Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS2811468 A
Publication typeGrant
Publication dateOct 29, 1957
Filing dateJun 28, 1956
Priority dateJun 28, 1956
Publication numberUS 2811468 A, US 2811468A, US-A-2811468, US2811468 A, US2811468A
InventorsStephen P Joffre
Original AssigneeShulton Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Impermeable polyethylene film and containers and process of making same
US 2811468 A
Images(6)
Previous page
Next page
Description  (OCR text may contain errors)

United States Patent IMPERMEABLE POLYETHYLENE FILM AND CfiN- TAINERS AND PROCESS OF MAKING SAME Stephen P. Jotfre, Little Falls, N. .L, assignor to Shulton Inc., Clifton, N. J., a corporation of New Jersey No Drawing. Application June 28, 1956, Serial Nor 594,342

16' Claims. (Cl. 117-95) This invention relates to polyethylene film and containers and more particularly to polyethylene film suitable for use as a wrapping material for foodstuffs and other perishable materials and to containers for perfume compositions, synthetic aromatic chemicals, natural isolates (fractions derived from natural sources, such, for example, as aromatic woods, barks, branches, flowers and fruits), other materials which are deleteriously affected either by the escape of vapors from the interior of the container through the walls thereof or by entry of constituents of the surrounding atmosphere through the walls of the container into contact with its contents, mineral and vegetable oils, aromatic hydrocarbons, e. g., toluene, aerosols in which a pressurized gas, such as nitrous oxide or the Freons are usedas the propellants, emulsions in which the oil phase is the continuous phase, etc. The expression container is used herein in a broad sense to include bottles, boxes, envelopes, and the like.

Polyethylene containers, particularly bottles, are widely used for storing and transporting perfume compositions containing synthetic aromatic materials, such as citrus oils, clove oils, eugenol, isoeugenol, ionones, orange oils, lemon oils, etc., and other materials. Examples of such containers are the flexible polyethylene bottles including the now popular polyethylene squeeze bottles and bottles made from filled polyethylene compositions, such, for example, as mixtures of polyethylene and pigments and/or fillers such as barium sulfate, metal powders, talc, clay, etc. The latter type of bottle, while lacking the flexibility of the former, like the former has the advantage of unbreakability as contrasted with glass, lightness in weight and the other advantages of polyethylene.

It is known that polyethylene is chemically inert to perfume compositions and aromatic chemicals, e. g., it will not dissolve therein or react therewith. Nor are the individual constituents of perfume compositions adversely affected by contact with polyethylene. Yet when perfume compositions are packaged in polyethylene containers not only does a rapid change in the character of the perfume occur but also Weight losses from the sealed containers are considerable. In addition, distortion' of the container frequently occurs. These changes in the composition of the perfume and the consequent weight losses are due to escape of the light notes (the fugitive or more volatile constituents), and sometimes also the medium notes through the Walls of the poly* ethylene container, i. e. polyethylene is permeable to the constituents present in the perfume and the solvent employed (usually alcohol), permitting their escape in vapor or gaseous formthrough the walls of the sealed polyethylene container.

fragrance, light, medium and heavy notes must be blended judiciously. It has been the uniform experience of the perfume industry that any well constituted odor containing these three phases becomes unbalanced after storage in a sealed polyethylene container, even though no liquid leakage takes place from the container. The lighter notes disappear far more rapidly than the medium notes and the medium notes permeate the polyethylene walls more rapidly than the heavy notes. After awhile the unequal rate of permeation throws the fragrance completely out of balance.

Polyethylene containers can not be used, as a practical matter, for the storage of mineral or vegetable oils or emulsions in which oil is the continuous phase, because such oils ditiuse through the walls. Attempts to' store aromatic hydrocarbons, such as toluene, in polyethylene containers has resulted in the collapse and distortion of such containers. Nor have polyethylene containers been found suitable for packaging aerosols in which a pres surized gas such as nitrous oxide or theFreo'n s chloro fl-uoro methanes or ethanes) including Freon 1 14 (di chlorotetrafluoro' ethane) is used as the propellant because such pressurized gases escape through the walls with consequent loss of pressure within the container.-

Polyethylene film, because of its" clarity, tensile strength, relatively low moisture permeability, ease of handling, heat sealing ability and prope'rfy of transmitting ultra-violet light, permitting surface" sterilization of material wrapped with such film by means of ultra-violet light, is an eminently satisfactory wrapping material for materials which are not deleteriously infected by atmosphen'c' gases, such as oxygen, air, carbon dioxide, or which donot contain flavor or odor constituents which escape through the polyethylene. The use ofpol y'ethyl'ene film for packaging foodstuffs and other perishable mater-ials deleteriously affected by atmospheric gases; has been discouraged, if not substantially completelyavoided, because of the relatively high permeability of polyethylene to atmospheric gases, particularly air and ox yg" cause spoilage, including changes'in odor, flavor. Likewise, the packaging of meats; che'e's cooked foods, dried fruits, etc., in polyethylene filrmwrapriers, has frequently resulted in' discoloration, rancidity and poor flavor or" the packaged material.

ethylenes, including polymeric trifluorochlo'roethyl'enev and copolymers of vinyl chloride and vin'ylidene' .chlo?" ride from which containers may be made by injection into a mold or by blowing into a mold, etc. However, containers made from such polymers either sacrifice the desirable flexibility characteristics of polyethylene; are

prohibitively expensive, or are objectionable for other reasons.

