text:
|Publication number
|Publication type
|Application number
|Publication date
|Oct 19, 1982
|Filing date
|Dec 17, 1981
|Priority date
|Jan 26, 1981
|Fee status
|Also published as
|Publication number
|Richard M. Wise
|Original Assignee
|The General Tire & Rubber Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (4), Non-Patent Citations (2), Referenced by (10), Classifications (26), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation-in-part of U.S. Patent Application Ser. No. 06/228,844 filed Jan. 26, 1981, now abandoned.
This invention relates to the adhesion of rubber to glass fibers using a composition of a graft polymer or overpolymer of a rubbery vinyl pyridine copolymer on a polyacrylate seed polymer, desirably with a polybutadiene, and a phenolic resin.
An object of the invention is to provide a composite of a glass fiber reinforcing element adhesively bonded to a rubber compound, e.g., glass fiber tire cords adhesively bonded to provide carcass plies and belt plies for making tires. Another object is to provide glass fiber reinforcing elements, e.g., such as those used in the belt and the carcass plies of tires, with a minor amount of an adhesive so that the adhesive containing elements may subsequently be bonded to rubber on curing. A further object is to provide a method for bonding glass fibers, particularly glass fiber textiles, fibers, cords, yarns and so forth, to rubber compounds using a single dip. A still further object is to provide a glass fiber or cord adhesive dip composition. Yet another object is to provide a rubbery over- or graft copolymer of a vinyl pyridine copolymer (shell) on a polyacrylate seed (core) which is useful in making glass tire cord adhesives. These and other objects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description and working examples.
According to the present invention it has been discovered that a composition comprising an aqueous alkaline dispersion of a rubbery graft or overpolymerized copolymer of a shell of a rubbery diene-vinyl pyridine copolymer on a seed or core of an acrylate polymer, said acrylate polymer having a Tg of not above about -20° C., desirably also containing polybutadiene, and a heat reactable water soluble phenolic-aldehyde resin, in certain amounts, is very useful as a treating, dipping or coating material for use in bonding glass fiber reinforcing elements to rubber compounds. Sufficient alkaline material such as aqueous KOH, NaOH or NH4 OH may be added to the dispersion (or to one or more of the ingredients of the dispersion before mixing them together) to obtain the desired pH, prevent coagulation of the latex and to provide for stabilization. This will vary with the pH of the resin and the latex, all of which may vary from batch to batch. Since the amount of each compound may vary, the amount of alkaline material required can also vary. After drying the adhesive on the glass fiber reinforcing element to remove water and to heat cure or heat set the adhesive on the element, the adhesive containing element can then be combined or calendered with a curable rubber compound and the resulting assembly cured, usually in a mold, to provide a laminate exhibiting good adhesive properties at ambient and elevated temperatures.
Glass cords coated with the graft copolymer containing adhesive exhibit improved breaking characteristics at low temperatures. The use of the graft copolymer may reduce the breakage which may be experienced in glass cords such as in belts in tires during normal operation at cold or low temperatures.
The present method involves only one dipping step, and the process or method can be varied to provide the desired pick-up or solids on the cord by varying the concentration of the dip or the speed of the cord through the dip to give the amount needed to develop the requisite adhesive bond. Thus, while the cord can be run through successive dips of the same or varying amounts of the above materials to get the desired buildup, this is unnecessary as satisfactory results generally can be accomplished in one dip.
The glass fiber reinforcing element or cord comprises a plurality of substantially continuous and parallel glass fibers or monofilaments. The reinforcing element or fibers contain little or no twist. In other words, twist is not intentionally applied to the element or fibers; the only twist, if any, in the element or fibers is that occasioned on passing through the glass fiber processing apparatus and on packaging or winding up the cord to form a bobbin or spool. However, in a continuous process, the elements can proceed directly from the glass processing apparatus, can be dipped in the aqueous adhesive cord dip, dried, and given a twist of about 1.5 turns per inch thereafter. The elements then are woven into tire fabric having about one quite small pick thread or element, nylon or polyester, which may be a monofilament, per inch and calendered with a rubber ply or skim stock. The glass fiber reinforced ply stock is then ready to be used in the manufacture of a tire or for other purposes.
Glass compositions useful in making the fibers for the reinforcing element or glass tire cord are well known to the art. One type of glass that may be used is a glass known as E glass and described in "Mechanics of Pneumatic Tires," Clark, National Bureau of Standards Monograph 122, U.S. Dept. of Commerce, issued November, 1971, pages 241-243, 290, and 291. The number of glass filaments or fibers employed in the glass fiber reinforcing element or cord can vary considerably depending on the ultimate use or service requirements. Likewise, the number of strands of glass fibers used to make a glass fiber reinforcing element or cord can vary widely. In general, the number of filaments in the glass fiber reinforcing element or cord for a passenger car tire can vary from about 500 to 3,000 and the number of strands in the reinforcing element can vary from 1 to 10, preferably the number of strands is from 1 to 7 and the total number of filaments about 2,000. In this connection reference is made to Wolf, "Rubber Journal," February, 1971, pages 26 and 27 and U.S. Pat. No. 3,433,689.
Shortly after the glass fibers are formed they are usually sized (by spraying or dipping and so forth and air drying) with a very small amount or fractional amount by weight of a material which acts as a protective coating during processing and handling of the glass fibers in forming the strands or reinforcing elements and during packaging. During the subsequent dipping in the aqueous adhesive tire cord dip, it is believed that the size is not removed. Materials for use as sizes for glass fibers are well known to the art. It is preferred to use a silane as a size, especially a silane which has groups which can bond or coordinate chemically or physically with at least parts of the surface of the glass of the glass fiber and with at least one or more of the components of the glass fiber aqueous adhesive cord dip. A very useful size to employ on the glass fibers is gammaamino-propyl triethoxy silane, or similar aminoalkyl alkoxy silanes, which, when applied to the glass fibers, hydrolyzes and polymerizes to form a poly(aminosiloxane) in which a portion of the polymer is attached to the glass and another portion contains amine groups (having active hydrogen atoms) for reaction with components of the cord dip such as the phenolic resin, the polybutadiene compound or the graft vinyl pyridine copolymer compound. Chrome complexes having functional groups, also, can be used. Glass fiber sizing compounds are known, and some compositions are shown in U.S. Pat. Nos. 3,252,278; 3,287,204 and 3,538,974.
The water soluble thermosetting (heat reactable) phenolic-aldehyde resin is made by reacting an aldehyde with a phenolic compound. The preferred aldehyde to use is formaldehyde, but acetaldehyde and furfural, also, may be used. In place of formaldehyde one may use paraformaldehyde or other formaldehyde donors such as hexamethylenetetramine and so forth. Also, it is preferred to start with formalin, usually a 37% solution of formaldehyde in water, which is easier to use. Mixtures of aldehydes can be used. The phenolic compound can be phenol itself, resorcinol (preferred), the cresols, the xylenols, p-tert butylphenol or p-phenyl phenol or mixture thereof. The reactants are reacted in water usually in the presence of a catalyst. One may start with a thermoplastic resin by reacting less than a molar amount of the aldehyde with the phenolic compound to form a condensation product and then may add sufficient aldehyde at the time the dip is formulated to convert the product to a thermosetting or infusible resin on heating. Alternatively, one may react a molar excess of the aldehyde with the phenolic compound to form a thermosetting type condensation product on heating and which should be used promptly. However, the alternative reaction is somewhat longer. In any event, the final product on heating is a thermoset phenolic-aldehyde resin. Alkaline material is generally added before use. Information on the preparation of the water soluble thermosetting phenolic-aldehyde resins will be found in "Encyclopedia of Chemical Technology," Kirk-Othmer, Volume 15, Second Edition, 1968, Interscience Publishers Division of John Wiley & Sons, Inc., New York, pages 176 to 208; "Technology of Adhesives," Delmonte, Reinhold Publishing Corp., New York, N.Y., 1947, pages 22 to 52, "Formaldehyde," Walker, A.C.S. Monograph Series, Reinhold Publishing Corp., New York, N.Y., Third Edition, 1964, pages 304 to 344; and "The Chemistry of Phenolic Resins," Martin, John Wiley & Sons, Inc., New York, 1956.
The rubbery graft copolymer of overpolymerized copolymer comprises a seed or core of an acrylate polymer and a shell of a vinyl pyridine polymer. The copolymer is made by first forming a seed latex of an acrylate polymer by polymerizing an acrylate monomer by free radical aqueous emulsion polymerization to at least 85% conversion and preferably to completion. Thereafter, there is added to the seed acrylate polymer latex a conjugated diene monomer and a vinyl pyridine monomer and additional water, free radical initiator, modifier if desired, and emulsifier or surfactant and so forth, and the polymerization is continued PG,8 preferably to completion to form the graft or overpolymerized copolymer of the diene and vinyl pyridine on the seed acrylate polymer to provide the graft copolymer. It is felt that grafting is a suitable way for describing the overall copolymerization process.
The acrylate monomer to be used to form the seed acrylate polymer is a monomer which will form an acrylate polymer having a glass transition (Tg) temperature of not above about -20° C. Examples of such monomers are ethyl acrylate, n-propyl acrylate, n-butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate, decyl acrylate, methoxy ethyl acrylate, ethoxy ethyl acrylate, methoxy propyl acrylate and ethoxy propyl acrylate and the like. These monomers, thus, have the general formula CH2 ═CH--COOR where R is an alkyl group of 2 to 10 carbon atoms or a --R'OR" group where R' is an alkylene group of 2 to 3 carbon atoms and R" is an alkyl group of 1 to 2 carbon atoms. It will be noted that poly(n-butyl acrylate) has a Tg of -55° C. and poly(2-ethyl hexyl acrylate) has a Tg of -77° C. (DSC). Also, there may be used as the acrylate monomer, monomers having the formula H2 C═C(CH3)COOR'' ' where R''' is an alkyl group of 8 to 18 carbon atoms such as n-octyl methacrylate, n-dodecyl methacrylate, hexadecyl methacrylate and n-octadecyl methacrylate and the like. Poly (n-octyl methacrylate) has a Tg of -20° C. and poly(n-octadecyl methacrylate) has a Tg of -100° C. Mixtures of these acrylate monomers may be used to make the seed polymer latex. Of these acrylate monomers it is preferred to use n-butyl acrylate or 2-ethyl hexyl acrylate and mixture thereof.
