JP2009242538A - Rubber composition for inner liner joint tape and pneumatic tire - Google Patents

Abstract

An object of the present invention is to prevent a failure caused by a failure at the time of manufacturing a tire in a joint portion of an inner liner, improve the durability of the tire by improving the heat resistance of the joint tape, and further increase the durability of the tire at the time of manufacturing the tire. Improves peelability from the sheet.
SOLUTION: The rubber component contains 75 to 95 parts by weight of a halogenated butyl rubber or a blend of this and butyl rubber, and 25 to 5 parts by weight of a diene rubber, and contains 100 parts by weight of the rubber component. And 1-5 parts by weight of processing aids containing a fatty acid metal salt and a peptizer, and 0-5 parts by weight of a tackifier. Moreover, it is a pneumatic tire which coat | covers the inner liner joint part 3 of a tire inner surface with the joint tape 4 which consists of this rubber composition.
[Selection] Figure 1

Description

  The present invention relates to a rubber composition used for a joint tape of an inner liner joint portion of a tubeless tire, and a pneumatic tire using the joint tape.

  In general, for tubeless tires, butyl rubber or halogenated butyl rubber, which is non-breathable on the inner surface of the tire, is used as a main rubber component in order to prevent the pressure inside the tire from permeating outside the tire and reducing the internal pressure. An inner liner made of a rubber composition is provided.

  Normally, tubeless tires are formed by laminating members such as an inner liner, carcass, belt, and tread on a molding drum to form an unvulcanized tire, which is inserted into the mold and expanded and deformed by shaping using a bladder. The product tire is vulcanized by heating while pressing against the molding surface. At that time, in order to improve releasability from the bladder after vulcanization, a water-soluble release agent is applied to the inner liner of the inner surface of the unvulcanized tire.

  When the release agent is applied to the inner surface of the unvulcanized tire in this way, the release agent penetrates into the joint part of the inner liner or the joint part entrains the release agent, and the joint part is Problems such as opening or air trapping at the intrusion part of the release agent are caused, which contributes to air leakage and durability of the tubeless tire.

  In order to solve the problem in the joint portion, a protective tape made of a polyethylene film or the like or a joint tape made of a rubber sheet is applied to the joint portion of the inner liner (see Patent Document 1).

  For example, in Patent Document 2, after coating the joint portion of the inner liner with a joint tape made of a rubber composition containing carbon black, a plasticizer, and a resin on halogenated butyl rubber, a release agent is applied to the tire inner surface. It is disclosed to prevent the release agent from entering the joint portion.

Patent Document 3 discloses that the inner liner rubber composition is composed of halogenated butyl rubber and diene rubber as rubber components, and the modulus at 200% elongation when unvulcanized is 0.2 to 0.4 MPa. It has been proposed to solve the problem of the joint part at the time of tire manufacture.
JP-A-4-247933 Japanese Patent Laid-Open No. 7-9807 Japanese Patent Laid-Open No. 2007-9121

  However, in the technique described in Patent Document 2, since halogenated butyl rubber is used alone as a rubber component, the adhesiveness (tackiness) between the inner liner and the joint tape is poor, and the joint tape is peeled off by the tire before vulcanization. In some cases, the release agent permeates from the peeled portion, and the above problem has not been sufficiently solved.

  Further, even the technique described in Patent Document 3 has not yet solved the problem that the inner liner is peeled off due to the expansion deformation at the time of tire vulcanization, and thereby the release agent enters the joint portion.

  Therefore, the present inventor, in Japanese Patent Application No. 2007-190497, which has not been disclosed at the time of filing of the present application, 75 to 95 parts by weight of a halogenated butyl rubber or a blend of a halogenated butyl rubber and a butyl rubber, and 25 to 5 parts by weight of a diene rubber The rubber component contains carbon black, the modulus at 200% elongation when unvulcanized is 0.2 to 0.3 MPa, and the modulus retention after 1 minute in the stretched state of 200% is 30 to 30%. A rubber composition of 55% is proposed. With this rubber composition, it is possible to surely prevent the release agent from entering from the inner liner joint part, prevent failures caused by troubles during tire manufacture, and improve the heat resistance of the joint tape. It is possible to improve the durability.