In'the case of wraps for foodstufis and otherperishable materials, development has proceeded along the dir'ec tion of (1) laminated films in which one film which isa good gas or vapor barrier but lacking in other desirable characteristics is bonded to another film'h'aving the desired qualities, e. g., polyethylene bonded to cellophane; (2) coated films, e; g., films coated with waxes'orr s'insi includingthe polyvinyls; and (3) special plastics, such as- Afck Saran (polyvinylidene chloride), Mylar (polyester), which, while substantially impermeable to gases, are difficult to handle, lack ultra-violet transmission necessary for the sterilization of the surface of goods packaged therein, e. g., fresh meat, generate static electricity when handled, lack heat-scalability, are excessively costly, etc.

It is among the objects of the present invention to provide a polyethylene film and/or container, which film and walls of which container are relatively impermeable to the passage of atmospheric gases therethrough, and this without sacrifice to the desirable properties of the polyethylene, such as its clarity, tensile strength, ability to transmit ultra-violet light, and heat-sealing ability.

It is another object of this invention to provide polyethylene containers which are of improved impermeability to the passage of gases or vapors through the walls thereof and which containers, in the case of flexible polyethylene containers, such as squeeze bottle, retain the flexibility and other desirable characteristics of polyethylene, i. e., the improvement in the impermeability of the container is without sacrifice to the other desirable properties of polyethylene.

It is still another object of this invention to provide a polyethylene wrap or container which minimizes, if not completely prevents, the loss of aromatic flavor constituents from foods like cheese packaged in such wraps or containers; such loss, it will be appreciated, not only reduces customer acceptance of the food item but can also lead to flavor contamination of other food items stored in proximity therewith.

Still another object of the present invention is to provide a process for producing such polyethylene films or containers of improved impermeability which process is relatively simple and economical to carry out.

Other objects and advantages of this invention will be apparent from the following detailed description thereof. In accordance with this invention, polyethylene film and/ or containers are fluorinated to produce fluorinated polyethylene film and/ or container walls containing from 0.03% to 3.5%, preferably from 0.05% to 1.5% by weight of fluorine based on the weight of the polyethylene. Surprisingly, I have found that the formation of such fluorinated polyethylenes results in a polyethylene film and/or container which is of surprisingly improved impermeability, and this without sacrifice to the desirable properties of the polyethylene.

It is important that the fluorination be carried out so as to produce a fluorinated polyethylene containing from 0.03% to 3.5% by weight of fluorine, based on the weight of the polyethylene. The desired improvement in the impermeability of the polyethylene is obtained as long as it is reacted with the fluorine to form fluorinated polyethylene containing fluorine in the amounts above indicated. While the explanation for the improvement in impermeability is not fully understood, it is believed due to the replacement of some of the hydrogen atoms of the polyethylene with fluorine which form an electrical lattice-work to prevent passage therethrough af vapors and/or gases. It will be understood that the above explanation is advanced for the purpose of facilitating a better understanding of the invention and that this invention is not to be confined to or limited by the above explanation.

Fluorination of the polyethylene to an. extent to introduce more than approximately 3.5% by weight of fluorine does not result in the desired improvement in the impermeability of the polyethylene and may deleteriously' affect other desirable properties of the polyethylene, such as its tensile strength and clarity. On the other hand; the fluorination of polyethylene so as to introduce fluorine in amount less than 0.03% based on the weight of the polyethylene does not result in the desired improvement in the impermeability.

The polyethylene, such as bottles and film, subjected to fluon'nation may have a thickness of from 0.25 to I 250 mils; in the case of film the thickness is from 0.25 to 25 mils. All commercial polyethylenes employed for the production of containers or in the form of film may be fluorinated in accordance with this invention to render them substantially impermeable. Such polyethylene usually consists of polymers of ethylene having a molecular weight of at least 10,000, preferably from 14,000 to 60,000.

In the fluorination of the polyethylene film, the film should be free of lint and grease. This is preferably accomplished by washing the film with a low boiling grease removing solvent, such as carbon tetrachloride, acetone, ether or perchloroethylenes, to remove all grease, dust and foreign matter which, if not removed, might cause ignition of the polyethylene. Thereafter, the film is contacted with pure fluorine or a mixture of fluorine and an inert gas containing at least about 10% fluorine. The fluorination may be continuous by continuously passing the film through the fluorine or fluorine mixture maintained in a suitable sealed chamber provided with gas-tight seals through which the film enters and leaves. Alternatively a wound reel of the film can be unrolled and rerolled in the treatment chamber.

Instead of the continuous treatment hereinabove described, the treatment may be a batch operation involving festooning or otherwise arranging the clean film within the reactor to expose both sides, then introducing the fluorine or fluorine mixture into the reactor and permititng the film to remain in contact with the fluorine for the desired time interval. While not preferred, if desired the fluorination treatment may be carried out so that only one side of the film is fluorinated to form a layer of fluorinated polyethylene containing from 0.03% to 3.5%, preferably from 0.05% to 1.5% fluorine.

