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US2223026A - Metal container - Google Patents

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Publication number
US2223026A
US2223026A US175627A US17562737A US2223026A US 2223026 A US2223026 A US 2223026A US 175627 A US175627 A US 175627A US 17562737 A US17562737 A US 17562737A US 2223026 A US2223026 A US 2223026A
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United States
Prior art keywords
coating
plasticizer
metal
cellulose nitrate
lacquer
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Expired - Lifetime
Application number
US175627A
Inventor
Percy M Clark
Charles B Hemming
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Priority to US175627A priority Critical patent/US2223026A/en
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Publication of US2223026A publication Critical patent/US2223026A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/14—Linings or internal coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • B05D7/18—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes based on cellulose derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type

Definitions

  • This invention relates to a metal container for the packaging of food products or other perishable materials and more particularly to the production of an interiorly coated metal U container, the coating of which is capable of protecting the metal from corrosion due to corrosive agents present in the packed material.
  • Metal containers interiorly coated with organic coatings of the oleoresinous type have been l used for many years in the packaging of various foods, especially Where the acid nature of the materials tends to attack the metal container and subsequently cause contamination of the food material through the absorption of the l5 products formed by the corrosive action. It has been found in general* that various classes of foodstuffs demand various types of protective coatings and much work has been done by the manufacturers of tin cans to provide coatings for each specific use.
  • the presentfinvention is unique and commercially of interest in that the several defects of the nitrocellulose compositions and coating methods heretofore available for lining the interior of metal cans utilized in the packaging of beer, food products or other perishable materials; are eliminated.
  • An object of this invention is'the provision of an interiorly coated container for the packaging of beer and the like, the coating of which is Water-resistant, tough, flexible, adherent, insoluble, non-toxic, substantially impermeable to water and capable of protecting the metal from corrosion due to corrosive agents present in the packed material.
  • Other objects will become apparent as the description of the invention proceeds.
  • a priming coat is first applied to the metal surface before the application of the lacquer top coat.
  • the qualifications for the primer are freedom from taste-contamination after baking, good adhesion to the metal surface and satisfactory coverage.
  • the primer may be applied to flat sheets of black iron or tin or silver-plated metal by a roller coating machine at a prescribed coating weight which normally is about 4 milligrams of dry coating per square inch.
  • the primer is baked at a temperature of l about380425 F. for to 15 minutes. Sections of the flat sheets are then formed into cylinders and the top coat applied to the interior .by any suitable means, preferably by spraying.
  • the can ends are usually coated with the lacquer before being formed. However, it is practicable to form the can ends directly following the baking of the primer and before the application of the lacquer top coat. In this case the lacquer would normally be applied by spraying.
  • a suitable primer composition consists of, an" mixture of.5.5 parts of mineral spirits, 61.5 parts of hydrogenated naphtha of boiling range about 135 "to 190 C., and 33'parts of a synthetic resin APer cent by weight Chinawood oil 12.3, Glycerine"- 18.8 Linseed oil 24.7 Phthalic anhydride 44.2
  • This resin is prepared by any of the methods well known and widely practiced in the art.
  • An alternative priming composition may consist of an oleoresinous varnish of conventional type, being prepared in the customary manner from drying oils .and natural or synthetic gums. In general, it has been shown -that oil lengths above gallons in this type of base coat are liable to give a pronounced taste-contamination and the selection of the raw material for its preparation should be made with a view to minimizing its taste-producing characteristics.
  • the lacquerA top ⁇ coat is applied byspraying, roller-coating or dipping. It is then baked at a temperature not to exceed 300 F. for 8 to 10 minutes.
  • the following examples are illustrative as representing the preferred embodiment of this invention:
  • Example 4 Per cent by weight Cellulose nitrate 15.0
  • the viscosity characteristic of the cellulose nitrate used in the above examples is about 3 seconds as determined in accordance with procedure outlined in A. S. T. M. specifications D-30l-33, Formula B. 'Use of a lower viscosity material is possible but in general it leads to somewhat brittle films which do not permit satisfactory forming of the coated sheet metal.
