 229910001447 ferric ion Inorganic materials 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000011514 reflex Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000001054 red pigment Substances 0.000 abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 235000013980 iron oxide Nutrition 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- MKUWVMRNQOOSAT-UHFFFAOYSA-N but-3-en-2-ol Chemical compound CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 1
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 240000004160 Capsicum annuum Species 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 150000007945 N-acyl ureas Chemical class 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GKRZNOGGALENQJ-UHFFFAOYSA-N n-carbamoylacetamide Chemical compound CC(=O)NC(N)=O GKRZNOGGALENQJ-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- IPWFJLQDVFKJDU-UHFFFAOYSA-N pentanamide Chemical compound CCCCC(N)=O IPWFJLQDVFKJDU-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2220/00—Methods of preparing the interference pigments
- C09C2220/10—Wet methods, e.g. co-precipitation
Abstract
TRANSPARENT IRON OXIDE PIGMENTS
Abstract of the Disclosure The present invention relates to a process for preparing transparent iron oxide pigments comprising reacting an iron compound, an ammonia releasing compound and water in a non-aqueous solvent in which both the iron compound and the ammonia releasing compound have appreciable solubility. The reaction is performed by refluxing this composition. Where a red pigment is desired, a high boiling alcohol may be employed whereby the refluxing is carried out above 200°C which thus converts the pigment to a red iron oxide pigment during the reflex step. In order to get a metallic finish, aluminum flake pigment may be added to a mixture of the iron compound and solvent prior to addition of the ammonia-releasing salt.
Abstract of the Disclosure The present invention relates to a process for preparing transparent iron oxide pigments comprising reacting an iron compound, an ammonia releasing compound and water in a non-aqueous solvent in which both the iron compound and the ammonia releasing compound have appreciable solubility. The reaction is performed by refluxing this composition. Where a red pigment is desired, a high boiling alcohol may be employed whereby the refluxing is carried out above 200°C which thus converts the pigment to a red iron oxide pigment during the reflex step. In order to get a metallic finish, aluminum flake pigment may be added to a mixture of the iron compound and solvent prior to addition of the ammonia-releasing salt.
Description
TRANSPARENT IRON OXIDE PIGMENTS
Background ox the Invention The instant invention relates to transparent iron oxide pigments. More specifically, the instant invention relates to a process for substantially improving the transparency of such pigments.
Iron oxide pigments are found in nature as mineral deposits. There are three types of iron oxide pigments which are found in nature as mineral deposits. These are laminator hematite, and magnetites Laminate is yellow and has a chemical formula of Fox where x is an into-germ As can be seen from its formula, it is a hydrated iron(III~oxide. Hematite is red and has a chemical formula of Foe. It is an an hydrous iron(III)oxide. Magnetize is black and has a chemical formula of Foe. It is considered to be a spinet containing iron) and iron(III)ions.
In addition to the natural mineral deposits, iron oxide pigments can be obtained synthetically. The prior art preparation of iron oxide pigments is well known. Reference is made to various topics concerning iron oxide such as "Pigments (Inorganic)," pages 816-818, vol. 17, Encyclopedia of Chemical Technology, by Kirk-Othmer, 3rd Edition, published by John Wiley Sons. Synthetic methods for preparing iron oxide pigments generally involve the alkali precipitation of iron) compounds from a soluble iron)-~.;231~
salt and the oxidation of the precipitated iron) compound to an iron(III~oxide pigment slurry. The pigment produced by such methods corresponds to the yellow hydrated iron-(III~oxide previously described. The yellow pigment is recovered from the slurry by filtration, washing, and drying. The alkali precipitation must occur under acidic conditions; otherwise, dark brown or black undesirable color shades will be produced. Iron oxide pigments of various yellow shades can be prepared by controlling the temperature and rate of oxidation. Red, orange and other colors can be prepared by calcining the yellow pigments at high tempera-lures.
Iron oxide pigments which have an average particle size less than 0.1 micron are considered to be transparent because they can transmit visible light. Stated another way, "transparent pigment" is pigment having a majority of the particles smaller than the wavelength of light. Iron oxide pigments which have an average particle size greater than 0.1 microns and which cannot transmit visible light are considered to be opaque.
