Release agent for tire bladder, tire bladder, and pneumatic tire

Abstract

A release agent for being coated onto a tire bladder made of a zinc-oxide-incorporated butyl rubber during pneumatic-tire molding, the release agent containing (A) organopolysiloxane, which contains a carboxy group indicated by the general formula (1) below ##STR00001##
(in the formula, R.sup.1 is a substituted or unsubstituted C1-C30 monovalent hydrocarbon group excluding R.sup.2, R.sup.2 is a carboxy-group-substituted C1-C30 monovalent organic group, R.sup.3 is R.sup.1 or R.sup.2, and n is an integer of 3 to 2000.). This release agent produces a longer service life of a tire bladder and leads to reduced tire production cost because the amount of silicone that migrates to the tire side is low when the tire is released, and repeated mold-release performance is enhanced.

Claims

1. A release agent for application to a tire bladder made of zinc oxide-containing butyl rubber when molding pneumatic tires, which release agent is an aqueous emulsion composition comprising: (A) 100 parts by weight of a carboxyl group-containing organopolysiloxane of general formula (1) ##STR00011## wherein R.sup.1 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 30 carbon atoms other than R.sup.2, R.sup.2 is a carboxyl group-substituted monovalent organic group of 1 to 30 carbon atoms, R.sup.3 is R.sup.1 or R.sup.2, and n is an integer from 3 to 2,000, (B) from 1 to 30 parts by weight of a surfactant, and (C) from 30 to 10,000 parts by weight of water.

2. A method of producing a tire bladder for molding pneumatic tires, comprising the step of applying the release agent of the composition of claim 1 to a tire bladder surface made of zinc oxide-containing butyl rubber and subsequently heating at a temperature of between 80 and 250 C.

3. The release agent for a tire bladder of claim 1, which further comprises a water-soluble polymer in an amount of 0.1 to 10 parts by weight per 100 parts by weight of component (C).

4. The release agent for a tire bladder of claim 1, which further comprises an inorganic powder selected from among calcium carbonate, magnesium carbonate, kaolin, clay, talc, mica, sericite and carbon black.

5. The release agent for a tire bladder of claim 1, wherein R.sup.2 in formula (1) is the carboxyl group-substituted monovalent organic group of the following formula (2) or (3): ##STR00012## wherein R.sup.4 and R.sup.5 each are a divalent hydrocarbon group.

6. The release agent for a tire bladder of claim 1, wherein component (A) is a mixture of an organopolysiloxane having a carboxyl group at one end of the molecular chain and an organopolysiloxane having carboxyl groups at both ends of the molecular chain.

7. The release agent for a tire bladder of claim 1, which further comprises an organopolysiloxane without carboxyl groups together with component (A).

8. The release agent for a tire bladder of claim 7, wherein the organopolysiloxane without carboxyl groups is selected from among a dimethylpolysiloxane and a polysiloxane obtained by substituting some of the methyl groups on the dimethylpolysiloxane with monovalent hydrocarbon groups substituted with halogen atoms and/or substituents selected from among acryloyloxy, methacryloyloxy, epoxy, amino and mercapto groups.

9. A method of claim 2, wherein the application is carried out such that the amount of the organopolysiloxane of component (A) becomes 0.5 to 20 g/m.sup.2.

10. A method of molding a pneumatic tire, comprising the step of placing a green tire in a mold, inserting the tire bladder obtained by a method of claim 2 or 9 in the inside of the green tire, introducing into the interior of the tire bladder a high-temperature, high-pressure gas so that the green tire is pressed against the mold, molding, and curing the tire.

11. The release agent for a tire bladder of claim 1, wherein the carboxyl group-containing organopolysiloxane of general formula (1) in component (A) includes: (A-1) a carboxyl group-containing organopolysiloxane wherein n is an integer of 3 or more and less than 150, and (A-2) a carboxyl group-containing organopolysiloxane wherein n is an integer of 150 or more and not more than 2,000.

12. The release agent for a tire bladder of claim 11, wherein the blending ratio of components (A-1) and (A-2), expressed by weight, is from 95:5 to 10:90.

Description

EMBODIMENT FOR CARRYING OUT THE INVENTION

(1) The invention is described more fully below.