The diene monomer used to make the shell of the graft copolymer is a conjugated diene having from 4 to 6 carbon atoms such as butadiene-1,3, isoprene, 2,3-dimethyl butadiene-1,3, or piperylene. Mixtures of these monomers may be used. It is preferred to employ butadiene-1,3. The vinyl pyridine monomer to copolymerize with the diene monomer to make the shell of the graft copolymer has from 7 to 9 carbon atoms and can be 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-methyl-5-vinyl pyridine, 2,4-dimethyl-6-vinyl pyridine and 5-ethyl-2-vinyl pyridine or mixture of the same. Of these vinyl pyridines, it is preferred to employ 2-vinyl pyridine.
Butadiene-vinyl pyridine copolymers are well known as shown by U.S. Pat. Nos. 2,561,215; 2,615,826 and 3,437,122 and British Pat. No. 595,290.
In the final rubbery graft copolymer of the present invention on a dry weight basis there are from about 8 to 20% by weight of the acrylate monomer, from 3 to 20% by weight of the vinyl pyridine monomer and from 60 to 89% by weight of the diene monomer, preferably there are from about 10 to 15% by weight of acrylate monomer, from 7 to 15% by weight of the the vinyl pyridine monomer and from 70 to 83% by weight of the diene monomer.
Aqueous alkaline latices of rubbery polybutadienes made by free radical aqueous emulsion polymerization of butadiene-1,3 are known. The polybutadiene should have a glass transition temperature, Tg, of not above about -70° C.
On a dry weight basis the % by weight ratio of the butadiene-vinyl pyridine-acrylate graft copolymer to the polybutadiene is from about 20:80 to 60:40, preferably about 40% of the acrylate graft copolymer and 60% of polybutadiene.
The latex of the graft copolymer and the latex of the polybutadiene can readily be blended or mixed together.
Very minor amounts by weight of other copolymerizable monomers optionally additionally may be copolymerized with the acrylate of the seed polymer (preferred), with the butadiene and vinyl pyridine of the shell copolymer or with the butadiene of the polybutadiene so long as the useful properties and Tgs of these polymers for use as glass cord adhesives are not adversely affected. Examples of such monomers are styrene, acrylonitrile, vinyl acetate, methylmethacrylate, methyl acrylate, methacrylamide, butadiene-1,3, isoprene, piperylene, 2,3-dimethyl butadiene-1,3, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinyl benzene (preferred), trimethylol propane trimethacrylate, trimethylol propane triacrylate, 1,3-butylene glycol diacrylate, triallyl cyanurate and the like and mixtures thereof. The polyunsaturated monomers may afford some crosslinking if desired to control the flow at elevated temperatures of one or more of the dry polymers or copolymers or of the seed or shell of the graft copolymer. The crosslinking polyunsaturated monomer is preferably used or copolymerized with said acrylate monomer of the core or seed and in an amount of from about 0.05 to 1.5 parts by weight per 100 parts by weight of said acrylate monomer.
Polymerization of the monomers is effected by free-radical initiators (free-radical formers or free-radical forming systems, catalysts) such as ammonium, potassium or sodium persulfate, H2 O2 and the like in an amount sufficient for polymerization of the monomers and to obtain the desired molecular weight. Other free-radical initiators can be used which decompose or become active at the temperature used during polymerization. Examples of some other free-radical initiators are cumene hydroperoxide, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, bis (p-methoxy benzoyl) peroxide, t-butyl peroxy pivalate, dicumyl peroxide, isopropyl percarbonate, di-sec-butyl peroxydicarbonate, azobisdimethyl-valeronitrile, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile and 2,2'-azobis (methylisobutyrate) and the like and mixtures of the same. Only minor amounts of initiators are necessary to effect polymerization.
Emulsifiers such as soaps, surfactants or dispersing agents are used in an amount sufficient to obtain an aqueous emulsion of the water and monomers and resulting polymers. Examples of some emulsifiers are potassium laurate, potassium soap of disproportionated rosin, potassium stearate, potassium oleate, sodium lauryl sulfate, sodium dodecyl sulfonate, sodium decyl sulfate, sodium salt of condensed naphthalene sulfonic acid and sodium rosinate and the like and mixtures thereof. Other well known surfactants can be used.
Chain transfer agents or modifiers are well known in the emulsion copolymerization of vinyl and diene monomers to make polymers. They are used generally to modify the molecular weight and to reduce cross-linking. While many types have been proposed, it is preferred to use the alkyl and/or aralkyl mercaptans having from 8 to 18 carbon atoms. Of these, the tertiary alkyl mercaptans are much preferred. Examples of some mercaptans are n-octyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, t-dodecyl mercaptan, p-tridecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan and so forth and mixtures thereof. If little or no mercaptan is used and polymerization is continued to completion, gel may occur and the molecular weight can be very high or infinite although some low molecular weight fractions may be found.
NaOH, KOH, NH4 OH and so forth may be added to the polymerization reactor before, during or after polymerization to control the pH as desired. Polymerization may be conducted under acidic conditions, and after polymerization, the latex may be converted to the alkaline side.
The water should be free of deleterious materials, and preferably should be distilled or ion exchanged. Sufficient water is used to enable formation of the emulsions and to enable proper mixing or stirring of the ingredients during polymerization to obtain the desired rate and degree of polymerization, heat transfer and so forth. The solids content of the resulting aqueous alkaline latices or dispersions, graft copolymer and/or polybutadiene, thus, may vary from about 25 to 60% by weight, and the pH can be from about 7.0 to 11.5.
Stabilizers, antioxidants and chelating agents may be used during polymerization. Also the use of shortstops at the end of free radical polymerization is well known; they are not only used to stop the polymerization in the reactor at the desired conversion but also to prevent further polymerization, cross-linking etc., during stripping, work-up and so forth. Examples of some shortstops are hydroquinone, sodium sulfide, hydroxyl ammonium acid sulfate, hydroxyl ammonium sulfate, sodium diethyl dithiocarbamate, diethylhydroxylamine, sodium dimethyl dithiocarbamate, potassium dimethyl dithiocarbamate, dimethylammonium dimethyldithiocarbamate, hydroxylamine sulfate plus sodium hydrosulfite and so forth.
Temperatures used during polymerization should be sufficient to effect polymerization by activation of the initiator and double bonds of the monomers. They should not be too high to cause a run-away reaction and not too low to retard polymerization. In general, the temperature may be from about 2° to 90° C. If even lower temperatures are used, it may be desirable to add an inert anti-freeze material to the polymerization media.
Polymerization should preferably be conducted in a closed reactor, such as a pressure reactor, fitted with a stirrer or other agitating means, heating and cooling means, with means to flush with or pump in an inert gas such as nitrogen, helium, argon, neon and the like in order to polymerize preferably under inert or non-reactive conditions, with means to charge the monomers, water, initiators and so forth, venting means, and with means to recover the polymer and so forth. The reactor should be cleaned or flushed out between polymerization runs to remove traces of shortstops, initiators, modifier, residues and so forth which might interfere with subsequent polymerizations. There should be sufficient agitation or stirring of the polymerization media to ensure thorough mixing, diffusion, contact and so forth. All of the polymerization ingredients except the shortstop may be charged to the reactor at the same time, intermittently, incrementally or continuously. Also, the ingredients may be added separately or in a mixture.
The rubbery polymers are, thus, made in water using free radical initiators, chelating agents, modifiers, emulsifiers, surfactants, stabilizers, short stopping agents and so forth by known techniques. They may be hot or cold polymerized, and polymerization may or may not be carried to about 100% conversion. If polymerization is carried out with appropriate amounts of chain transfer agents or modifiers and conversions are stopped below 100% conversion, low or no gel polymers are possible. Free radical aqueous emulsion polymerization and materials for the same are well known as shown by:
(1) Whitby et al, "Synthetic Rubber," John Wiley & Sons, Inc., New York, 1954;
(2) Schildknecht, "Vinyl and Related Polymers," John Wiley & Sons, Inc., New York, 1952;
(3) "Encyclopedia of Polymer Science and Technology," Interscience Publishers a division of John Wiley & Sons, Inc., New York, Vol. 3 (1965), Vol. 5 (1966), Vol. 7 (1967) and Vol. 9 (1968);
(4) "Materials, Compounding Ingredients and Machinery for Rubber," Publ. by "Rubber World," Bill Communications Inc., New York, 1977; and
(5) Bovey et al, "Emulsion Polymerization," Interscience Publishers, Inc., New York, 1955.
The gel content of the rubbery graft copolymer is determined by taking a sample of the particular latex involved, coagulating the rubber and separating the rubber from the water, milling the rubber obtained, dissolving the rubber in toluene and filtering the mixture to determine the gel content. See Whitby et al supra.
A method of aqueous free radical emulsion polymerization to high conversions to obtain rubbery polymers like rubbery vinyl pyridine copolymers, rubbery polybutadienes and rubbery butadiene copolymers having little or no gel is fully disclosed in U.S. Pat. No. 4,145,494 granted Mar. 20, 1979, and entitled "Aqueous Free Radical Emulsion Polymerization".
