US3423234A - Dripless container coated with fluoroaliphatic siloxanes - Google Patents

Description

Jan. 21, 1969 R. F. HEINE 3,423,234

DRIPLESS CONTAINER COATED WITH FLUOROALIPHATIC sznoxmms Filed April 14, 1967 Sheet of 2 }40 I 7 W INVENTOR.

5/67/1420 E HE/NE Jan. 21, 1969 R. F. HEINE 3, 3

' DRIPLEKSS CONTAINER COATED WITH FLUOROALIPHATIC SILOXANES- Filed April 14, 1967 Sheet g of 2 7 /0 CONfl/NER L/P PROF/LES Di Qffi? a; Q: L1? L Q; U x} J, E

NVENTOR. 19/67/1420 A flE/ME 4770RNE United States Patent 3,423,234 DRIPLESS CONTAINER COATED WITH FLUOROALIPI-IATIC SILOXANES Richard F. Heine, White Bear Lake, Minn., assignor to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation of Delaware Continuation-impart of application Ser. No. 467,209, June 28, 1965. This application Apr. 14, 1967, Ser. No. 630,874 U.S. Cl. 117-124 7 Claims Int. Cl. C03c 17/30; C07f 7/12 ABSTRACT OF THE DISCLOSURE Containers having a substantially dripless orifice, the dripless character being conferred by a soluble hydrolytically stable polar surface adherent fluoroaliphatic siloxane.

Related appplication This application is a continuation-in-part of my 00- pending US. patent application S.N. 467,209, filed June 28, 1965, and now abandoned.

Background Since time immemorial those persons having occasion to dispense liquids, especially oils, from container orifices have been troubled by the well-known nuisance and attendant waste and mess caused by the drops of liquid clinging to exterior container surfaces about the orifice thereof, and frequently running down the container exterior side. These drops result when a container is reverted to its normal upright storage position following partial inversion during a dispensing operation.

Heretofore, the art has appreciated that organosiloxanes impart hydrophobic properties to polar substrate surfaces, especially glass (see Melrose US. Pat. No. 3,047,417). The art has also appreciated that curable fluoroaliphatic-substituted organosiloxanes have both oleophobic and hydrophobic properties (see Holbrook et al. US. Pat. No. 3,012,006). Such prior art compositions, however, suffer from a number of disadvantages for use in making dripless containers. For one thing, the organosiloxanes, through hydrophobic, are not oleophobic, and therefore cannot be used to produce dripless containers for nonaqueous liquids, e.g., oils. For another, the fluoroaliphatic-substituted siloxanes heretofore used for curable coating surfaces have been hydrolytically unstable.

The art has always previously considered it necessary, when producing a siloxane coating on a surface to use a curable siloxane in order to avoid subsequent removal of the coating by liquids contacting the same. Curability has been provided either by using siloxanes free of hydrolyzable groups which are curable by use of extreme temperatures (e.g., from 175 to 500 F.), or by using siloxanes containing hydrolyzable groups which can 'be subsequently crosslinked, as by controlled hydrolysis.

As those in the art will appreciated, the use of high heat to cure is undesirable, particularly because such heat tends to produce bottle breakage and distortion, so high heat curable siloxanes are disadvantageous for coating surfaces. On the other hand, in using hydrolytically curable siloxanes, the treating solutions cannot contact moisture, such as that in air, during use and. storage, or else, in a Patented Jan. 21, 1969 relatively short time, such siloxane is hydrolyzed into a crosslinked, insoluble, infusible resin completely unsuited for surface treatment, so these siloxanes, too, are disadvantageous for coating surfaces.

So far as is known, no one has heretofore produced, from soluble uncured siloxanes, hydrolytically stable coatings on polar surfaces which coatings are not only oleophobic and hydrophobic, but also dura'bly adherent to such surfaces.

Summary It has now be unexpectedly discovered that post-pour dripping in containers with polar surfaces in their orifice regions can be substantially completely eliminated if such orifice region surfaces are coated with a soluble hydrolytically stable polar surface adherent fluoroaliphatic siloxane.