  However, it has been found that joint tapes using this rubber composition have problems in actual tire production. That is, in general, the joint tape is wound with a non-polar resin sheet such as a polyethylene sheet sandwiched between the joint tapes, and when the tire is manufactured, the joint tape is peeled off from the resin sheet and attached to the inner liner joint part. Thus, in the step of peeling from the resin sheet, if it is a joint tape using the rubber composition, it is difficult to peel off from the resin sheet, not only is the workability inferior, but the joint tape is stretched at the time of peeling and becomes unusable. It became clear that the problem of sporadic occurred.

  The present invention has been made in order to solve such a problem, and prevents a failure due to a failure during manufacture of the tire in the joint portion of the inner liner and improves the heat resistance of the joint tape. An object of the present invention is to improve the tire manufacturing workability by improving the peelability of the joint tape from the resin sheet at the time of manufacturing the tire while improving the durability.

  The rubber composition for an inner liner joint tape according to the present invention comprises 75 to 95 parts by weight of a halogenated butyl rubber or a blend of a halogenated butyl rubber and a butyl rubber, and 25 to 5 parts by weight of a diene rubber, and carbon black. 1 to 5 parts by weight of a processing aid containing a fatty acid metal salt and a peptizer is blended with 100 parts by weight of the rubber component, and 0 or 5 parts by weight or less of a tackifier is blended. It will be.

  Moreover, the pneumatic tire according to the present invention is formed by covering the inner liner joint portion of the tire inner surface with a joint tape made of the rubber composition.

  According to the present invention, using a rubber component obtained by blending a predetermined amount of a diene rubber with a butyl rubber composed of a halogenated butyl rubber or a blend of a halogenated butyl rubber and a butyl rubber, the amount of the tackifier is suppressed, and By blending a specific processing aid, while preventing the failure caused by the trouble at the time of tire manufacture in the joint part of the inner liner, and improving the durability of the tire by improving the heat resistance of the joint tape, It is possible to improve the tire manufacturing workability by improving the peelability of the joint tape from the resin sheet during tire manufacturing.

  Hereinafter, matters related to the implementation of the present invention will be described in detail.

  In the rubber composition of the present invention, the rubber component comprises 100 parts by weight of 75 to 95 parts by weight of butyl rubber composed of halogenated butyl rubber or a blend of halogenated butyl rubber and butyl rubber, and 25 to 5 parts by weight of diene rubber. Used.

  Examples of the halogenated butyl rubber (halogenated IIR) include chlorinated butyl rubber (CIIR) and brominated butyl rubber (BIIR). These may be used alone or in combination of two or more.

  As the butyl rubber, halogenated IIR may be used alone, or a blend of halogenated IIR and butyl rubber (IIR) may be used. Butyl rubber is excellent in non-breathability, heat resistance, weather resistance, etc., but is inferior in vulcanization speed and adhesion to other rubbers. By blending IIR with halogenated IIR, the non-breathability and heat resistance of IIR In addition, the vulcanization speed can be increased while ensuring the property, weather resistance, etc., and the co-vulcanizability and adhesion with other rubbers can be improved. When the IIR is blended, the halogenated IIR is preferably 50% by weight or more, that is, the halogenated IIR: IIR = 100 to 50% by weight: 0 to 50% by weight.

  As the halogenated IIR and IIR, those having a Mooney viscosity ML (1 + 8) at 125 ° C. of 27 to 52 are preferred, and those having a Mooney viscosity ML (1 + 8) of 27 to 37 are more preferred. This makes it easy to adjust the unvulcanized modulus (green modulus) of the rubber composition and the stress relaxation rate in the stretched state to a range suitable for the use conditions of the joint tape. Here, Mooney viscosity is a value measured according to JIS K6300.