(2) In a first aspect of the invention, a release agent for a tire bladder made of zinc oxide-containing butyl rubber for use in molding pneumatic tires includes (A) an organopolysiloxane having a carboxyl group at an end of the molecular chain.

(3) The organopolysiloxane having a carboxyl group at an end of the molecular chain serving as component (A) has general formula (1) below.

(4) ##STR00003##

(5) In the formula, R.sup.1 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 30 carbon atoms other than R.sup.2. The number of carbon atoms on R.sup.1 is preferably from 1 to 20, and more preferably from 1 to 6. Illustrative examples of R.sup.1 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl and triacontyl groups; aryl groups such as phenyl, tolyl and naphthyl groups; aralkyl groups such as benzyl and phenethyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl groups; and monovalent hydrocarbon groups in which some or all hydrogen atoms bonded to carbon atoms on the foregoing groups are substituted with atoms such as halogen atoms (fluorine, chlorine, bromine or iodine atoms) and/or substituents such as acryloyloxy, methacryloyloxy, epoxy, amino and mercapto groups.

(6) R.sup.2 in formula (1) is a carboxyl group-substituted monovalent organic group of 1 to 30 carbon atoms. The number of carbon atoms on R.sup.2 is preferably from 2 to 20, and more preferably from 2 to 15. R.sup.2 is exemplified by monovalent organic groups of formulas (2) and (3) below.

(7) ##STR00004##

(8) R.sup.4 and R.sup.5 in these formulas are divalent hydrocarbon groups. Illustrative examples include alkylene groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, undecylene, dodecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene, henicosylene, docosylene, tricosylene and tetracosylene groups; arylene groups such as the p-phenylene group; and also alkylene-arylene groups in which an alkylene group and an arylene group are bonded together.

(9) R.sup.3 in general formula (1) is R.sup.1 or R.sup.2. The organopolysiloxane of component (A) may be a mixture of an organopolysiloxane having a carboxyl group at one end of the molecular chain that is R.sup.1 and an organopolysiloxane having carboxyl groups at both ends of the molecular chain that is R.sup.2.

(10) The subscript n in general formula (1) is an integer from 3 to 2,000. A composition that includes (A-1) a carboxyl group-containing organopolysiloxane in which n is an integer of 3 or more and less than 150, and (A-2) a carboxyl group-containing organopolysiloxane in which n is an integer of 150 or more and not more than 2,000 is preferred.

(11) The organopolysiloxane of component (A-1) necessarily has a low carboxyl equivalent weight, and moreover has a low viscosity. When the amount of carboxyl groups is low, the reactivity with the zinc oxide included within the tire bladder decreases. When the amount of carboxyl groups is high, the tire bladder wettability by the organopolysiloxane decreases. The subscript n in component (A-1) is an integer of preferably from 5 to 100.

(12) The organopolysiloxane of component (A-2) necessarily has a high carboxyl equivalent weight, and moreover has a high viscosity. This organopolysiloxane (A-2) acts to increase the tire bladder wettability by the carboxyl group-containing organopolysiloxane. The amount of adhesion to the tire bladder increases when the organopolysiloxane (A-1) having numerous carboxyl groups is used together with organopolysiloxane (A-2) relative to the use of organopolysiloxane (A-1) alone. Moreover, the slip properties with respect to the tire when the tire bladder is stripped from the tire increases. At a low viscosity, the wettability improving action and the slip properties decrease; when the viscosity is too high, the amount of carboxyl groups becomes low and so reactivity with the zinc oxide included in the tire bladder declines. The subscript n is preferably an integer from 200 to 1,500.

(13) No limitation is imposed on the blending ratio between the organopolysiloxane of component (A-1) and the organopolysiloxane of component (A-2). However, expressed in terms of the weight ratio, the blending ratio is preferably between 95:5 and 10:90, and more preferably between 85:15 and 20:80.

(14) An organopolysiloxane without carboxyl groups may be used together with the organopolysiloxane having a carboxyl group on the end of the molecular chain of component (A). Examples of organopolysiloxanes without a carboxyl group include dimethylpolysiloxanes and polysiloxanes obtained by substituting some of the methyl groups on a dimethylpolysiloxane with monovalent hydrocarbon groups substituted with halogen atoms (fluorine, chlorine, bromine or iodine atoms) and/or substituents such as acryloyloxy, methacryloyloxy, epoxy, amino and mercapto groups.