  • dicyclohexyl hexahydrophthalate dimethyl cyclohexyl phthalate, dicyclohexyl tartrate, tricyclohexyl citrate, ⁇ cyclohexyl benzoyl benzoate and trlcyclohexyl phosphate, and other cyclohexanol derivatives of carboxylic acids, when subjected to suitable puriiication treatments to render them odorless and tasteless are likewise suitable for use in the products of the present invention.
  • plasticizer which is the flexibillzing of the cellulose nitrate coating
  • this class of plasticizing materials greatly reduces the permeability of the lacquer 'lm to the passage of Water.
  • plasticizers of which dibutyl" phthalate, castor oil and butyl oleate are representative when added to nitrocellulose in at least up to about equal parts by weight f cel-r ⁇ lulose nitrate and plasticizer.
  • compositions of the present invention as regards liquid water permeability is clearly illustrated in the attached series of curves.
  • the curves are derived by plotting the liquid water pemeability of iilms prepared from the severaly compositions against plasticizer content and indicate the improved permeability factor which is obtained as the cyclohexanol derivative plasticizer content is increased to the desired range. .
  • the relatively poor permeability characteristic of compositions containing dibutyl phthalate and butyl oleate is also i1- lustrated for comparison.
  • Numerical data from which the curves were increasing amounts at iirst cause a sharp lowering* in perplotted was obtained as follows: A composition such as Example 2 is coated on both sides of a sheet of plain, transparent regenerated cellulose such as Cellophane to an overall thickness of .0004 inch of dry film. The coating is dried in a dry oven at 180-200 F. for one minute with circulating air. The dried film is then afxed across the top of a Petri dish, approximately 21/2 inches in diameter by means of a molten adhesive composed of beeswax 85% and damar 15%, a quantity of water sufficient to completely cover the coated Cellophane when the dish is inverted, having been previously placed in the dish.
  • a molten adhesive composed of beeswax 85% and damar 15%
  • the dish is accurately weighed, inverted and placed on a rack arranged so as to allow free circulation of air across the lm. It is then placed in a thermostatically controlled oven at a temperature of 104 F. in which a relative humidity of less than 2% is maintained with forced air circulation, the air entering the oven having been dried by passing it through a series of bottles containing concentrated sulfuric acid. At the end of 18 hours the dish is removed from the oven and again accurately weighed. The results are expressed as grams of water lost per square meter per hour as utilized in plotting the curves on the accompanying graphs.
  • this type of modifier greatly improves the adhesion and flexibility of the cellulose nitrate iilm and aids in the elimination of the last traces of solvent from the lacquer coatingl It is tasteless, odorless, non-toxic and inert to hydrolysis.
  • This invention provides an interiorly coated metal container which is commercially satisfactory for the packaging of beverags, particularly malt beverages, food products and other perishable materials.
  • the new container meets the need in the industry for a can in which beer may be satisfactorily packed. It provides an interior surface coating which is poreless, substantially imperviousto water, odorless and tasteless and capable of withstanding the deteriorating effect of beer and other beverages such as fruit juices and perishable foodstuffs which may also be safely packaged in the new containers.
  • a metal container for beer and other beverages, foodstuffs and the like consisting of a tin plated metallic body interiorly coated with an alkyd resin priming coat and a top vcoat consisting of cellulose nitrate and a plasticizer compatible therewith, said plasticizer consisting of a cyclohexyl ester of acarboxylic acid in the ratio of between l parts by weight of cellulose nitrate to l0 parts of said plasticizer and 10 parts by weight of cellulose nitrate and 3 parts of said plasticizer.
