# Patent

## Title
Inner liner rubber composition and pneumatic tire

## Abstract

Inner liner rubber composition for a pneumatic tire, which enables improvements in handling stability, fuel economy, elongation at break, sheet processability, air barrier properties, and compounding cost in a balanced manner. Also, pneumatic tire including inner liner formed from the rubber composition. The rubber composition includes: reclaimed butyl rubber; halogenated butyl rubber other than the reclaimed butyl rubber; at least one semi-reinforcing filler selected from finely ground bituminous coal having a specified average particle size, talc, mica, and hard clay; and carbon black having a specific N2SA and/or silica having a specific N2SA. The rubber composition has a predetermined reclaimed butyl rubber content, a predetermined combined content of the reclaimed butyl rubber and the halogenated butyl rubber, a predetermined total semi-reinforcing filler content, and a predetermined combined content of the carbon black and the silica.

## Background
TECHNICAL FIELD
The present invention relates to an inner liner rubber composition and a pneumatic tire formed from the same.
BACKGROUND ART
The fuel efficiency of automobiles has been conventionally improved by reducing the rolling resistance of tires (in other words, by improving the performance in terms of rolling resistance). As automobiles have been required to have still more improved fuel economy recently, rubber compositions for tire components have been required to be excellent in low heat build-up. Therefore, rubber compositions with a low tan δ and low heat build-up have begun to be used in, for example, the tread portion or the sidewall portion.
Meanwhile, in the inner liner portion inside a tire, butyl rubbers with low air permeability are generally used in order to retain air. These butyl rubbers, however, have higher hysteresis losses than those of diene rubbers used in the tread portion and the sidewall portion. Thus, it is difficult to readily prepare an inner liner rubber composition with a low tan δ.
The tan δ of an inner liner rubber composition can be lowered by reducing the amount of carbon black; however, the viscosity of the unvulcanized rubber composition is then reduced correspondingly, leading to difficulty in controlling the rubber thickness in the molding process, which means deteriorated sheet processability. In this context, Patent Literature 1 discloses that the balance between the reduction in tan δ and the retention of sheet processability can be improved by partially replacing carbon black with finely ground bituminous coal. Meanwhile, Patent Literature 2 discloses that the moisture barrier properties of tires are improved by using in an insulation a rubber composition that includes a rubber component containing a large amount of natural rubber in combination with finely ground bituminous coal. However, Patent Literatures 1 and 2 still leave room for improvement in improving handling stability, fuel economy, elongation at break, sheet processability, air barrier properties, and compounding cost in a balanced manner.
CITATION LIST
Patent Literature
Patent Literature 1: JP H05-43755 A
Patent Literature 2: JP 4550763 B
SUMMARY OF INVENTION
Technical Problem
The present invention aims to solve the above problems and provide an inner liner rubber composition that enables improvements in handling stability, fuel economy, elongation at break, sheet processability, air barrier properties, and compounding cost in a balanced manner; and a pneumatic tire including an inner liner formed from the inner liner rubber composition.
Solution to Problem
The claimed invention relates to an inner liner rubber composition, including: a rubber component containing a reclaimed butyl rubber and a halogenated butyl rubber other than the reclaimed butyl rubber; at least one semi-reinforcing filler selected from the group consisting of finely ground bituminous coal, talc, mica, and hard clay; and at least one of a carbon black having a nitrogen adsorption specific surface area of 20 to 35 m2/g and a silica having a nitrogen adsorption specific surface area of 40 to 120 m2/g, wherein the finely ground bituminous coal has an average particle size of 50 μm or less, the inner liner rubber composition has a reclaimed butyl rubber content of 5 to 30 mass % and a combined content of the reclaimed butyl rubber and the halogenated butyl rubber of 70 to 100 mass %, each based on 100 mass % of the rubber component, and the inner liner rubber composition has a total semi-reinforcing filler content of 3 to 45 parts by mass and a combined content of the carbon black and the silica of 20 to 60 parts by mass, each per 100 parts by mass of the rubber component.
The rubber composition preferably includes, per 100 parts by mass of the rubber component: 1 to 20 parts by mass of a mixed resin and 0.8 to 2.9 parts by mass of zinc oxide.
The rubber composition preferably has a phenylenediamine antioxidant content of 0.5 parts by mass or less per 100 parts by mass of the rubber component.