(15) In the first aspect of the invention above, the organopolysiloxane having a carboxyl group at an end of the molecular chain of component (A) may be dissolved in a volatile organic solvent. The organic solvent is an ingredient included so as to increase the coatability onto the tire bladder and adjust the coating amount and viscosity. Any amount of an organic solvent that can dissolve the organopolysiloxane of component (A), such as, for example, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, ethanol, isopropyl alcohol, hexane or heptane, may be used.

(16) The release agent for use on a tire bladder made of zinc oxide-containing butyl rubber when molding pneumatic tires of the second aspect of the invention is a composition that is an aqueous emulsion of component (A), and contains component (A), (B) a surfactant, and (C) water.

(17) The surfactant serving as component (B) is not limited as to the type thereof, and may be a nonionic surfactant, an anionic surfactant, a cationic surfactant or an amphoteric surfactant. Moreover, one surfactant may be used alone or two or more may be used together.

(18) Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglyceryl fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes and polyoxyethylene polyoxypropylene-modified organopolysiloxanes.

(19) Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, sulfates of fatty acid alkylolamides, alkylbenzenesulfonates, polyoxyethylene alkylphenyl ether sulfonates, -olefin sulfonates, -sulfo fatty acid esters, alkylnaphthalenesulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyltaurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acylamino acid salts, monoalkyl phosphates, dialkyl phosphates and polyoxyethylene alkyl ether phosphates.

(20) Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylene alkyldimethylammonium salts, dipolyoxyethylene alkylmethylammonium salts, tripolyoxyethylene alkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts and monoalkylamide amine salts.

(21) Examples of amphoteric surfactants include alkyl dimethyl amine oxides, alkyl dimethyl carboxybetaines, alkylamide propyl dimethyl carboxybetaines, alkyl hydroxysulfobetaines and alkyl carboxymethyl hydroxyethyl imidazolinium betaines.

(22) When a nonionic surfactant is used as the surfactant of component (B), the hydrophilic-lipophilic balance (HLB) value thereof is preferably from 11 to 17. At an HLB value lower than 11 or higher than 17, emulsification of component (A) may not be possible, or it becomes difficult to obtain an emulsion having good stability. The HLB value in this invention is the value calculated by the Griffin formula expressed as follows.
HLB=[molecular weight of polyoxyethylene moiety/molecular weight of polyoxyethylene alkyl ether]20
When a combination of two or more nonionic surfactants of differing HLB values is used, the above HLB value becomes the weight-averaged value of these.

(23) The amount of component (B) is from 1 to 30 parts by weight, and preferably from 5 to 15 parts by weight, per 100 parts by weight of component (A). At less than 1 part by weight, it is difficult to obtain an emulsion of good stability; at more than 30 parts by weight, further improvement in the emulsion stability is unlikely.

(24) The amount of water serving as component (C) is from 30 to 10,000 parts by weight per 100 parts by weight of component (A). At less than 30 parts by weight, the viscosity of the emulsion becomes high, making application to a tire bladder difficult. At more than 10,000 parts by weight, the coating amount of component (A) on the tire bladder becomes low, resulting in a decline in the release properties. The amount of component (C) should be such as to set the coating amount of component (A) on the tire bladder to the desired amount.

(25) Emulsification of component (A) may be carried out using an ordinary emulsifying disperser. Examples of such emulsifying dispersers include high-speed rotary centrifugal radiation-type stirrers such as homogenizing dispersers, high-speed rotary shear-type stirrers such as homogenizing mixers, high-pressure jet-type emulsifying dispersers such as homogenizers, colloid mills and ultrasonic emulsifiers.