The technique of polymerizing or copolymerizing one or more monomers in the presence of a polymer or a substrate, "grafting technique," is known and is frequently called graft polymerization or graft copolymerization. In this connection, please see "Proceedings Of The Third Rubber Technology Congress," 1954, W. Heffer & Sons, Ltd., Cambridge, pages 185-195; "Copolymerization," High Polymers, Vol. XVIII, Ham, Pages 323-324, 335-420 and 573, Interscience Publishers a division of John Wiley & Sons, New York, 1964; "Block and Graft Polymers," Burlant and Hoffman, Reinhold Publishing Corporation, New York, 1960; "Block and Graft Copolymers," Ceresa, Butterworth & Co. (Publishers) Ltd., London, 1962; and "Graft Copolymers," Polymer Reviews, Vol. 16, Battaerd and Tregear, Interscience Publishers, a division of John Wiley & Sons, New York, 1967. The graft copolymer shell may contain all graft copolymer but also may be a mixture of homopolymers, copolymers as well as the graft itself. Thus, if the conversion of the seed or core is not complete, then when the Bd and VP are charged, the shell may contain some acrylate homopolymer, Bd homopolymer, B-acrylate, Bd-VP and Bd-VP-acrylate copolymers and so forth as well as the graft. However, what is generally believed is that the VP (vinyl pyridine) moieties are on the outside of the latex particles where the adhesive effect is obtained and the acrylate is on the inside.
The pH of the latex and of the dip should be on the alkaline side and the pH of any surfactants and stabilizers, including freeze-thaw stabilizers and other additives should be on the alkaline side or compatible or be neutral to avoid improper coagulation of the latex or latices.
Water is used in the adhesive in an amount sufficient to provide for the desired dispersion of the rubber or latex particles, and for the solution of the phenolic resin and any other additives, to obtain the desired viscosities, and for the proper solids content to get the necessary pickup of solids on and penetration between the fibers of the cord. The amount of water in the adhesive cord dip generally may vary so as to provide a solids content of from about 30 to 50%, preferably from about 35 to 45%, by weight. Too much water may require redipping or use of excess heat to evaporate the water on drying. Too little water may cause uneven penetration or too slow coating speeds.
In addition to the surfactants or wetting agents, and any antioxidants already in the latex, additional surfactants and antioxidants may be added to the dip in minor amounts. Also, other anti-degradants may be added as well as wax. An example of a useful wax is a wax emulsion, a blend of paraffin and microcrystalline waxes in water.
On a dry weight basis the phenolic-aldehyde resin is used in an amount of about 3 to 15, preferably from about 4 to 10, parts by weight per 100 parts by weight of rubbery graft copolymer or total of said graft copolymer and said polybutadiene in the adhesive composition.
To apply the latex adhesive to the glass fiber cords in a reliable manner, the cords are fed through the adhesive dip bath while being maintained under a small predetermined tension and into a drying oven where they are dried under a small predetermined tension (to prevent sagging without any appreciable stretching). As the cords leave the oven they enter a cooling zone where they are air cooled before the tension is released. In each case the adhesive-coated cords leaving the dip are dried in the oven at from about 200° to 600° F. (93.3° to 315.6° C.) for from about 300 to 5 seconds. The time the cord remains in the adhesive is about a few seconds or more or at least for a period of time sufficient to allow wetting of the cord and at least substantial total impregnation of the fibers of the cord. The dipping of the cords and the drying or curing of the adhesive treated glass fiber cords may be accomplished in one or more dip tanks and in one or more ovens at different times and temperatures.
The single-cord H-pull, H-adhesion, test is employed to determine the static adhesion of the dried (heat set or cured) adhesive coated glass fiber cords to rubber. In each case the rubber test specimens are made from a vulcanizable rubber composition comprising rubber, reinforcing carbon black and the customary compounding and curing ingredients. In every case the cords to be tested are placed in parallel positions in a multiple-strand mold of the type described in the single-cord H-pull adhesion test ASTM designated D 2138-72, the mold is filled with the unvulcanized rubber composition, the cords being maintained under a tension of 50 grams each, and the rubber is cured. Each rubber test specimen is 1/4 inch thick and has a 3/8 inch cord embedment. After the rubber has been cured, the hot cured rubber piece is removed from the mold, cooled and H-test specimens are cut from said piece, each specimen consisting of a single cord encased in rubber and having each end embedded in the center of a rubber tab or embedment having a length of around 1 inch or so. The specimens are then aged at least 16 hours at room temperature. The force required to separate the cord from the rubber is then determined at room temperature or 250° F. (121° C.) using an INSTRON tester provided with specimen grips. The maximum force in pounds required to separate the cord from the rubber is the H-adhesion value. All the data submitted in the working examples which follow are based upon identical test conditions, and all of the test specimens were prepared and tested in the same way generally in accordance with ASTM Designation: D 2138-72.
The flexibility of single yarns dipped and dried with the adhesive of this invention was determined by the MIT test (as described in TAPPI Standard Method T423 m-50 for the folding endurance of paper) in which the sample is flexed at three cycles per second through a total arc of 270° until the sample breaks. The number of flexes to failure is recorded as a direct measure of the low temperature endurance of the yarn. The temperature of flexing can be varied from about -40° C. to about +130° C. Two variations of the test are:
Method A--a single processed yarn is flexed under 500 grams tension.
Method B--a single processed yarn embedded in rubber is flexed under one kilogram tension; the sample being approximately 6" long, 3/16" wide, and 0.030" thick.
Glass cords or fabric coated with the adhesive of the present invention using the one-step or single dip of this invention can have from about 10 to 40%, preferably from about 15 to 25%, by weight (dry) solids of the adhesive dip on the cord based on the weight of the cord and can be used in the manufacture of carcasses, belts, flippers and chafers of radial, bias, or belted-bias passenger tires, truck tires, motorcycle tires, off-the-road tires and airplane tires, and, also, in making transmission belts, V-belts, conveyor belts, hose, gaskets, tarpaulins and the like.
While the adhesive containing glass fiber reinforcing element can be adhered to vulcanizable natural rubber and rubbery butadiene-styrene copolymer or blend thereof by curing the same in combination together, it is apparent that the heat cured adhesive containing glass fiber reinforcing element can be adhered to other vulcanizable rubbery materials, by curing or vulcanizing the same in combination with the rubber, such as one or more of the foregoing rubbers as well as nitrile rubbers, chloroprene rubbers, polyisoprenes, polybutadienes, acrylic rubbers, isoprene-acrylonitrile rubbers and the like and mixtures of the same. These rubbers can be mixed with the usual compounding ingredients including sulfur, stearic acid, zinc oxide, magnesium oxide, silica, carbon black, accelerators, antioxidants, antidegradants and other curatives, rubber compounding ingredients and the like well known to those skilled in the art for the particular rubbers being employed. Also, the adhesive dip of the present invention may also be used to adhere cords, yarns and the like of other natural and synthetic fibers to rubber compounds.
The following examples will serve to illustrate the present invention with more particularity to those skilled in the art. In these examples the parts are parts by weight unless otherwise indicated.
The latex preparations described below were carried to completion in nitrogen flushed polymerization bottles in a water bath with agitation.
______________________________________1. Preparation of poly (BA) seed latex Parts By Weight Dry Wet______________________________________n-Butyl acrylate 200 200Water -- 280SIPEX UB (30% in water) 9.0 30.0Potassium persulfate 0.6 0.6Total 209.6 510.6______________________________________
The polymerization temperature was 50° C. Latex converted to alkaline side.
______________________________________2. Preparation of polystyrene seed latex Parts By Weight Dry Wet______________________________________Styrene 200 200Water -- 256.6DRESINATE 214 (20%in water) 8.0 40.0Potassium persulfate 0.5 0.5SULFOLE 120 0.5 0.5Total 209.0 497.6______________________________________
The polymerization temperature was 50° C. Alkaline latex as produced.
______________________________________3. Preparation of 70/15/15 Bd/BA/VP terpolymer latex Parts By Weight Dry Wet______________________________________Butadiene-1,3 140 140n-Butyl acrylate 30 302-Vinylpyridine 30 30Water -- 255SIPEX UB (30% in water) 4.0 13.34Potassium persulfate 0.6 0.6SULFOLE 120 0.4 0.4Total 205.0 469.34______________________________________
The polymerization temperature was 60° C. Alkaline latex as produced.
______________________________________4. Preparation of 70/15 Bd/VP copolymer latex Parts By Weight Dry Wet______________________________________Butadiene-1,3 140 1402-Vinylpyridine 30 30Water -- 231.4SIPEX UB (30% in water) 5.1 17.0Potassium persulfate 0.51 0.51Sodium carbonate 0.26 0.26SULFOLE 120 0.34 0.34Total 176.21 419.51______________________________________
The polymerization temperature was 50° C. Alkaline latex was produced.
______________________________________5. Preparation of a 70/15/15 Bd/VP/BA graft latex from 15parts poly(BA) seed Parts By Weight Dry Wet______________________________________Butadiene-1,3 140 1402-Vinylpyridine 30 30Poly(BA) latex (fromRun 1. above) 30 74.81Water -- 210.74SIPEX UB (30% in water) 6 20.00Potassium persulfate 0.6 0.6SULFOLE 120 Variable* --______________________________________ *Between 0.4-1.6 parts
The polymerization temperature was 60° C. Alkaline latex as produced.
______________________________________6. Preparation of a 70/15/15/ Bd/VP/St graft latex from 15parts polystyrene seed Parts By Weight Dry Wet______________________________________Butadiene-1,3 140 1402-Vinylpyridine 30 30Polystyrene latex (fromRun 2. above) 30 71.94Water -- 203.96DRESINATE 214 (20%in water) 6.0 30.0Potassium persulfate 0.6 0.6SULFOLE 120 1.2 1.2Total 207.8 477.7______________________________________
The polymerization temperature was 50° C. Alkaline latex as produced.
The aqueous cord adhesive dips were prepared by mixing a resorcinol-formaldehyde (RF) resin with the desired latex such that there were 7.5 dry parts RF resin per 100 parts by weight latex solids with a total solids content of 40%. The 7.5 parts dry RF resin is composed of 6.82 dry parts neutralized PENACOLITE R-2170 (RF resin)+0.68 dry parts formaldehyde. An example is shown below.
