Patent Publication Number: US-4840742-A

Title: Silicone containing emulsions as bladder lubricants

Description:
This application is a continuation-in-part application of Ser. No. 07/014,735, filed Feb. 13, 1987, abandoned. 
    
    
     The present invention relates to aqueous emulsions and more particularly to aqueous organopolysiloxane emulsions which may be used as bladder lubricants. 
     BACKGROUND OF THE INVENTION 
     In manufacturing tires, the actual shaping of the tire is caused by inflating a rubber bag inside a green tire carcass to force the tire against the mold surface. Generally, there is substantial movement between the outer contact surface of the bladder, and the inner surface of the green tire during the expansion phase of the bladder prior to fully curing the tire. Likewise, there is also considerable relative movement between the outer contact surface of the bladder and the cured inner surface of the tire after the tire has been molded and vulcanized and the bladder has been collapsed and stripped from the inner tire surface. 
     It is essential that there be sufficient lubrication between the bladder and the inner tire surface in order to reduce friction between the bladder and the inside of the raw tire in order to allow for optimum slip of the bladder during the shaping process when the raw tire and bladder are in contact with one another. Finally, at the termination of the vulcanization cycle, the lubricant allows for the release and removal of the bladder from inside the tire. 
     Aqueous organopolysiloxane emulsions containing treated inorganic silicates have been used as lubricants for molding tires. These emulsions are described in, for example, U.S. Pat. No. 4,184,880 to Huber et al, in which an aqueous diorganopolysiloxane emulsion containing dispersed inorganic silicates which have been treated with organosilicon compounds to impart hydrophobic properties to the surfaces of the inorganic silicates have been employed as release agents for manufacturing tires. Also, U.S. Pat. No. 3,713,851 to Cekada describes aqueous organopolysiloxane emulsions which have been used as bag lubricants for molding tires in which the emulsion contains an alkyl methyl siloxane fluid including non-flowing gums, polyalkylene glycols, mica, carboxymethyl cellulose, lecithin and water. U.S. Pat. No. 4,431,452 to Comper et al discloses a lubricating composition for a tire bladder comprising (1) a hydroxylterminated polydimethylsiloxane having a viscosity up to about 25,000,000 centistokes at 25° C., (2) a hydroxyl-terminated polydimethylsiloxane having a viscosity up to about 120,000 centistokes at 25° C., (3) a polyalkylene glycol, (4) bentonite clay, and (5) a surfactant. U.S. Pat. No. 3,872,038 to Adams et al describes an aqueous emulsion which is useful as a bladder lubricant comprising (1) a silicone gum, (2) an organopolysiloxane fluid, (3) polyglycols, (4) mica, (5) lecithin, (6) sodium carboxymethyl cellulose, (7) emulsifying agents and (8) water. 
     A bladder lubricant is described in U.S. Pat. No. 4,359,340 to Comper et al in which an aqueous emulsion comprising (1) a polydimethylsiloxane having a viscosity up to about 25,000,000 centistokes at 25° C., (2) a methylhydrogen silane having a viscosity of from 20 to 40 centistokes at 25° C., or a dimethylhydrogen silane having a viscosity of from 80 to 120 centistokes at 25° C., (3) a metal salt of an organic acid and (4) a surfactant is applied to the bladder surface. 
     An aqueous emulsion for treating organic fibers is described in U.S. Pat. No. 4,436,856 to Huhn et al in which the aqueous emulsion containing (1) an organopolysiloxane having at least two monovalent SiC-bonded organic radicals per molecule with a basic nitrogen atom, (2) an organopolysiloxane having at least 3 Si-bonded hydrogen atoms per molecule, (3) a catalyst for the condensation of Si-bonded condensable groups, (4) an emulsifier, and (5) a diorganopolysiloxane containing an Si-bonded terminal hydroxyl group. 
     A bladder release composition is described in U.S. Pat. No. 4,678,815 to Hoffman, in which the composition comprises (1) a hydroxyl-containing organopolysiloxane gum, (2) an organohydrogenpolysiloxane, (3) a lubricant having a melting range of from 25 to 80° C., (4) a thickening agent, (5) a surfactant, and (6) water. 
