US2363103A - Coating materials and process for - Google Patents
Coating materials and process for Download PDFInfo
- Publication number
- US2363103A US2363103A US2363103DA US2363103A US 2363103 A US2363103 A US 2363103A US 2363103D A US2363103D A US 2363103DA US 2363103 A US2363103 A US 2363103A
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- US
- United States
- Prior art keywords
- mixture
- oil
- temperature
- acids
- polylactylic
- Prior art date
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- Expired - Lifetime
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- 239000000463 material Substances 0.000 title description 19
- 238000000576 coating method Methods 0.000 title description 16
- 238000000034 method Methods 0.000 title description 15
- 239000011248 coating agent Substances 0.000 title description 13
- 239000000203 mixture Substances 0.000 description 29
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 15
- 150000007513 acids Chemical class 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000013013 elastic material Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000007779 soft material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000004359 castor oil Substances 0.000 description 8
- 235000019438 castor oil Nutrition 0.000 description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 8
- 229910001570 bauxite Inorganic materials 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000004347 Perilla Nutrition 0.000 description 2
- 244000124853 Perilla frutescens Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000004225 ferrous lactate Substances 0.000 description 2
- 229940037907 ferrous lactate Drugs 0.000 description 2
- 235000013925 ferrous lactate Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- MPFUOCVWJGGDQN-UHFFFAOYSA-N butan-1-ol;1,2-xylene Chemical compound CCCCO.CC1=CC=CC=C1C MPFUOCVWJGGDQN-UHFFFAOYSA-N 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
Definitions
- This invention relates to coating materials and more particularly with such coating materials which may be used as a substitute for tin on metal containers to protect the metal from corrosion and to preserve products which may be placed in the containers.
- the coatings are unstable and tend to contaminate food products on long storage. Also, many coatings will not withstand high temperatures which are often necessary in packaging foods in metal containers. Many of the prior art coatings require the use Of chemicals which are not available in times of war in the great quantities demanded by the canning industry.
- the general object of this invention is the provision of a protective coating of the type mentioned and a process of making it which will obviate the difliculties mentioned above.
- the protective. coating of this invention can be applied directly to the surface of metal containers,
- the coating of this invention may be applied to metals, such as iron, steel, aluminum, tin, and various alloys, without the necessity of using a primer, and it has beenfound not to contami nate food in any way. Foods especially susceptible to taste contamination were found not to be affected at all.
- the coating will adhere better ifthe surface of the iron is first subjected to a hot dip phosphate treatment.
- my invention comprises heating March a, 1883, as 370 o. G. 757) a mixture comprising polylactylic acids (also known as, polylactyllactic acids) and a drying oil, preferably in the presence of a catalyst. whereupon the mixture becomes resinifie-d to a soft, elastic, and soluble material.
- drying oils includes the class of oils known as "semidrying oils, and oils which may become drying oils during the process of this invention.
- any oil of this class may be used, such as castor oil, dehydrated castor oil, corn oil, linseed oil, tung oil, oiticica oil, Perilla oil, and soya bean oil.
- the catalysts which may be employed are, activated bauxite, cobalt salts (such as cobalt oxide, ferrous lactate, powdered iron, aluminum powder, magnesium turnings, magnesium methoxide, vanadium pentoxide, and cobalt oxide.
- the catalyst appears tocatalyze both a condensation and polymerization reaction. A better product is formed if the mixture also includes a material such as fumaric acid or maleic anhydride. rcsinified material is then dissolved in a solvent, such as xylene, acetone, butyl alcohol, benzene, and Iglycol monomethyl ether, or a mixture of two or more of these solvents, to which is added a drying agent, which should be of a non-toxic nature so as to eliminate the possibility of any food poisoning.
- a solvent such as xylene, acetone, butyl alcohol, benzene, and Iglycol monomethyl ether
- Suitable drying agents are zinc naphthenate, cobalt naphthenate, andmanganese naphthenate.- If desired, thinning agents may be used, such as toluene and petroleum solvents.