As used in this application the term container has generic reference to structures such as vessels, conduits, troughs, bottles, cups, drinking glasses, flasks, jugs, crooks, drums, tanks, steins, pans, and the like, which are suitable for the storage or dispensing of liquid, especially oils of marine or vegetable origin, especially hand-held containers. Container is not limited to closed or closable vessels or the like, although the invention is most applicable to such vessels. Containers can be constructed of siliceous materials, metals, plastics, cellulosic materials, the like substances having polar surfaces.

The term polar, as used herein in reference to a container surface, refers to the fact that such surfaces exert an attractive force towards molecules contacting such surfaces when such contacting molecules have, or have readily induced therein, net positively and net negatively charged regions, so that such molecules, when contacted with such surfaces, adhere thereto.

The term lip, lip region or equivalent has reference to that portion of an aperture to the interior of such a container or to the portion of the container which is used for dispensing the liquid therefrom Whether or not such is in a special form or position. Thus, for example, a bottle conventionally is equipped with a spout portion in its upper (as when in an upright position), and it is the open end of the spout portion of the bottle which is the lip of the orifice. The terminal region of a spout which joins a containers interior surfaces with its exterior surfaces is specifically referred to herein as the orifice.

The term hydrolytically stable has reference to the fact that fluoroaliphatic siloxanes useful in this invention are free of hydrolyzable groups attached directly to silicon atoms so that such siloxanes will not convert, particularly in the presence of atmospheric moisture from an organic solvent soluble form to an organic solvent insoluble polymeric form.

In accordance with the present invention, it has been discovered that one can employ soluble, hydrolytically stable, fluoroaliphatic siloxanes for coating polar surfaced orifice regions of containers and thereby produce adherent dripless coatings which are uncured, oleophobic and hydrophobic. The adherency of these coatings to such polar surfaces is demonstrated 'by the fact they can be repeatedly contacted with organic oils or water without appreciably affecting the dripless character of an orifice coated therewith. Thus, for example, a glass bottle Whose mouth is once coated with such a siloxane and which is then filled with an oil can dispense (as by pouring) the oil therefrom in a substantially dripless manner in portions over an indefinitely long period of time. The last portion of oil characteristically is dispensed or poured from this treated bottle under condition which are as free of dripping as is the first portion,

Drawing description In the appended drawings:

FIGURE 1 is a side elevational view of the spout region of a conventional liquid container, the lower portion thereof being broken away, showing a liquid pouring operation in progress;

FIGURE 2 is a similar view of the spout of FIGURE 1, but showing same at the moment liquid flow ceases and a drop forms on the container exterior surfaces;

FIGURE 3 is a similar view of the spout of FIGURE 2, but showing same as the drop of liquid subsequently runs down the container exterior surfaces;

FIGURE 4 is a side elevational view of the spout region of a liquid container similar to that in FIGURES 1 and 3, but which has been treated and constructed in accordance with the teachings of the present invention, some parts thereof broken away, and showing a pouring o eration in progress;

FIGURE 5 is a similar view of the spout of FIGURE 4 showing same at the moment liquid flow ceases, the liquid running back into the bottle interior and none collecting on the exterior of the lip;

FIGURE 6 is a similar view of the spout of FIGURE 5, but showing how the container exterior surfaces remain free from liquid following a pouring operation;

FIGURE 7 is an enlarged sectional view taken axially along the line 77 of FIGURE 6 showing a preferred spout construction of the present invention;

FIGURE 8 is a view similar to FIGURE 7, but showing another spout lip region construction;

FIGURE 9 is an enlarged view illustrating constructional details for lips in preferred containers used in the present invention;

FIGURE 10 shows profiles of lip regions in a plurality of containers.

Turning to the figures, there is seen illustrated in FIG- URES 1 through 3 a conventional pouring operation from a spout with drop formation occurring on its lip 14 (see FIGURE 2) as pouring ceases. Thus, as the bottle (not shown) associated with spout 15 is reverted so as to place spout 15 in an upright position, the liquid therein flows back into the lower regions of the bottle and a break in the liquid stream leaving the bottle occurs over lip 14 causing a drop 16 of liquid to remain behind on lip 14 as the liquid flows back into the bottle from lip 14. This drop 16 usually proceeds to travel by gravity down in the inside surface of the bottle. Also adhesion between the liquid and container surfaces causes liquid to run down the outside of the bottle.