The rubber composition preferably has a tan δ at 70° C. of 0.20 or lower.
The rubber composition preferably includes, per 100 parts by mass of the rubber component, 0.1 to 3 parts by mass of an alkylphenol-sulfur chloride condensate represented by the following formula (1):




wherein R1, R2 and R3 are the same as or different from one another and each represent a C5 to C12 alkyl group; x and y are the same as or different from each other and each represent an integer of 1 to 3; and t represents an integer of 0 to 250.

The claimed invention also relates to a pneumatic tire, including an inner liner formed from the rubber composition.
Advantageous Effects of Invention
The present invention provides an inner liner rubber composition including predetermined amounts of a reclaimed butyl rubber, a halogenated butyl rubber, a specific semi-reinforcing filler, and a specific carbon black and/or a specific silica. Accordingly, the use of the rubber composition in a tire inner liner enables the production of a pneumatic tire that is improved in handling stability, fuel economy, elongation at break, sheet processability, air barrier properties, and compounding cost in a balanced manner.


DESCRIPTION OF EMBODIMENTS
The inner liner rubber composition of the present invention contains predetermined amounts of a reclaimed butyl rubber, a halogenated butyl rubber, a specific semi-reinforcing filler, and a specific carbon black and/or a specific silica.
The reclaimed butyl rubber used in the present invention refers to the butyl rubber fraction included in ground particles of a rubber product that contains a large amount of butyl rubber (s), such as a tire tube or a bladder used in the production of tires, or the butyl rubber fraction included in a product obtained by heating/pressuring the ground particles, and encompasses a revulcanizable rubber obtained by decomposition of crosslinking bonds (devulcanization) of the rubber component. In general, about 50 mass % of the ground particles corresponds to the reclaimed butyl rubber. The reclaimed butyl rubber contains sulfur as well, but the sulfur is deactivated so as not to be involved in crosslinking.
Examples of commercial products of the reclaimed butyl rubber include a rubber reclaim from tubes produced by Muraoka Rubber Reclaiming Co., Ltd. and a rubber reclaim from bladders produced by Car Quest Co., Ltd. The rubber reclaim from tubes of Muraoka Rubber Reclaiming Co., Ltd. is prepared by heat treating butyl tubes under pressure. The rubber reclaim from bladders of Car Quest Co., Ltd. is prepared by grinding bladders in an extruder. Each of these reclaimed butyl rubbers may be used alone, or two or more of them may be used in combination.
The rubber composition of the present invention contains a halogenated butyl rubber (X-IIR) in addition to the reclaimed butyl rubber. Since the reclaimed butyl rubber typically contains a large amount of non-halogenated butyl rubber (regular butyl rubber), its combined use with a halogenated butyl rubber ensures good air barrier properties and a proper vulcanization rate.
Herein, when referred to simply as “halogenated butyl rubber”, the term refers to a halogenated butyl rubber other than the reclaimed butyl rubber.
Examples of the halogenated butyl rubber include brominated butyl rubbers (Br-IIR) and chlorinated butyl rubbers (Cl-IIR). Preferred among these are chlorinated butyl rubbers, because they are excellent in vulcanization rate and scorch resistance when used in a system concomitantly containing natural rubber (NR).
The reclaimed butyl rubber content, based on 100 mass % of the rubber component, is 5 mass % or more, preferably 8 mass % or more. A reclaimed butyl rubber content of less than 5 mass % may not have a sufficient effect in reducing the compounding cost. The reclaimed butyl rubber content is 30 mass % or less, preferably 25 mass % or less. A reclaimed butyl rubber content of more than 30 mass % may make it impossible to ensure satisfactory air barrier properties and a sufficient vulcanization rate.
The halogenated butyl rubber content, based on 100 mass % of the rubber component, is preferably 40 mass % or more, more preferably 50 mass % or more, and still more preferably 60 mass % or more. A halogenated butyl rubber content of less than 40 mass % may not ensure satisfactory air barrier properties and a sufficient vulcanization rate. The halogenated butyl rubber content is preferably 80 mass % or less, and more preferably 75 mass % or less. If the halogenated butyl rubber content is more than 80 mass %, then the effect of improving performance is likely to reach a plateau and therefore tends not to match the increase in compounding cost.