- This solution is then applied directly to the surface of the metal to be coated, such as by dipping, roller coating, and spraying, and then baked until hard; The time and temperature of baking will vary with the composition of. the coating solution and the surface to which it is applied. Ordinarily the baking may be accomplished at a temperature between C.
- Example 1 13.7 parts of polylactylic acids, 6.7 parts of castor oil, 2 parts of fumaric acid, and 2 parts of activatedbauxite granules (20/60) mesh were 7 mixed in an open vessel, while'heatlng with continuous stirring, arid the temperature raised to a out 265 chloride), ferric oxide, chromic As the second phase of the process, the
- the resulting coating was found to be tough and hard, to adhere excellently to the metal, and to resist decomposition by steam, acids, such as hydro'chloric and acetic acids of various concentrations, alcohols, and weak alkalies, such as, 1% sodium hydroxide.
- acids such as hydro'chloric and acetic acids of various concentrations, alcohols, and weak alkalies, such as, 1% sodium hydroxide.
- the same coating solution was applied to a steel container and baked in the same manner, after which two additional coats were baked on in the same way over the first coat.
- Five gallon milk cans coated in this way were put into regular dairy service for a period ofone to two months and were found not to contaminate the milk in any way.
- Example 2 100 parts of polylactylic acids, 50 parts of soya bean oil, parts of fumaric acid, and 1 part of activated bauxite granules were dissolved in an excess of xylene-butanol solvent mixture to aid in blending the ingredients and heated under a reflux condenser until the ingredients became blended. The condenser was then removed and the solvent was permittedto boil off. The temperature was increased to about 260 to 270 C. and maintained thereat for about 6 hours.
- the brown rubbery resin resulting was dissolved in a mixture of 50 parts of xylene and 50 parts of butanol to make a solid content of 30%, filtered, and 0.3% of zinc naphthenate and 0.6% of cobalt naphthenate were added to the solution.
- the same procedure as explained in Example 2 was followed in baking the resin on an iron surface, and the baked product was tested and found to be resistant against steam, weak alkalies, and alcohols.
- Example 3 Same as Example 2, except that linseed oil was used instead of soya bean oil.
- Example 4 100 parts of polylactylic acids, 50 parts of castor oil, 5 parts of maleic anhydride, and 1 part of ferric oxide were dissolved in a mixture of xylene and isoamyl alcohol. By gradually heating the mixture to 260 C. the solvent was boiled oil. The mixture was then held at a temperature between 260 and 265 C. and stirred for about 3 hours until the resin became viscous. The resultin resinous composition was dissolved in benzene to make a coating solution. The solution was spread on an iron surface and baked 90 minutes in an oven, the temperature of which was gradually increased from 150 to 210 C.
- Example 5 500 parts of polylactylic acids, 500 parts of castor oil, and 2 parts of concentrated sulphuric acid were mixed together and the temperature gradually raised to 260 C. over a period of 2 hours to blend the materials. The temperature was then held between 260 and 280 C. for about 3v hours, with constant stirring. The resulting resinous compound was then dissolved in benzene to make a coating composition containing 30% -01 the resin'by weight. This material was spread Example 6 The same as Example 1, except that ferrous lactate was used instead of activated bauxite granules.
- Example 7 The same as Example 1, except that cobalt chloride was used instead of activated bauxite granules.
- Example 8 The same as Example 1, except that magnesium I methoxide was used instead of activated bauxite granules.