Yellow and red transparent iron oxides are used in combination with aluminum flake pigments to produce autumn-live metallic top coats. The metallic effect is dependent on the degree of transparency of the pigment.
I .7 Iron oxide pigments produced by the alkali precipitation of iron compounds from a soluble iron salt contain salts as a result of the hydrolysis reaction which have to be subsequently washed after the pigment is lit-toned. Also because of the high surface tension of the water, the pigment undergoes agglomeration during drying which makes the pigment hard to disperse. Accordingly, it is the purpose of the instant invention to provide a process for producing extremely fine iron oxide pigments. It is an additional purpose of the instant invention to be able to produce extremely fine red iron oxide pigments during the normal processing, i.e., a one-step reaction whereby the necessity of calcining the yellow iron oxide pigment to get red is eliminated. It is also a purpose of the instant invention to be able to produce a metallic pigment for automobile top coats whereby fracturing of the aluminum flake particles is minimized and the aluminum flake is included during the normal process to produce the yellow or red iron oxide pigment.
Summary of the Invention The present invention relates to a process for preparing transparent iron oxide pigments comprising reacting an iron compound, an ammonia releasing compound and water in a non-aqueous solvent in which both the iron compound and the ammonia-releasing compound have appreciable ~23~7 volubility. The reaction is performed by refluxing this composition. Where a red pigment is desired a high boiling alcohol may be employed whereby the refluxing is carried out above 200C which thus converts the pigment to a red iron oxide pigment during the reflex step. In order to get a metallic finish, aluminum flake pigment may be added to a mixture of the iron compound and solvent prior to addition of the ammonia-releasing salt.
Description o the Preferred Embodiments The iron compounds that are the raw material for the instant invention can be any of the available and known iron salts such as ferrous and ferris sulfate and ferrous and ferris chloride. Ferrous chloride (Fake) is the preferred iron compound for the instant invention In a preferred embodiment the iron compound is mixed with the non-aqueou~ solvent in an amount of about 1 to 50 percent by weight of the solvent or to the limit of volubility. The optimum is about 15%. This composition is then heated to dissolve the iron compound after which the ammonia-releasing compound is added preferably in about stoichiometric amount. The amount of ammonia-releasing compound is about 1 to 20 percent by weight based on the weight of the solvent, optimum about 5 percent. A preferred ammonia-releasing compound is urea. Other suitable ammonia-releasing compounds include various aliphatic and aromatic ~3~LS~'7 asides, amide-nitrile, various ureides traction products of urea with various acid chlorides or anhydries) such as acetylurea. Particularly asides may be used for this purpose such as formamide, acetamide, propionamide, n-butylamide, n-Valeramide, strummed, benæamide, succinmide, and phthalimide. And even more particularly, cyanamide such as calcium cyanamide and other nitrites such as acetonitrile, n-valeronitrile, benzonitrile, p-tolunitrile.
Any polar solvent capable of dissolving the iron compound and the ammonia-releasing compound in equivalent quantities may be employed. Such solvents include various alcohols such as methyl ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, Natalie, n-octyl, n-decyl, n-dodecyl, n-tetra-decal, n-hexadecyl, n-octadecyl, isopropyl, isobutyl, sea-bottle, tert-butyl, isopentyl, Amy, tert-pentyl, cyclopean-tunnel, cyclohexanol, ally, crotyl, methylvinylcarbinol, bouncily ~-phenylethyl, ~-phenylethyl, diphenylcarbinol, triphenylcarbionol, cinnamyl, and glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, glycerol and pentaerythritol. The solvent selected will depend on the iron salt employed, the ammonia-releasing compound and also on whether a yellow or red iron oxide is desired. The ammonia and iron salt are preferably reacted in statue-metric quantities since quantities other than these are uneconomic. Where the iron compound is a ferrous salt, the US
proper proportion is two moles of the ammonia released or 1 mole of urea per mole of ferrous ion. Where a ferris salt is employed, the proportion is 1.5 moles of urea or 3 moles of the ammonia released per mole of ferris ion. A small amount of water is then added and the composition relaxed for from 1 to 24 hours at the reflex temperature of the selected solvent. The amount of water is the stoichiometric amount necessary to produce the desired pimento It may range from about 0 to 5 percent based on the weight of the solvent. The yellow iron oxide pigment generally has a formula Fox. The amount of water added is preferably the stoichiometric amount to provide the desired amount of combined water. In general, it is preferred that the letter x have an average value of 1. For producing yellow iron oxide, a preferred solvent is ethanol which reflexes at from OWE to 80C. Where it it desired to produce a red pigment, a preferred solvent is decal alcohol which has a reflex temperature of 180 to 230C and the mixture should be heated to a temperature above 200C in order to get a red rather than a yellow iron oxide pigment. After refluxing, the product is washed with the non-aqueous solvent, lit-toned, and dried. Conventional filtration and drying equipment may be employed. In order to produce a metallic finish, aluminum flake pigment is added to the mixture of iron compound and solvent prior to the addition of the ammonia releasing salt.