When, however, a similarly constructed spout 17 with a lip 18 is first treated with a fluoroaliphatic siloxane in accordance with the teachings of this invention and then liquid is poured therefrom as before, substantially all of the liquid in the region of lip 18 flows back down into the interior portions of the associated vessel (not shown) after the bottle is reverted to its original upright position. Substantially no liquid residue in the form of drops remains present on the lip 18, and no drops are present to run down the exterior sides when the spout 17 is in its normal upright position, as illustrated in FIGURE 6. Also adhesion between container surface and liquid is minimized preventing liquid running down the outside of the vessel.

The appearance of a preferred form of bottle lip 28 for use in the present invention is illustrated in FIGURE 7. Here the exterior surface of a portion of one side of a spout 18 of a bottle (not shown) is on the right side in the drawing, while the interior surface 19 thereof is on the left side of the drawing, both being apart from the lip 28. The exterior surface 20 is conveniently substantially parallel to geometric axis 13 of the spout 18 and/or to interior surface 19. When the direction of slope of the exterior surface 20 and the interior surface 19 forming the lip 28 are both extended as shown by the respective lines 21 and 22 in FIGURE 8, it is seen that a projected lip angle 23 is formed which is preferably not more than about This projected lip angle 23 is in effect thus formed by the projected meeting of the exterior surface 19 with interior surface 20.

The appearance of a lip 12 on a spout 11 which is not especially suitable for use in the present invention is illustrated by FIGURE 8. In the spout 11, an interior surface 26 is generally in spaced, parallel relationship to an exterior surface 27. Surfaces 26 and 27 are separated from one another by a substantially flat lip 12 which is substantially perpendicular to both the exterior surface 27 and the interior surface 26. When an untreated spout 11 is reverted to upright osition following inversion in a pouring operation, not only does a drop 29 typically run down the exterior surface 27, but also there is a tendency for droplets 31, of smaller size, to form and rest on the lip 28. These small droplets 31 are then squeezed out when a cap or stopper (not shown) is placed thereover. Such additional liquid further adds to the liquid on exterior surface 27 which drains down the outside of the container coating the surface thereof and eventually Wetting the support for the container.

The preferred geometry of lip constructions taught by the present invention is illustrated by FIGURE 9 Where an enlarged (dimensions proportional) sectional view through the axis of a spout 33 of an upright vessel (not shown) is illustrated. In the lip region 38 of spout 33 the exterior surface 36 and the interior surface 37 meet to form a rim or lip 38, whose apex region or apex 39 is closer to the exterior surface 36 than to the interior surface 37 measured over the lip 38 from one surface to the other, for example, from exterior surface 36 beginning at point 41 to the interior surface 37 ending at point 42. The apex angle 43 formed by the meeting of lip 38 and apex centerline 40 on the side of exterior surface 36 is preferably greater than the corresponding angle 44 formed by the meeting of lip 38 and the apex centerline 40 on the side of interior surface 37. The horizontal surface portions (referring to FIGURE 9) of apex 39 are so designed that they provide a bearing or sealing surface for closure means (not shown) such as a screw-on-type cap or the like, thereby to provide a (demountable) leakproof closure. Those skilled in the art of container manufacture will readily appreciate that such bearing or sealing surface must be of such a design as to be readily fabricatable in mass production and at the same time be capable of withstanding repeated application of closure means without failure.