- the process comprising heating a mixture comprising polylactylic acids and afatty drying oil at a temperature and for a period of time sum,- cient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
- the process comprising heating a mixture comprising polylactylic acids and a fatty drying oil in the presence of a catalyst at a temperature and for a period of time suflicient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
- the process comprising heating a mixture comprising polylactylic acidspa fatty drying oil, and fumaric acid at a temperature and for a period of time sufficient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
- the process comprising heating a mixture comprising polylactylic acids, a fatty drying oil, and malelc anhydride at a temperature and for a period of time sufficient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
- the process comprising heating a mixture comprising polylactylic acids and an oil chosen from the group consisting of castor oil, dehydrated castor oil, corn oil, linseed oil, tung oil, oiticica oil, perilla oil, and soya bean oil at a temperature and for a period of time suflicient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
- an oil chosen from the group consisting of castor oil, dehydrated castor oil, corn oil, linseed oil, tung oil, oiticica oil, perilla oil, and soya bean oil
- the process comprising heating a mixture comprising polylactylic acids, castor oil, and fumaric acid in the presence of activated bauxite at a temperature and for a period of time sufllcient to cause the mixture to become resinifled to a soft and elastic material, followed by bakin the material .on a metal surface.
- the process comprising heating'a mixture comprising polylactylic acids and a fatty drying oil in the presence of activated bauxite at a temperature and for a period of time sumcient to cause the mixture to become resinifled to a soft and elastic material, followed by baking the material on a metal surface.
- the process comprising heating a mixture comprising polylactylic acids and a fatty drying oil in the presence of vanadium pentoxide at a temperature and for a period of time sufllcient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
- the process comprising heating a mixture comprising polylactylic acids and a fatty drying oil in the presence of salts of cobalt at a temperature and for a. period of time sufficient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
- a soft and elastic resin which can be baked on metal surfaces comprising the product formed
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
, a1 containers.
Patented Nov. 21, 1944 UNITED STATES PATENT OFFICE COATING MATERIALS AND PROCESS FOR MAKING THEM Paul D. Watson, Alexandria, Va., assignor to the (Granted under the m or amended April 30, 1928;
patented, may be manufactured. and used by or p for the Government of the United States of America for governmental purposes without the payment to me of any royalty thereon.
This invention relates to coating materials and more particularly with such coating materials which may be used as a substitute for tin on metal containers to protect the metal from corrosion and to preserve products which may be placed in the containers.
At the present time the prospective shortage of tin has increased the demand for a substitute for this material for the purpose of coating met- Although some substitutes are available at the present time, they possess ob- Jectionable features, such as the necessityfor the surface of the metal to be first coated with a as represented by Secretary of Agriculture, ofllce No Drawing. Application April 30, 1942,
Serial No. 441,236
12 Claims. (Cl. 269-18) primer. The primer is necessary to obtain a cally with the metal, or both. In some cases.
the coatings are unstable and tend to contaminate food products on long storage. Also, many coatings will not withstand high temperatures which are often necessary in packaging foods in metal containers. Many of the prior art coatings require the use Of chemicals which are not available in times of war in the great quantities demanded by the canning industry.
The general object of this invention is the provision of a protective coating of the type mentioned and a process of making it which will obviate the difliculties mentioned above. The protective. coating of this invention can be applied directly to the surface of metal containers,
not involve the use of materials which are or which may become scarce, insofar as it can be foreseen at present, in either normal times or in times of war. 1 i
- The coating of this invention may be applied to metals, such as iron, steel, aluminum, tin, and various alloys, without the necessity of using a primer, and it has beenfound not to contami nate food in any way. Foods especially susceptible to taste contamination were found not to be affected at all. In using iron, the coating will adhere better ifthe surface of the iron is first subjected to a hot dip phosphate treatment. In general, my invention comprises heating March a, 1883, as 370 o. G. 757) a mixture comprising polylactylic acids (also known as, polylactyllactic acids) and a drying oil, preferably in the presence of a catalyst. whereupon the mixture becomes resinifie-d to a soft, elastic, and soluble material. It is to be understood that the term drying oils" as used herein includes the class of oils known as "semidrying oils, and oils which may become drying oils during the process of this invention. In general, any oil of this class may be used, such as castor oil, dehydrated castor oil, corn oil, linseed oil, tung oil, oiticica oil, Perilla oil, and soya bean oil. Examples of the catalysts which may be employed are, activated bauxite, cobalt salts (such as cobalt oxide, ferrous lactate, powdered iron, aluminum powder, magnesium turnings, magnesium methoxide, vanadium pentoxide, and cobalt oxide.