______________________________________ Parts Dry Wet______________________________________Latex (41% solids in water) 59.53 145.19PENACOLITE R-2170 (40.0% solids in water,neutralized) 4.06 10.15Formaldehyde (37% in water) 0.41 1.11Water -- 3.55Total 64.00 160.00______________________________________
The glass yarn (1/0 ECH 15 sized glass yarn from Owens-Corning Fiberglas Corporation) was immersed in the cord dip to impregnate and coat the cord or yarn and passed through a heated oven. The entrance temperature was 163° C., the exit temperature was 219° C., and the passage time was 45 seconds. The desired dip pickup was approximately 20% by weight on the cord.
Recipe for the rubber compound used for the determination of H-adhesion of the glass yarns to rubber is shown below. The rubber compound containing the dried adhesive coated glass yarns was cured at 152° C. for 20 minutes.
______________________________________Rubber CompoundIngredient Parts by Weight______________________________________Smoked Sheet (natural rubber) 50SBR-1502 50ENDOR 0.15HAF carbon black 35Zinc oxide 3Stearic acid 1PICCO 100 2Styrenated phenol (antioxidant) 1ASTM 103 oil (plasticizer) 7Diphenyl guanidine 0.15NOBS #1 (vulcanization accelerator) 0.9Sulfur 2.6______________________________________
Table I, below, compares the H-adhesions of dried adhesive coated glass yarns cured in the rubber using 70/15/15 overall compositions of Bd/VP/BA and Bd/VP/St each made in three different ways: (a) graft latex, (b) blend and (c) terpolymer.
TABLE I__________________________________________________________________________H-Adhesion of the Glass Yarns in 70/15/15 Overall CompositionsOf Bd/VP/BA and Bd/VP/St Latex Dips Prepared InThree Different Ways1 ASTM-D-2138-72 H-Adhesion in RubberVaried Compound (Newtons)Monomer Type of Latex ca 25° C. 121° C.__________________________________________________________________________n-butyl Graft (poly (BA) seed + Bd and VPacrylate monomers, Run 5 above) 147 93 Blend (15 poly (BA) + 70/15 BD/VP copolymer, Runs 1 and 4, above) 151 93 Terpolymer (the three monomers added together, Run 3, above) 138 98styrene Graft (polystyrene seed + Bd and VP monomers, Run 6 above) 182 116 Blend (15 polystyrene + 70/15 Bd/VP copolymer, Runs 2 and 4, above) 44 18 Terpolymer2 (the three monomers added together) 156 102__________________________________________________________________________ 1 All of the dips contained 7.5 parts of the RF resin per 100 parts by weight latex solids. 2 A 70/15/15 Bd/VP/St aqueous, free radical emulsion polmerized late having the following typical properties: Brookfield Viscosity, cps: 30; pH: 10.7; Mooney Viscosity, ML4 @ 100° C.: 40; Surface Tension, dynes/cm: 48.
The blend with polystyrene, that shows the poor adhesion, produced a very brittle yarn at ambient temperature whereas the other two yarns containing styrene were flexible. The three yarns containing BA were all flexible. The latex prepared with polystyrene seed showed the highest adhesion, higher than the styrene terpolymer. The yarn containing the styrene terpolymer can be considered a control yarn because this terpolymer simulates a normal VP latex used in tire cord adhesives. The three yarns containing BA show equivalent results and are considered as good as the yarn containing the styrene terpolymer.
Table II, below, compares the flex properties of the glass yarns using 70/15/15 overall compositions of Bd/VP/BA and Bd/VP/St each made in three different ways as described above. The yarns contained the dried adhesive dip only; they were not embedded in the rubber compound (Method A).
TABLE II__________________________________________________________________________Flex Properties of Glass Yarns Processed in 70/15/15 OverallCompositions of Bd/VP/BA and Bd/VP/St Latices Prepared InThree Different Ways1 Number of Flexes by MIT Test MethodVaried A2Monomer Type of Latex -30° C. 25° C. 120° C.__________________________________________________________________________n-butyl Graft [poly(BA) seed + Bd and VPacrylate monomers, Run 5, above]3 8683 2341 2973 Blend [15 poly(BA) + 70/15 Bd/VP copolymer, Runs 1 and 4, above] 2365 1271 1560 Terpolymer (the three monomers added together, Run 3) 4883 1071 1178styrene Graft (polystyrene seed + Bd and VP monomers, Run 6, above) 5197 950 1579 Blend (15 polystyrene + 70/15 Bd/VP copolymer, Runs 2 and 4, above) 388 202 1273 Terpolymer4 (the three monomers added together) 1385 995 1237__________________________________________________________________________ 1 All of the dips contained 7.5 parts of the RF resin per 100 parts by weight of latex solids. 2 Processed yarn not embedded in rubber. 3 0.2 parts Sulfole 120/100 parts latex monomers was used. 4 A 70/15/15 Bd/St/VP aqueous, free radical emulsion polymerized latex having the following typical properties: Brookfield Viscosity, cps: 30; ph: 10.7; Mooney Viscosity, ML4 @ 100° C.: 40; Surface Tension dynes/cm; 48.
The latex prepared with poly(BA) seed shows the best flexing at all three temperatures. The latex prepared with polystyrene seed shows much better flexing at -30° C. than the terpolymer latex containing styrene, but is not as good as the latex prepared from poly(BA) seed. The brittle yarn produced by the polystyrene blend accounts for its poor flexing at -30° C. and 25° C.
Table III below shows the flex properties and H-adhesions of the dry adhesive coated glass yarns using the graft copolymer latices of this invention that were prepared on a five-gallon scale. Blends of these latices with 60 parts of a poly(Bd) latex were made. These latices and latex blends are then compared with a Bd/VP/St control.
The two 60/40 blends of poly Bd/graft copolymer latex containing poly(BA) seed show much better flexing at -30° C. than the blend using a 70/15/15 Bd/VP/St latex. The 70/15/15 Bd/VP/St terpolymer latex alone shows poor low temperature flexing. The 80/10/10 graft compositions showed a little lower adhesion than the 70/15/15 graft compositions.
TABLE III______________________________________Flex Properties and H-Adhesion of Glass Yarns Processed InAdhesion Dip Containing Poly(BA) Seed Prepared On AFive-Gallon Scale ASTMOverall Graft D-2138-72Bd/VP/BA Number of H-AdhesionLatex Com- Flexes at In the Rubberposition Made -30° C. by CompoundWith MIT Test (Newtons) Poly(BA) Latex In (Method- caSeed1 Final Dip2 B)3 25° C. 121° C.______________________________________70/15/15* All graft copolymer 12,724 151 9370/15/15* Blend. 60/40 poly Bd4 /above graft copolymer*, dry wt. basis 40,814 116 8080/10/10# All graft copolymer 42,128 125 8580/10/10# Blend. 60/40 poly Bd4 /above graft co- polymer#, dry wt. basis 55,811 89 5870/15/15Bd/St/VPterpolymer5 All VP type(control) (control) 1,359 138 8570/15/15Bd/St/VPterpolymer5 Blend. 60/40(control) polyBd4 /VP 21,416 111 80 (control)______________________________________ 1 Bd and VP monomers polymerized in presence of poly(BA) seed latex. 0.6 parts Sulfole 120/100 parts of latex monomers was used. 2 All of the final dips contained 7.5 parts of the RF resin per 100 parts by weight latex solids. 3 Yarn samples embedded in skin of rubber and cured. 4 An aqueous, free radical, emulsion polymerized poly(Bd) latex having the following properties: Brookfield Viscosity, cps: 100-250; pH: 10-11; Surface Tension, dynes/cm: 53-62; particle size: 1500 A; total solids content: 51-53%. 5 A 70/15/15 Bd/St/VP aqueous, free radical, emulsion polymerized latex having the following properties: Brookfield Viscosity, cps: 44.5; pH: 10.3; Mooney Viscosity, ML4 @ 100° C.: 66; Surface Tension, dynes/cm: 40. *Tg of about -70° C. and #Tg of about -75° C., both determined by Differential Thermal Analysis.
A number of additional seed based latices were prepared and evaluated in glass tire cord adhesives. The latex variables included the type of seed, amount of crosslinking agent in the preparation of seed and the amount of mercaptan used in the final graft stage. The seed latices were prepared in a manner similar to Item 1 in above Example I except for the addition of DVB (divinyl benzene) in the cases shown. The final graft latices were prepared in a manner similar to Item 5 in Example I above except for the addition of 0.4 part potassium carbonate to increase the polymerization rate of the VP. The overall Bd/VP/EHA or BA (2-ethyl hexyl acrylate or n-butyl acrylate) graft latex composition in each case was 70/15/15. These latices are compared with a Bd/VP/St terpolymer control in blends with 60 parts poly(Bd) latex.
The sample for testing breakage was a composite simulating a tire section consisting of two polyester plies (polyester cord layers already calendered with rubber), two glass belts, and a rubber layer, the composite having a thickness of approximately 1 cm. The glass belts were made by first twisting the dip processed glass yarns (same as in Example 2, above) into 3/0 cords (1.5 turns per inch) and then drum winding the cords onto a 25 mil thick rubber sheet at 16 ends per inch to form the belts. The polyester rubber layers, glass rubber layers and the rubber layer on top were combined and cured. The 2"×7" (5.1 cm×17.8 cm) test piece was subjected to an oscillation of 0.7" (1.78 cm) compression and 0.2" (0.51 cm) tension at two cycles per second for a total of 30,000 cycles at ambient temperature (20°-25° C.). The rubber was then buffed off so that the top glass belt could be examined for breakage.
Recipe for the rubber compound used for the determination of this glass breakage in this test is shown below. The rubber composite was cured at 149° C. for 45 minutes.
The rubber compound used for H-adhesion testing is the same as that described in Example II, above.