  As the diene rubber, natural rubber (NR), polyisoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), and the like can be used. One type may be used, or two or more types may be used in combination. You can also. Among them, NR or IR is preferable from the viewpoints of optimizing the green modulus, improving the tackiness, and improving the adhesiveness and workability of the butyl rubber.

  In the present invention, if the blending amount of the butyl rubber in the rubber component is less than 75 parts by weight, the amount of diene rubber increases, so that the tackiness is increased and improved, but the heat resistance is lowered and the tire is easily cured. Reduces the durability. Further, when the butyl rubber exceeds 95 parts by weight and the diene rubber is reduced, the tackiness is lowered, so that troubles such as peeling of the tape at the tire molding or tire before vulcanization and floating are easily caused.

  The rubber composition of the present invention contains carbon black. As carbon black, those usually used for rubber are used. Carbon black having an iodine adsorption (IA) of 15 to 55 g / kg and a DBP (dibutyl phthalate) absorption of 75 to 125 ml / 100 g is used. From the viewpoint of tackiness and elongation characteristics when not vulcanized, carbon black such as FEF, GPF, SRF and the like is preferable. These carbon blacks may be used alone or in combination of two or more. Here, IA is a value measured according to JIS K6217-5, and DBP absorption is a value measured according to JIS K6217-4.

  You may mix | blend the white filler for rubber | gum with the rubber composition of this invention with carbon black. Examples of the white filler for rubber include calcium carbonate, magnesium carbonate, clay, talc, mica, and the like, among which clay and surface-treated clay are preferable.

  The blending amount of the carbon black and the white filler is preferably 40 to 70 parts by weight with respect to 100 parts by weight of the rubber component in total. When this amount is less than 40 parts by weight, the green modulus is low, the film tends to be stretched at the time of application, adversely affects joint disengagement and workability, and the rubber strength after vulcanization also decreases. On the other hand, if it exceeds 70 parts by weight, the strength and modulus when unvulcanized increases, so that the workability of the pasting also decreases, tackiness decreases, and the joint tape easily peels off from the joint part. In addition, it becomes easy to harden due to heat generation, and cracks are likely to occur in the joint tape by running.

  The rubber composition of the present invention contains a processing aid containing a fatty acid metal salt and a peptizer. Thus, by using a fatty acid metal salt as a processing aid, the peelability from a resin sheet such as a polyethylene sheet can be improved. In addition, by using a peptizer together with the fatty acid metal salt, it is possible to improve the tackiness by suppressing the recombination of the molecular chain radial of the rubber component polymer cut by mastication, and to improve the stickiness to the inner liner rubber. Can be maintained. In other words, even with the fatty acid metal salt alone, the peelability from the resin sheet can be improved, but the tackiness is lowered, and it is easy to cause problems such as tape peeling and floating at the time of tire molding or before vulcanization. By including a peptizer together with the metal salt, the peelability from the resin sheet can be improved while maintaining tackiness.

  The amount of the processing aid is 1 to 5 parts by weight per 100 parts by weight of the rubber component. When the blending amount is less than 1 part by weight, the effect of improving the peelability from the resin sheet is hardly obtained. On the other hand, when the amount exceeds 5 parts by weight, the tackiness is lowered, and it is easy to cause problems such as peeling of the tape and floating at the time of molding the tire or the tire before vulcanization.

  The fatty acid of the fatty acid metal salt is a saturated or unsaturated fatty acid having 6 to 28 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid. And nervonic acid. These may be used alone or in combination of two or more. Preferably, a saturated fatty acid having 14 to 20 carbon atoms is used. Examples of the metal forming the salt of these fatty acids include alkali metals such as potassium and sodium, alkaline earth metals such as magnesium, calcium and barium, zinc, nickel and molybdenum, and zinc is particularly preferable. These fatty acid metal salts may be used alone or in combination of two or more.