~23~S~7 The non-aqueous solvent could also have some volubility for water. Once the iron salt and ammonia releasing compound are dissolved in the solvent the hydrol-Isis of the ferrous ion commences when urea releases the ammonium ion. Unlike the hydrolysis reaction in the presence of strong alkali such as sodium hydroxide or ammonium hydroxide, this reaction occurs slowly producing extremely fine particles of yellow iron oxide. Also the non-aqueous reaction affords quick filtering and drying of the pigment without causing any agglomeration and disperse ability problems that are characteristic of the aqueous system. No milling is thus necessary.
By suspending the aluminum flakes in the solvent prior to adding the ammonia releasing compound, iron oxide pigment can be deposited on the aluminum flakes. The resultant pigment can then be dispersed by a Cowls disk solver which is a gentler form of dispersion and less likely to have an undesirable effect upon the aluminum flake pigment.
The examples which follow provide details which will enable those of ordinary skill in the art to practice this invention. All parts are by weight and all tempera-lures are in degrees Centigrade throughout the application unless otherwise indicated.
~23~
Example 1 Three hundred ~300) milliliters of ethanol were placed in a three-neck 500 milliliter flask assembly equipped with a stirrer, thermometer, and a reflex con-denser. 45 grams of Fake were added followed by heating to 60C to dissolve the ferrous chloride, said heating being continued until a clear reddish solution is obtained. Urea in the amount of 15 grams was then added and hydrolysis began as soon as the urea was added since the ferrous chloride already contained some water. An add-tonal S milliliters of water was then added followed by refluxing for 3 hours. This was followed by filtration, washing the cake with 100 milliliters of alcohol and drying. About 18 grams of transparent yellow iron oxide was recovered.
Example 2 Example 1 was repeated with the exception that before adding the urea, one gram of aluminum flake pigment sold by the U. S. Bronze Company as 807 Grade was added.
The resultant pigment had a golden yellow color and could be dispersed with a Cowls dissolver to give a metallic color effect. After dispersing with the Cowls dissolver a pigment with a brilliant yellow metallic color was obtained.
Example 3 _ Three hundred t300) milliliters of decal alcohol were placed in a three-neck 500 milliliter flask assembly equipped with a stirrer, thermometer, and a reflex con denser. Ten grams of Fake were added and stirred followed by heating to 60C to dissolve the ferrous Shelley-ride, said heating being continued until a clear reddish solution was obtained. Urea in the amount of 15 grams was then added and hydrolysis began as soon as the urea was added since the ferrous chloride already contained some water. An additional 5 milliliters of water was then added followed by refluxing for 3 hours. The temperature was raised to 200C and held for 4 hours. This was followed by filtration, washing the cake with 100 milliliters of decal alcohol and drying. About 4 grams of transparent red iron oxide were recovered.
Example 4 Example 3 was repeated with the exception that before adding the urea, 0.5 gram of aluminum flake pigment sold by the U. S. Bronze Company as 807 Grade was added.
The resultant pigment was dispersed with a Cowls dissolver to give a metallic color effect. After dispersing with the Cowls dissolver a pigment with a brilliant yellow metallic color was obtained.
~3~L5~Lt7 Example S
Three hundred (300) milliliters of ethanol are placed in a three-neck 500 milliliter flask assembly equipped with a stirrer, thermometer, and a reflex con-denser. 48 grams of Phase HO are added followed by heating to 60C to dissolve the ferris sulfate, said heating being continued until a clear reddish solution is ox-twined. Urea in the amount of 15 grams is then added and hydrolysis begins as soon as the urea is added since the ferris sulfate already contains some water. An additional 5 milliliters of water is then added followed by refluxing for 3 hours. This is followed by filtration washing the cake with 100 milliliters of alcohol and drying. About 10 grays of transparent yellow iron oxide are recovered.