______________________________________Rubber Compound For Glass BreakageIngredient Parts by Weight______________________________________Natural rubber 46.50PEPTON 76 (peptizer) 0.13SBR-1551 38.50Cis-polybutadiene 15.00FEF carbon black 45.00Hi-Sil 210 15.00AGERITE SUPERFLEX 2.67Aromatic oil 5.00Zinc oxide 3.00Stearic acid 1.50COHEDUR RL 4.70TBBS 1.20CRYSTEX 3.00______________________________________
Table IV, below, shows the breakage properties and H-adhesions of the adhesive coated glass cords using the graft copolymer latexes of this invention in which the seed polymer was from 2-ethylhexyl acrylate. Except for one case (highest DVB in the seed and lowest amount of mercaptan in the graft copolymer) the breakage was low and not significantly affected by the variation of DVB and mercaptan. In general, the seed latexes gave significantly lower breakage than the conventional Bd/VP/St terpolymer latex.
Table V, below, shows the breakage properties and H-adhesions of the adhesive coated glass cords using the graft copolymer latexes of this invention in which the seed polymer was from n-butyl acrylate (BA). The breakage was low in all cases using this seed polymer, the amount of DVB in the seed and the amount of mercaptan in the graft copolymer preparation having little effect on the breakage. In all cases the seed based latexes gave significantly lower breakage than the conventional Bd/VP/St terpolymer latex.
The breakage characteristics of glass cords containing the seed based latexes of this invention compared very favorably with those of the commercial cords. Six production control samples tested at ambient temperature (20°-25° C.) over a period of several months showed an average of 8.7 breaks.
TABLE IV______________________________________BREAKAGE PROPERTIES AND H-ADHESIONOF GLASS CORDS1 IN ADHESIVE DIPS2 CON-TAINING POLY(EHA) SEED; 60/40 LATEX BLENDPOLY(Bd)/GRAFT COPOLYMER (Series A)Parts by Parts by ASTM D-2138-72Weight5 Weight6 H-AdhesionDVB in Mercaptan in in Rubber Number ofPreparation Preparation Compound Breaks in Com-of Seed of Graft (Newtons) posite at Am-Latex Latex3 Ca. 25° C. 121° C. bient Temp.8______________________________________0.7 1.1 94 68 2.250.1 1.1 97 71 1.250 1.1 120 81 2.000.7 0.6 96 80 1.750.1 0.6 93 77 2.750 0.6 94 68 1.000.7 0.2 86 59 7.000.1 0.2 96 62 1.500 0.2 77 71 0.75Control terpolymer latex 116 89 4.00using styrene4______________________________________ 1 The Hadhesions were determined in the form of yarns. 2 All the dips contained 7.5 parts RF resin7 per 100 parts by weight of latex solids. 3 The overall composition of the graft latex polymers was 70/15/15 b weight Bd/VP/EHA. 4 A 70/15/15 Bd/VP/St aqueous, free radical emulsion polymerized latex having the following typical properties: Brookfield Viscosity, cps: 30; pH: 10.7; Mooney Viscosity, ML4 @ 100° C.: 40; Surface Tension dynes/cm: 48. 5 PBW based on 100 parts by weight of EHA. 6 PBW based on 100 parts by weight of monomers used in shell. 7 Same RF resin as in preceeding example. 8 About 20-25° C.
The POLY(Bd) used in the blends was the same emulsion polybutadiene as used in the preceeding examples.
TABLE V______________________________________BREAKAGE PROPERTIES AND H-ADHESIONOF GLASS CORDS1 IN ADHESIVE DIPS2 CON-TAINING POLY(BA) SEED; 60/40 LATEX BLENDPOLY(Bd)/GRAFT COPOLYMER (Series B)Parts by Parts by ASTM D-2138-72Weight5 Weight6 H-AdhesionDVB in Mercaptan in in Rubber Number ofPreparation Preparation Compound Breaks in Com-of Seed of Graft (Newtons) posite at Am-Latex Latex3 Ca. 25° C. 121° C. bient Temp.8______________________________________0.7 1.1 94 74 1.750.1 1.1 103 78 2.750 1.1 114 77 1.750.7 0.6 100 71 2.250.1 0.6 102 73 1.000 0.6 92 67 1.750.7 0.2 94 76 0.500.1 0.2 78 64 1.000 0.2 90 73 0.50Control terpolymer latex 116 89 4.00using styrene4______________________________________ 1 The Hadhesions were determined in the form of yarns. 2 All the dips contained 7.5 parts RF resin7 per 100 parts by weight of latex solids. 3 The overall composition of the graft latex polymers was 70/15/15 b weight Bd/VP/BA. 4 A 70/15/15 Bd/VP/St aqueous, free radical emulsion polymerized latex having the following typical properties: Brookfield Viscosity, cps: 30; pH: 10.7; Mooney Viscosity, ML4 @ 100° C.: 40; Surface Tension dynes/cm: 48. 5 PBW based on 100 parts by weight of BA. 6 PBW based on 100 parts by weight of monomers used in shell. 7 Same RF resin as used in preceeding examples. 8 About 20-25° C.
The POLY(Bd) used in the blends was the same emulsion polybutadiene as used in the preceeding examples.
SIPEX UB--Sodium lauryl sulfate, American Alcolac.
DRESINATE 214--Potassium soap of disproportionated rosin. Hercules, Inc.
SULFOLE 120--t-dodecyl mercaptan. Phillips Petroleum, Rubber Chems Div.
TAMOL N--Sodium salt of condensed naphthalene sulfonic acid. Rohm and Haas Co.
SBR-1502--Cold nonstaining aqueous emulsion, free-radical polymerized copolymer of butadiene-1,3 and styrene (target bound styrene of 23.5%), nominal Mooney viscosity ML 1+4 (212° F.) of 52.
ENDOR--Activated zinc salt of pentachlorothiophenol. Peptizer to improve processability. duPont.
PICCO--Resin tackifier. Hercules, Process Chemicals Div.
NOBS #1--90% N-oxydiethylene benzothiazyl-2-sulfenamide and 10% 2,2'Di-benzothiazyl disulfide. American Cyanamid Co.
PENACOLITE R-2170--Aqueous solution of resorcinol-formaldehyde resin or condensation product made with excess resorcinol (requiring formaldehyde to convert it to an infusible resin). Solids, % resin 75±2; pH of 0.5-2.0. Viscosity, 23° C. (Brookfield) poises of 35-85. Specific gravity 23°/23° C. of 1.23-1.26. Koppers Company, Inc.
PEPTON 76--Activated dithio-bisbenzanilide on an inert carrier. American Cyanamid Co.
SBR-1551--Nonstaining cold aqueous free radical emulsion polymerized copolymer of butadiene-1,3 and styrene (target bound styrene of 23.5%), nominal Mooney viscosity ML 1+4 (212° F.) of 52.
Cis-polybutadiene--stereospecific, solution polymerized, 92-93% cis, nominal Mooney viscosity ML 1+4 at 100° C. of 45-47.
Hi-Sil 210--Precipitated hydrated amorphous silica. PPG Industries.
AgeRite Superflex--Diphenylamine-acetone reaction product. R. T. Vanderbilt.
COHEDUR RL--A mixture of resorcinol and COHEDUR A, which is the hexa or pentamethyl ether of hexamethylol melamine, with a small amount of dibutyl phthalate plasticizer for viscosity control. Naftone, Inc.
TBBS--N-tert-Butylbenzothiazole-2-sulfenamide. American Cyanamid Co.
CRYSTEX--Insoluble sulfur with 20% oil. Stauffer Chemical.
BA--n-butyl acrylate.
VP--2-vinyl pyridine.
EHA--2-ethyl hexyl acrylate
DVB--divinyl benzene (commercial DVB is about 55% pure; the working examples parts by weight are based on 100% DVB (the commercial product being adjusted for impurities).
|Cited Patent
|Filing date
|Publication date
|Apr 26, 1954
|Dec 24, 1957
|Goodyear Tire & Rubber
|Bonded composite structure containing ozone resistant tripolymer rubber composition and adhesive
|Jun 24, 1975
|Oct 12, 1976
|Rohm And Haas Company
|Process for manufacture of acrylic core/shell polymers
|Apr 23, 1979
|Feb 17, 1981
|The General Tire & Rubber Company
|Adhesion of polyamide or polyester cords to rubber
|Sep 25, 1978
|Jul 7, 1981
|Rohm And Haas Company
|Heteropolymer acrylic latices and textiles treated therewith
|"Encyclopedia of Polymer Science and Technology", vol. 5, 1966, John Wiley & Sons, Inc. p. 433.
|Kovac, "Tire Technology", The Goodyear Tire Rubber Company Third Edition, 1970, pp. 61-63.
|Citing Patent
|Filing date
|Publication date
|May 4, 1984
|Jul 30, 1985
|Ube Industries, Ltd.
|Bead filler rubber composition
|May 4, 1984
|Aug 13, 1985
|501 UBE Industries, Ltd.
|Rubber composition for coating tire cord
|Dec 7, 1987
|Feb 7, 1989
|Basf Corporation
|Styrene grafted isoprene psa's
|Aug 28, 1987
|Feb 28, 1989
|Basf Aktiengesellschaft
|Aqueous binder dispersions for the preparation of paints and finishes
|Sep 26, 1988
|Jun 20, 1989
|Basf Aktiengesellschaft
|Aqueous binder dispersions for the preparation of paints & finishes
|Aug 27, 1987
|Aug 29, 1989
|Sumitomo Naugatuck Co., Ltd.
|Adhesive composition
|Mar 24, 1992
|Dec 7, 1993
|Bando Chemical Industries, Ltd.
|Fiber reinforced rubber articles
|Mar 30, 1994
|Jan 24, 1995
|The Goodyear Tire & Rubber Company
|Shortstopping of free radical polymerizations
|May 15, 2007
|Oct 5, 2010
|Rohm And Haas Company
|Heterocyclic latex copolymer and methods of making and using same
|May 15, 2007
|Dec 6, 2007
|Tirthankar Ghosh
|Latex copolymer and methods of making and using same
|U.S. Classification
|524/504, 524/548, 156/331.6, 428/378, 524/808, 525/243, 525/73, 524/516, 524/510, 525/279, 524/501, 156/335, 525/902
|International Classification
|Cooperative Classification
|European Classification
|Jul 26, 1982
Owner name: GENERAL TIRE & RUBBRER COMPANY, THE, A CORP. OF OH
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:WISE, RICHARD M.;REEL/FRAME:004015/0298
Effective date: 19811215
Owner name: GENERAL TIRE & RUBBRER COMPANY, THE, A CORP. OF OH
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WISE, RICHARD M.;REEL/FRAME:004015/0298
Effective date: 19811215
|Mar 14, 1986
|Fee payment
Year of fee payment: 4
|Mar 22, 1990
|Fee payment
Year of fee payment: 8
|May 24, 1994
|Maintenance fee reminder mailed
|Oct 16, 1994
|Lapse for failure to pay maintenance fees
|Dec 27, 1994
|Expired due to failure to pay maintenance fee
Effective date: 19941019


text:
I will be in Costa Rica next week, staying for 2 weeks, and want to do as much as possible while also having an enjoyable and relaxing vacation. Obviously there are a lot of amazing options. I am curious to hear what others absolutely think I should not miss while traveling through the country in the month of October. I am throwing the trip together literally last minute and it's my first time in Central America, let alone CR. I love exploring, hiking, paddling, scuba diving, you name it. And definitely hope to take in some culture as well. Please help (and thank you in advance too)!