  The peptizer can be used as long as it can react with the molecular chain radical of the cut rubber component polymer to suppress recombination. For example, 2,2′-dibenzamide diphenyl disulfide (DBD) , Zinc salt of 2-benzamidothiophenol, xylyl mercaptan, β-naphthyl mercaptan and the like, and DBD is particularly preferable.

  As processing aids containing these fatty acid metal salts and peptizers, the fatty acid metal salts and peptizers can be added to the rubber composition separately to make them both in the rubber composition. In that case, it is preferable from the viewpoint of the effect of the present invention that both are added simultaneously, that is, in the same mixing step at the time of kneading the rubber composition. More preferably, a single processing aid contains a fatty acid metal salt and a peptizer, that is, a fatty acid metal salt processing aid containing a peptizer. This is advantageous in terms of management of the kneading process of the rubber composition. As such a processing aid, a processing aid comprising a fatty acid zinc salt containing DBD is sold as “Actiplast MS” by Rhein Chemie, and its use is recommended.

  In the said processing aid containing a fatty-acid metal salt and a peptizer, it is preferable to contain 5-10 weight% of a peptizer. If the content of the peptizer is less than 5% by weight, it is difficult to maintain tackiness, and if it exceeds 10% by weight, the molecular chain scission of the rubber component polymer becomes excessive and the modulus (M300) is too low. .

  A tackifier can be mix | blended with the rubber composition of this invention. The tackiness can be improved by blending a tackifier. However, if too much tackifier is blended, even if the above processing aid is blended, the peelability from the resin sheet will deteriorate, so the tackifier is 5 parts by weight or less with respect to 100 parts by weight of the rubber component. It is preferable to blend in. The tackifier is not an essential component and may not be blended.

  The tackifier is not particularly limited, and can include various adhesive resins such as petroleum hydrocarbon resins, chroman resins, phenol resins, terpene resins, rosin derivatives, and these can be used alone. May be used in combination of two or more.

  In the rubber composition of the present invention, in addition to the above components, zinc white, stearic acid, softening agents such as wax and oil, antioxidants, vulcanizing agents such as sulfur, which are commonly used in the rubber industry, A rubber compounding agent such as a vulcanization accelerator can be appropriately compounded within a normal range. The rubber composition is prepared by kneading according to a conventional method using a rubber kneader such as a normal Banbury mixer or kneader.

  The rubber composition is processed into a tape shape using a rubber roll, a calendar device, a cutting device, or the like, and a joint tape is manufactured in a state where the resin sheet is sandwiched and wound. The unvulcanized joint tape thus obtained is peeled off from the resin sheet in the tire molding step and is attached so as to cover the joint portion of the inner liner on the tire inner surface. In addition, although the thickness and width of the joint tape are not particularly limited, the thickness is about 0.1 to 2 mm and the width is about 10 to 30 mm, which are appropriately processed according to the tire size and application.

  In the pneumatic tire of the present invention, the joint portion of the inner liner on the inner surface of the unvulcanized tire is covered with the joint tape, and then a release agent is applied to the inner surface of the unvulcanized tire, followed by vulcanization by a conventional method. Manufactured by doing.

  In that case, even if the joint part of the inner liner covers the joint tape 4 on the so-called butt joint part 3 in which both ends 1 and 2 of the inner liner 10 are abutted and joined as shown in FIG. Alternatively, as shown in FIG. 2, the joint tape 9 may be covered with a so-called overlapping joint portion 8 in which both ends 5 and 6 of the inner liner 20 are overlapped and joined.