(26) A water-soluble polymer may be included in the aqueous emulsion of the invention for such purposes as to adjust the coating amount on the tire bladder, prevent dripping during application and improve wettability. The water-soluble polymer, which is not particularly limited, is exemplified by nonionic water-soluble polymers, anionic water-soluble polymers, cationic water-soluble polymers and amphoteric water-soluble polymers. Examples of nonionic water-soluble polymers include copolymers of vinyl alcohol and vinyl acetate, polymers of acrylamide, polymers of vinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, polyethylene glycol, polymers of isopropyl acrylamide, polymers of methyl vinyl ether, starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum and xanthan gum. Examples of anionic water-soluble polymers include polymers of sodium acrylate, copolymers of sodium acrylate and sodium maleate, copolymers of sodium acrylate and acrylamide, polymers of sodium styrene sulfonate, copolymers of sodium polyisoprene sulfonate and styrene, polymers of sodium naphthalene sulfonate, carboxymethyl starch, starch phosphate, carboxymethylcellulose, sodium alginate, gum arabic, carrageenan, sodium chondroitin sulfate and sodium hyaluronate. Examples of cationic water-soluble polymers include polymers of dimethyldiallylammonium chloride, polymers of vinylimidazoline, polymers of methylvinylimidazolinium chloride, polymers of acryloylethyltrimethylammonium chloride, polymers of methacryloylethyltrimethylammonium chloride, polymers of acrylamide propyl trimethylammonium chloride, polymers of methacrylamide propyl trimethylammonium chloride, epichlorohydrin/dimethylamine polymers, polymers of ethyleneimine, quaternized polymers of ethyleneimine, polymers of allylamine hydrochloride, polylysine, cationic starch, cationized cellulose, chitosan and derivatives of these obtained by, for example, copolymerizing these with a monomer having a nonionic group or an anionic group. Examples of amphoteric water-soluble polymers include copolymers of acryloylethyltrimethylammonium chloride with acrylic acid and acrylamide, copolymers of methacryloylethyltrimethylammonium chloride with acrylic acid and acrylamide, and products of the Hoffman degradation of acrylamide polymers.

(27) When these water-soluble polymers are included, the content thereof is preferably from 0.1 to 10 parts by weight per 100 parts by weight of component (C).

(28) In addition, wetting agents, defoamers and preservatives may be included in the aqueous emulsion of the invention.

(29) In order to increase the slip properties with the tire when the tire bladder is stripped from the molded tire, the release agent of the invention may also include an inorganic powder such as calcium carbonate, magnesium carbonate, kaolin, clay, talc, mica, sericite or carbon black.

(30) In the practice of this invention, the release agent of the first aspect or the release agent of the second aspect is applied to a tire bladder.

(31) The tire bladder used in the invention is made of a composition which is composed primarily of butyl rubber and preferably includes halogenated butyl rubber and/or chloroprene. The butyl rubber composition must contain zinc oxide. Zinc oxide reacts with the carboxyl groups on the organopolysiloxane having carboxyl groups at the ends of the molecular chain that serves as component (A), resulting in better adhesion of the organopolysiloxane to the tire bladder surface and improved repetitive releasability.

(32) In addition to the above rubber ingredients, fillers such as carbon black, resins, castor oil, and vulcanization accelerators may be suitably included according to the intended purpose. Zinc oxide is included in an amount of preferably 0.1 to 10 parts by weight, and more preferably 3 to 5 parts by weight, per 100 parts by weight of the rubber ingredients.

(33) The release agent of the first aspect of the invention or the release agent of the second aspect of the invention is applied to the tire bladder surface by a method such as spraying, dipping or brush coating, following which it is heated for a period of from several tens of minutes to several hours at a temperature of between 80 C. and 250 C. When the heating temperature is low, the reactivity of the organopolysiloxane of component (A) with zinc oxide decreases. When the temperature is high, the tire bladder deteriorates. The heating temperature is preferably between 100 C. and 200 C.

(34) The coating amount of the release agent is not particularly limited, although application is preferably carried out such that the amount of the organopolysiloxane of component (A) becomes 0.5 to 20 g/m.sup.2, and especially 1.0 to 10 g/m.sup.2.

(35) This invention uses a tire bladder that has been coated in this way with a release agent to mold pneumatic tires. A green tire is placed in a mold, the tire bladder coated with release agent is inserted on the inside of the tire, the green tire is pressed against the mold by introducing into the interior of the tire bladder a high-temperature, high-pressure gas, such as 150 to 200 C. steam having a pressure of about 1 to 3 MPa, and molding and curing of the tire, which takes from several minutes to several hours, is carried out. The bladder and the molded and cured tire are then taken out of the mold. A green tire is again placed in the mold, the tire bladder is inserted on the inside of the tire, and the same operations are repeated.

