US 2164495 A
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Patented July 4, i939 UNITED STATES PATENT OFFICE OIL, GREASE, AND HIDROOABBON RESIST- TEBIAL ANTHA No Application December 19, 1938, Serial No. 116,825
1 Claim. ((11. 91-48) This invention relates to oil, grease and hydrocarbon resistant material, particularly to oil, grease and hydrocarbon resistant fibrous materials, and more particularly to fibrous materials 5 carrying as a coating a flexible film, which is impervious to oils, greases and hydrocarbons, such as gasoline and the like.
The use of disposable non-refillable containers for lubricating oils and panicularly motor oils has become quite common in recent years. The majority of such containers are made of tinned sheet metal, but these containers are relatively expensive, diflicuit to seal because of the tendency of the oil to creep on the metal surface and dimcult to dispose of conveniently. Moreover, when such containers are emptied, a considerable portion of the oil remains within them due to its high attraction for the metal surface, entailing waste.
It has recently been proposed to use fibrous containers such as containers made from paper, pulp, or the like, in place of the metal containers heretofore used... Such containers are relatively inexpensive being made from cheap materials,
such as pressed waste newspaper pulp, and are easily disposed of after use. Such containers are;
of course, nbrmally highly pervious to hydrocarbons, such as motor oil, and therefore, to be usable, must be provided with a flexible, inexpensive lining which is permanently impervious to oil. Certain coating compositions have been proposed for use in this connection, but so far as known, none of them is entirely successful.
The principal object or this invention is the production of an interiorly coated fibrous container which is highly suitable for merchandising of oils, greases and hydrocarbons.
Another object of this invention is to make an oil, grease and hydrocarbon resistant material with inexpensive fibrous materials as the base,
and to provide therefor an inexpensive oil, grease and hydrocarbon impervious flexible lining.
Another object of this invention is to-accomplish the foregoing objects by a simple and economical process.
Other objects will be apparent to those skilled in the art as the description of this invention proceeds.
In the practice of the invention, there is first provided a fibrous material, such as fiber board,
cardboard, paperboard, cloth, or pressed paper pulp, and the like. Thus, it it isdesired to make a container from pressed paper pulp, beaten paper pulp is pressed into the shape of the finished container by spinning or blowing into molds of de- 5 sired shape. Such molds may be formed trom wire screen or other foraminous or porous material, as is well understood in the art of fabricating paper pulp. A suitable container may be made from preformed cardboard or paperboard 10 if desired. Thus, sheet paper, cardboard, paperboard, pulpboard, cloth, asbestos board, asbestos paper, or the like, may be subjected to the treatment below described and supplied to the trade for use wherever oil, grease and hydrocarbon resistant fibrous material is desired, or for the subsequent fabrication of containers therefrom by the usual methods known in the paper manufacture art, such as folding, cutting,'and adhering with an oil, grease and hydrocarbon resistant ad- 20 hesive which has an adhesive attraction for the treated surfaces of the product. Within the purview 01 the invention, there may be used the untreated, uncoated materials above enumerated or' such materials which have been treated or coated 25 with other substances than those shown below, as, for instance, rubber-impregnated or rubbercoated paper or cloth, which, oi-course, is sub ject to extremely high deterioration when left in contact with oils, greases and hydrocarbons.
By the term hydrocarbon as used in this specification and claim, it is intended to include all organic compounds containing as elements only carbon and hydrogen, including all saturated ali- ,phatic hydrocarbons, such as gasoline, petroleum 35 naphtha, benzene, ligroin, kerosene, spindle oil,
' petroleum oil, such as lubricating and motor oil,
to solid'an'd even gaseous hydrocarbons. Thus. material treated bythe process herein disclosed might be used for the retention of gaseous hydrocarbons such as in gas-holders, gas tanks, etc.
By the term oil and grease-resistant" as used in this specification and claim, there is; con-. templated resistance to oily and greasy hydrocarbons included in the above enumeration, as well as resistance to vegetable and animal oils such as peanut butter, mayonnaise, linseed oil, hydrogenated cottonseed oil and to the higher fatty acids such as stearic acid, oleic acid, etc. In general, by the term oil, grease and hydrocarbon-=resistant there is contemplated resistance to any oily or greasy or hydrocarbon material;
It has been discovered that by the application of a plurality of coatings to the fibrous base material to be rendered oil, grease and hydrocarbon resistant, at least one of which coatings is a cellulose derivative and at least one oi which is a water-miscible organic binder such as glue or wateresoluble gums fiexibilized with cert sugars either alone or in combination with polyhydric alcohols, that the resulting material is highly impervious to hydrocarbons, oils and are and retains the imperviousness indefinitely. ere
may be use only the two coatings referred to,
or other coatings in addition.