The time of treatment will depend on the particular equipment used, the film to be treated, the concentration of fluorine used, and the temperature. In general, a treatment time (contact time between the polyethylene and the fluorine) of from about 5 minutes to about 3 hours will give satisfactory results at room temperature (2025 C.). It is preferred to operate at room temperature, although temperatures as high as 50 C. may be employed. The more concentrated the fluorine atmosphere, the shorter the treatment time. Also, elevating the temperature to not exceeding 50 C. will permit Shortening the treatment time. In the case of films in the lower portion of the 0.25 to 25 mils thickness range, it is preferred to use a relatively short treatment time. Treatment times exceeding 3 hours may be used but are not preferred because they do not result in material further improvement in the impermeability of the polyethylene.

Following the above noted conditions, it has been found the film is not charred nor is there any material loss of clarity or tensile strength; the impermeability of the film to gases is, however, greatly improved as will be evident from the test data given below.

The fluorination of polyethylene containers is carried out by first cleaning each container so that it is free from lint and oil, introducing the clean container into a chamber, evacuating this chamber, then introducing fluorine gas into this chamber and continuing this introduction to the desired extent. Maintenance of each container in the chamber in contact with the fluorine gas for from 20 to minutes usually suflices to produce the desired level of fluorination. Thereafter, the container is removed from the chamber and its interior and exterior flushed with air or other inert gas, such as nitrogen, to remove residual fluorine gas.

. In lieu of the above procedure, each container after cleaning, as above described, may be introduced into an The time of treatment of the containers will depend on the equipment used, the containers to be treated, the concentration of fluorine used and the temperature. At

atmospheric temperature, a treatment time of from min-.

utes to 3 hours will give satisfactory results. Elevating the temperature or using more concentrated fluorine atmospheres, or both, will permit the use of shorter treatment times. Treatment times exceeding 3 hours may be employed but are not preferred because they do not result in further improvement in the impermeability of the polyethylene. Excessively long treatment times should not be used because they adversely affect the tensile strength of the polyethylene.

The cleaning of the containers before they are subjected to fluorination is desirably efiected by washing the container with a suitable solvent for oil or grease, such as carbon tetrachloride, acetone, ether or perchloroethylene, and thereafter removing residual traces of the solvent, for example, by blowing clean air over and through the washed containers. Unless the containers are clean when subjected to fluorination, particularly at temperatures above room temperature, there is the danger that when the container is fluorinated the polyethylene will ignite. By observing the conditions hereinabove set forth, namely, at temperatures below 50 C., preferably at room temperature, and utilizing clean containers, particularly in that they are free of lint and oil or grease, this danger is eliminated.

While it is preferred to fluorinate both the interior and exterior of the container, as hereinabove described, only the interior or only the exterior of the container may be so treated and still obtain the desired improvement in theimpermeability of the walls of the container.

In all modifications, including the fluorination of polyethylene film, instead of an atmosphere containing 100% fluorine, the fluorine may be diluted with an inert gas. The fluorine concentration may vary from 2% to 100% by weight, the balance, if any, being the inert gas, such as nitrogen, air, Freon (chlorofluoro alkanes, e. g., methanes and ethanes), etc. When a diluted fluorine is used, it is important to dry the diluent, i. e., substantially anhydrous conditions should be maintained during the fluorination. The presence of moisture tends to result inundesirable side reactions with the fluorine.

While the fluorination desirably is carried out at room temperature (2025 C.) any desired temperature below 50 C. may be used.

The following comparative data shows the surprising improvement in impermeability of polyethylene films and containers effected by the present invention.

CONTAINERS In all of the container examples, flexible bottles were employed made of a commercial polyethylene having an average molecular weight of 21,000; the bottles were oval shaped and the walls thereof varied in thickness from 20 to 60 mils.

Example] Pre-formed clean polyethylene bottles, each of 5% 02. capacity, were treated with a stream of fluorine gas at room temperature (20-25 C.) for six hours and for twelve hours. A 1 cm. diameter punch taken from the thickest aspect of the bottle wall from bottles which were fluorinated for 6 hours contained approximately 0.3% fluorine. The bottles fluorinated for 12 hours contained approximately 1.5% fluorine. The bottles were then flushed with air until no residual odor remained and filled to capacity with liquid allyl caproate and then sealed. This material was used as a test liquid because of its high volatility and distinctive odor and also because it has been found to be an excellent medium for indicating the permeability characteristics of polyethylene.

1 The filled bottles were then weighed, stored on open 6 shelves at room'temperature for the periods indicated in the table which follows and at the termination of each' of these periods the bottles again weighed and the gross losses in weight noted. An identical, fluorine untreated bottle was subjected to the same test for control purposes. The data on this test is given in Table 1 which follows:

i TABLE 1 Percent Loss in Gross Weight Bottle Type 10 days 21 days 40 days (a; Untreated bottle 0.8 2. 42 5.67 (b fihnfluorlne treatment 0.0009 0.007 0. 0512 (c) 12 hr. fluorine treatment 0.020 0.104 0.400

From the above data, it will be noted the untreated bottle lost at the end of 40 days times more weight than the bottle treated for 6 hours. The strong characteristic odor of allyl caproate was readily detectable from the untreated bottle whereas it was not noticeable from the outer walls of the treated bottles.