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Top 5 Things To Do In Costa Rica
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Pacuare river rafting would probably be the only standout, no-brainer.
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You'll be there at the height of the rainy season which is a factor, but if you want a real adventure then hike across Corcovado National Park. You can go from Los Patos to Sirena to San Pedrillo in 2-3 days.
Even if you don't do that then at least look into visiting Corcovado, a wild and beautiful place.
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It's not the ideal time to go as far as the weather but I'm still really looking forward to the trip. Corcovado is definitely on my list but I'm thrilled by both suggestions. River rafting sounds like a lot of fun and it's great to get such a strong endorsement. Additional ideas from anyone who stumbles across this post will be greatly appreciated. Anyone think it's worth going scuba diving at this time of year? Thanks!!!
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Be advised, though, that much of Corcovado and the surrounding area shuts down during October because the intense rains make travel by foot or car nearly impossible. I would choose other areas.
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I agree; I probably wouldn't go to the Osa this time of year. Our guide told us that late September and into October is heavy, heavy rainy season. Even he leaves the property. If you're up for adventure activities, the Sky Trek zipline in the Arenal area is pretty cool - 600 feet in the air, beautiful views of the lake and volcano, and you travel at up to 55 mph. There's also nice hiking at the Hanging Bridges and the waterfall. The natural hot springs are great too. I'd consider going to Tortuguero to see the turtles lay their eggs. You can do a lot of exploring on the canals, and there's tons of wildlife in that area.
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Church and State
By Editorial Staff
Published May 2, 2008
Some Common Misunderstandings
By Don Long
Under the guise of the First Amendment, sometimes called the "Separation of Church and State amendment," the United States government has discouraged the public practice of the Christian faith. The U.S. Supreme Court banned the posting of the Ten Commandments in public buildings. It has banned prayer in public schools. The government continues an aggresive stand against any display of religious faith in civic areas or other public lands. This is not right. The purpose of the First Amendment was not to withdraw Christianity from society, but to protect it from government manipulation.
Christianity not only played a major role in America's independence, but also in the formation of this new country's government. References to God, the Lord, Jesus Christ, and the Creator abound in such historical documents as the Declaration of Independence, the Mayflower Compact, and the Articles of Confederation. In addition to this the symbols of this nations' faith, the Lincoln Memorial, the Washington Monument, the Liberty Bell, and scores of others, all have verses from the Bible engraved upon them. These memorials and historical documents testify to the fact that Christians took the leadership in our country.
Prompted by religion, and the freedom to worship God according the dictates of Scripture and conscience, many early colonists came to this land. A major cause of the colonies breaking away from the British was England's attempt to establish a national religion in the colonies. The colonists felt it was not government's role to regulate Christianity.
The First Amendment states "Congress shall make no law respecting an establishment of religion, or prohibiting the free exercise thereof." This amendment prohibits government from establishing a national religion. It guarantees the free exercise of religion without entanglement by the government. It is not a mandate requiring the elimination of Christian influence on society.
Religion and government are inseparable. Government laws and regulations are based on people's convictions. Convictions are based on people's beliefs concerning right and wrong. Theft is illegal because it is believed to be wrong. Any belief in a standard higher than one's own self constitutes a religion. Government merely reflects the religious view of a nation. It should not control that view. – continued on the next page
The current distorted view of the First Amendment has brought about the government intrusion into religion which the amendment was to protect people from. It prohibits the free exercise of religion. There is nothing in the First Amendment to suggest the separation of Church and State; that is like suggesting people should not be involved in government.
Don Long is a member of CHANGE.
Forerunner - Home » Pass The Word » Pass The Word - May/June 1996
Your comments are welcome!
Along with the Anti-Christians ,who want separation of Church and State……
Are Christians who believe that forgiveness and reconciliation with God , is a higher faith that can not be forced by the State….
As Christianity tries to shrink the separation of Church and State…… It's CHRISTIANITY that is shrinking……
All of wonderful and most powerful things that Christ did to define what Christianity is…..and his instructions for us…..Is way HIGHER than Justice
How will a combined Church/State , legislate Forgiveness…the core of CHRISTIANITY..???
Want to see a higher Faith……See my site. carpenteroftheforest.com
Love and growth….Mike
Posted by Mike Akimoff on 03/16/2010 11:21 PM #
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The modern technology of real-time ultrasound now reveals the actual responses of a 12-week old fetus to being aborted. As the unborn child attempts to escape the abortionist's suction curette, her motions can be seen to become desperately agitated and her heart rate doubles. Her mouth opens – as if to scream – but no sound can come out. Her scream doesn't have to remain silent, however … not if you will become her voice. This newly re-mastered version features eight language tracks and two bonus videos.
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The dramatic classic film of Martin Luther's life was released in theaters worldwide in the 1950s and was nominated for two Oscars. A magnificent depiction of Luther and the forces at work in the surrounding society that resulted in his historic reform efforts, this film traces Luther's life from a guilt-burdened monk to his eventual break with the Roman Catholic Church.
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A Revival Account: Asbury 1970 (DVD)
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Certain to challenge you to greater holiness and a deeper commitment to full-scale revival. Original news and private footage has been included. If you are a student who longs to see a spiritual awakening at your school, you must see this video!
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The Four Keys to the Millennium (Book)
Foundations in Biblical Eschatology
By Jay Rogers, Larry Waugh, Rodney Stortz, Joseph Meiring. High quality paperback, 167 pages.
All Christians believe that their great God and Savior, Jesus Christ, will one day return. Although we cannot know the exact time of His return, what exactly did Jesus mean when he spoke of the signs of His coming (Mat. 24)? How are we to interpret the prophecies in Isaiah regarding the time when "the earth will be full of the knowledge of the LORD as the waters cover the sea" (Isa. 11:19)? Should we expect a time of great tribulation and apostasy or revival and reformation before the Lord returns? Is the devil bound now, and are the saints reigning with Christ? Did you know that there are four hermeneutical approaches to the book of Daniel and Revelation?
These and many more questions are dealt with by four authors as they present the four views on the millennium. Each view is then critiqued by the other three authors.
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TONYMOLY Red Appletox Honey Cream 80ml N/A Store Home Ask a Question Email a Friend Item Description
Tonymoly Red Apple Tox Honey Cream contains Manuka Honey extract from the wild trees of New Zealand that provide an immunity and anti-bacterial effect. Royal Jelly extract cools down skin troubles, making it good for sensitive skin.
Black honey is rich in minerals and amino-acid, which nourishes and moisturizes skin. Apple acid ingredients smoothes skin while Propolis provides anti-oxidants. Sticky texture relaxes the muscle membrane to give elasticity.
How to use
Apply appropriate amount to face, tap slightly until absorbed completely. Used as cream usually, use 1 to 2 times a week, provide elasticity to skin.
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We accept PayPal payment. We can also accept credit cards / bank transfer via PayPal.
Payments are expected within 7 days once the sale ended. Please note that the unpaid item alert process is automated and will commence after seven days if payment has not been received.
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Shipping Period Expedited Flat Rate Shipping : EMS Tracking number Included 2~5 business days Asia 3~6 business days Europe, Australia, United States, Canada 5~9 business days Other countries
Shipping options are basically set up as a Economy airmail.
If you would like to include a tracking number as well as insurance, please choose "Standard Int'l Shipping" and you will be charged with about USD2.50.
WE SHIP TO WORLDWIDE (Except some countries). All orders will be shipped from South Korea.
We ship items within 1 business day after a cleared payment.
PLEASE NOTE: You may be subject to import duties, taxes, and/or customs fees which may be imposed by your local government when you receive your package.
Expedited shipping cost varies depending on a location.
Transit times are controlled by the carrier, customs and weather related variables. We are not under control over these factors.
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We want our customers to feel safe knowing they can return their items, no questions asked! If you are not happy with your items for any reason, simply follow these 3 easy steps!
Send a message to us via to get the return mailing address.
Write down 'RETURN' clearly on the envelop and return to the address provided. Buyers will be contacted to arrange refund of merchant value once the returned item is received. Please note that postage is NOT refundable.
All returns must be postmarked within 14 days of receipt of your package.
All original box and sealed must be attached with no signs of use.
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Our company is a privately held a direct wholesaler, and our management shares more than 13 years of experience in cosmetic industry.
Our mission is "to meet consumer demand in a demanding world".
Our vision is to engender and satisfy the loyal customer who knows exactly what they want, when they want it and how they like it. Our vision includes hands-on customer service making sure each and every customer is treated royally and completely taken care of to his or her satisfaction. We can guarantee you will be happy with our pricing.