     Aqueous organopolysiloxane emulsions employed heretofore as bladder lubricants in manufacturing tires have several disadvantages. For example, the preformulated aqueous organopolysiloxane emulsions have stability problems, such as ingredient settling, compaction and/or degradation during storage and/or during transportation, or upon inordinate temperature changes, such as freeze-thaw cycles. 
     In addition, many of the compositions, particularly those with hydroxyl-containing organopolysiloxanes and methylhydrogenpolysiloxane fluids have a tendency to crosslink. When the crosslink density increases the number of releases also increases; however, an increase in crosslinked density results in a reduction in lubricity. 
     In order to improve the lubricity and improve venting between the bladder and the inside of the tire, it has been necessary to either increase the amount of filler or increase the amount of silicone polymer present in the composition. When the amount of filler is increased, settling and compaction become a problem. 
     It has been found that the addition of mica, a small amount, for example, up to about one percent based on the weight of the emulsion, will enhance the lubricity of the crosslinked composition; however, when the compositions contain methylhydrogenpolysiloxanes, the composition may release hydrogen. Therefore, the addition of mica to a composition will compensate for increased crosslinked density by enhancing the lubricity of the composition. 
     Also, some of the organopolysiloxane compositions contain catalysts which have a tendency to accelerate the degradation of the resultant emulsion and release hydrogen as a by-product. 
     Furthermore, many of the aqueous organopolysiloxane compositions have to be applied to the bladder just prior to shaping the tire, otherwise good lubricity and release properties are not achieved. 
     As a result of this invention, it is now possible to prepare a composition having increased crosslinked density with improved lubricity. Also, it is possible to prepare aqueous organopolysiloxane emulsions which do not release hydrogen during storage. Moreover, the aqueous organopolysiloxane emulsions of this invention can be applied to the inside of a green tire carcass and allowed to stand overnight without affecting the release properties. Furthermore, the inside of a green tire carcass can be coated with the aqueous organopolysiloxane emulsions away from the press area and then transferred to the press area where they are molded. 
     Therefore, it is an object of the present invention to provide an aqueous organopolysiloxane composition which may be used as a bladder lubricant. Another object of the present invention is to provide a composition which is stable over a long period of time. Another object of the present invention is to provide an aqueous organopolysiloxane emulsion which will give numerous releases per application. Still another object of the present invention is to provide an aqueous organopolysiloxane emulsion having improved lubricity irregardless of the crosslinked density. A further object of the present invention is to provide a method for preparing a stable aqueous organopolysiloxane emulsion. Still a further object of the present invention is to provide an aqueous emulsion containing mica and an organohydrogenpolysiloxane which is stable over long periods of time. 
     SUMMARY OF THE INVENTION 
     The foregoing objects and others, which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing aqueous organopolysiloxane emulsions comprising (1) a hydroxyl-containing organopolysiloxane gum having a plasticity value of from 50 to 100, (2) an organohydrogenpolysiloxane having an average of at least 2 Si-bonded hydrogen atoms per molecule, (3) a lubricant having a melting range of from 25 to 80° C., (4) mica, (5) a thickening agent, (6) surfactant and (7) water. 
     The aqueous organopolysiloxane emulsions are preferably prepared by mixing the surfactant with sufficient water and acid to form a paste; then the lubricant and hydroxyl-terminated organopolysiloxane gum is added to the paste with mixing and then the methylhydrogenpolysiloxane fluid is added with continual mixing. To the resultant mixture is then added the remainder of the water, mica and sufficient ammonium hydroxide to increase the pH to a level of from 8 to 10. After mixing for a period of time, the thickening agent and sufficient acid is then added with agitation to reduce the pH to a range of from 4 to 6. After the emulsion has been thoroughly mixed, it is then preferably filtered. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The hydroxyl-containing organopolysiloxane gum may be represented by the formula ##STR1## where R, which may be the same or different represents monovalent hydrocarbon radicals or halogenated monovalent hydrocarbon radicals having from 1 to 18 carbon atoms and n is a number greater than 100. In the above formula, R represents alkyl radicals such as methyl, ethyl, propyl, butyl, octyl, dodecyl and octadecyl radicals; aryl radicals such as phenyl, diphenyl and naphthyl radicals; alkenyl radicals such as vinyl and allyl radicals; cycloalkyl radicals such as cyclobutyl, cyclopentyl and cyclohexyl radicals; alkaryl radicals such as tolyl, xylyl and ethylphenyl radicals; aralkyl radicals such as benzyl, alpha phenylethyl, beta phenylethyl and alpha phenylbutyl radicals and halosubstituted radicals described above. 