Background ox the Invention The instant invention relates to transparent iron oxide pigments. More specifically, the instant invention relates to a process for substantially improving the transparency of such pigments.
Iron oxide pigments are found in nature as mineral deposits. There are three types of iron oxide pigments which are found in nature as mineral deposits. These are laminator hematite, and magnetites Laminate is yellow and has a chemical formula of Fox where x is an into-germ As can be seen from its formula, it is a hydrated iron(III~oxide. Hematite is red and has a chemical formula of Foe. It is an an hydrous iron(III)oxide. Magnetize is black and has a chemical formula of Foe. It is considered to be a spinet containing iron) and iron(III)ions.
In addition to the natural mineral deposits, iron oxide pigments can be obtained synthetically. The prior art preparation of iron oxide pigments is well known. Reference is made to various topics concerning iron oxide such as "Pigments (Inorganic)," pages 816-818, vol. 17, Encyclopedia of Chemical Technology, by Kirk-Othmer, 3rd Edition, published by John Wiley Sons. Synthetic methods for preparing iron oxide pigments generally involve the alkali precipitation of iron) compounds from a soluble iron)-~.;231~
salt and the oxidation of the precipitated iron) compound to an iron(III~oxide pigment slurry. The pigment produced by such methods corresponds to the yellow hydrated iron-(III~oxide previously described. The yellow pigment is recovered from the slurry by filtration, washing, and drying. The alkali precipitation must occur under acidic conditions; otherwise, dark brown or black undesirable color shades will be produced. Iron oxide pigments of various yellow shades can be prepared by controlling the temperature and rate of oxidation. Red, orange and other colors can be prepared by calcining the yellow pigments at high tempera-lures.
Iron oxide pigments which have an average particle size less than 0.1 micron are considered to be transparent because they can transmit visible light. Stated another way, "transparent pigment" is pigment having a majority of the particles smaller than the wavelength of light. Iron oxide pigments which have an average particle size greater than 0.1 microns and which cannot transmit visible light are considered to be opaque.
Yellow and red transparent iron oxides are used in combination with aluminum flake pigments to produce autumn-live metallic top coats. The metallic effect is dependent on the degree of transparency of the pigment.
I .7 Iron oxide pigments produced by the alkali precipitation of iron compounds from a soluble iron salt contain salts as a result of the hydrolysis reaction which have to be subsequently washed after the pigment is lit-toned. Also because of the high surface tension of the water, the pigment undergoes agglomeration during drying which makes the pigment hard to disperse. Accordingly, it is the purpose of the instant invention to provide a process for producing extremely fine iron oxide pigments. It is an additional purpose of the instant invention to be able to produce extremely fine red iron oxide pigments during the normal processing, i.e., a one-step reaction whereby the necessity of calcining the yellow iron oxide pigment to get red is eliminated. It is also a purpose of the instant invention to be able to produce a metallic pigment for automobile top coats whereby fracturing of the aluminum flake particles is minimized and the aluminum flake is included during the normal process to produce the yellow or red iron oxide pigment.
Summary of the Invention The present invention relates to a process for preparing transparent iron oxide pigments comprising reacting an iron compound, an ammonia releasing compound and water in a non-aqueous solvent in which both the iron compound and the ammonia-releasing compound have appreciable ~23~7 volubility. The reaction is performed by refluxing this composition. Where a red pigment is desired a high boiling alcohol may be employed whereby the refluxing is carried out above 200C which thus converts the pigment to a red iron oxide pigment during the reflex step. In order to get a metallic finish, aluminum flake pigment may be added to a mixture of the iron compound and solvent prior to addition of the ammonia-releasing salt.