  • a metalcontainer for foodstuffs containing water having a. coating on at least the surface of the said metal container which is in contact with the foodstuff, said coating comprising in proportion parts of nitrocellulose and from 3 to 10 parts of a highly puried cyclohexyl ester of a carboxylic acid as a plasticizer.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)

Description

No'v.-26 1940. P. M. CLARK ETAL 2,223,026
' METAL CONTAINER Filed Nov. 20, 1957 TUNMODIFI D NIT ROCELLULO. E FILVI Bu'fyl Oleafe #www yl Pwfhaiafe GRAMS 0F WATER PASSED PER SQUARE METER PER HOUR PERCENT PLASTICIZER Percy M. C Zar/f I N VEN T0125 Char/e: Henwnmg Patented Nov. 26, 1940 UNITED STATES PATENT OFFICE METAL CONTAHNER Delaware Application November 20, 1937, Serial No. 175,627 I 3 Claims.
This invention relates to a metal container for the packaging of food products or other perishable materials and more particularly to the production of an interiorly coated metal U container, the coating of which is capable of protecting the metal from corrosion due to corrosive agents present in the packed material.
Metal containers interiorly coated with organic coatings of the oleoresinous type have been l used for many years in the packaging of various foods, especially Where the acid nature of the materials tends to attack the metal container and subsequently cause contamination of the food material through the absorption of the l5 products formed by the corrosive action. It has been found in general* that various classes of foodstuffs demand various types of protective coatings and much work has been done by the manufacturers of tin cans to provide coatings for each specific use.
A more recent development in the can industr'y has been the production of cans for the packaging of beer. It was found that the usual coatings were unsatisfactory and incapable of delivering the beer in a condition suitable for public consumption. Several factors appeared to cause this condition, among them, absorption of flavor-forming ingredients by the can coating, and the presence in the coating of soluble ingredients which when absorbed by the beer, markedly changed the taste thereof. In particular, it has been found that beer is especially subject to contamination land deterioration. Two types of coated containers have been developed which are being used commercially in large numbers at the present-time. The first is a metal can with or without an organic primer coating and having a heavy wax coating as the top coat. The second type is a container with an organic priming coat and having a vinyl resin top coating.
Prior to and during the development of the above types of cans, considerable work was done by the industry in attempting to develop nitrocellulose lacquers for use as top coats and that these results were uniformly unsuccessful. Several reasons can be ascribed to these failures. First, failure to select suitable materials with which to modify the nitrocellulose. Second, failure to study the baking conditions and the solvent compositions required to give coatings free from traces of residual solvent which if present would cause serious contamination of the beer. Third, failure to Work with modifiers purified to the extent absolutely necessary for this work, and finally and more importantly, failure to recognize the necessity of reducing the permeability of the nitrocellulose film coating to Water to a point much lower than commonly reached. Unmodifed nitrocellulose coatings are much more permeable to water than is generally recognized, and when not suitably modified are inferior to the vinyl resin and Wax coatings in commercial use.
The presentfinvention is unique and commercially of interest in that the several defects of the nitrocellulose compositions and coating methods heretofore available for lining the interior of metal cans utilized in the packaging of beer, food products or other perishable materials; are eliminated. An object of this invention is'the provision of an interiorly coated container for the packaging of beer and the like, the coating of which is Water-resistant, tough, flexible, adherent, insoluble, non-toxic, substantially impermeable to water and capable of protecting the metal from corrosion due to corrosive agents present in the packed material. Other objects will become apparent as the description of the invention proceeds.
These objects are accomplished by utilizing a specic type of modifier, consisting of a cyclohexyl derivative, in cellulose nitrate compositions, thus affording a lacquer which when 0 coated on the interior of metal cans provides a convenient and commercially useful container.
In the practice of the invention, a priming coat is first applied to the metal surface before the application of the lacquer top coat. The qualifications for the primer are freedom from taste-contamination after baking, good adhesion to the metal surface and satisfactory coverage. The primer may be applied to flat sheets of black iron or tin or silver-plated metal by a roller coating machine at a prescribed coating weight which normally is about 4 milligrams of dry coating per square inch. The primer is baked at a temperature of l about380425 F. for to 15 minutes. Sections of the flat sheets are then formed into cylinders and the top coat applied to the interior .by any suitable means, preferably by spraying. The can ends are usually coated with the lacquer before being formed. However, it is practicable to form the can ends directly following the baking of the primer and before the application of the lacquer top coat. In this case the lacquer would normally be applied by spraying.
whichy isa reaction product of zvExample 1 A suitable primer composition consists of, an" mixture of.5.5 parts of mineral spirits, 61.5 parts of hydrogenated naphtha of boiling range about 135 "to 190 C., and 33'parts of a synthetic resin APer cent by weight Chinawood oil 12.3, Glycerine"- 18.8 Linseed oil 24.7 Phthalic anhydride 44.2
This resin is prepared by any of the methods well known and widely practiced in the art.