The combined content of the reclaimed butyl rubber and the halogenated butyl rubber, based on 100 mass % of the rubber component, is 70 mass % or more, preferably 75 mass % or more, and more preferably 80 mass % or more. A combined content of less than 70 mass % may not achieve satisfactory air barrier properties. Although the combined content may be 100 mass %, it is preferably 95 mass % or less, and more preferably 90 mass % or less, in terms of sufficiently maintaining the finished quality of the joint of the inner liner, the adhesion to a neighboring component, and the peeling resistance after vulcanization.
Examples of other usable rubbers include, but not limited to, natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), epoxidized natural rubber (ENR), chloroprene rubber (CR), styrene-isoprene-butadiene copolymer rubber (SIBR), and styrene-isobutylene-styrene block copolymers (SIBS). Among these, NR and IR are preferred in terms of adhesion, and ENR and SIBS are preferred in terms of air barrier properties.
The NR is not particularly limited and may be one generally used in the tire industry, such as SIR20, RSS#3, and TSR20.
The NR content, based on 100 mass % of the rubber component, is preferably 5 mass % or more, and more preferably 10 mass % or more. A NR content of less than 5 mass % tends to lead to deterioration in adhesion and sheet processability. The NR content is preferably 40 mass % or less, and more preferably 35 mass % or less. A NR content of more than 40 mass % corresponds to reduction in the butyl rubber content, which may make it impossible to ensure satisfactory air barrier properties.
The rubber composition of the present invention contains as an extending filler at least one semi-reinforcing filler selected from the group consisting of finely ground bituminous coal, talc, mica, and hard clay. These semi-reinforcing fillers do not form polymer gels during kneading, which allows for good sheet processability. In terms of sheet processability and cost, the semi-reinforcing filler is preferably finely ground bituminous coal, common talc, or hard clay, and in terms of air barrier properties, it is preferably high aspect ratio mica or flat talc (e.g. HAR produced by Nihon Mistron Co., Ltd.).
Examples of the bituminous coal that may be contained in the rubber composition of the present invention include general coals. Such bituminous coal may be incorporated in the form of ground particles in the rubber composition.
The finely ground bituminous coal has an average particle size of 50 μm or less, preferably 30 μm or less. The average particle size of more than 50 μm may not lead to sufficiently improved fuel economy. The lower limit of the average particle size of finely ground bituminous coal is not particularly limited and is preferably 1 μm or more.
The talc preferably has an average particle size of 50 μm or less, and more preferably 30 μm or less. The average particle size of more than 50 μm may not lead to sufficiently improved fuel economy. The lower limit of the average particle size of talc is not particularly limited and is preferably 1 μm or more.
The mica preferably has an average particle size of 50 μm or less, and more preferably 30 μm or less. The average particle size of more than 50 μm may not lead to sufficiently improved fuel economy. The lower limit of the average particle size of mica is not particularly limited and is preferably 1 μm or more.
The hard clay preferably has an average particle size of 50 μm or less, and more preferably 30 μm or less. The average particle size of more than 50 μm may not lead to sufficiently improved fuel economy. The lower limit of the average particle size of hard clay is not particularly limited and is preferably 0.5 μm or more, and more preferably 1 μm or more.
The average particle sizes of these semi-reinforcing fillers each refer to an average particle size on a mass basis as determined from a particle size distribution measured in accordance with JIS Z 8815-1994.
The total semi-reinforcing filler content, per 100 parts by mass of the rubber component, is 3 parts by mass or more, preferably 8 parts by mass or more, and more preferably 10 parts by mass or more. A total semi-reinforcing filler content of less than 3 parts by mass may not ensure sufficient sheet processability. The total semi-reinforcing filler content is 45 parts by mass or less, preferably 40 parts by mass or less. A total semi-reinforcing filler content of more than 45 parts by mass may make it impossible to ensure sufficient elongation at break.
The rubber composition of the present invention contains carbon black and/or silica as a reinforcement. The reinforcement preferably includes at least carbon black, and may include a combination of carbon black and silica.