Description o the Preferred Embodiments The iron compounds that are the raw material for the instant invention can be any of the available and known iron salts such as ferrous and ferris sulfate and ferrous and ferris chloride. Ferrous chloride (Fake) is the preferred iron compound for the instant invention In a preferred embodiment the iron compound is mixed with the non-aqueou~ solvent in an amount of about 1 to 50 percent by weight of the solvent or to the limit of volubility. The optimum is about 15%. This composition is then heated to dissolve the iron compound after which the ammonia-releasing compound is added preferably in about stoichiometric amount. The amount of ammonia-releasing compound is about 1 to 20 percent by weight based on the weight of the solvent, optimum about 5 percent. A preferred ammonia-releasing compound is urea. Other suitable ammonia-releasing compounds include various aliphatic and aromatic ~3~LS~'7 asides, amide-nitrile, various ureides traction products of urea with various acid chlorides or anhydries) such as acetylurea. Particularly asides may be used for this purpose such as formamide, acetamide, propionamide, n-butylamide, n-Valeramide, strummed, benæamide, succinmide, and phthalimide. And even more particularly, cyanamide such as calcium cyanamide and other nitrites such as acetonitrile, n-valeronitrile, benzonitrile, p-tolunitrile.
Any polar solvent capable of dissolving the iron compound and the ammonia-releasing compound in equivalent quantities may be employed. Such solvents include various alcohols such as methyl ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, Natalie, n-octyl, n-decyl, n-dodecyl, n-tetra-decal, n-hexadecyl, n-octadecyl, isopropyl, isobutyl, sea-bottle, tert-butyl, isopentyl, Amy, tert-pentyl, cyclopean-tunnel, cyclohexanol, ally, crotyl, methylvinylcarbinol, bouncily ~-phenylethyl, ~-phenylethyl, diphenylcarbinol, triphenylcarbionol, cinnamyl, and glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, glycerol and pentaerythritol. The solvent selected will depend on the iron salt employed, the ammonia-releasing compound and also on whether a yellow or red iron oxide is desired. The ammonia and iron salt are preferably reacted in statue-metric quantities since quantities other than these are uneconomic. Where the iron compound is a ferrous salt, the US
proper proportion is two moles of the ammonia released or 1 mole of urea per mole of ferrous ion. Where a ferris salt is employed, the proportion is 1.5 moles of urea or 3 moles of the ammonia released per mole of ferris ion. A small amount of water is then added and the composition relaxed for from 1 to 24 hours at the reflex temperature of the selected solvent. The amount of water is the stoichiometric amount necessary to produce the desired pimento It may range from about 0 to 5 percent based on the weight of the solvent. The yellow iron oxide pigment generally has a formula Fox. The amount of water added is preferably the stoichiometric amount to provide the desired amount of combined water. In general, it is preferred that the letter x have an average value of 1. For producing yellow iron oxide, a preferred solvent is ethanol which reflexes at from OWE to 80C. Where it it desired to produce a red pigment, a preferred solvent is decal alcohol which has a reflex temperature of 180 to 230C and the mixture should be heated to a temperature above 200C in order to get a red rather than a yellow iron oxide pigment. After refluxing, the product is washed with the non-aqueous solvent, lit-toned, and dried. Conventional filtration and drying equipment may be employed. In order to produce a metallic finish, aluminum flake pigment is added to the mixture of iron compound and solvent prior to the addition of the ammonia releasing salt.
~23~S~7 The non-aqueous solvent could also have some volubility for water. Once the iron salt and ammonia releasing compound are dissolved in the solvent the hydrol-Isis of the ferrous ion commences when urea releases the ammonium ion. Unlike the hydrolysis reaction in the presence of strong alkali such as sodium hydroxide or ammonium hydroxide, this reaction occurs slowly producing extremely fine particles of yellow iron oxide. Also the non-aqueous reaction affords quick filtering and drying of the pigment without causing any agglomeration and disperse ability problems that are characteristic of the aqueous system. No milling is thus necessary.
By suspending the aluminum flakes in the solvent prior to adding the ammonia releasing compound, iron oxide pigment can be deposited on the aluminum flakes. The resultant pigment can then be dispersed by a Cowls disk solver which is a gentler form of dispersion and less likely to have an undesirable effect upon the aluminum flake pigment.
The examples which follow provide details which will enable those of ordinary skill in the art to practice this invention. All parts are by weight and all tempera-lures are in degrees Centigrade throughout the application unless otherwise indicated.