Observe that some containers such as hand-held glass bottles (of half gallon size or less) are commonly equipped with cross-sectionally circular spouts having orifices and lips of rather small diameter (say less than 1 /2 or 2 inches); such are known commonly as narrow-mouth bottles. This invention is particularly applicable to such narrow-mouth bottles, though dripless orifices can also be obtained in accordance with the teachings of the present invention when wide-mouth bottles (those containers with orifices and lips having relatively larger diameters, for example those with almost or the same as the diameter of the bottle) are coated with a fluoroaliphatic siloxane in accordance with the teachings of this invention. However, to obtain best results in achieving dripless action when using a wide-mouth bottle, it is preferable to pour only a small stream of liquid from the container interior of a lip of a wide-mouth bottle. This is presumably because, when a wide stream is poured out of a fluoroaliphatic siloxane treated lip of a wide-mouth bottle, the weight of the liquid may in some instances overcome the oleophobic properties of the treated glass surface and dripping may occur, although defnitely less than with nontreated containers. However, since, in commerce, bottles are commonly of the narrow-mouth variety, no particular attention need be paid by the user to the rate of pouring from a container treated with a fluoroaliphatic siloxane in accordance with the teachings of the invention.

Although the soluble hydrolytically stable polar surface adherent fluoroaliphatic siloxanes useful in this invention impart a useful degree of driplessness to container orifices independently of shape, it is preferred to coat with such siloxanes containers having orifices which have lip shapes as shown in FIGURE (and as described above). Containers having orifices coated with such siloxanes are preferred products of this invention.

Embodiment description The total thickness of a hydrolytically stable, polar surface adherent fluoroaliphatic siloxane coating on container lips can be very thin. While even a monomolecular layer can produce the desired results, in practice, coating thicknesses preferably range from about 0.002 to as thick as about 10 mils (5 10 cm. to 2.5 10- cm.). Depending on the method of coating, very thin coatings can give erratic results, while thick coatings tend to be readily abraded away from the orifice surface by container closure means (e.g., screw cap, stopper, or the like) and are therefore wasteful and without significant utility. A more preferred range for coaating thicknesses is from about 0.024 to 0.24 mil (about 6 10 cm. to 6 10 cm.).

Thus, for fluoroaliphatic siloxanes having a density of about 1.5 a coating weight per sq. cm. of orifice surface area which is preferred is from about .0001 gm. to .001 gm. These coating thicknesses and weights are especially applicable to hydrolytically stable fluoroaliphatic siloxanes usable in this invention where the amount of fluorine contained therein is from about 40 to 50% of the total molecular weight. Since the efiiciency of the dripless properties tends to be related to the quantity of fluorine in the fluoroaliphatic group thereof, such materials which have a higher fluorine content can be used in proportionally thinner coatings while such compounds which have a lower fluorine content can be used in proportionally thicker coatings to obtain generally equivalent results.

Silanes useful as starting materials for producing soluble hydrolytically stable polar surface adherent fluoroaliphatic siloxanes useful in this invention have the following general formula:

where R is the radical C F Y R, or a monovalent hydrocarbon radical containing less than carbon atoms, such as alkyl, aryl, or the like; X is chlorine, bromine, fluorine, or an alkoxy radical (substituted or unsubstituted); Y R" is a divalent bridging radical; R" is a divalent alkylene radical or a divalent monohaloalkylene radical containing at least one and not more than 11 carbon atoms each, the carbon atoms being attached only to hydrogen atoms or carbon atoms, except for the carbon atom bonded to the silicon atom which may additionally be bonded to no more than one halogen atom, such halogen being chlorine or bromine; Y is a divalent linking group (linked to both a carbon of C F and a carbon of R), such as an ester (CO SO ether (-'-O, (CH O, S), amine or amide (CON SO N group; R' is hydrogen or a lower alkyl radical; n is an integer from 3 through 18; m is the integer 0 or 1; s is an integer between 1 and 6; and q is the integer 1 or 2.

Compounds of Formula 1 are known in the art and can be prepared by conventionally known methods. The term hydrolysis, hydrolyzed products, or equivalent includes hydrolysis accomplished in the presence of water or of moisture vapor (for example, accomplished in air alone). The term lower has reference to less than seven carbon atoms.

Hydrolysis of the compounds of Formula 1 produces soluble hydrolytically stable polar surface adherent fluoroaliphatic siloxanes useful for container lip coating in accordance with this invention. Such siloxanes are characterized by the formula.

where R, Y R", R", Y, n, m, and q are as defined above, and r ranges from 2 through 7.