The carbon black has a nitrogen adsorption specific surface area (N2SA) of 20 m2/g or more, preferably 25 m2/g or more. A carbon black having a N2SA of less than 20 m2/g may not achieve sufficient reinforcement. The carbon black has a N2SA of 35 m2/g or less. A carbon black having a N2SA of more than 35 m2/g may cause the rubber composition to be too hard, possibly leading to reduced elongation at break.
The nitrogen adsorption specific surface area of carbon black refers to a value measured in accordance with JIS K 6217-2:2001.
The silica has a nitrogen adsorption specific surface area (N2SA) of 40 m2/g or more, preferably 70 m2/g or more. A silica having a N2SA of less than 40 m2/g may not achieve sufficient reinforcement. The silica has a N2SA of 120 m2/g or less. A silica having a N2SA of more than 120 m2/g may cause deterioration in air barrier properties and tan δ.
The N2SA of silica refers to a value measured by the BET method in accordance with ASTM D3037-81.
The combined content of the carbon black and the silica is 20 to 60 parts by mass per 100 parts by mass of the rubber component, in terms of achieving favorable reinforcement. The lower limit of the combined content of the carbon black and the silica is preferably 30 parts by mass or more, and more preferably 35 parts by mass or more. The upper limit is preferably 50 parts by mass or less, and more preferably 45 parts by mass or less.
In terms of achieving favorable reinforcement, the carbon black content, per 100 parts by mass of the rubber component, is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 35 parts by mass or more, and is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 45 parts by mass or less.
The silica content is preferably 0 to 30 parts by mass per 100 parts by mass of the rubber component. The use of the silica improves elongation at break; however, it may cause shrinkage of the rubber composition.
The rubber composition of the present invention preferably contains a mixed resin. The mixed resin serves to fill the gap between a reinforcement (e.g. carbon black) and a polymer, thereby further improving air barrier properties. The mixed resin refers to a mixture of two or more resins. Examples of the resins used for the mixed resin include aromatic hydrocarbon resins such as phenolic tackifying resins, chroman resins, indene resins, and chroman-indene resins; and aliphatic hydrocarbon resins (e.g. C5, C8, and C9 resins). Two or more of these can be mixed and used as the mixed resin. Preferred among these are combinations of an aromatic hydrocarbon resin and an aliphatic hydrocarbon resin.
Specific examples of the mixed resin include Struktol 40MS produced by Struktol Company, Rhenosin 145A produced by Rhein Chemie Corp., and Promix 400 produced by Flow Polymers Inc.
The mixed resin content, per 100 parts by mass of the rubber component, is preferably 1 part by mass or more, and more preferably 2 parts by mass or more. A mixed resin content of less than 1 part by mass may not sufficiently improve air barrier properties. The mixed resin content is preferably 20 parts by mass or less, more preferably 12 parts by mass or less, and still more preferably 8 parts by mass or less. A mixed resin content of more than 20 parts by mass may remarkably reduce the viscosity of the kneaded rubber mixture, possibly causing deterioration in sheet processability and tan δ.
The rubber composition of the present invention preferably contains stearic acid. The stearic acid content, per 100 parts by mass of the rubber component, is preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more. A stearic acid content of less than 0.5 parts by mass is likely to lead to difficulty in dispersing zinc oxide, which tends to deteriorate sheet processability and elongation at break. The stearic acid content is preferably 2.7 parts by mass or less, more preferably 2.0 parts by mass or less, and still more preferably 1.8 parts by mass or less. A stearic acid content of more than 2.7 parts by mass is likely to excessively increase the lubricity during kneading, which tends to deteriorate filler dispersibility and elongation at break.
The rubber composition of the present invention preferably contains zinc oxide. Zinc oxide serves to promote crosslinking in the isoprene units of a butyl rubber, and thereby enhances E* and reduces tan δ. The zinc oxide content, per 100 parts by mass of the rubber component, is preferably 0.8 parts by mass or more, and more preferably 1.0 part by mass or more. A zinc oxide content of less than 0.8 parts by mass may fail to sufficiently enhance E* and sufficiently reduce tan δ. The zinc oxide content is preferably 2.9 parts by mass or less, more preferably 2.0 parts by mass or less, and still more preferably 1.8 parts by mass or less. If the zinc oxide content exceeds 2.9 parts by mass, undispersed agglomerates of zinc oxide may cause rubber scorch, possibly causing deterioration in sheet processability. Moreover, some voids are formed around the undispersed agglomerates of zinc oxide, and therefore air may flow through the voids, possibly resulting in poor air barrier properties. In addition, the compounding cost increases.