~23~
Example 1 Three hundred ~300) milliliters of ethanol were placed in a three-neck 500 milliliter flask assembly equipped with a stirrer, thermometer, and a reflex con-denser. 45 grams of Fake were added followed by heating to 60C to dissolve the ferrous chloride, said heating being continued until a clear reddish solution is obtained. Urea in the amount of 15 grams was then added and hydrolysis began as soon as the urea was added since the ferrous chloride already contained some water. An add-tonal S milliliters of water was then added followed by refluxing for 3 hours. This was followed by filtration, washing the cake with 100 milliliters of alcohol and drying. About 18 grams of transparent yellow iron oxide was recovered.
Example 2 Example 1 was repeated with the exception that before adding the urea, one gram of aluminum flake pigment sold by the U. S. Bronze Company as 807 Grade was added.
The resultant pigment had a golden yellow color and could be dispersed with a Cowls dissolver to give a metallic color effect. After dispersing with the Cowls dissolver a pigment with a brilliant yellow metallic color was obtained.
Example 3 _ Three hundred t300) milliliters of decal alcohol were placed in a three-neck 500 milliliter flask assembly equipped with a stirrer, thermometer, and a reflex con denser. Ten grams of Fake were added and stirred followed by heating to 60C to dissolve the ferrous Shelley-ride, said heating being continued until a clear reddish solution was obtained. Urea in the amount of 15 grams was then added and hydrolysis began as soon as the urea was added since the ferrous chloride already contained some water. An additional 5 milliliters of water was then added followed by refluxing for 3 hours. The temperature was raised to 200C and held for 4 hours. This was followed by filtration, washing the cake with 100 milliliters of decal alcohol and drying. About 4 grams of transparent red iron oxide were recovered.
Example 4 Example 3 was repeated with the exception that before adding the urea, 0.5 gram of aluminum flake pigment sold by the U. S. Bronze Company as 807 Grade was added.
The resultant pigment was dispersed with a Cowls dissolver to give a metallic color effect. After dispersing with the Cowls dissolver a pigment with a brilliant yellow metallic color was obtained.
~3~L5~Lt7 Example S
Three hundred (300) milliliters of ethanol are placed in a three-neck 500 milliliter flask assembly equipped with a stirrer, thermometer, and a reflex con-denser. 48 grams of Phase HO are added followed by heating to 60C to dissolve the ferris sulfate, said heating being continued until a clear reddish solution is ox-twined. Urea in the amount of 15 grams is then added and hydrolysis begins as soon as the urea is added since the ferris sulfate already contains some water. An additional 5 milliliters of water is then added followed by refluxing for 3 hours. This is followed by filtration washing the cake with 100 milliliters of alcohol and drying. About 10 grays of transparent yellow iron oxide are recovered.
Claims (25)
1. A process for preparing transparent iron oxide pigment comprising reacting an iron compound, an ammonia releasing compound and water in a non-aqueous solvent in which both the iron compound and ammonia releasing compound have appreciable solubility, and in which water has some solubility by refluxing for a period of about 1 to 24 hours.
2. The process of claim 1 wherein said refluxing is followed by washing with non-aqueous solvent, filtration and drying.
3. The process of claim 2 wherein the amount of iron compound is about 1 to 50 percent, the amount of said ammonia releasing compound is about 1 to 20 percent, the amount of water is about 0 to 5 percent, all based on the weight of the solvent.
4. The process of claim 3 wherein said iron compound is a ferrous compound and said ammonia releasing compound is urea.
5. The process of claim 4 wherein said iron compound is ferrous chloride.
6. The process of claim 4 wherein the mole ratio of released ammonia to ferrous ion is about 2:1.
7. The process of claim 3 wherein said iron compound is a ferric compound and said ammonia releasing compound is urea.
8. The process of claim 7 wherein said iron compound is ferric sulfate.
9. The process of claim 7 wherein the mole ratio of released ammonia to ferric ion is 3:1.
10. The process of claim 3 wherein said solvent is ethanol and the reflux temperature is from about 60 to 80°C.
11. The process of claim 1 wherein said solvent is a high boiling alcohol, the reflux step is carried out at a temperature of at least about 200°C and the product produced is a red iron oxide.
12. The process of claim 11 wherein said refluxing is followed by washing with non aqueous solvent, filtration and drying.
13. The process of claim 12 wherein the amount of iron compound is about 1 to 50 percent, the amount of said ammonia releasing compound is about 1 to 20 percent, the amount of water is about 0 to 5 percent, all based on the weight of the solvent.