Example II Clean polyethylene bottles of 5% oz. capacity were fluorinated by passing a stream of gas from the inside of one bottle to the inside of the next bottle, the bottles being connected with fluorine resistant tubing. The bottles were treated with a stream of fluorine at room temperature for diiferent periods of time indicated in the table which TABLE 2 Time of Percent Bottle Treatment, Gross Loss hours in Weight Control (untreated) None 4. 0 Treated it 0. 00174 130.- 1 0. 00224 Do." 2 0. 00199 D0 3 0. 00542 Do 4 0.00293 During and at the end of the test, the strong character istic odor of allyl caproate was readily detected from the untreated bottle, whereas the outer walls of the treated bottles did not have any noticeable odor.

Example 111 The polyethylene bottles were first thoroughly cleaned to remove lint, oil and grease and then were placed in a chamber at room temperature. The air was evacuated from this chamber. Fluorine gas was slowly fed into the chamber so that at the end of an hour atmospheric pressure was established in the chamber. The fluorine gas was then permitted to remain in contact with the polyethylene bottles for another hour and thereafter the entire system was flushed with air until no residual odors remained.

Bottles thus treated were then filled with (a) the test liquid allyl caproate, (b) with a fragrance sold commercially under the trade name of Desert Flower Toilet Water and (c) with a lotion sold commercially under the trade name of Old Spice After-Shave Lotion. The bottles were weighed, stored on open shelves at room-temperature, again weighed at the end of the test period indicated in the table which follows, and the gross loss in weight noted. Untreated polyethylene bottles were subjected to the same treatment for control purposes. The data otbained on this test is given in Table 3 which follows:

During and at the end of the test period the strong characteristic odor of allyl capr oate and Desert Flower Toilet Water Was readily detected from the outer walls of the untreated bottles (the control bottles) whereas there was no noticeable odor of the test liquids on the outer walls of the treated bottles. Likewise, the untreated bottles containing Old Spice After-Shave Lotion had a faint spice odor on their outer walls, while this was not noticeable with the treated ones. In Table 3-A below is given the concentration of fluorine and the diluent used in treating polyethylene bottles made from polyethylene having an average molecular weight of 21,000 to 23,000; this table also gives the fluorine content and treatment times of the resultant bottles.

1 In this example, the bottles were placed in a closed chamber, the chamber sealed and evacuated and an amount of fluorine introduced into the chamber equal to 5- of the volume of the chamber.

FILMS All film permeability data hereinafter given was obtained using the apparatus and the test procedure described in the article by A. Cornwell Sherman, entitled Apparatus for measuring the gas permeability of film materials of low permeability, published in Industrial and Engineering Chemistry, Analytical Edition, vol. 16 (No. 1), pages 58 through 60, January 15, 1944.

Example IV In the film examples, the molecular weight of the polyethylene was about 23,000.

25 ft. of polyethylene film, 8 inches wide and 1.2 mils in thickness were washed with carbon tetrachloride to remove oily residues and foreign matter. The fihn was then air dried and festooned in the gas-tight treatment chamber to expose both sides of the film. The chamber was then evacuated and filled with dry nitrogen. This evacuation and filling process was twice repeated in order to flush the treatment chamber of any initial undried moisture-bearing atmospheric air. The treatment chamber, after this flushing, was evacuated to approximately 28 inches of vacuum and then filled with fluorine gas, over a 30 to 40 minute time interval until the vacuum was about 14 inches. At this point, the fiow of fluorine gas into the chamber was stoppedv and dry nitrogen gas was introduced into the chamber until the pressure was one atmosphere. The treatment chamber then contained 50% fluorine gas and 50% nitrogen.

The polyethylene film was permitted to remain in the treatment chamber for 30 minutes and thereafter the chamber was flushed with dry nitrogen to remove substantially all of the fluorine gas. The chamber was then opened, the film removed, washed with cold tap water, air dried and stored for 48 hours in an air conditioned room having a relative humidity of 45-50% and at a temperature of 7678 F.

The resultant film was clear and showed no reduction in tensile strength. The film before and after treatment was tested to determine its permeability to oxygen and carbon dioxide with the following results:

OXYGEN PERMEABILITY Film before treatment 303 Film after treatment 46 CARBON DIOXIDE PERMEABILITY Filmv before treatment 995 Film after treatment 148 The above values and all permeability values hereinafter given are in terms of the number of cubic centimeters of the particular gas under test transmitted per hundred square inches of film surface per 24 hours.

Example V Sheets of polyethylene film 8" wide, 10 long, and 2 mils in thickness, were washed with carbon tetrachloride to remove anyoily residues and foreign matter. The film was air dried and placed in the gas-tight treatment chamber, which was flushed with dried air. The treatment chamber was then filled with a mixture of 50% by volume fluorine gas and 50% by volume of dried air and the film permitted to remain in this mixture for 30 minutes. The chamber was then flushed with dried air to remove substantially all of the fluorine gas. The chamber was then opened to the atmosphere; the film removed, washed with cold water, dried in air, and then stored for 48 hours in an air conditioned room, as in Example IV.