The rubber composition of the present invention preferably contains an antioxidant. The antioxidant is not particularly limited, and those used in the rubber field may be used. Examples thereof include quinoline, quinone, phenol, and phenylenediamine antioxidants. Preferred among these are quinoline antioxidants, because they effectively suppress oxidation degradation and are less likely to cause rubber scorch. Examples of the quinoline antioxidants include 2,2,4-trimethyl-1,2-dihydroquinoline polymers and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and preferred are 2,2,4-trimethyl-1,2-dihydroquinoline polymers.
The quinoline antioxidant content, per 100 parts by mass of the rubber component, is preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more. If the quinoline antioxidant content is less than 0.5 parts by mass, the quinoline antioxidant may not sufficiently suppress oxidation degradation of the inner liner and neighboring components. The quinoline antioxidant content is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, and still more preferably 1.2 parts by mass or less. If the quinoline antioxidant content is more than 2.0 parts by mass, slip of the rotor tends to easily occur, which may cause deterioration in filler dispersibility, elongation at break, and kneading efficiency.
The use of a phenylenediamine antioxidant such as N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine or N-isopropyl-N′-phenyl-p-phenylenediamine may cause a butyl rubber to scorch easily during kneading. Hence, the phenylenediamine antioxidant content in the rubber composition of the present invention is preferably as low as possible. From such a point of view, the phenylenediamine antioxidant content is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and still more preferably 0 parts by mass (substantially not contained), per 100 parts by mass of the rubber component.
The rubber composition of the present invention preferably contains an alkylphenol-sulfur chloride condensate represented by the following formula (1). This further improves fuel economy. Additionally, the co-crosslinking with a neighboring component is improved and therefore good peeling resistance (adhesion) is achieved.




In the formula, R1, R2 and R3 are the same as or different from one another and each represent a C5 to C12 alkyl group; x and y are the same as or different from each other and each represent an integer of 1 to 3; and t represents an integer of 0 to 250.
The symbol t is an integer of 0 to 250, preferably an integer of 0 to 100, still more preferably an integer of 10 to 100, and particularly preferably an integer of 20 to 50, because the alkylphenol-sulfur chloride condensate disperses well into the rubber component. The symbols x and y are preferably both 2 so that high hardness can be efficiently achieved. The symbols R1 to R3 are each preferably a C6 to C9 alkyl group because the alkylphenol-sulfur chloride condensate disperses well into the rubber component.
The alkylphenol-sulfur chloride condensate may be prepared by a known method. For example, a method in which an alkylphenol is reacted with sulfur chloride at a molar ratio of, for example, 1:0.9-1.25 may be applied. Specific examples of the alkylphenol-sulfur chloride condensate include Tackirol V200 (in the formula (1), R1, R2 and R3 are each an octyl group (—C8H17); x and y are each 2; and t is 0 to 100) and TS3101 (in the formula (1), R1, R2 and R3 are each a dodecyl group (—C12H25); x and y are each 2; and t is 150 to 200), both produced by Taoka Chemical Co., Ltd.
In the rubber composition of the present invention which contains the alkylphenol-sulfur chloride condensate, the alkylphenol-sulfur chloride condensate content, per 100 parts by mass of the rubber component, is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more. An alkylphenol-sulfur chloride condensate content of less than 0.1 parts by mass may not sufficiently improve fuel economy. The alkylphenol-sulfur chloride condensate content is preferably 3 parts by mass or less, and more preferably 1.5 parts by mass or less. An alkylphenol-sulfur chloride condensate content of more than 3 parts by mass may lead to too fast a vulcanization rate, possibly causing rubber scorch more frequently.
The rubber composition of the present invention may optionally contain additives (e.g. oil, vulcanization accelerators and sulfur) generally used for the preparation of rubber compositions, in addition to the above components.
Examples of the oil include aromatic oils, process oils, and paraffin oils. Preferred among these are paraffin oils, because they have good bleed resistance with respect to butyl rubbers, and are less likely to cause problems such as sulfur bloom and adhesion failure.
The oil content, per 100 parts by mass of the rubber component, is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, for good sheet processability. The oil content is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less, in terms of ensuring satisfactory air barrier properties and filler dispersibility.