An alternative priming composition may consist of an oleoresinous varnish of conventional type, being prepared in the customary manner from drying oils .and natural or synthetic gums. In general, it has been shown -that oil lengths above gallons in this type of base coat are liable to give a pronounced taste-contamination and the selection of the raw material for its preparation should be made with a view to minimizing its taste-producing characteristics.
`Other commercially available priming compositions of similar constitution and properties may also be utilized as suitable base coats for the improved lacquer top coats hereinafter described.
The lacquerA top `coat is applied byspraying, roller-coating or dipping. It is then baked at a temperature not to exceed 300 F. for 8 to 10 minutes. The following examples are illustrative as representing the preferred embodiment of this invention:
Example 2 Y Per cent by weight Cellulose nitrate 14.6
Dicyclohexyl phthalate 4.4
Ethyl alcohol (denatured) 3.7
' Ethyl acetate (absolute) 77.3
Example 3 Per cent l by 'weight Cellulose nitrate' 14.6 Dicyclohexyl .hexahydrophthalate 7.3
Ethyl alcohol (denatured),. 3.1
Ethyl acetate (absolute) 50.0
Isopropyl acetate l 24.4
Example 4 Per cent by weight Cellulose nitrate 15.0
Dimethyl cyclohexylphthalate 5.8
Ethyl alcohol (denatured) 4.0
Ethyl acetate 30.0
Methyl ethyl ketone 30.0
Isobutyl acetate 15.2
The viscosity characteristic of the cellulose nitrate used in the above examples is about 3 seconds as determined in accordance with procedure outlined in A. S. T. M. specifications D-30l-33, Formula B. 'Use of a lower viscosity material is possible but in general it leads to somewhat brittle films which do not permit satisfactory forming of the coated sheet metal. Use
.of higher viscosity cellulosenitrate while preferable from the viewpoint of giving tougher lms resultsin av lacquer having very low solids at the required spraying or applying viscosity.` It-is desirable to use the lowest viscosity cellulose ni'- trate commensurate with the flexibility desired o1V the iilmv in order to produce the most economical shes. l v y In Exam le 2, absolute ethyl acetate is used as they sole volatile solvent forthe cellulose nitrate. The small amount of denatured ethyl alcohol is brought into thecomposition by the alcohol wet cellulose nitrate of commerce. This represents a volatile solvent vehicle which has been found to be the easiest to completely eliminate in the baking operation of the lacquer top coat.V It is possible to employ a variety of other solvent 'combinations providing satisfactory baking conditions are set up. Medium boiling solvents such as isopropyl acetate, isobutyl acetate,
normal butyl acetate, and in some instances volbaking treatment will invariably contaminate the packed product.
Highly purified, odorless and tasteless dicyclohexyl phthalate was found to be outstandingly superior as a plasticizer in the cellulose nitrate. compositions for the purpose indicated. However, dicyclohexyl hexahydrophthalate, dimethyl cyclohexyl phthalate, dicyclohexyl tartrate, tricyclohexyl citrate,` cyclohexyl benzoyl benzoate and trlcyclohexyl phosphate, and other cyclohexanol derivatives of carboxylic acids, when subjected to suitable puriiication treatments to render them odorless and tasteless are likewise suitable for use in the products of the present invention. v
In addition to the normal function of the plasticizer which is the flexibillzing of the cellulose nitrate coating, this class of plasticizing materials greatly reduces the permeability of the lacquer 'lm to the passage of Water. The great majority of plasticizers of which dibutyl" phthalate, castor oil and butyl oleate are representative, when added to nitrocellulose in at least up to about equal parts by weight f cel-r` lulose nitrate and plasticizer.