     The hydroxyl-containing organopolysiloxane gum may be a linear or branched chain compound having an average of from 1.9 to 2.1 organic radicals per silicon atom in which the hydroxyl groups are linked to the silicon atoms along the chain as well as in the terminal units. It is preferred that the organopolysiloxane gum have at least two Si-bonded hydroxyl groups per molecule. In addition to the R 2  SiO units shown above, the organopolysiloxane gum may also contain units which correspond to the following formulas 
     
         SiO.sub.4/2, RSiO.sub.3/2 and R.sub.3 SiO.sub.1/2, 
    
     where R is the same as above. These organopolysiloxane gums can be either homopolymeric or copolymeric materials containing 2 or more different siloxane units and the organic radicals attached to any one silicon atom can h=the same or different. Mixtures of polymers can, of course, also be used, if desired. Preferably, at least 75 molar percent of the silicon atoms present in the organopolysiloxane gum are substituted with alkyl radicals, among which the methyl radicals are preferred. Other organic radicals which may be present are preferably vinyl and/or phenyl radicals. Generally, these gums will have an R/Si ratio of from about 1.9 to 2.1 organic groups per silicon atom and a plasticity value of from 50 to about 100 millimeters as measured by the parallel plate plastometer test described in A.S.T.M. Test D-926-67. 
     The organohydrogenpolysiloxanes employed in the emulsions of this invention generally consist of units of the formula ##STR2## where R&#39; represents hydrogen, a monovalent hydrocarbon radical or a halogenated monovalent hydrocarbon radical having from 1 to 18 carbon atoms in which at least 2 and preferably 3 Si-bonded hydrogen atoms are present per molecule and m is 1, 2 or 3. Preferred organohydrogenpolysiloxanes are those consisting of R&#39;SiO units, R&#39; 2  SiO units and R&#39; 3  SiO 0 .5 units in which R&#39; is the same as aboe and an Si-bonded hydrogen atom is present for each 3 to 100 silicon atoms. It is preferred that the organohydrogenpolysiloxanes have a viscosity of from about 5 to 100 mPa.s and more preferably from about 30 to 80 mPa.s at 25° C. 
     The organohydrogenpolysiloxanes may also contain monovalent hydrocarbon radicals having aliphatic unsaturation as well as Si-bonded hydrogen atoms in the same molecule. 
     It is preferred that the monovalent hydrocarbon radicals represented by R&#39; each contain from 1 to 18 carbon atoms. Examples of suitable hydrocarbon radicals are alkyl radicals such as the methyl, ethyl, n-propyl, isopropyl radicals as well as the octadecyl radicals; cycloalkyl radicals such as the cyclohexyl and cycloheptyl radicals; aryl radicals such as the phenyl radical; alkaryl radicals such as the tolyl radicals and aralkyl radicals such as the benzyl and the beta phenylethyl radicals. Examples of substituted hydrocarbon radicals represented by R&#39; are halogenated hydrocarbon radicals such as the 3,3-trifluoropropyl radical and the ortho-, para- and meta-chlorophenyl radicals. Because of their availability, it is preferred that at least 50 percent of the R&#39; radicals which do not contain Si-bonded hydrogen atoms be methyl radicals. 