The catalyst appears tocatalyze both a condensation and polymerization reaction. A better product is formed if the mixture also includes a material such as fumaric acid or maleic anhydride. rcsinified material is then dissolved in a solvent, such as xylene, acetone, butyl alcohol, benzene, and Iglycol monomethyl ether, or a mixture of two or more of these solvents, to which is added a drying agent, which should be of a non-toxic nature so as to eliminate the possibility of any food poisoning. Suitable drying agents are zinc naphthenate, cobalt naphthenate, andmanganese naphthenate.- If desired, thinning agents may be used, such as toluene and petroleum solvents. This solution is then applied directly to the surface of the metal to be coated, such as by dipping, roller coating, and spraying, and then baked until hard; The time and temperature of baking will vary with the composition of. the coating solution and the surface to which it is applied. Ordinarily the baking may be accomplished at a temperature between C. and 260 Example 1 13.7 parts of polylactylic acids, 6.7 parts of castor oil, 2 parts of fumaric acid, and 2 parts of activatedbauxite granules (20/60) mesh were 7 mixed in an open vessel, while'heatlng with continuous stirring, arid the temperature raised to a out 265 chloride), ferric oxide, chromic As the second phase of the process, the
C. and maintained for about 7% hours until the resulting resin became viscous, soft, and
elastic. A 50% yield of a brown rubbery resin was obtained. This resin was dissolved in a mixture of xylene and butyl alcohol to form a solution containing 30% of resin and then filtered. On the basis of the resin content, 0.2% of zinc naphthenate and 0.4% of cobalt naphthenate were added to form the final coating solution. The surface of an iron container was then coated with this solution by dipping. Excesses of the solution were permitted to drain off the metal surface and the remaining amount permitted to dry. The coated container was then baked for 90 minutes in an oven, the temperature of which was gradually increased from 150 to 210 C. The resulting coating was found to be tough and hard, to adhere excellently to the metal, and to resist decomposition by steam, acids, such as hydro'chloric and acetic acids of various concentrations, alcohols, and weak alkalies, such as, 1% sodium hydroxide.
The same coating solution was applied to a steel container and baked in the same manner, after which two additional coats were baked on in the same way over the first coat. Five gallon milk cans coated in this way were put into regular dairy service for a period ofone to two months and were found not to contaminate the milk in any way.
Example 2 100 parts of polylactylic acids, 50 parts of soya bean oil, parts of fumaric acid, and 1 part of activated bauxite granules were dissolved in an excess of xylene-butanol solvent mixture to aid in blending the ingredients and heated under a reflux condenser until the ingredients became blended. The condenser was then removed and the solvent was permittedto boil off. The temperature was increased to about 260 to 270 C. and maintained thereat for about 6 hours. The brown rubbery resin resulting was dissolved in a mixture of 50 parts of xylene and 50 parts of butanol to make a solid content of 30%, filtered, and 0.3% of zinc naphthenate and 0.6% of cobalt naphthenate were added to the solution. The same procedure as explained in Example 2 was followed in baking the resin on an iron surface, and the baked product was tested and found to be resistant against steam, weak alkalies, and alcohols.
Example 3 Same as Example 2, except that linseed oil was used instead of soya bean oil.
Example 4 100 parts of polylactylic acids, 50 parts of castor oil, 5 parts of maleic anhydride, and 1 part of ferric oxide were dissolved in a mixture of xylene and isoamyl alcohol. By gradually heating the mixture to 260 C. the solvent was boiled oil. The mixture was then held at a temperature between 260 and 265 C. and stirred for about 3 hours until the resin became viscous. The resultin resinous composition was dissolved in benzene to make a coating solution. The solution was spread on an iron surface and baked 90 minutes in an oven, the temperature of which was gradually increased from 150 to 210 C.