Tests on this film before and after treatment, to determine air and Freon 114 (dichloro-tetrafluoro ethane) permeability, gave the following results:

am PERMEABILITY before treatment 135 A sheet of polyethylene film 8 wide, 12' long, and 5 mils in thickness, was washed with acetone to remove any oily residues and foreign matter, then air dried, and placed in the gas-tight treatment chamber, which was thereafter flushed with dried air. The treatment chamber was then filled with a mixture of fluorine and dried air so as to contain 40% fluorine by volume. The film remained in this atmosphere within the treatment chamber for 10 hours. Thereafter, the treatment chamber was flushed with dried air to remove substantially all of the fluorine. The film was thereafter removed from the chamber, washed in cold tap water and dried. It was then tested for oxygen permeability, with the following results:

Film before treatment Film after treatment 28 In Table 4, which follows, there are given the permeability values for different thicknesses of film, before and after treatment, subjected to fluorination treatment, using g the different concentrations of fluorine in the treatment chamber, and the time of treatment indicated in the table. The fluorination procedure otherwise was substantially the same as hereinabove described in connection with Example IV.

TABLE 4 OXYGEN PERMEABILITY Percent by Vol- Percent time Fluorine Permea- Permea- Reducand Diluent Duration bility of bility of tion in Film Thick- Concentration of Treat- Film Film Permeaness, Mils in Treatment ment in Before After bility Chamber Hours Treat- Treat- Efiected ment ment by Treatment F Diluent 85 15 air 2 116 23 78.5 85 15 air-- 1 167 39 76.4 50 50 Na... it 256 44 82.7 50 50 Na... it 303 46 84.8

CARBON DIOXIDE PERMEABILITY 85 15 air 1 600 136 77.2 50 50 N2 92 995 148 85.2 50 50 Namit 814 122 85.0 90 Air-.- 1 406 161 60.2

FREON 114 PERMEABILI TY 2.0 50 50 Air-.. /1 13s 25 21.9

1 Air in all examples was dried air.

In all of the above examples, the fluorinated polyethylene retained its original tensile strength, clarity, heatsealing ability, and its property of transmitting ultraviolet light. The percentage transmittance of the treated and untreated polyethylene film for wave lengths of from 230 to 280 millimicrons (the ultra-violet range) shows little or no difference for film fluorinated in accordance with this invention and for the untreated film. In one comparative test the fluorinated film showed a percentage transmittance of about 28% for radiation having a wave length of 230 millimicrons, the percentage transmittance gradually increasing with increase in the wave length to approximately 70% in the case of radiation having a wave length of about 380 millimicrons. The untreated film showed a transmittance in this same range of wave lengths of only 1% or 2% greater than the treated film.

The treated film takes print much better than the un-' treated film. Thus, for example, when untreated film was printed using inks specially prepared for printing on polyethylene and scotch tape applied over the printed area, it was found that the printing could readily be removed with the scotch tape, in the case of untreated film, but the scotch tape remained clear, i. e., would not remove the printing in the case of the treated film.

The impermeable containers embodying this invention have all the desirable properties of the polyethylene; in the case of flexible bottles, such as squeeze bottles, the fluorination treatment does not deleteriously affect the flexibility of the polyethylene.

In the case of the more rigid type of polyethylene bottles, the treatment of this invention does not have any deleterious effect on the desirable properties of the polyethylene, i. e., does not cause substantial rigidification or otherwise deleteriously affect the polyethylene.

Bottles treated in accordance with this invention will be found eminently satisfactory for the packaging and storage of toilet waters, cosmetic lotions, colognes, liquid deodorants, etc.

The present invention provides polyethylene film and containers which are substantially impermeable to gases, such as oxygen, air, nitrogen, nitrous oxide, carbon dioxide, the Freons, sulfur dioxide, ethylene, other preserving or pressurizing gases or fluids, and to the vaporizable constituents, including the light and medium notes l0 of perfume compositions, and this without sacrifice to the flexibility, heat scalability and ultra-violet light transmitting properties of the polyethylene.

Films embodying this invention provide an excellent wrapping material for foodstufis and other perishable materials deleteriously aitected by atmospheric gases.

Films embodying this invention may be formed into a bag to provide a membrane in an aerosol package, separating Freon, nitrous oxide or other gaseous propellants from the foodstuff or other material placed in the bag within the aerosol package. For example, anchovy paste, mayonnaise, jams, etc., may be packaged in such fluorinated polyethylene bags disposed in a suitable container,

such as a metal container having a Freon or other gaseous I propellant, the polyethylene bag serving to maintain the foodstuff out of contact with the gaseous propellant, while the foodstuff is within the container. In this way, the foodstufi may be dispensed in the form of a ribbon or controlled stream from the container by releasing the pressure, and this without intermingling of the foodstuff with the propellant.