The superiority of the compositions of the present invention as regards liquid water permeability is clearly illustrated in the attached series of curves. The curves are derived by plotting the liquid water pemeability of iilms prepared from the severaly compositions against plasticizer content and indicate the improved permeability factor which is obtained as the cyclohexanol derivative plasticizer content is increased to the desired range. .The relatively poor permeability characteristic of compositions containing dibutyl phthalate and butyl oleate is also i1- lustrated for comparison.
Numerical data from which the curves were increasing amounts at iirst cause a sharp lowering* in perplotted was obtained as follows: A composition such as Example 2 is coated on both sides of a sheet of plain, transparent regenerated cellulose such as Cellophane to an overall thickness of .0004 inch of dry film. The coating is dried in a dry oven at 180-200 F. for one minute with circulating air. The dried film is then afxed across the top of a Petri dish, approximately 21/2 inches in diameter by means of a molten adhesive composed of beeswax 85% and damar 15%, a quantity of water sufficient to completely cover the coated Cellophane when the dish is inverted, having been previously placed in the dish. The dish is accurately weighed, inverted and placed on a rack arranged so as to allow free circulation of air across the lm. It is then placed in a thermostatically controlled oven at a temperature of 104 F. in which a relative humidity of less than 2% is maintained with forced air circulation, the air entering the oven having been dried by passing it through a series of bottles containing concentrated sulfuric acid. At the end of 18 hours the dish is removed from the oven and again accurately weighed. The results are expressed as grams of water lost per square meter per hour as utilized in plotting the curves on the accompanying graphs.
Minimum permeability is obtained when the cellulose nitrate-plasticizer ratios are within the range of 10-3 to 10-5 parts by weight. A satisfactory permeability reduction occurs with this new type of lacquer coat within the range of 10-3 to 10--10 parts by weight of cellulose nitrate to plasticizer.
In all instances this type of modifier greatly improves the adhesion and flexibility of the cellulose nitrate iilm and aids in the elimination of the last traces of solvent from the lacquer coatingl It is tasteless, odorless, non-toxic and inert to hydrolysis.
This invention provides an interiorly coated metal container which is commercially satisfactory for the packaging of beverags, particularly malt beverages, food products and other perishable materials. The new container meets the need in the industry for a can in which beer may be satisfactorily packed. It provides an interior surface coating which is poreless, substantially imperviousto water, odorless and tasteless and capable of withstanding the deteriorating effect of beer and other beverages such as fruit juices and perishable foodstuffs which may also be safely packaged in the new containers.
It is apparent that many Widely different em-A bodiments of this invention may be made without departing from the spirit and scope thereof and, therefore, it is not intended to be limited except as indicated in the appended claims.
We claim:
1. A metal container for beer and other beverages, foodstuffs and the like consisting of a tin plated metallic body interiorly coated with an alkyd resin priming coat and a top vcoat consisting of cellulose nitrate and a plasticizer compatible therewith, said plasticizer consisting of a cyclohexyl ester of acarboxylic acid in the ratio of between l parts by weight of cellulose nitrate to l0 parts of said plasticizer and 10 parts by weight of cellulose nitrate and 3 parts of said plasticizer.
2. A metalcontainer for foodstuffs containing water, having a. coating on at least the surface of the said metal container which is in contact with the foodstuff, said coating comprising in proportion parts of nitrocellulose and from 3 to 10 parts of a highly puried cyclohexyl ester of a carboxylic acid as a plasticizer.
' 3. The container of claim 2 in which the plasticizer is selected from the group consisting of cyclohexyl and methyl cyclohexyl esters of the mono and dibasic carboxylic acids.
PERCY' M. CLARK. CHARLES B. HEMMING.
US175627A 1937-11-20 1937-11-20 Metal container Expired - Lifetime US2223026A (en)

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