EXAMPLES

(36) The invention is illustrated more fully below by way of Working Examples and Comparative Examples, although these Examples are not intended to limit the invention. In the following Examples, unless noted otherwise, all references to percent (%) are by weight.

(37) [Evaluation of Adherence to Zinc Oxide-Containing Butyl Rubber]

(38) Gauze impregnated with organopolysiloxane or organopolysiloxane emulsion was used to apply organopolysiloxane or organopolysiloxane emulsion to a 2 mm thick sheet of butyl rubber formulated with zinc oxide, following which the rubber sheet was placed in a thermostatic chamber set to 150 C. and heated for 50 minutes. The rubber sheet was then immersed for 10 minutes in 1-butanol, in addition to which the side of the sheet to which organopolysiloxane or organopolysiloxane emulsion had been applied was wiped with a 1-butanol-impregnated gauze. After 24 hours of air drying, the amount of organopolysiloxane remaining on the butyl rubber sheet was measured using a fluorescence x-ray spectrometer.

(39) [Test of Tire Bladder Releasability]

(40) A test piece obtained by applying organopolysiloxane or organopolysiloxane emulsion to slab rubber (cured) from a cured bladder and then rinsing the rubber with butanol was laminated to a tire inner liner (uncured) and repeatedly press-cured at 190 C. for 15 minutes. The force when pulling these apart after carrying out the above operation ten or more times was determined.

(41) ##STR00005##

Working Example 1

(42) The organopolysiloxane of average formula (4) below having carboxyl groups at both ends of the molecular chain, a viscosity of 126 mm.sup.2/s and a carboxyl equivalent weight of 880 g/mol was furnished for use.

(43) An organopolysiloxane mixture which had a viscosity of 34,000 mm.sup.2/s and a carboxyl equivalent weight of 59,600 g/mol and was composed of the organopolysiloxane of average formula (5) below having a carboxyl group at one end of the molecular chain, the organopolysiloxane of average formula (6) below having carboxyl groups at both ends of the molecular chain and the dimethylpolysiloxane of average formula (7) below in the weight ratio 5:2.5:2.5 was furnished for use.

(44) The organopolysiloxane of average formula (4) in an amount of 300 g was mixed together with 200 g of the mixture of the organopolysiloxanes of average formulas (5), (6) and average formula (7). Using the resulting mixture, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

(45) ##STR00006##

Working Example 2

(46) An amount of 250 g of the organopolysiloxane of average formula (4) having carboxyl groups at both ends of the molecular chain, a viscosity of 126 mm.sup.2/s and a carboxyl equivalent weight of 880 g/mol was mixed with 250 g of the organopolysiloxane of average formula (6) below having carboxyl groups at both ends of the molecular chain, a viscosity of 66,700 mm.sup.2/s and a carboxyl equivalent weight of 27,200 g/mol. Using the resulting mixture, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

Working Example 3

(47) An organopolysiloxane mixture which had a viscosity of 60 mm.sup.2/s and a carboxyl equivalent weight of 1,440 g/mol and was composed of the organopolysiloxane of average formula (8) below having a carboxyl group at one end of the molecular chain, the organopolysiloxane of average formula (9) below having carboxyl groups at both ends of the molecular chain and the dimethylpolysiloxane of average formula (10) below in the weight ratio 5:2.5:2.5 was furnished for use.

(48) The organopolysiloxane of average formula (6) above having carboxyl groups at both ends of the molecular chain, a viscosity of 66,700 mm.sup.2/s and a carboxyl equivalent weight of 27,200 g/mol was furnished for use.

(49) The mixture of organopolysiloxanes of average formulas (8), (9) and (10) in an amount of 350 g and 150 g of the organopolysiloxane of average formula (6) were mixed together and dissolved. Using the resulting mixture, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