  In the rubber composition described above, the inner liner of the joint tape in the tire molding process or during storage of unvulcanized tires is obtained by using a blend of butyl rubber and diene rubber at a predetermined ratio as a rubber component. It is possible to reliably prevent peeling from the joint part, eliminate problems such as air accumulation caused by the penetration of the release agent into the joint part, and improve the durability of the tire. Further, by improving the heat resistance of the joint tape, it is possible to suppress the hardening of the rubber and prevent a failure caused by cracking or peeling of the joint tape, thereby improving the durability of the tire. In addition, by suppressing the blending amount of the tackifier, blending the specific processing aid improves the peelability of the joint tape from the resin sheet during tire manufacture without impairing these effects. Thus, the tire manufacturing workability can be improved.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

  According to the formulations shown in Tables 1 and 2 below, the rubber compositions of Examples and Comparative Examples were prepared by kneading using a normal capacity 20 liter Banbury mixer. The details of each component in the table are as follows.

NR (natural rubber): RSS # 3
IR (polyisoprene rubber): “IR2200” manufactured by JSR Corporation
BIIR (brominated butyl rubber): “Bromobutyl 2222” (31 ML (1 + 8) 125 ° C.) manufactured by ExxonMobil,
IIR (butyl rubber): “Butyl 268” (50 ML (1 + 8) 125 ° C.) manufactured by ExxonMobil,
CB (carbon black): GPF, “Seast V” manufactured by Tokai Carbon Co., Ltd. (IA = 26 g / kg, DBP absorption amount = 87 ml / 100 g),
・ Clay: “Hard Top Clay” manufactured by Shiraishi Calcium Co., Ltd.
・ Tackifier: Petroleum hydrocarbon resin, “Escollet 1102” manufactured by ExxonMobil,
・ Processing aid 1: Saturated fatty acid zinc salt, "Acchiplast PP" manufactured by Rhein Chemie,
-Processing aid 2: Fatty acid zinc salt containing 5 to 10% by weight of DBD as a peptizer (constituent fatty acid is composed mainly of saturated fatty acid having 18 carbon atoms), "Acchiplast MS" manufactured by Rhein Chemie,
・ Zinc flower: “Zinc flower 3” manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
・ Vulcanization accelerator DM: “Noxeller DM-P” manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: “5% oil-treated powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.

  About each rubber composition obtained, tackiness (adhesiveness), tape peelability, tire moldability (1) related to tape peeling failure, tire moldability (2) related to joint opening failure, heat resistance and heat resistance The tape condition of was evaluated. Each evaluation method is as follows.

-Tackiness (index): An unvulcanized rubber sheet having a thickness of 1 mm was prepared using a test roll, and the tackiness was measured by a tack tester (manufactured by Toyo Seiki Seisakusho) using this sheet to evaluate the tackiness. The value of Example 4 is indicated by an index with a value of 100, and the larger the value, the better the tackiness.

Tape peeling property: A joint tape having a width of 25 mm and a thickness of 1 mm was prepared using a test roll, and a polyethylene sheet was overlaid. After leaving for 1 day, a peel test between the joint tape and the polyethylene sheet was performed using an autograph, the peel strength was measured, and the value of Example 1 was shown as an index of 100. The smaller the value, the better the peelability.

-Tire moldability (1): Using a rubber roll, a joint tape having a width of 25 mm and a thickness of 1 mm was wound and wound in a state in which a polyethylene sheet was sandwiched. Using this joint tape, 100 unvulcanized tires each having a tire size of 11R22.5 14PR were molded. Then, the problem of peeling between the joint tape and the polyethylene sheet at the time of molding was investigated. When the number of defects was 100 or less when molding 100 tires, “◯”, 2 to 4 “△”, and 5 or more “×”. It was.

・ Tire moldability (2): After molding the above unvulcanized tire, investigate the malfunction due to the opening of the inner liner joint within 24 hours. Two to four lines were designated as “Δ”, and five or more pieces were designated as “x”.