, To form the cellulose derivative coating, there is employed as coating material the usual lac que'r' made up of the cellulose derivative, suit able solvents therefor, and suitable plasticizers and softeners, but. it is preferred to use an aqueous emulsion of a cellulose derivative or of a cellulose derivative lacquer. As cellulose derivative, cellulose nitrate, cellulose acetate, ethyl cellulose, etc., may be used, but cellulose nitrate is preferred. A suitable formula for the emul sion which is preferred is given in the examples below, but it is to be understood that other formulae and proportions may be used and that any coating of a cellulose derivative is deemed to fall within the spirit of this invention. The
coating is produced by any appropriate coating process. Thus, in the case of a pressed pulp container, cellulose derivative solution or emulsion may be poured into the interior and the container rotated while emptying it, allowing it to drain drip-free and drying thoroughly. prefer-=- abiy under forced draft conditions, and at elevated temperature.
As the water-miscible organic binder there may be used any of the protein glues, such as albumin, casein, soya bean casein, zein, gelatin, animal glue, hide glue or bone glue, although animal, hide or bone glue are preferred, or there may be used any of the water-soluble gums such as gum karaya, gum tragacanth, gum arable (gum acacia), dextrine (British gum), etc. To
render this film flexible there is incorporated in I the initial coating composition a water-soluble sugar or a sugar syrup, such as the trisaccharides, such as raflinose, the disaccharides, such as sucrose (cane sugar), lactose, maltose, the monosaccharides, such as mannose, glucose, invert sugar (dextrose and levulose) fructose, galactose, arabinose, xylose, rhamnose. etc, or syrups of any of these sugars. For cheapness it'ls preferred to use the cheaper, more available sugars such Films made from the water-miscible binder above described flexibilized with these sugars are exceedingly impervious to hydrocarbons.
The sugars are less effective flexibilizing agents than the polyhydric alcohols, although they impart suflicient flexibility for many purposes. If desired, however, greater. flexibility may be secured by using suitable proportions of the polyhydric alcohols with the sugars in compounding the water-miscible organic binder coating. Such "preferred to we a ratio of one to two parts of flexibiliner to one part of the binder.
The fie xibilized coating may be applied by any mown coating process. Thus, it may be applied to preformed containers in the same manner as above descri for the cellulose derivative coating, but it is preferable to heat it before coating with it.
Oil, grease and hydrocarbon resistance is obtained in the product whether there is first ap-' plied the cellulose derivative coating, followed by the fiembilized water-miscible organic coating, or whether the-coatings are applied in the reverse order with the nembilized water-miscible organic coating next to the base material and eposed thereupon the cellulose derivative coating. However, the first mentioned order is preferred, especially when using an aqueous cellulose derivative lacquer emulsion on a fibrous base since the water of the emulsion is taken up the porous material very rapidly, resulting in a high adherence of the lacquer, and a very much shortened drying time. is necessary ore the fiexibilized coating is applied. Moreover, containers so prepared in which the oilrepellant coat is in direct contact with the hydrocarbon oil drain more completely on emptying.
-The flexibilized water-miscible organic binder coat shows such a high adherence to the cellulose derivative undercoat that the two coats cannot be separated. The cellulose derivative undercoat protects the water-miscible organic film from atmospheric moisture or dryness which might penetrate through the fiber base, while the water-miscible organic coating protects the cellulose derivative undercoat from contact with the oii,grease or hydrocarbon material which might tend to dissolve the plasticizer therefrom, resulting in leakage. Thus, it i seen that the dissimilar coats described cooperate in a new and novel manner and produce results which would not be obtainable with two cellulose derivative coats or two water-miscible organiccoats. Moreover. a more economical coating is obtained using the coatings described. However, with water-miscible organic binder as the first coat, and cellulose derivative as the second coat, many of the advantages of the invention are attained and the container will not fail altogether in humid climates.