(50) ##STR00007##

Working Example 4

(51) A 300 mL glass beaker was charged with 60 g of the organopolysiloxane of average formula (4) having carboxyl groups at both ends of the molecular chain, a viscosity of 126 mm.sup.2/s and a carboxyl equivalent weight of 880 g/mol. To this was added 40 g of an organopolysiloxane mixture which had a viscosity of 34,000 mm.sup.2/s and a carboxyl equivalent weight of 59,600 g/mol and was composed of the organopolysiloxane of average formula (5) having a carboxyl group at one end of the molecular chain, the organopolysiloxane of average formula (6) having carboxyl groups at both ends of the molecular chain and the dimethylpolysiloxane of average formula (7) in the weight ratio 5:2.5:2.5. Using a homogenizing mixer, the beaker contents were mixed together at a speed of 2,000 rpm. Next, 9 g of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=8 moles (available from Kao Corporation under the trade name Emulgen 1108), 2 g of a 60% aqueous solution of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=50 moles (available from Kao Corporation under the trade name Emulgen 1150S-60) and 27 g of water were added. Using a homogenizing mixer, the beaker contents were stirred at a speed of 7,000 rpm, whereupon an oil-in-water system formed and an increase in viscosity was confirmed. Stirring was continued for another 15 minutes. Next, under stirring at 2,000 rpm, 112 g of water was added, after which the beaker contents were transferred to a 1-liter glass beaker, 750 g of a 2% aqueous solution of carboxymethylcellulose sodium (available from DKS Co., Ltd. under the trade name Cellogen F) was added and the system was stirred at 2,000 rpm, giving a white emulsion.

(52) Using the emulsion thus prepared, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

Working Example 5

(53) A 300 mL glass beaker was charged with 50 g of the organopolysiloxane of average formula (4) having carboxyl groups at both ends of the molecular chain, a viscosity of 126 mm.sup.2/s and a carboxyl equivalent weight of 880 g/mol, and 50 g of the organopolysiloxane of average formula (6) having carboxyl groups at both ends of the molecular chain, a viscosity of 66,700 mm.sup.2/s and a carboxyl equivalent weight of 27,200 g/mol. Using a homogenizing mixer, the beaker contents were mixed together at a speed of 2,000 rpm. Next, 9 g of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=8 mol (available from Kao Corporation under the trade name Emulgen 1108), 2 g of a 60% aqueous solution of a polyoxyethylene alkyl ether for which the number of molecules of ethylene oxide added=50 moles (available from Kao Corporation under the trade name Emulgen 1150S-60) and 27 g of water were added. Using a homogenizing mixer, the beaker contents were stirred at a speed of 7,000 rpm, whereupon an oil-in-water system formed and an increase in viscosity was confirmed. Stirring was continued for another 15 minutes. Next, under stirring at 2,000 rpm, 112 g of water was added, after which the beaker contents were transferred to a 1-liter glass beaker, 750 g of a 2% aqueous solution of carboxymethylcellulose sodium (available from DKS Co., Ltd. under the trade name Cellogen F) was added and the system was stirred at 2,000 rpm, giving a white emulsion.

(54) Using the emulsion thus prepared, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

Working Example 6

(55) A 300 mL glass beaker was charged with 60 g of the organopolysiloxane of average formula (4) having carboxyl groups at both ends of the molecular chain, a viscosity of 126 mm.sup.2/s and a carboxyl equivalent weight of 880 g/mol. To this was added 40 g of an organopolysiloxane mixture which had a viscosity of 34,000 mm.sup.2/s and a carboxyl equivalent weight of 59,600 g/mol and was composed of the organopolysiloxane of average formula (5) having a carboxyl group at one end of the molecular chain, the organopolysiloxane of average formula (6) having carboxyl groups at both ends of the molecular chain and the dimethylpolysiloxane of average formula (7) in the weight ratio 5:2.5:2.5. Using a homogenizing mixer, the beaker contents were mixed together at a speed of 2,000 rpm. Next, 9 g of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=8 moles (available from Kao Corporation under the trade name Emulgen 1108), 2 g of a 60% aqueous solution of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=50 moles (available from Kao Corporation under the trade name Emulgen 1150S-60) and 27 g of water were added. Using a homogenizing mixer, the beaker contents were stirred at a speed of 7,000 rpm, whereupon an oil-in-water system formed and an increase in viscosity was confirmed. Stirring was continued for another 15 minutes. Next, while stirring at 2,000 rpm, 112 g of water was added. The beaker contents were transferred to a 1-liter glass beaker, 5 g of an emulsion containing 42% of the dimethylpolysiloxane of average formula (13) below having a viscosity of 1,950,000 mm.sup.2/s and 745 g of a 2% aqueous solution of carboxymethylcellulose sodium (available from DKS Co., Ltd. under the trade name Cellogen F) were added, and the system was stirred at 2,000 rpm, giving a white emulsion.