     Examples of suitable lubricants which may be employed in the aqueous emulsions of this invention are waxes and esters of higher fatty acids, which have a melting range of from 25 to 80° C., and more preferably from about 30 to 70° C. Preferred examples of suitable fatty acid esters and waxes are lanolin, beeswax, spermaceti, Japan wax, bayberry, citrus peel oils, sugar cane wax, candelillia and synthetic waxes such as carbowax. 
     The aqueous emulsions of this invention also contain mica, which preferably has a particle size of from about 100 to 600, and more preferably from about 160 to 400 mesh. Mica not only imparts lubricity and release properties to these emulsions, but also provides channels through which entrapped air can escape. 
     Examples of suitable surfactants which may be employed in the aqueous emulsions of this invention are anionic, cationic and nonionic surfactants such as alkyl or aryl polyglycol ethers or alkylphenyls such as polyoxyethylene alkyl phenyls, polyoxyethylene sorbitan hexastearate, polyoxyethylene isotridecyl ether, trimethylnonyl ether of polyethylene glycol containing from 6 to 15 ethylene oxide units per molecule, polyoxyethylene sorbitan oleate having a saponification number of from 102 to 108 and a hydroxyl number of from 25 to 35. It is preferred that a mixture of nonionic surfactants, such as ethoxylated alkyl phenyls having varying chain lengths be employed. 
     Several thickening agents may be employed in the emulsions of this invention to aid in the stability of the emulsion. Examples of suitable thickening agents are magnesium aluminum silicate, water-soluble cellulose such as sodium carboxymethyl cellulose, sodium carboxymethyl hydroxy ethyl cellulose, hydroxy ethyl cellulose, methyl cellulose, methyl hydroxy propyl cellulose, ethyl hydroxy ethyl cellulose, methylethyl cellulose and methyl hydroxy ethyl cellulose. The thickening agent increases the viscosity of the emulsion, and stabilizes the emulsion over a pH range of from 3 to 11 and keeps the internal phase droplets suspended and separated. It also reduces the tendency of diluted emulsions to thin or break at room temperature, as well as at elevated temperatures. 
     The aqueous organopolysiloxane emulsions of this invention preferably contain from about 1 to 70 percent by weight based on the weight of the emulsion of an organopolysiloxane gum having Si-bonded hydroxyl groups and more preferablyfrom about 15 to 55 percent by weight of an organopolysiloxane gum having Si-bonded terminal hydroxyl groups. The amount of organohydrogenpolysiloxane fluid may range from about 0.1 up to about 25 percent by weight and more preferably from about 0.2 to about 10 percent by weight. It has been found that the ratio of organohydrogenpolysiloxane fluid to hydroxyl-terminated organopolysiloxane gum is critical and the higher the ratio the greater the number of releases per application. However, when the amount of the organopolysiloxane gum exceeds about 70 percent by weight or the amount of organohydrogenpolysiloxane exceeds about 25 percent by weight, then there is a substantial decrease in the stability as well as the release properties of the resultant emulsion. The amount of lubricant may range from about 0.05 up to about 40 percent by weight and more preferably from about 0.3 up to about 20 percent by weight, based on the total weight of the aqueous emulsion. 
     The amount of mica added to the aqueous emulsion may range from about 0.1 to about 20 percent by weight and more preferably from about 0.3 to 10 percent by weight, based on the weight of the aqueous emulsion. When the amount of mica exceeds more than about 25 percent by weight, it has a tendency to settle out of the emulsion. Generally, the surfactant will range from about 1 to about 10 percent by weight and more preferably from about 2 to 8 percent by weight, based on the weight of the organopolysiloxane emulsion. It is preferred that two or more nonionic surfactants be employed in order to obtain optimum stability of the emulsion. 
     The amount of thickening agent employed in the aqueous organopolysiloxane emulsions may range from about 2 to 12 percent by weight and more preferably from about 4 to 8 percent, based on the weight of the aqueous organopolysiloxane emulsion. The amount of water will generally range from about 10 to about 90 percent by weight and more preferably from about 25 to 85 percent by weight, based on the weight of the aqueous organopolysiloxane emulsion. 