The siloxanes of Formula 2 may be linear or cyclic and are usually a mixture of both. If linear, the terminal groups are usually a hydrolysis product of Formula 1 in which q is 2; the bulk of the material is generally of a cyclic structure in which three or more SiO groups are joined together in alternating SiO structure.

Preferred compounds of Formulas 1 and 2 are those Where R is lower alkyl and n ranges from 5 to 10.

To coat the orifice of a container as above described with a fluoroaliphatic siloxane of Formula 2, one first suspends (that is, forms a true solution or a colloidal dispersion) such material in an aqueous or nonaqueous liquid carrier or solvent. Because of the generally extremely stable character of materials of Formula 2, a very wide variety of liquids can be used as carriers, including, in general, Water and common organic liquids such as alcohols, esters, aldehydes, ketones, hydrocarbons (both aromatic and aliphatic), etc., as well as various substituted derivatives thereof, especially the halogenated analogues.

In general, it is preferred to use as carriers liquids in which materials of Formula 2 are soluble to at least about 5% by weight (such as a halogenated hydrocarbon), or in which a relatively stable suspension can be prepared, such as water because it has been found that when one uses such a solution or suspension of a fluoroaliphatic siloxane for coating, intimate contact is achievable between the surfaces of the orifice and the container being coated. Such a contact is essential in order to effect good and uniform deposition of the siloxane on the container surface.

If the suspension of a fluoroaliphatic siloxane involves the use of an aqueous dispersing liquid medium, then it Will be appreciated that the aqueous medium itself will not Wet siliceous or glass surfaces which have already been treated Wtih a lubricant such as a stearate or a silicon as is frequently used in glass bottle manufacture to coat bottle surfaces When the bottles leave the lehr. For this reason, such pretreated bottles or containers are preferably coated with a material of Formula 2 in an organic liquid that will wet the treated surface and provide the necessary intimate contact described above.

Even if one does not use a glass or siliceous container, but instead employs acontainer formed of some material, such as metal (e.g., iron, copper or aluminum), or a plastic (e.g., polyethylene, propypropylene, polyethylene terephthalate, polyvinylidene chloride polymer, or the like), the material of Formula 2 tends to orient so that the fluorocarbon portion is protruding outwardly from the surface and the silicon containing radical is adjacent or in contact with the surface so coated.

Containers may be treated with a suspension or solution of material of Formula 2 as above described by any conventional technique, including dipping, spraying, brushing, swabbing, roller coating, or any other method of wet ting the container surface. While only the container lip or spout itself need be coated, it is sometimes convenient and desirable to allow the coated region to extend away from the orifice down the sides of the spout or container to a point where the interior orifice surface comes into continuous, spaced, parallel relationship with the exterior container surface in order to facilitate and enhance retrac- 7 8 tion of liquid back into the container at the end of a pour- C. at 0.2 mm. Hg pressure is separated. This compound ing operation when a container is reverted to its normal has the formula: position of rest (generally upright). CBFHCHZCHCISKCHOCIZ Drying following a coating operation tends to make the fluoroaliphatic siloxane insoluble so that it becomes extremely difficult to remove by the mere fiowage or The compound having Formula 5 may be hydrolyzed 5 to a siloxane having the formula passage of liquid thereover during a normal pouring op- (6) [CBF1'ICH2CHCISI(CH3)O]Y eration augmented only by the force of gravity. Where r is as defined above, as in the first example and a The following examples illustrate preparation of fiuoro treating solution p p using that e carbon compounds, container coating solutions and coated 10 The fellowlng examples are Prevlded to better under containers in accordance with the present invention: Stand the Present inventioll- Tabular PresentationS are used in the interest of conserving space. EXAMPLE A Referring to Table 1, in each example the indicated A fluorocarbon silane compound is prepared as fiuorochemical (if one is used) is coated by the indicated lows: To 56.5 grams of N-allyl-N-ethylperfiuorooctanecoating {method P the l p of a p each e sulfonamide in 150 ml. of dry isopropyl ether is added 16 l h P p 6 and construction material grams of methyldichlorosilane and 0.1 gram of 5% poware mdlcated: the P e f each P being qeseflbed y dared platinum on Charcoal catalyst The mixture is a reference numeral which refers to a specific enlarged stirred and refluxed 16 hours, cooled and filtered. The Profile Show G R of the drawmgs' In solvent and excess chlorosilane are removed under vac- 20 10 Genterhne mdlciates for each Profile the mum to leave 67 grams of a White Solid representing a spectrve lnterior and exterior surfaces. Although the proportions of each profile correspond approximately to g s giigf z of the fluorocarbon dlchlorosflane of the respective shape of the actual lips involved in each example, these profiles are not drawn to scale. The par- (3) C8F17SO2N(C2H5)(cH2)3Si(CH3)c12 ticular fluorochemical used is indicated by a reference number which indicates a specific numbered formula in ThlS fiuOIOCafbOIl sllane compound 15 formulatable for the present specification reproduced above. In every case treating container surfaces as follows: 100 ml. of an ether h li treated exhibits dripless properties. Optimum solution of grams of the fluorocarbon dichlorosilane d i l properties are d d b vthe bi i of of Formula 3 is dropped with stirring into 100 ml. o fluorochemical of compound (2) coated on bottle lips water. After two hours, the ether layer is separated and having profile numbers 4, 7 and 8.