(56) Using the emulsion thus prepared, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

(57) ##STR00008##

Working Example 7

(58) A 300 mL glass beaker was charged with 67.5 g of the organopolysiloxane of average formula (4) having carboxyl groups at both ends of the molecular chain, a viscosity of 126 mm.sup.2/s and a carboxyl equivalent weight of 880 g/mol. To this was added 22.5 g of an organopolysiloxane mixture which had a viscosity of 60 mm.sup.2/s and a carboxyl equivalent weight of 1,440 g/mol and was composed of the organopolysiloxane of average formula (8) having a carboxyl group at one end of the molecular chain, the organopolysiloxane of average formula (9) having carboxyl groups at both ends of the molecular chain and the dimethylpolysiloxane of average formula (10) in the weight ratio 5:2.5:2.5. To this was further added 10 g of the organopolysiloxane of average formula (14) having amino groups on side chains of the molecule, a viscosity of 55,100 mm.sup.2/s and an amino equivalent weight of 10,500 g/mol. Using a homogenizing mixer, the beaker contents were mixed together at a speed of 2,000 rpm. Next, 9 g of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=8 moles (available from Kao Corporation under the trade name Emulgen 1108), 2 g of a 60% aqueous solution of a polyoxyethylene alkyl ether having a number of moles of ethylene oxide added=50 moles (available from Kao Corporation under the trade name Emulgen 1150S-60) and 27 g of water were added. Using a homogenizing mixer, the beaker contents were stirred at a speed of 7,000 rpm, whereupon an oil-in-water system formed and an increase in viscosity was confirmed. Stirring was continued for another 15 minutes. Next, under stirring at 2,000 rpm, 112 g of water was added. The beaker contents were transferred to a 1-liter glass beaker, 320 g of a 2% aqueous solution of hydroxypropyl methylcellulose (available from Shin-Etsu Chemical Co., Ltd. under the trade name Metolose 90SH-100000) and 430 g of water were added, and the system was stirred at 2,000 rpm, giving a white emulsion.

(59) Using the emulsion thus prepared, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

(60) ##STR00009##

Working Example 8

(61) Mica (available from Shiraishi Calcium Kaisha, Ltd. under the trade name Takaramica M-101) in an amount of 5 g was added to 1,000 g of an emulsion obtained in the same way as in Working Example 4. Using a homogenizing mixer, the system was mixed for 5 minutes at a speed of 2,000 rpm.

(62) Using the emulsion thus prepared, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

Comparative Example 1

(63) An amount of 300 g of the dimethylpolysiloxane of average formula (11) having a viscosity of 101 mm.sup.2/s and 200 g of the dimethylpolysiloxane of average formula (12) having a viscosity of 30,200 mm.sup.2/s were mixed together and dissolved. Using this mixture, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

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Comparative Example 2

(65) A 300 mL glass beaker was charged with 60 g of the dimethylpolysiloxane of average formula (11) having a viscosity of 101 mm.sup.2/s and 40 g of the dimethylpolysiloxane of average formula (12) having a viscosity of 30,200 mm.sup.2/s. Using a homogenizing mixer, the beaker contents were mixed together at a speed of 2,000 rpm. Next, 9 g of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=8 moles (available from Kao Corporation under the trade name Emulgen 1108), 2 g of a 60% aqueous solution of a polyoxyethylene alkyl ether for which the number of moles of ethylene oxide added=50 moles (available from Kao Corporation under the trade name Emulgen 1150S-60) and 10 g of water were added. Using a homogenizing mixer, the beaker contents were stirred at a speed of 7,000 rpm, whereupon an oil-in-water system formed and an increase in viscosity was confirmed. The homogenizing mixer was changed to a homogenizing disperser and the system was stirred at a speed of 2,000 rpm for 15 minutes. Next, the stirrer was returned once again to a homogenizing mixer, 119 g of water was added and the system was stirred at 2,000 rpm. The contents were then transferred to a 1-liter glass bearer, 750 g of a 2% aqueous solution of carboxymethylcellulose sodium (available from DKS Co., Ltd. under the trade name Cellogen F) was added, and the system was stirred at 2,000 rpm, giving a white emulsion.