     The lubricity of the aqueous emulsions of this invention may be further enhanced by the addition of polyalkylene glycols; however, it has been found that the addition of polyalkylene glycols reduces the number of releases per application. 
     Polyalkylene glycols which may be incorporated in the silicone emulsions are those having the general formula 
     
         HO(R&#34;O).sub.x H 
    
     where R&#34; is an alkylene radical having from 1 to 4 carbon atoms, x is a number of from 1 to 300 and has a melting point in the range of from 0 to 80° C. 
     Suitable examples of radicals represented by R&#34; are methylene, ethylene, propylene, butylene radicals and mixtures thereof. 
     Specific examples of polyalkylene glycols are polyethylene glycols, polypropylene glycols, polybutylene glycols, poly(ethyleneoxy-propylene)glycols, poly(ethyleneoxy-butylene) glycols and poly (propyleneoxy-butylene) glycols. 
     The amount of polyalkylene glycols which may be added to the organopolysiloxane emulsions of this invention may range from about 0 to 15 percent and more preferably from 0.5 to 10 percent by weight based on the weight of the organopolysiloxane emulsion. 
     Other ingredients which may be added to the organopolysiloxane emulsions are low molecular weight organopolysiloxanes having a viscosity of from about 5 to 60,000 mPa.s at 25° C. and more preferably from about 10 to 10,000 mPa.s at 5° C. 
     These organopolysiloxanes may be represented by the formula ##STR3## where R is the same as above and y has an average value of from 1.9 to 2.1. The organopolysiloxanes preferably have from about 1.9 to 2.1 organic radicals per silicon atom. In addition to the R 2  SiO units, the organopolysiloxanes may contain RSO 3/2 , R 3  SiO 1/2  and SiO 4/2  units in minor amounts, where R is the same as above. 
     Examples of suitable organopolysiloxane fluids are trihydrocarbonsilyl-endblocked polydiorganosiloxanes such as trimethylsilyl-endblocked polydimethylsiloxanes, triethyl silyl-endblocked polydiethylsiloxanes and copolymers having dimethylsiloxane units, diphenylsiloxane units or methylphenyl and dimethylsiloxane units. Preferably, the organopolysiloxanes are trimethylsilyl-endblocked polydimethylsiloxanes. These organopolysiloxanes are well known in the art and consist predominately of diorganosiloxane units (R 2  SiO). 
     The amount of low molecular weight organopolysiloxane fluids which may be incorporated in the emulsions of this invention may range from about 0 to 35 percent and more preferably from about 2 to 25 percent by weight based on the weight of the organopolysiloxane emulsion. 
     Ingredients such as antifoams and preservatives, e.g., bactericides may be added to these organopolysiloxane emulsions. The amount of antifoam will generally range from about 0 to 0.7 weight percent, based on the weight of the organopolysiloxane emulsion. Generally, from about 0 to about 0.3 weight percent of bactericide may be employed in these emulsions. More preferably though, the amount of bactericide will range from about 0.05 to about 0.2 weight percent, based on the weight of the aqueous emulsion. Other additives which may be included in the aqueous emulsions of this invention are rust inhibitors such as sodium nitrite, sodium nitrate and coloring agents and the like, which can be added in minor amounts to the emulsions of this invention. 
     Although the aqueous organopolysiloxane emulsions of this invention may be prepared, for example, in a mechanical mixing apparatus, it is preferred that the nonionic surfactant and acid be mixed in a mechanical mixer with sufficient water to form a paste or grease-like composition. After the grease or paste-like composition has been formed, the lubricant is then mixed in a mechanical mixing apparatus with the paste, then the hydroxyl-terminated gum is added slowly with mixing and then the methylhydrogenpolysiloxane fluid. The remainder of the water is then added slowly with mixing until the particle size of the micelles is below about 5 microns. The antifoam, bactericide and mica are added with sufficient base to increase the pH to a range of from 8 to 10. The mixture is then mixed for a period of time in order to form a pre-polymer and then the thickening agent and sufficient acid is added to reduce the pH to a range of from 4 to 6. After mixing for a period of time, the resultant oil-in-water emulsion is then filtered. 