TABLE l.-SILICEOUS ORIFICES COATED WITH FLUOROGARBON COMPOUNDS CONTAINDIG SILICON RADICALS Aperture Design Fluorochemical Treating Mix Dripless Properties Coating Liquid No. Profile Size Material Form. Weight Liqu d Type Method Poured Rating Comments No. (Inches) No. Percent Carrier Min. Oil None. Severe dripping. Min Oil do Do. 4 1. Sol. Spray Min. Oil Fair Drop remains on top of lip. 6 0. $01.... Dip Min. Oil Good. No drop remains on top. 4 3 Sol Swab-.. Veg. Oil... Fair. Fair when broad stream poured.

Goo Good when narrow stream poured.- 4 10. 801--.. Brush Alcohol Good 4 1. SoL-.. Roller Min. Oil Fair Large drop remains on top when Coated. container reverted to upright. 6 0. $01...- D p Min. 011 do Drop remains on top of hp. 4 5. $01.-.. Dip Veg. Oil..." Good 6 2, SOL-.. Roller Veg. Oil do 1 1 means dia eter. 2 8" means side. 3 1,1,l-trichl0roethane. 4 Trichlorotn'fiuoroethane, OClzFCFzOl. 5 Mineral oil available commercially under the trademark Nujol."

the ether removed under vacuum to leave a viscous liquid The following exemplary materials of Formula 2 when fluoroaliphatic siloxane product of the formula: 50 prepared as described in Example A and coated as de- (4) [C8F17SO2N(C2H5)(CHQSSKCHQOL, scribed in Example 1, produce dripless container lip surfaces in accordance with the teachings of the present where r is on the average about 3. Thislprodulct 1s then invention dissolved in a solvent, such as 1,1,1-trich oroet ane, or a chlorofluorocarbon, such as CFCI CF CI for use. The e ls z z z z l- 3) lr foregoing method represents a generally useful method [CIOF2ISOBCH2CHZOQIIIZCHZSI(CH3)O11.

for converting the silanes of Formula 1 to the siloxanes [C F OCH CH S1(C H )O],.

of Formula 2. 'z 15 2 2 2 KQ s) lr Acetone or methyl ethyl ketone are also solvents for [C F S(CH Si(CH )O] this siloxane product of Formula 4, but are less desirable [C F CH N(CH )CH CH CH Si(CI-I )O] because of their associated flammability hazard. Generally, [C F CONHCH CH CH Si((1 1.1 )O

such treating solutions of this siloxane product of For- [09F19QH2CH2Si(CH3)0]r mula 4 preferably contain from 0.05 to 10.0 weight per- [C8F17SO2N(CH3)(CH2)11Si(CH3)O]r cent thereof. This treating solutlon 1s then used for the [cqFlscHzcHzsucHgoh coating of an orifice. I claim: 7