Our service department is always available to work with any issues you may have with your purchase and our knowledgeable sales staff can help you with your purchase. They are here to help you with a smile.
In addition, we have a team of specialists who are ready to provide customer support when you need it. Our goal is not only to sell you quality products at the lowest prices, but also to build a trusting and lasting relationship.Postage Offers Sample Gift Payment Methods we are Cosmeticmarket2012 © 2014 Cosmeticmarket2012 - All Rights Reserved.
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Maple-Roasted Chicken Thighs with Sweet Potatoes
This autumnal take on roast chicken is perfect for a chilly fall night. The ingredients — maple syrup, chicken thighs, and sweet root vegetables — are rustic and really satisfying.
Total Time:
Level: Moderate
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- 4 large skinless chicken thighs
- 2 small sweet potatoes
- 1 small onion
- 8 oz. baby carrots
- 8 oz. parsnips
- ¼ c. maple syrup
- Preheat oven to 450° F.
- In 15 1/2" by 10 1/2" jelly-roll pan or large shallow roasting pan, combine chicken, sweet potato chunks, onion, baby carrots, maple syrup, 1 teaspoon salt, and 1/2 teaspoon pepper, and toss to coat.
- Roast chicken mixture 40 to 45 minutes or until juices run clear when thickest part of thigh is pierced with tip of knife and liquid in pan thickens slightly, stirring vegetables once and turning chicken over halfway through roasting.
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LONDON — Customer watchdog Passenger Focus released a study showing that ticket machines were daunting for passengers catching a train for the first time, or those buying a different type of ticket from what they usually purchase. A spokesman for the Association of Train Operating Companies responded that Passenger Focus's own figures showed last month that — from a survey of more than 30,000 rail users — seven out of 10 were satisfied with ticket-buying facilities at stations. For the full story, click here.
The Penske Tech Center will be the nation's first vehicle storage and maintenance facility to operate completely off-wire.
The straightforward and user-friendly system superimposes the corridor map on top of a Google map, which shows the precise location of the train.
The five additional six-car X'Trapolis trainsets will enhance the Melbourne's Metropolitan Rail Network's capacity.
The four car train, manufactured by Hitachi Rail Italy, is a key component of the first driverless rail transit system in the U.S.
Applicants can request funds for safety improvements to railroad infrastructure, including railroad crossings, track, tunnels, bridges, yards and other areas.
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Getting Rogered
Hey, was there any Astros-related news this weekend? (Besides dropping another series in St. Louis, we mean.)
Oh, yeah: Houstonians got introduced to the real Roger Clemens.
For years now St. Roger has been a altruistic icon who pitched because of his simple love of Houston. Anyone who suggested otherwise (like, say, the Houston Press or fans of the Yankees, BoSox or Blue Jays), were dismissed as carping whiners who didn't understand the real Roger.
Until this weekend, when true colors emerged.
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We have no beef with Clemens making all the money he wants; it can be tough to keep your kids in state-of-the-art Hummers. We're just glad his decision to sign with the Yankees was handled with the complete lack of class that we – as a sometimes lonely voice on the subject – have come to expect from Roger.
We also look forward to the New York media dealing with Clemens' demands for extensive time off and limited travel, the questions about steroids, the drama-queen stunts he pulls to get attention. As long as he wins, none of that will matter, but if he goes in the tank then he won't get the "wounded warrior" treatment the locals here lavished on him.
The best thing about the signing? It gives us a chance to revisit the infamous opening of a column by the Houston Chronicle's John P. Lopez during the 2005 NL playoffs:
MAMA called and Roger Clemens had to listen - that's just how Houston boys are brought up. Mama was the city he called home. And Mama was the woman whose warm hug and spitfire inspiration helped carry Clemens to places he never imagined.
It was because of a mother who inspired him, a family that encouraged him and a friend named Andy Pettitte who prodded him that Clemens decided to pull on the hometown jersey two years ago.
It still brings a tear to the eye. Although maybe not in the way Lopez intended. - Richard Connelly
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Asked to provide end-to-end solutions for its clients, broadcast systems integrator Beck Associates recently connected several local broadcasters with RTS and Telex RadioCom intercom systems.
One broadcaster contracted Beck Associates to integrate an ADAM system by RTS, featuring the new AIO-16 16-port analog I/O card kit, TIF-4000 telephone interface, breakout panels and KP-32 Classic keypanels. The system is configured for 144 matrix ports, which leaves plenty of room for expansion without having to invest in a new frame. For crewmembers on set, Beck specified BP-325 two-wire beltpacks by RTS and a BTR-800 wireless system by Telex.
In Tucson, Beck integrated a similar system with a pair of smaller Cronus DSP matrices featuring eight-port AIO cards, KP-32 Classic keypanels, BP-325 beltpacks and a BTR-800 wireless system.
RTS Cronus is a modular, 2RU, 32-port digital matrix intercom that can hold up to four AIO analog or RVON-C VoIP cards with eight ports each. With its advanced DSP architecture, Cronus has the ability to link up to four units into a single 128-port matrix. It can be preconfigured for fiber with a connection up to 9.3mi distant or via coax for short runs of up to 300ft. When connected as a single matrix, the individual intercom controls remain autonomous at each matrix. The Cronus is available with an analog card or the RVON-C VoIP card.
For more information, visit www.boschcommunications.com or www.becktv.com.
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Utah Utes football: Star Lotulelei reaches for the stars in the classroom
Tom Smart, Deseret News
SALT LAKE CITY — Starlite is proving be star bright for the Utah Utes.
Although he goes by a shortened version of his first name, defensive tackle Star Lotulelei isn't cutting any corners on the field, or in the classroom. He's put sure-fire NFL riches on hold to complete his sociology degree and play his senior season of college football.
It's a decision he doesn't regret.
"There was never any doubt when I decided to stay," said Lotulelei, who is on track to graduate this fall.
Lotulelei is taking a lot of pride in completing his education. It's something his parents have always pushed for and he's determined to get it done.
Utah coach Kyle Whittingham isn't surprised.
"Education is very important to Star," he said while noting that Lotulelei is married and has a family. "We all know that a football career can be a fleeting proposition and to have that degree in hand in December is very important to him. I'm proud of him for making that decision."
Lotulelei's coach at Bingham High, Dave Peck, is equally pleased with how things have worked out at Utah.
"I think it tells you how he has grown up and matured as a person. Back when he was younger, Star really struggled in school and it just wasn't something that he felt was real important to him," Peck said before noting that Lotulelei narrowly got into the University of Utah after attending Snow College. He wound up in Ephraim when academic woes stymied his original commitment to BYU. "Over the last couple of years, I tell you, I just think he's matured a ton. I think his decision to go back and work on getting his degree was huge because he probably would have been a first-round draft choice this year.
"You look at all the money that goes along with it and that would be a tough decision to turn that down," Peck added. "It's him growing up and him really looking at things a little bit different than he maybe would have a few years ago. I'm really proud of how he's come along and what he's accomplished."
On the field, Lotulelei reached the pinnacle of success last season by receiving the Morris Trophy as the Pac-12's top defensive lineman — an award voted upon by the players. In addition, the 6-foot-4, 325-pounder earned first-team all-conference honors and was named the top lineman in Utah's Sun Bowl victory over Georgia Tech.
"There's a lot of things I need to work on even though I had those accomplishments last season," Lotulelei said after a spring practice at Rice-Eccles Stadium.
Improving his techniques and getting in better shape are among the things the senior wants to work on before moving on to the NFL.
"We challenged him to be better than he was last year, which is really, really good," said Utah defensive coordinator Kalani Sitake. "So I think he's really excited to do that."
Lotulelei knows it'll be a challenge, but he's looking forward to it.
"I'm really trying polish up right now, polish up on technique and all that stuff with the rest of the D-line, the rest of the defense," Lotulelei said while praising pretty much everyone in the program for his success. He considers the Morris Trophy to be more of a team award than an individual accolade.
Lotulelei's humbleness, Whittingham noted, is part of what makes him a great leader.
"I can't say enough good things about Star, from his leadership to his play to how he conducts himself off the field to academically," Whittingham said. "He certainly would have been drafted high this year had he come out. But it's our belief that he can come back and have a great senior year. He'll improve his stock even more, plus he'll have a degree in hand."
The combination, thereof, adds to Lotulelei's appeal as a leader.
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The pump in review has surpassed all my expectations. I us it to pump water from a creek that is over 300 away and 80 feet below the property i water. There is plenty of pressure and sufficient water flow at these distances and elevations. The large gas tank gives it a long run time. The high discharge pressure shortens the watering time because of the distance the sprinkler is significantly improved, The only problem noted upon delivery was loose gas tank nuts and a pinched ignition wire that prevented the engine from starting. Once corrected, engine cranks up on first few pulls of the starter rope. This pump is a good economic alternative to the more expensive pumps, especially if it is to be used for irrigation purposes.
- How did the color on site compare with the actual product? Color very accurate
- Please tell us about the quality of the product. The quality was above average
- How accurate was the on site description of the product? The discription of the product was accurate
awesome use it to pump water 80 feet up hill with 400 feet of hose.
The first pump i purchased met my performance expectations. However it had a head gasket failure in the second season of use. I attempted to purchase a seal for the pump but was told by the distributor no parts were available. Recently A piece broke out of the impeller which did major damage to the inside of the pump case. I did order a new one but only because it is cheap.
I use this to water wild plants I have growing on a flood plain and I am pumping out of a small stream.
- Please tell us about the quality of the product. good starts easy pumps a lot of water even at low RPM


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Viking Gloves: Cut Resistant Rubber Latex Work Gloves 73347
$3.00 7 Reviews 2
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$30.00 1 Review 15
Viking Jackets: Men's Zip Front Poly/PVC Fleece Jacket 402NB
$44.00 1 Review 22
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Thank you very much for your notification that you have received my return and status of my new order. Because of your commitment to customer satisfaction and prompt follow up on customer concerns, I recommend your store to my associates with utmost confidence."