(66) Using the emulsion thus prepared, the evaluation of adherence to butyl rubber and the releasability test described above were carried out. The results are presented in Table 1.

(67) TABLE-US-00001 TABLE 1 Evaluation of adherence to Tire bladder bladder rubber (amount of releasability organopolysiloxane, g/m.sup.2) test Working Example 1 2.28 good Working Example 2 2.93 fair Working Example 3 1.90 good Working Example 4 1.67 good Working Example 5 2.25 fair Working Example 6 1.65 good Working Example 7 1.14 good Working Example 8 1.10 good Comparative Example 1 0.009 NG Comparative Example 2 0.004 NG

(68) Compared with the carboxyl group-lacking methylpolysiloxanes and emulsions thereof in Comparative Examples 1 and 2, the carboxyl group-containing organopolysiloxanes or organopolysiloxane mixtures containing the same, and emulsions thereof, in Working Examples 1 to 8, when applied to a butyl rubber sheet which was subsequently rinsed with butanol, resulted in a higher amount of polysiloxane remaining thereon and also better releasability

Working Example 9

(69) Toluene (700 g) was added to 300 g of the organopolysiloxane prepared in Working Example 1, and mixing and dissolution carried out. The resulting solution was applied with a spray to the surface of a tire bladder made of zinc oxide-containing butyl rubber, and subsequently heated at 150 C. for 50 minutes. Tire curing/molding was carried out using the resulting bladder, and the bladder life was evaluated. The results are shown in Table 2.

Working Example 10

(70) The emulsion prepared in Working Example 4 was applied with a spray to the surface of a tire bladder made of zinc oxide-containing butyl rubber, and subsequently heated at 150 C. for 50 minutes. Tire curing/molding was carried out using the resulting bladder, and the bladder life was evaluated. The results are shown in Table 2.

Working Example 11

(71) The emulsion prepared in Working Example 5 was applied with a spray to the surface of a tire bladder made of zinc oxide-containing butyl rubber, and subsequently heated at 150 C. for 50 minutes. Tire curing/molding was carried out using the resulting bladder, and the bladder life was evaluated. The results are shown in Table 2.

Working Example 12

(72) The emulsion prepared in Working Example 6 was applied with a spray to the surface of a tire bladder made of zinc oxide-containing butyl rubber, and subsequently heated at 150 C. for 50 minutes. Tire curing/molding was carried out using the resulting bladder, and the bladder life was evaluated. The results are shown in Table 2.

Working Example 13

(73) The emulsion prepared in Working Example 7 was applied with a spray to the surface of a tire bladder made of zinc oxide-containing butyl rubber, and subsequently heated at 150 C. for 50 minutes. Tire curing/molding was carried out using the resulting bladder, and the bladder life was evaluated. The results are shown in Table 2.

Working Example 14

(74) The emulsion prepared in Working Example 8 was applied with a spray to the surface of a tire bladder made of zinc oxide-containing butyl rubber, and subsequently heated at 150 C. for 50 minutes. Tire curing/molding was carried out using the resulting bladder, and the bladder life was evaluated. The results are shown in Table 2.

Comparative Example 3

(75) The emulsion prepared in Comparative Example 2 was applied with a spray to the surface of a tire bladder made of zinc oxide-containing butyl rubber, and subsequently heated at 150 C. for 50 minutes. Tire curing/molding was carried out using the resulting bladder, and the bladder life was evaluated. The results are shown in Table 2.

(76) TABLE-US-00002 TABLE 2 Working Working Working Working Working Working Example Example Example Example Example Comparative Example 9 10 11 12 13 14 Example 3 Bladder 130 120 110 150 110 110 100 life Note: Values indicated are relative to an arbitrary value of 100 for the bladder life in Comparative Example 3.

(77) Compared with the emulsion of the carboxyl group-lacking methylpolysiloxane in Comparative Example 3, the organopolysiloxane mixtures including the carboxyl group-containing organopolysiloxanes, and the emulsions of the carboxyl group-containing organopolysiloxanes, or the emulsions of the organopolysiloxane mixtures including the carboxyl group-containing organopolysiloxanes, in Working Examples 9 to 14, resulted in a longer bladder life.