Moreover, the present invention provides a substantially impermeable container which may be'used in storing or packaging toluene, other aromatic solvents, mineral oils, including'refined petroleum oils, vegetable oils, such as corn oil, peanut oil, cottonseed oil, and emulsions in which oil is the continuous phase, providing an unbreakable container in which the flexible properties of the polyethylene may be utilized, e. g., a squeeze bottle for storing and dispensing such oils, emulsions, etc. Hence, polyethylene bottles embodying this invention may be used as squeeze bottles for storing and dispensing as a spray such oils and oil emulsions.

' In this specification, unless otherwise indicated, pere centages are on a weight basis. The pressures hereinabove given are in' terms of inches of mercury. T he expression polyethylene, it will be understood, includes the polymethylenes which are produced by the polymeriza tion of ethylene. e r p j This application is a continuation-impart of copending application Serial No. 492,030, filed March 3, 1955, which application (but not the invention thereof) has been abandoned in favor of this application.

Since certain changes in carrying out the process and in the containers embodying this invention may be made without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense. Thus, instead of using gaseous fluorine for the fluorination treatment, a solution of fluorine in a suitable solvent may be employed.

What is claimed is:

1. A polyethylene film having at least one surface fluorinated, to contain not more than about 3.5% by weight of fluorine and enough fluorine so that said surface is substantially impermeable to the passage of atmospheric gases therethrough.

2. A polyethylene film containing from 0.03% to 1.5% by weight of fluorine.

3. A polyethylene container having its walls fluorinated, to contain not more than about 3.5% by weight of fluorine and enough fluorine so that the walls of said container are substantially impermeable to the passage therethrough of the light notes of perfume compositions.

4. A polyethylene container having its walls fluorinated to contain less than about 3.5% by weight of fluorine and enough fluorine to render the walls substantially impermeable to the passage therethrough of the light notes of a perfume composition.

5. Apolyethylene container having fluorinated polyethylene walls containing from 0.03% to 3.5% by Weight of fluorine.

6. A polyethylene container having a wall thickness of from 0.25 to 250 mils and having fluorinated polyamass 11 ethylene walls containing from 0.03% to 3.5% by weight 'offluorinep" 'j 7,. A polyethylene container having a. wall thickness of from 0.25 to mils and having fluorinated polyethylene walls containing from 0.05% to 1.5 by weight of fluorine. i I l 8. A'polyethylene container constitute'd of polyethylene having a molecular weight of from 14,000 to 60,000, a 'wall'thickness of from 0.25 to 250 mils and having fluorinated polyethylenewalls containing from 0.03% to 3.5% by Weight of fluorine. i V 9. A container of polyethylene having a molecular weight of from 14,000 to 60,000, -a'wall thickness of from 0.25 *to 250 mils and having thewalls' 'fluorinated to contain'from 0.03 to 3.5 by weight of fluorine based on'the' weight of the polyethylene. I p

10. A process of fluorinating 'a wall constituted of polyethylene -to render it substantially? impermeable to the passage therethrough' of aromatic flavor constituents which comprises fluorinating the said wallto'contaiiinot more than about 3.5 by weight of fluorineto render the polyethylene substantially impermeable to the passage therethrough of said aromatic flavor constituents.

11. A process of fluorinating a polyethylene surface adapted to form a container which comprises contacting said polyethylene surface with fluorine to form a fluorinated polyethylene surface containing from 0.03% to 3.5 by weight of fluorine.

12. A process of fluorinating polyethylene film which comprises cleaning the film to remove grease and foreign matter therefrom, subjecting the cleaned polyethylene film to contact with fluorine gas for from 5 minutes to 3 hours to fluorinate said polyethylene to a maximum of 3.5% by weight of fluorine, and flushing said polyethylene with a gas to remove residual fluorine therefrom.

13. A process of treating polyethylene containers which process comprises fluorinating the walls of said containers to introduce from 0.03% to 3.5% of fluorine based on the weight of the polyethylene walls.

14. A process of treating polyethylene containers which 12 7 process comprises cleaning the containers to remove lint and oil therefrom, passing fluorine into contact with the walls of said containers while maintaining said walls at a'temperature below C. and continuing said passage of fluorine into contact with the Walls of said containers until the polyethylene Walls contain from 0.03% to 3.5 by Weight of fluorine based on the weight of the polyethylene, discontinuing passage of the fluorine into contact with the Walls of said polyethylene containers and flushing the walls with an inert gas to remove unreacted fluorine therefrom.

. 15. A process of treating polyethylene containers,

which process comprises cleaning the interior and exterior walls of the container to remove lint and oil therefrom, introducing the clean container into a chamber,

evacuating said chamber, introducing fluorine into said chamber into contact with the interior and exterior walls of said container, maintaining said container in contact with the fluorine until the polyethylene walls of the container contain from 0.03% to 3.5 by weight of fluorine, removing the container from the chamber and flushing the walls of the container with an inert gas to remove unreacted fluorine.

16. The process as defined in claim 15, in which the temperature of the container while in contact with the fluorine is maintained below 50 C.