     In adjusting the pH of the emulsion to a range of from 8 to 10, any basic material may be added to the mixture. Examples of suitable bases which may be employed are alkali metal hydroxides, alkaline earth metal hydroxides and ammonium hydroxide. Specific examples of alkali metal hydroxides are sodium hydroxide and potassium hydroxide. Other bases which may be employed are alkali and alkaline earth metal carbonates, such as sodium carbonate, calcium carbonate, sodium bicarbonate and sodium metasilicate as well as ammonia and ammonium hydroxide. 
     Examples of suitable acids which may be employed in the aqueous emulsions of this invention are inorganic as well as organic acids. Specific examples of inorganic acids which may be employed are hydrochloric acid, orthophosphoric acid, and sulfuric acid. Examples of organic acids which may be employed are oxalic acid, tartaric acid, maleic acid, citric acid, formic acid, lactic acid, acetic acid and benzoic acid. 
     The aqueous organopolysiloxane emulsions of this invention may be used as bladder lubricants in manufacturing rubber tires in which a green tire is placed in a tire mold and the bladder is coated with the silicone emulsion of this invention. The mold is closed and the bladder expanded by application of internal pressure to force the tire outward against the mold surface to shape and cure the tire. The mold is then opened and the bladder collapsed and the shaped and cured tire is removed from the mold. 
     In addition to applying the aqueous silicone emulsions of this invention to the expandable bladder, these emulsions may be applied to the inside of a green tire carcass and then inserted in the mold. 
     It has been observed that when the silicone emulsions of this invention have been applied to the outersurface of an expandable bladder, that from 30 to 40 tires could be molded with one application of the emulsion. In the following examples, all parts and percentages are by weight unless otherwise specified. 
    
    
     EXAMPLE 1 
     An aqueous silicone emulsion is prepared by adding 0.5 parts of glacial acetic acid to a mixer containing 58 parts of water and 56 parts of a poly(ethyleneoxide) alkyl phenol having an HLB of 15 (Igepal® DM-730, available from General Aniline and Film Corporation) and 19 parts of a poly(ethyleneoxide) alkyl phenol having an HLB of 10.6  (Igepal® DM-530, available from General Aniline and Film Corporation) and then mixed in a mechanical mixer to form a paste or grease. To the resultant paste is added with mixing, 6.3 parts of lanolin, 450 parts of a hydroxy-terminated organopolysiloxane gum having a plasticity value of about 50 millimeters, 100 parts of a polydimethylsiloxane having a viscosity of about 1000 mPas. at 25° C., about 40 parts of a methylhydrogenpolysiloxane fluid having an average of at least three Si-bonded hydrogen atoms per molecule and a viscosity of about 30 mPa.s at 25° C. and about 245 parts of water. 
     About 5.0 parts of a 10 percent silicone antifoam emulsion having a viscosity of 3000 cps at 25° C. (available as SWS-214 from SWS Silicones Corporation), 1.5 parts of a bactericide, 10 parts of mica (325 mesh) and 1.0 part of ammonium hydroxide (28 percent ammonia in water) are added to the resultant oil-in-water emulsion. The emulsion is mixed for about 2 hours at room temperature, then about 90.0 parts of a thickening agent containing about 1.5 percent by weight of Carbopol® A-941 containing acrylic acid polymers having a molecular weight of about 1,250,000 (available from B. F. Goodrich Chemical Company) and sufficient acetic acid are added to the oil-in-water emulsion with mixing to provide a pH of from 4 to 6. The resultant emulsion is filtered, then diluted 1:1 with water and sprayed onto the outer surface of a bladder and the coated bladder inserted inside a green tire carcass in a mold. The mold is closed and the bladder is expanded against the inside surface of the tire, which in turn presses the outer surface of the tire against the mold. After the tire is shaped and cured, the bladder is collapsed and the tire removed therefrom. It has been observed that from 30 to 40 tires could be molded with one application of the emulsion to the flexible bladder. 