J. Tucker from Cullman, Alabama


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The Rex the Dinosaur's Car Moon Break adventure at dusk
The Rex the Dinosaur's Car Moon Break entrance is like a skulk across Moontown. The adventure cars are shaped like Buddie the Cab, and while you drive you can break them by hugging the other guests.
Avoid Pirate Mode
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A Pants Aflame production


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Recent News
The commissioners have approved more than $6.5 million for the Franklin County YouthWorks program, a work experience and internship program for TANF eligible youth and young adults ages 14-24 years old.
Approximately 1,950 young people will receive summertime work experience that pays at least $10 an hour and lasts 8 to 12 weeks. The program provides eligible youth an opportunity to engage in positive activities outside of school and develop important job readiness skills.
The Community Partnership Program is a competitive grant process whereby the Commissioners support local community-based organizations. Proposals must demonstrate how effectively and efficiently the initiative or program aligns with the Commissioners' Core Principles.
In conjunction with National County Government month, the commissioners have released their second annual State of the County report.
The report, available at report.franklincountyohio.gov, is a compendium of the many ways that the lives of Franklin County residents are touched by county government on a regular basis, as well as of the investments the commissioners have made in public safety, economic development, and environmental protection.
From Business First: Franklin County is in rare company for having fully recovered from the Great Recession that ended nearly seven years ago, according to a report from the National Association of Counties.
Of 3,069 counties nationwide, only 214, or 7 percent, had fully recovered by last year in four areas - economic output (gross domestic product), employment, unemployment rate and home prices.
The Franklin County Board of Commissioners in partnership with the Franklin County Auditor are enhancing the public's access to information through an electronic record project dubbed Citizen Transparency, which makes millions of financial records available online in a safe, secure and easily searchable system.
The new system provides any member of the public with immediate access to current information and historical data on the County's revenues and expenditures, including payroll.
ALERT Franklin County is a mass notification and warning system developed to quickly notify residents of weather emergencies, crime alerts, road closures and more.
You choose the community notifications and locations you want and how you want to receive them. Notifications can be received via text message, email, cell phone, home phone or work phone.
Board of Commissioners Agencies
- Animal Care & Control
- Benefits & Risk Management
- Child Support Enforcement
- Economic Development
& Planning
- Fleet Management
- Homeland Security
& Justice Programs
- Human Resources


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Canada's double standard for dual citizens
The first person who came to mind when I heard about the Queen's award of the Order of Merit to former prime minister Jean Chrétien was Conrad Black. It is ironic that Chrétien is receiving an honour from the same country that he advised not to honour another Canadian citizen. Instead, Black was forced by Chrétien to give up his citizenship in order to become Lord Black of Crossharbour.
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I know there is an institutional difference between the honour received by Chrétien and the title of "Lord" offered to Black; I also know that the former media tycoon is in a U.S. jail, that he had a choice to make between becoming a Lord in the British Parliament or keeping his Canadian citizenship, and that he made the wrong choice.
But this column is not about Black. It's simply about a Canadian citizen who was not properly treated by his Canadian prime minister.
In Chrétien's book My Years as Prime Minister, he complains about the personal attacks he had to face from the National Post, the paper created by Black, and then writes about his decision to deny the Canadian government's consent for Black's appointment to the House of Lords. In the book, Chrétien mentions the 90-year-old Nickle Resolution, "which asked the king to discontinue the practice of bestowing titles of honour on Canadians."
But since that resolution, many things have changed.
Canadians can now enjoy dual citizenship, and the federal government has always decided not to intervene in the relationship between the other country's government and people that country considers citizens, even if they are also Canadians.
For example, many young people born in Canada to parents of Italian origin have had to serve in the Italian army even if they never had Italian citizenship. Many Canadians of Italian origin asked the Canadian government to intervene and defend its citizens. The answer was always the same: The Canadian government doesn't intervene in the decisions of other governments regarding their citizens.
I don't understand why for Chrétien Canadian citizens could serve in a foreign army but could not be members of a foreign parliament.
In fact, they can and are. Right now, we have two Canadian citizens who are members of the Italian Parliament: MP Gino Bucchino, a doctor with dual citizenship, and Senator Basilio Giordano, a Canadian Italian journalist from Montreal. The year before Giordano was elected to the Italian Senate, he ran against Justin Trudeau for the Liberal candidacy in a Montreal riding. The election of Bucchino and Giordano to the Italian Parliament was officially accepted by the Canadian government of Paul Martin in 2005 and confirmed by the present government of Stephen Harper.
I'm not saying that this is right, and I'd be glad if the Canadian government would clearly define the rights and duties that come with Canadian citizenship and better define the concept of dual citizenship.
But in the meantime, we have to make sure that there is consistency in how all Canadian citizens are treated.
We might like or dislike Black, and we needn't forget that he is in an American jail. But this is not about him. The issue is the treatment by a Canadian prime minister of a Canadian citizen who was forced to make a choice that was not imposed on others.
It is unfair that Canada is called upon to help Canadian citizens all over the world, even if they no longer live in Canada, and yet turns its back on a person who was forced to make a choice as a Canadian citizen. I agree that he made the wrong choice, but it was a choice that other Canadians didn't have to make.
Chrétien writes in his book that former British prime minister Tony Blair took only two weeks to give British citizenship to Black. I hope that Harper's government will decide to take no more time to give Black – who is not a foreigner but a Canadian-born and Canadian-educated individual who has contributed much to this country – back a citizenship that fell through the cracks of a dispute between two very stubborn and proud men.
I don't care if Black is a bad or a good Canadian but he is as much a Canadian as you or I.
Angelo Persichilli is the political editor of Corriere Canadese. His column appears Sunday.
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text: Zest set to expand Indonesia services By Lorenz S. Marasigan, BusinessMirror Posted at Jun 26 2014 07:56 AM | Updated as of Jun 26 2014 03:56 PM MANILA - Budget carrier operator Zest Airways Inc. is looking at expanding its operations to Indonesia. AirAsia Zest Chairman Marianne M. Hontiveros said in an interview that Indonesia is an exciting destination for her airline, noting that the country has a lot of potential for both business and tourism. Indonesia destinations that AirAsia Zest eyes are Jakarta, Bali and Bandung. Hontiveros said Jakarta has a good potential for both the leisure and business travelers. For the tourism market, "Bali and Bandung are interesting. There's a lot of places there that will attract tourists," the executive said. AirAsia Zest flies to 20 local destinations from Manila, Clark (Pampanga) and Kalibo (Aklan). It also flies from Manila to Incheon and Pusan in South Korea, Kuala Lumpur in Malaysia, Shanghai and Jinjian City in China, Macau, and Taipei in Taiwan. At present, only Philippine Airlines and Cebu Pacific mount flights to destinations in Indonesia. Civil Aeronautics Board Executive Director Carmelo L. Arcilla said the country's air-services regulator is considering holding negotiations with its Indonesian counterpart to expand the countries' decades-old air pact. He said his agency will seek talks with the Indonesian Directorate General of Civil Aviation to update the current air-services agreement with the nation signed in 1972. "Our previous request was overtaken by time. We will propose to hold air talks sometime in the third quarter," he said. Share Facebook Twitter GPlus LinkedIn Pinterest Kakaotalk Viber WeChat Read More: Indonesia Zest Airways Inc AirAsia Zest /video/sports/05/06/16/curry-wont-play-for-warriors-in-game-3-vs-blazers/video/sports/05/06/16/raptors-hold-off-heat-in-overtime-to-level-series/nation/regions/05/06/16/best-mothers-day-gift-mom-finds-long-lost-son-via-facebook/lifestyle/05/06/16/10-things-to-do-this-weekend-may-6-8/nation/05/06/16/ex-cj-corona-laid-to-rest


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Download our free Treatwell app.
Earn up to 48 Reward points. Read more »
Cannot be used in conjunction with any other offer. Subject to availability. No cash alternative. No change given on voucher. Voucher valid for the introductory session only and cannot be used for on-going courses.
Our standard 24 hours cancellation policy applies.
Wellness Centre
Online bookings let you pick date/time for your visit.
If you purchase an eVoucher you will need to book with the venue directly.
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|Wellness Centre in Clapham Junction, London


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The ajax loader module provides you alternatives to the default drupal core ajax throbber. When this module is configured, it overrrides the default drupal throbber.
(the custom throbbers are pure CSS)
See the README.txt file for detailed installation instructions.
Bookkeeping provides double entry bookkeeping inside Drupal. This can be integrated with any system via the API or Rules to keep track of the movement of money between accounts. Comes with a basic integration with Drupal Commerce.
This data can then be exported for import into out accounting systems.
This module shows a loading layer on page loading events. These may be triggered by form submission or clicking a hyperlink.
Hyperlinks may be excluded from trigger by adding a "no-loading-animation" class. Further "javascript" and "#" hyperlinks are automatically excluded. Loading and animation may be aborted by pressing "ESC".
It is possible to change the loading animation image and customize the layout by overriding the library.
This simple module turns your website into a email gateway. This might be
useful if you have some other webservices/applications but wants all
messages sent from Drupal site. Another usecase could be if you have some
important mail hooks implemented and wants them to be applied for email
messages from other applications.
After module installation allowed clients would be able to send json-ed
email messages via POST request to the dedicated address - /mailspool/in .
Then Drupal perform usual routing for a received message.
This module provides the drush command to delete all the dummy contents through drush Command.
Currently it will work with the command,drush delete-all article
drush delete-all article
drush cc drush
drush delete-all machine-name-of-content-type
Adds a jump menu to the toolbar that allows administrators to view the current page's entity and to quickly go to a different entity.
Drupal is a registered trademark of Dries Buytaert.


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|Viewing Single Post From: YR: Sharon Newman in 'The Burning Ranch'
|Oct 2 2012, 02:03 PM
no character has ever not been written that way why is sharon different?
|YR: Sharon Newman in 'The Burning Ranch' · Y&R & B&B: News, Spoilers & Discussion


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