References Cited in the file of this patent UNITED STATES PATENTS 2,129,289 S011 Sept. 6, 1938 2,450,408 Baymiller Oct. 5, 1948 2,502,841 Henderson Apr. 4, 1950 FOREIGN PATENTS 710,523 Great Britain June 16, 1954 OTHER REFERENCES Modern Plastics, vol. 25, No. 6, February 1948, page 76; 117118.

mam-- We

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2129289 *Apr 10, 1935Sep 6, 1938Ig Farbenindustrie AgManufacture of new fluorine compounds
US2450408 *Sep 16, 1943Oct 5, 1948Armstrong Cork CoTextile fiber drafting element
US2502841 *Feb 5, 1946Apr 4, 1950Visking CorpMethod of modifying the surface characteristics of polyethylene structures and product resulting therefrom
GB710523A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2836318 *Aug 13, 1957May 27, 1958Plax CorpCoated plastic articles
US2836319 *Aug 13, 1957May 27, 1958Plax CorpCoated plastic articles
US3062905 *May 22, 1958Nov 6, 1962Standard Oil CoSeparation process
US3279940 *May 13, 1963Oct 18, 1966Gulf Oil CorpPolyethylene and polypropylene containers coated with a polyester resin
US3862284 *May 10, 1973Jan 21, 1975Air Prod & ChemProcess for producing blow molded thermoplastic articles having improved barrier properties
US3865615 *May 7, 1973Feb 11, 1975Air Prod & ChemNon-thrombogenic plastics
US3940520 *Feb 19, 1974Feb 24, 1976Air Products And Chemicals, Inc.Sulfo-fluorination of synthetic resins
US3988491 *Jan 17, 1974Oct 26, 1976Air Products And Chemicals, Inc.Fluorination of polyesters and polyamide fibers
US4009304 *Dec 12, 1974Feb 22, 1977Air Products And Chemicals, Inc.Fluorinated polyester tire reinforcement materials
US4020223 *Oct 30, 1975Apr 26, 1977Air Products And Chemicals, Inc.Fluorination of polyolefin and polyacrylonitrile fibers
US4153659 *Aug 1, 1977May 8, 1979Air Products And Chemicals, Inc.Enhancing solvent barrier property of pigmented polymeric bodies
US4296151 *Jun 12, 1980Oct 20, 1981Phillips Petroleum CompanyAliphatic monoolefin polymers and conjugated diene-vinyl aromatic copolymers, receptivity to coating
US4330576 *Jul 19, 1978May 18, 1982Warner-Lambert CompanyRazor blade coating and method
US4391128 *Apr 20, 1981Jul 5, 1983Air Products And Chemicals, Inc.Back-diffusion quality control method for barrier treated containers
US4422991 *Feb 22, 1982Dec 27, 1983Dayco CorporationMethod of making hose construction
US4552847 *Sep 28, 1983Nov 12, 1985Air Products And Chemicals, Inc.Visual quality control method for barrier treated containers
US4576837 *Mar 19, 1985Mar 18, 1986Tarancon CorporationMethod of treating surfaces
US4617077 *Sep 27, 1985Oct 14, 1986Kautex-Werke Reinold Hagen AgBlow molding process
US4659674 *Sep 28, 1983Apr 21, 1987Air Products And Chemicals, Inc.Diffusing permeate through polymeric article, ionizing permeate, measuring with ion selective electrode
US4699585 *Oct 10, 1986Oct 13, 1987Kautex-Werke Reinold Hagen AgBlow molding apparatus
US4701290 *Mar 13, 1986Oct 20, 1987Mexxer Griesheim GmbhControlling treatment fuel tanks of automobiles; impervious
US4743419 *Nov 7, 1986May 10, 1988The Dow Chemical CompanyOn-line film fluorination method
US4752428 *Jan 28, 1987Jun 21, 1988Air Products And Chemicals, Inc.Injection molding process with reactive gas treatment
US4754138 *Jun 17, 1985Jun 28, 1988Harold EdelsteinFluorination of inner surfaces yields vials impervious to organic solvents; nondeforming, nonsticking
US4771110 *Feb 4, 1986Sep 13, 1988Air Products And Chemicals, Inc.Polymeric materials having controlled physical properties and processes for obtaining these
US4800053 *Apr 26, 1988Jan 24, 1989Air Products And Chemicals, Inc.Injection molding process with reactive gas treatment
US4828585 *Jan 11, 1988May 9, 1989The Dow Chemical CompanySurface modified gas separation membranes
US4830810 *May 29, 1986May 16, 1989Audi Ag.Method of blow molding and fluorinating plastic containers
US4833205 *Feb 18, 1988May 23, 1989Air Products And Chemicals, Inc.Polymeric materials having controlled physical properties
US4861250 *Aug 29, 1988Aug 29, 1989The Dow Chemical CompanyMold sulfonation system
US4880675 *Apr 25, 1988Nov 14, 1989Air Products And Chemicals, Inc.Polyethylene,polypropylene, fluorine modified polyethlene used in food packaging
US4994308 *May 31, 1988Feb 19, 1991Tarancon CorporationDirect fluorination of polymeric materials by using dioxifluorine fluid (mixture of CO2 and F2)