Example 5 500 parts of polylactylic acids, 500 parts of castor oil, and 2 parts of concentrated sulphuric acid were mixed together and the temperature gradually raised to 260 C. over a period of 2 hours to blend the materials. The temperature was then held between 260 and 280 C. for about 3v hours, with constant stirring. The resulting resinous compound was then dissolved in benzene to make a coating composition containing 30% -01 the resin'by weight. This material was spread Example 6 The same as Example 1, except that ferrous lactate was used instead of activated bauxite granules.
Example 7 The same as Example 1, except that cobalt chloride was used instead of activated bauxite granules.
Example 8 The same as Example 1, except that magnesium I methoxide was used instead of activated bauxite granules.
Having thus described my invention, I claim:
1. The process comprising heating a mixture comprising polylactylic acids and afatty drying oil at a temperature and for a period of time sum,- cient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
2. The process comprising heating a mixture comprising polylactylic acids and a fatty drying oil in the presence of a catalyst at a temperature and for a period of time suflicient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
3. The process comprising heating a mixture comprising polylactylic acidspa fatty drying oil, and fumaric acid at a temperature and for a period of time sufficient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
4. The process comprising heating a mixture comprising polylactylic acids, a fatty drying oil, and malelc anhydride at a temperature and for a period of time sufficient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
5. The process comprising heating a mixture comprising polylactylic acids and an oil chosen from the group consisting of castor oil, dehydrated castor oil, corn oil, linseed oil, tung oil, oiticica oil, perilla oil, and soya bean oil at a temperature and for a period of time suflicient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
6. The process comprising heating a mixture comprising polylactylic acids, castor oil, and fumaric acid in the presence of activated bauxite at a temperature and for a period of time sufllcient to cause the mixture to become resinifled to a soft and elastic material, followed by bakin the material .on a metal surface.
'7. The process comprising heating'a mixture comprising polylactylic acids and a fatty drying oil in the presence of activated bauxite at a temperature and for a period of time sumcient to cause the mixture to become resinifled to a soft and elastic material, followed by baking the material on a metal surface.
8. The process comprising heating a mixture comprising polylactylic acids and a fatty drying oil in the presence of vanadium pentoxide at a temperature and for a period of time sufllcient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
9. The process comprising heating a mixture comprising polylactylic acids and a fatty drying oil in the presence of salts of cobalt at a temperature and for a. period of time sufficient to cause the mixture to become resinified to a soft and elastic material, followed by baking the material on a metal surface.
10. A soft and elastic resin which can be baked on metal surfaces comprising the product formed
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2433721A (en) * | 1947-12-30 | Polylactylic acid besins and pbocess | ||
US2453559A (en) * | 1944-05-27 | 1948-11-09 | Paul D Watson | Polylactylic acid resins and process for making them |
US2555385A (en) * | 1947-06-20 | 1951-06-05 | Paul D Watson | Metal polyactyllactate polymers |
US5206341A (en) * | 1991-11-21 | 1993-04-27 | Southern Research Institute | Polymers from hydroxy acids and polycarboxylic acids |
-
0
- US US2363103D patent/US2363103A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2433721A (en) * | 1947-12-30 | Polylactylic acid besins and pbocess | ||
US2453559A (en) * | 1944-05-27 | 1948-11-09 | Paul D Watson | Polylactylic acid resins and process for making them |
US2555385A (en) * | 1947-06-20 | 1951-06-05 | Paul D Watson | Metal polyactyllactate polymers |
US5206341A (en) * | 1991-11-21 | 1993-04-27 | Southern Research Institute | Polymers from hydroxy acids and polycarboxylic acids |
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