When reference is made to sorbitol, there is also contemplated a technical grade of sorbitol syrup prepared by the catalytic hydrogenation or electrolytic reduction of glucose and which may contain as impurities some 'unreduced glucose, ash and salts of organic acids.
In the following examples there are set forth several preferred embodiments of the invention.
It is to be understood, however, that the inv tion is not limited thereto.
Exmu l Coating'A (cellulose derivative) Water phase, 28%% by weight Per cent by weight Water 99 Sulfonated castor oil (75% grade) 1} 8811 Grams per gallon 5 Sodium salt of sulfonated lauryl alcohol extracted with methyl alcohol (Duponol Me) i 19 Methyl cellulose (Tylose 5-25) 11.1
Lacquer phase, Il by weight liquids, 1 gallon.
Per cent by volume Octyl acetat 7 m b Butyl acetate 25 Butyl alcohol 10 Toluol 2i Blown castor oil M 34 Solids.
Nitrocellulose (7 sec.) oz 25 The water phase is prepared by dissolving the sulfonated castor oil in the distilled water, then adding to one gallon of the resulting solution the sodium salt or .sulionated lauryl alcohol and the methyl cellulose in the proportion stated. The lacquer phase is made by dissolving the nitrocellulose in the pretdcuslyprepared mixture of solvents and plasticizer. The given proportion of lacquer phase is then emulsified in the water phase by passing the mixture through a colloid mill or honi'ogeniz-er.
Coat-mg B glue) Fer cent by weight Crystallized glucose 15 Hide glue (gel. strength 499-415 g.) 15 Water '79 The crystallized glucose and water are heated in a jacketed kettle with agitation to 176 F. The glue is added and heating is continued between 170 and 180 F. until the-mixture is uniiorm and grain-free. The water removed by evaporation is replaced. Preferably 1% of beta naphthol on the weight of the glue or similar anti-mold compound is added.
A container of pressed paper pulp sized throughout during manufacture with 10% of parafiin Wax is first coated with Coating A by filling the container with the lacquer emulsion and immediately pouring it out with a rotary motion. The excess is allowed to drain drip free and the container is then dried for 15 minutes at 150-160 F. or for 2 hours at -130 'F. in a drying chamber equipped with a fan for circulat ing the air. The container is then removed and coated with Coating B which is applied at a temperature of 160-180" F., the manner of application being otherwise identical with that of Coating A. The container is then dried for 16 hours at room temperature and then dried 2 hours at 150460 F. in the same type of drying chamber as described above.
Exzlmm 2 Coating A The same as in' Example 1.
Coating B (glue) Per cent by weight (dry basis) Invert sugar syrup (50% inverted) 15 Hide glue (gel. strength 400-415 g.).. 15
The coatings are prepared and applied to the paper pulp container in exactly'the same man- Water paper pulp container in exactly the same manner as that described in Example 1. In making up Coating B the glycerine, cane sugar and water are first heated, the glue being added later.
Empress i Coating A.
The same as in Example 1.
floating B er cent by weight (dry basis) Invert sugar syrup (5.0% inverted) l3 Casein 12 Ammonia, 26 1 Water; 7
Weigh the water (less th water in the sugar syrup) into an agitated, jacketed kettle and add the casein; stirring until all lumps are dispersed. r
Add the ammonia and heat slowly (in the course of 40 minutes) with stirring tolfiO" F. Add the invert sugar syrup and stir at -160" F. until homogeneous. Replace evaporated water.
The coatings are applied in exactly the same manner as in Example 1, except that Coating B should be applied at a temperature not exceeding F.
The fibrous containers produced as in Examples 1 to 4 are extremely impervious to hydrocarbons and are especially adapted for use as non-refillable containers for dispensing motor and lubricating oils. The use of pressed paper pulp for such containers is extremely advantageous since it is cheap and seamless. W'hile -reference has been made to containers made from such pulp sized with wax, it will be obvious that containers made from unsized pulp or from pup sized with other agents, such as 5% of rosin size, may be used.
EXAMPLE 5 Coating A The same as in Example 1.
- Coating B y Per cent by weight Glucose 7.5 Glycer 7.5 Hide glue (gel. strength 400-415 g.) 15.0 Water 70.0
This coating is made up as in Example 3, the glycerol, glucose andwater being first heated to 170 and the glue being then' added.