     EXAMPLE 2 
     A silicone emulsion is prepared in accordance with the procedure of Example 1, except that 40 parts of a hydroxyl-terminated organopolysiloxane gum having a plasticity value of 80 are substituted for the 450 parts of a hydroxyl-terminated organopolysiloxane gum and 6 parts of a methylhydrogenpolysiloxane fluid having a viscosity of 30 mPa.s at 25° C. are substituted for the 40 parts of methylhydrogenpolysiloxane fluid and 750 parts of water are substituted for the 303 parts of water. In addition, 12.5 parts of mica are substituted for the 10 parts of mica. The resultant silicone emulsion exhibits good stability and exhibits excellent release properties when applied to the bladder or the inside of a green tire carcass and then molded into a tire. 
     EXAMPLE 3 
     The procedure of Example 1 is repeated, except that 200 parts of a hydroxyl-terminated organopolysiloxane gum having a plasticity value of 80 are substituted for the 450 parts of hydroxyl-terminated organopolysiloxane gum and 6 parts of the methylhydrogenpolysiloxane fluid having a viscosity of 30 mPa.s at 25° C. are substituted for the 40 parts of methylhydrogenpolysiloxane fluid and 1000 parts of water are substituted for the 303 parts of water. The resultant emulsion exhibits good stability and exhibits excellent release properties when applied to the bladder or the inside of a green tire carcass and then molded into a tire. 
     EXAMPLE 4 
     The procedure of Example 1 is repeated, except that 275 parts of a hydroxyl-terminated organopolysiloxane gum are substituted for the 450 parts of hydroxyl-terminated organopolysiloxane gum and 15 parts of methylhydrogenpolysiloxane fluid are substituted for the 40 parts of methylhydrogenpolysiloxane fluid and 381 parts of water are substituted for the 303 parts of water. The resultant emulsion exhibits good stability at room temperature and exhibits excellent release properties when applied to the bladder or the inside of a green tire carcass and then molded into a tire. 
     EXAMPLE 5 
     The procedure of Example 1 is repeated, except that 430 parts of a hydroxyl-terminated organopolysiloxane gum are substituted for 450 parts of hydroxyl-terminated organopolysiloxane gum and 20 parts of lanolin are substituted for the 6.3 parts of lanolin. In addition, 200 parts of a dimethylpolysiloxane fluid having a viscosity of 1000 mPa.s at 25° C. are substituted for 100 parts of the dimethylpolysiloxane fluid having a viscosity of 1000 mPa.s at 25° C. The resultant emulsion exhibits good stability at room temperature and exhibits excellent release properties when applied to the bladder in the molding of a tire. 
     EXAMPLE 6 
     The procedure of Example 1 is repeated, except that 6.3 parts of spermaceti are substituted for the lanolin. The resultant emulsion exhibits good stability at room temperature and exhibits excellent release properties when applied to the bladder or the inside of a green tire carcass and then molded into a tire. 
     EXAMPLE 7 
     The procedure of Example 1 is repeated, except that 6.3 parts of a polyethylene glycol having a melting point below 80° C., 200 parts of a dimethylpolysiloxane fluid having a viscosity of 1000 mPa.s at 25° C. and 30 parts of mica are added to the composition. The resultant emulsion exhibits good lubricity and good stability at room temperature, but the number of releases is about 10 when applied to the bladder in molding tires. 
     EXAMPLE 8 
     The procedure of Example 1 is repeated, except that 450 parts of a hydroxyl-terminated organopolysiloxane gum having a plasticity value of about 120 are substituted for the hydroxyl-terminated organopolysiloxane gum having a plasticity value of 50 and 7.5 parts of mica are substituted for the 10 parts of mica. The resultant emulsion begins to &#34;break&#34; after a period of time. 
     EXAMPLE 9 
     The procedure of Example 1 is repeated, except that 93.3 parts of sodium carboxymethyl cellulose are substituted for the Carbopol. The resultant emulsion exhibits good storage stability and excellent release properties when applied to the bladder or the inside of a green tire carcass and then molded to form a tire.