Examples of the vulcanization accelerators include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde-amine, aldehyde-ammonia, imidazoline, and xanthate vulcanization accelerators. Preferred among these are thiazole vulcanization accelerators, and more preferred is di-2-benzothiazolyl disulfide, because they have a high melting point and are less likely to cause rubber scorch.
The vulcanization accelerator content, per 100 parts by mass of the rubber component, is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 0.8 parts by mass or more. A vulcanization accelerator content of less than 0.2 parts by mass may not ensure a sufficient vulcanization rate. The vulcanization accelerator content is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less. A vulcanization accelerator content of more than 5 parts by mass may cause too fast a vulcanization rate.
The sulfur is not particularly limited, and those generally used in the tire industry may be used.
For favorably forming a crosslinked structure, the sulfur content, per 100 parts by mass of the rubber component, is preferably 0.3 parts by mass or more, and more preferably 0.4 parts by mass or more, and is preferably 1.0 parts by mass or less, and more preferably 0.8 parts by mass or less.
The sulfur content herein includes the amount of sulfur derived from the alkylphenol-sulfur chloride condensate represented by the formula (1).
The rubber composition of the present invention can be prepared by a commonly used method. Specifically, for example, the above components are kneaded with a known kneading machine generally used in the rubber industry, such as a Banbury mixer, a kneader, or an open roll mill, and then the resulting mixture is vulcanized, whereby the rubber composition can be prepared.
The rubber composition (vulcanized rubber composition) of the present invention preferably has a tan δ at 70° C. of 0.20 or lower. A rubber composition with a tan δ of higher than 0.20 may not ensure sufficient fuel economy. The lower limit of the tan δ at 70° C. is not particularly limited, and is typically 0.10 or higher when the combined content of the reclaimed butyl rubber and the halogenated butyl rubber is 70 mass % or more.
The tan δ at 70° C. is measured according to the method described in the EXAMPLES below.
The pneumatic tire of the present invention can be used for passenger vehicles, heavy load vehicles, industrial vehicles and the like, and is particularly suitable for passenger vehicles.
The pneumatic tire of the present invention can be produced by a commonly used method using the above rubber composition. Specifically, the rubber composition is extruded and processed into the shape of an inner liner, arranged in a usual manner in a tire building machine, and assembled with other tire components to form an unvulcanized tire. The resultant unvulcanized tire is then heat-pressurized in a vulcanizer to produce a tire.
Examples
Hereinafter, the present invention will be described in more detail based on examples. The examples are not intended to limit the scope of the present invention.
NR: TSR20
Chlorinated butyl rubber: chlorobutyl HT1066 produced by Exxon Mobil Corporation
Rubber reclaim: rubber reclaim (butyl rubber: 50 mass %, carbon black N660: 33 mass %, other components: 17 mass %) produced by Car Quest Co., Ltd.
Carbon black N762: Statex N762 (N2SA: 29 m2/g) produced by Columbian Chemicals Company
Carbon black N660: N660 (N2SA: 35 m2/g) produced by Jiangxi Black Cat Carbon Black Co., Ltd.
Carbon black N550: ShoBlack N550 (N2SA: 40 m2/g) produced by Cabot Japan K. K.
Silica Z1085: Z1085Gr (N2SA: 85 m2/g) produced by Rhodia
Silica Z115GR: Z115Gr (N2SA: 115 m2/g) produced by Rhodia
Silica VN3: ULTRASIL VN3 (N2SA: 175 m2/g) produced by Degussa
Silane coupling agent: Si75 produced by Degussa
Mixed resin: 40MS (a mixture of an aromatic hydrocarbon resin and an aliphatic hydrocarbon resin) produced by Struktol Company
Mineral oil: Diana Process Oil PA32 (paraffin oil) produced by Idemitsu Kosan Co., Ltd.
Zinc oxide: zinc oxide #2 produced by Mitsui Mining & Smelting Co., Ltd.
Stearic acid: stearic acid “Tsubaki” produced by NOF Corporation
Antioxidant 6PPD: Antigene 6C produced by Sumitomo Chemical Co., Ltd.
Antioxidant RD: Nocrack 224 produced by Ouchi Shinko Chemical Industrial Co., Ltd.