14. The process of claim 13 wherein said iron compound is ferrous chloride and said ammonia releasing compound is urea.
15. The process of claim 14 wherein said solvent is decyl alcohol and the reflux temperature is from about 180° to 230°C.
16. The process of claim 1 wherein aluminum flake pigment is added to the solvent before the addition of the ammonia releasing salt.
17. The process of claim 16 wherein said refluxing is followed by washing with non-aqueous solvent, filtration and drying.
18. The process of claim 17 wherein the amount of iron compound is about 1 to 50 percent, the amount of said ammonia releasing compound is about 1 to 20 percent, the amount of water is about 0 to 5 percent, all based on the weight of the solvent.
19. The process of claim 18 wherein said iron salt is ferrous chloride and said ammonia releasing salt is urea.
20. The process of claim 18 wherein said solvent is ethanol.
21. The process of claim 1 wherein said solvent is a high boiling alcohol and said reflux step is carried out at a temperature of at least 200°C and where aluminum flake pigment is added to said solvent prior to the addition of the ammonia releasing compound.
22. The process of claim 21 wherein said refluxing is followed by washing with said solvent, filtration and drying.
23. The process of claim 22 wherein the amount of iron compound is about 1 to 50 percent, the amount of said ammonia releasing compound is about 1 to 20 percent, the amount of water is about 0 to 5 percent, all based on the weight of the solvent.
24. The process of claim 23 wherein said iron compound is ferrous chloride and said ammonia releasing compound is urea.
25. The process of claim 23 wherein said solvent is decyl alcohol and the reflux temperature is from about 180° to 230°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US657,579 | 1984-10-04 | ||
| US06/657,579 US4618375A (en) | 1984-10-04 | 1984-10-04 | Transparent iron oxide pigments |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231517A true CA1231517A (en) | 1988-01-19 |
Family
ID=24637791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000491603A Expired CA1231517A (en) | 1984-10-04 | 1985-09-26 | Transparent iron oxide pigment |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4618375A (en) |
| CA (1) | CA1231517A (en) |
| DE (1) | DE3534477A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3617430A1 (en) * | 1986-05-23 | 1987-11-26 | Merck Patent Gmbh | PEARL PIGMENT |
| US4741781A (en) * | 1986-10-29 | 1988-05-03 | Mobay Corporation | Iron oxide pigment suspensions and slurries |
| DE4217511A1 (en) * | 1992-05-27 | 1993-12-02 | Basf Ag | Gloss pigments based on multi-coated platelet-shaped metallic substrates |
| DE4223383A1 (en) * | 1992-07-16 | 1994-01-20 | Basf Ag | Glossy pigments with a coating containing metal sulfide |
| DE4421933A1 (en) * | 1994-06-23 | 1996-01-04 | Basf Ag | Glossy pigments with nitrogen-containing metal layers |
| WO2002020674A1 (en) * | 2000-09-07 | 2002-03-14 | Bayer Aktiengesellschaft | Method for producing an iron oxide nucleus containing aluminium |
| DE10044097A1 (en) * | 2000-09-07 | 2002-04-04 | Bayer Ag | Process for producing an iron oxide seed containing aluminum |
| ES2550489T3 (en) * | 2012-09-04 | 2015-11-10 | CANBEKTE, Hüsnü Sinan | Iron recovery method |
| CN103864151B (en) * | 2012-12-10 | 2016-01-20 | 浙江神光材料科技有限公司 | The preparation technology of transparent ferric oxide red |
| JP2022177647A (en) * | 2021-05-18 | 2022-12-01 | チタン工業株式会社 | Iron oxide pigment for cosmetic composition and cosmetic composition containing iron oxide pigment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4414033A (en) * | 1981-11-06 | 1983-11-08 | Basf Wyandotte Corporation | Process for preparing ferriferrocyanide pigments |
-
1984
- 1984-10-04 US US06/657,579 patent/US4618375A/en not_active Expired - Lifetime
-
1985
- 1985-09-26 CA CA000491603A patent/CA1231517A/en not_active Expired
- 1985-09-27 DE DE19853534477 patent/DE3534477A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE3534477A1 (en) | 1986-04-10 |
| US4618375A (en) | 1986-10-21 |
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