Coating A is first uniformly applied by spraying on 16 oz. cotton duck. The coated fabric is dried at 150-460" F. ior thirty'minutes. Then Coating B at a temperature of 150 -160 1".,is sprayed uniformly asa-second coat and dried at loo-160 F. for two hours. The fabric thus prepared is extremely resistant to penetration by hydrocarbons, and, for example, may be us'ed'in the fabrication of hose or tubing through which gasoline or other hydrocarbons are to be passed.
Coating A The same as in Example 1. Coating B resistance is a prime requisite, provided the tem-' perature to which it is subjected does not exceed 150? F.
This coating was made up by commingling the specified materials and subjecting them to slight heating while agitating in order to obtain a homogeneous mixture.'
Coating A was applied to a paper pulp cone exactly as in Example 1. Coating B was then applied over Coating A by adipping operation, followed by draining drip-tree, whereupon the container was dried for 2 hours at 140-150" F.
EXAMPLE 8 (Bax-ramp znn wrm Gnocosn) EXAMPLE 9 (Dnx'rm FLnxInmzEb wrrn Invna'r doses) This example is exactly like Example 7 except that 25% of Nulonioline (dry basis) was substituted for the dextrose in that example. Nulomoline is an impure invert sugar syrup comprisin to be limited to the above description and specific examples. Thus, any lacquer or. lacquer emulsion any suitable manner.
comprising a cellulose. derivative may be used. Any cellulose ester or ethermay be used. Other plasticizers and solvents than those shown may be used. Compatible resins, either naturalor synthetic, may be added to the cellulose derivative coating composition. The coats may be applied in dients,'o rder of mixing and temperatures 0! appli- The proportion of ingre cation, may all be varied considerably without departing from the spirit of the invention. Thus, if desired, instead of the drying procedure described ior Coating Bin the examples, the coating of the superimposed glue may be dried at atmospherictemperature for a period o'f'irom 15 minutes to twenty-four hours, preferablyior 16 hours, before being placed in the oven, in order to allow the melting point of the glue mixture to rise above that or the drying oven by evaporation of water, or formaldehyde or paraformaldehyde may be added in the glue mix so as to set the glue coating before 11 .1 or the glue-coating may be sprayed with aqueous formaldehyde-after its application and prior to drying; When formaldehyde is used in glue coat. it is highly preferred to use .l4-.16% of 100% formaldehyde (CI-I20) calculated on the weight of the glue. If desired, drying of the glue cost at elevated temperatures may be altogether eliminated by the use of the specified proportion OI formaldehyde and by the expedient of drying at room temperature for 16 hours. Other drying temperatures than those specified in the examples may be used ii desired. The coatings described in the examples may be used interchangeably. Thus, pressed paper pulp might be used as the base in Example 5, or fabric as the base in mamples l to l By "oil, grease and hydrocarbon-resistant as used in the claim is meant impermeable to and not decomposed by or chemically afiected by oils. greases and hydrocarbons generally, including those herein enumerated. It is not intended to be limited to such hydrocarbons as gasoline and motor oil to which the invention is particularly applicable. By water miscible organic binder" as used in the claim, there is meant watermiscible organic binders of the type herein disclosed and similar materials, namely, protein glues such as hide or .bone glue or casein, or the water-soluble gums such as gum arabic, dextrine, etc.- These binders are of the type that :lorm solutions or colloidal suspensions upon admixture with water. By g1ue" there is meant protein glues such as hide and bone glue, gelatine, casein, albumin, etc.
By "water-soluble gum" is meant such natural gums as are herein disclosed, dextrine and similar gums which are termed watersoluble by those skilled in the arts. The terms "a use of a water-miscible organic binder coating flexibilized with polyhydric alcohols in conjunction with a cellulose derivative coating for rendering materials oil. grease and hydrocarbon-resistant. In co-pending application. Serial Number 111,599, filed Nov. 19, 1936, there is disclosed a coating composition comprising a water-miscible organic binder fiexlbilized with sorbitol or mixtures of sorbitol and lower polyhydric alcohols.
Having described my invention, what I claim is: An oil, greaseand hydrocarbon-resistant fibrous material comprising a fibrous base provided with two superimposed flexible coatings, the first coating which is in contact with the fibrous base being highly resistant to moisture and consisting essentially of a plasticized cellulose derivative, and the second coating which is superimposed over said first coating and which is to be exposed to oil,
grease or hydrocarbon being highly resistant to oils, greases and hydrocarbons and consisting