Heat-resistant curability: The unvulcanized rubber sheet was left in a hot air circulation dryer adjusted to 140 ° C. The number of days until a crack was generated on the surface of the sheet when the taken-out sheet was bent was measured to evaluate the heat-curing property.

・ Tape condition after running on real vehicle: Two pneumatic tires manufactured in the above-mentioned evaluation of tire moldability are attached to the rear wheels of a plurality of large trucks two by two, and after running for 100,000 km on a general road, the tires are taken out. The presence or absence of cracks in the joint tape was visually observed. A case where no crack occurred in all six tires was evaluated as “◯”, and a case where even one crack occurred was evaluated as “x”.

  As shown in the above table, in Examples 1 to 10, it was possible to improve the peelability of the polyethylene sheet while maintaining good tackiness. Therefore, it was easy to peel off the joint tape from the polyethylene sheet while improving the tire durability by avoiding the trouble due to the opening of the joint part, and excellent in workability. Moreover, it was excellent also in heat-resistant curability.

  On the other hand, in Comparative Examples 1 and 2 in which the specific processing aid 2 was not blended, the peelability of the joint tape from the polyethylene sheet was poor and the manufacturing workability (tire moldability (1)) was poor. . Moreover, although the processing aid 2 is mix | blended, also in Comparative Examples 3 and 4 with too much compounding amount of a tackifier, the peelability of the joint tape from a polyethylene sheet is similarly bad, and it is inferior to manufacturing workability | operativity. It was. On the other hand, in Comparative Examples 5 and 6 in which the blending amount of the processing aid 2 is too large, the tackiness was low, and defects due to the opening of the joint portion were observed. Further, in Comparative Example 7 using the processing aid 1 containing no peptizer, although the peelability of the joint tape from the polyethylene sheet was improved, the tackiness was low, and problems due to the joint opening were observed.

  Moreover, also in Comparative Example 8 in which no diene rubber was blended, the tackiness was low, and defects due to the opening of the joint portion were observed. On the contrary, in Comparative Example 8 in which the blending amount of the diene rubber was large, the heat-curing property was deteriorated and the tire durability was inferior.

  The rubber composition for an inner liner joint tape of the present invention can be used as a joint tape for an inner liner in tubeless pneumatic tires such as passenger cars, light trucks, trucks and buses. Especially, it is used suitably for the tire for heavy loads whose use conditions are severe, and the durability can be improved.

It is a joint part sectional view explaining a butt joint. It is a joint part sectional view explaining an overlap joint.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Inner liner, 1, 2 ... Inner liner edge part, 3 ... Joint part, 4 ... Joint tape 20 ... Inner liner, 5, 6 ... Inner liner edge part, 8 ... Joint part, 9 ... Joint tape

Claims (5)

  75 to 95 parts by weight of a halogenated butyl rubber or a blend of halogenated butyl rubber and butyl rubber, and 25 to 5 parts by weight of a diene rubber, containing carbon black, with respect to 100 parts by weight of the rubber component A rubber composition for an inner liner joint tape comprising 1 to 5 parts by weight of a processing aid containing a fatty acid metal salt and a peptizer, and 0 part by weight or 5 parts by weight or less of a tackifier.   40 to 70 parts by weight in total of carbon black having an iodine adsorption amount of 15 to 55 g / kg and a DBP absorption amount of 75 to 125 ml / 100 g and a white filler for rubber with respect to 100 parts by weight of the rubber component. The rubber composition for an inner liner joint tape according to claim 1.   The rubber composition for an inner liner joint tape according to claim 1 or 2, wherein the peptizer is 2,2'-dibenzamide diphenyl disulfide, and the processing aid contains 5 to 10% by weight of the peptizer. .   The rubber composition for an inner liner joint tape according to any one of claims 1 to 3, wherein the diene rubber is natural rubber or polyisoprene rubber.   A pneumatic tire formed by covering an inner liner joint portion of a tire inner surface with a joint tape made of the rubber composition according to claim 1.

Images