EXAMP B 1. In a container of the type having polar exterior A fluorocarbon silane compound is prepared a f l. surfaces and polar interior surfaces in spaced relationl A i t f 300 grams f C F SO CL 50 grams ship to one another which meet at the end of a pouring of vinyl methyl dichlorosilane, and 1.5 grams of bis(isoneck to form a lip, the improvement which comprises butyronitrile) is stirred and heated slowly to 80 C. in coating said lip with a soluble, polar surface adherent, an oil bath. Gas evolution begins at about C. and hydrolytically stable fiuoroaliphatic siloxane of the forcontinues until the reaction is terminated, about four l hours. The product after cooling is vacuum distilled. Un-

reacted starting materials are removed in a forecut, then I: r

CnFzn+iYmR"SiO 210 grams of product having a boiling point of -105 75 9 Where R' is the radical c F Y R", or a monovalent hydrocarbon radical containing less than 15 carbon atoms;

Y R" is a divalent bridging radical;

R" is a divalent alkylene radical or a divalent monohaloalkylene radical containing at least one and not more than 11 carbon atoms each, the carbon atoms being attached to hydrogen atoms or carbon atoms, except for the carbon atom bonded to the silicon atom which may additionally be bonded to no more than one halogen atom, such halogen being chlorine or bromine;

Y is a divalent linking group linked to both a carbon of C F- and a carbon of R";

n is an integer from 3 through 18;

m is the integer or 1;

q is the integer 1 or 2; and

r ranges from 2 through 7.

2. The container of claim 1 in which, as respects said lip, the apex is closer to said exterior surface than to said interior surface measured over said lip from one surface to the other, the angle formed by the meeting of said lip and the apex on the side of said exterior surface being greater than the corresponding angle formed by the meeting of said lip and the apex on the side of said interior surface.

3. The container of claim 1 wherein said lip surfaces are siliceous.

4. The container of claim 1 wherein said polar exterior surface portions adjacent said lip have radially extending but spirally and circumferentially located rib-like projections adapted for threadably reeciving a mating cap.

5. In a method for rendering the lips of a polar surfaced orifice region of a container hydrophobic and oleophobic, the improvement which comprises contacting such lips with a solution having suspended therein a soluble hydrolytically stable polar surface adherent fluoroaliphatic siloxane of the formula:

[ I H JI Where:

R is the radical C F Y R", or a monovalent hydrocarbon radical containing less than 15 carbon atoms;

Y R" is a divalent bridging radical;

R" is a divalent alkylene radical or a divalent monohaloalkylene radical containing at least one and not more than 11 carbon atoms each, the carbon atoms being attached to hydrogen atoms or carbon atoms, except for the carbon atom bonded to the silicon atom which may additionally be bonded to no more than one halogen atom, such halogen being chlorine or bromine;

Y is a divalent linking group linked to both a carbon of C F and a carbon of R";

n is an integer from 3 through 18;

m is the integer 0 or 1;

q is the integer 1 or 2; and

r ranges from 2 through 7; and evaporating the carrier liquid.

6. The process of claim 5 wherein the container is characterized by having a lip whose apex is closer to said exterior surface than to said interior surface measured over said lip from one surface to the other, the angle formed by the meeting of said lip and the apex on the side of said exterior surface being greater than the corresponding angle formed by the meeting of said lip and the apex on the side of said interior surface.

7. The process of claim 5 wherein the container is formed of a siliceous material.

References Cited UNITED STATES PATENTS 3,012,006 12/1961 Holbrook et al. l17-161 X 3,047,417 6/1962 Melrose 11743 X 3,074,548 1/1963 Parks 117-95 3,179,290 4/1965 Whitney 22257l RALPH S. KENDALL, Primary Examiner.

HERBERT (ZOHEN, Assistant Examiner.

U.S. Cl. X.-R.

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