US5156783 *Jan 18, 1991Oct 20, 1992Solvay Automotive, Inc.Two stage process for sulfonating plastic containers
US5202161 *Jan 18, 1991Apr 13, 1993Solvay Automotive, Inc.Reducing permeability to unleaded gasoline by controlled sulfonation, then neutralization
US5242661 *Oct 17, 1991Sep 7, 1993Liquid Carbonic, Inc.Apparatus for direct fluorination of polymeric resins
US5244615 *Dec 3, 1992Sep 14, 1993Air Products And Chemicals, Inc.Process for the production of permeation resistant containers
US5260033 *Oct 15, 1991Nov 9, 1993Liquid Carbonic, Inc.Direct fluorination of polymers
US5785912 *Mar 24, 1995Jul 28, 1998National Power PlcMethod for the fabrication of an electrochemical cell having long term chemical stability
US5849818 *Jun 3, 1993Dec 15, 1998Walles; Wilhelm E.Skin sulfonated particles in matrices
US5882728 *Feb 3, 1996Mar 16, 1999Basf AktiengesellschaftMultilayer, fluorine-containing polymeric material
US6462142Nov 3, 1999Oct 8, 2002Air Products And Chemicals, Inc.Processes for improved surface properties incorporating compressive heating of reactive gases
US6576181Nov 27, 2000Jun 10, 2003Chinese Petroleum Corp.Method of making a high gasoline permeation resistant plastic container
US6896838Nov 21, 2001May 24, 2005Closure Medical CorporationNo mold release agent; e.g., post- chlorinated or fluorinated olefin polymer or polyester; e.g., octyl cyanoacrylate
US7621114Jul 17, 2008Nov 24, 2009Fenner U.S., Inc.Reinforced belt having reduced electrical resistivity and method for producing same
US7950213Jul 2, 2009May 31, 2011Fenner U.S., Inc.Reinforced belt having reduced electrical resistivity and method for producing same
US8440047May 23, 2007May 14, 2013Fenner U.S., Inc.Method for producing a stretch resistant belt
US20100200053 *Sep 16, 2009Aug 12, 2010United Solar Ovonic LlcPhotovoltaic device having a protective layer and methods for manufacturing that device
US20120240997 *Jun 8, 2012Sep 27, 2012Uday VardePhotovoltaic device having a protective layer and methods for manufacturing that device
US20130020507 *Oct 2, 2012Jan 24, 2013Life Technologies CorporationMethods for Detecting Defects in Inorganic-Coated Polymer Surfaces
DE3523137C1 *Jun 28, 1985Apr 30, 1986Audi Nsu Auto Union AgVerfahren zum Aufblasen und Fluorieren eines Kunststofftanks
DE3535602A1 *Oct 5, 1985Apr 9, 1987Hewing Gmbh & CoProcess for producing hollow articles fluorinated on the inner surface from thermoplastics by blow moulding
EP0063378A1 *Apr 19, 1982Oct 27, 1982Air Products And Chemicals, Inc.Process and apparatus for producing blow molded thermoplastic articles having improved weld strength
EP0176044A2 *Sep 20, 1985Apr 2, 1986Kautex-Werke Reinold Hagen AktiengesellschaftMethod for making hollow articles of thermoplastic material
EP0196468A2 *Mar 1, 1986Oct 8, 1986Messer Griesheim GmbhProcess for preparing fluorinated polymer surfaces
EP0210344A2 *Apr 19, 1986Feb 4, 1987Audi AgMethod of blow-moulding and fluorinating plastics tanks
EP0212554A2 *Aug 12, 1986Mar 4, 1987BASF AktiengesellschaftMethod of reducing the permeability of blow-moulded thermoplastic hollow bodies
EP0266439A1 *Nov 1, 1986May 11, 1988PVI Patent-Verwertungs- und Innovations-Gesellschaft mbHMethod of making internally fluorinated hollow articles
EP0276763A2 *Jan 21, 1988Aug 3, 1988Air Products And Chemicals, Inc.Injection molding process with reactive gas treatment
EP0339413A2 *Apr 17, 1989Nov 2, 1989Air Products And Chemicals, Inc.Hot-fillable plastic containers
EP0611791A1 *Feb 7, 1994Aug 24, 1994Bernd Dipl-Ing. MöllerProcess for treating the surface of articles
EP1609815A1Jun 16, 2005Dec 28, 2005Air Products And Chemicals, Inc.Process for reducing the permeability of plastics materials
WO1995027751A1 *Mar 24, 1995Oct 19, 1995Graham Edward CooleyMethod for the fabrication of an electrochemical cell
WO2009043572A1 *Sep 30, 2008Apr 9, 2009Beiersdorf AgVessels for cosmetic and dermatological products
Classifications
U.S. Classification428/35.7, 525/334.1, 427/237, 427/235, 8/DIG.900, 215/371, 264/83, 525/355, 427/255.4, 428/421
International ClassificationC08F8/20, B29C49/46, C08J7/12, B05D5/00
Cooperative ClassificationB29K2023/06, C08F8/20, B29C49/46, B29C2049/4617, C08J2323/06, B29C2049/4623, Y10S8/09, C08J7/126, B29K2995/0067
European ClassificationC08J7/12F, C08F8/20, B29C49/46