Finely ground bituminous coal 1: Austin Black 325 (average particle size: 5 μm, specific gravity: 1.3, BET specific surface area: 9.0 m2/g, oil content: 17 mass %) produced by Coal Fillers Inc.
Finely ground bituminous coal 2: Austin Black 325 (average particle size: 20 μm, oil content: 17 mass %) produced by Coal Fillers Inc.
Finely ground bituminous coal 3: Austin Black 325 (average particle size: 80 μm, oil content: 17 mass %) produced by Coal Fillers Inc.
Finely ground bituminous coal 4: Austin Black 325 (average particle size: 200 μm, oil content: 17 mass %) produced by Coal Fillers Inc.
Talc (flat talc): HAR (average particle size: 5.7 μm, specific gravity: 2.7, BET specific surface area: 22 m2/g) produced by Nihon Mistron Co., Ltd.
Mica: mica S-200HG (phlogopite, average particle size: 50 μm, aspect ratio: 55) produced by Repco Inc.
Hard clay: Crown Clay (average particle size: 0.6 μm) produced by Southeastern Clay Company
Calcium carbonate: Tancaru 200 (average particle size: 2.7 μm, specific gravity: 2.68, BET specific surface area: 1.5 m2/g) produced by Takehara Kagaku Kogyo Co., Ltd.
5% Oil-containing sulfur powder: HK-200-5 (oil content: 5 mass %) produced by Hosoi Chemical Industry Co., Ltd.
V200: Tackirol V200 (an alkylphenol-sulfur chloride condensate represented by the formula (1) in which R1, R2 and R3 are each an octyl group (—C8H17); x and y are each 2; and t is 0 to 100; sulfur content: 24 mass %; weight-average molecular weight: 9000) produced by Taoka Chemical Co., Ltd.
Vulcanization accelerator DM: Nocceler DM (di-2-benzothiazolyl disulfide) produced by Ouchi Shinko Chemical Industrial Co., Ltd.
Examples and Comparative Examples
According to each composition shown in Table 1 or 2, all of the chemicals except the zinc oxide, crosslinking agent(s) (sulfur, alkylphenol-sulfur chloride condensate), and vulcanization accelerator, were kneaded using a 1.7 L-Banbury mixer. Subsequently, to the kneaded mixture were added the zinc oxide, crosslinking agent(s), and vulcanization accelerator, and the resulting mixture was kneaded with a roll to prepare an unvulcanized rubber composition. The unvulcanized rubber composition was press vulcanized at 150° C. for 30 minutes to obtain a vulcanized rubber composition.
(Viscoelasticity Test)
The complex modulus (E*) and the loss tangent (tan δ) of the obtained vulcanized rubber compositions were measured at a temperature of 70° C., a frequency of 10 Hz, an initial strain of 10%, and a dynamic strain of 2%, using a viscoelasticity spectrometer VES (Iwamoto Seisakusho Co., Ltd.). An E*in the target range indicates good handling stability. The lower the tan δ is, the better the fuel economy is. The results of tan δ are also expressed in indices where the tan δ of Comparative Example 1 is 100. The higher the index is, the better the fuel economy is.
(Tensile Test)
A tensile test in accordance with JIS K 6251 “Rubber, vulcanized or thermoplastic—Determination of tensile stress-strain properties” was performed at room temperature on No. 3 dumbbell specimens formed of each vulcanized rubber composition to measure the elongation at break EB (%). The higher the EB is, the better the elongation at break (durability) is. The results of EB are also expressed in indices where the EB of Comparative Example 1 is 100. The higher the index is, the better the elongation at break is.
(Sheet Processability Test)
When extruded and processed, the unvulcanized rubber compositions were evaluated in terms of the following four properties: the scorch resistance of the extrudate, the flatness of the sheet, the shrinkage of the sheet, and the edge irregularities. The results of sheet processability of the unvulcanized rubber compositions are expressed in indices where the sheet processability index of Comparative Example 1 is 100. The higher the index, the better the sheet processability.
(Air Permeability Test)
The air permeabilities of the vulcanized rubber compositions were measured in accordance with ASTM D-1434-75M, and expressed in indices using the following equation. The higher the index of air barrier properties, the lower the air permeability of the vulcanized rubber composition, and, in turn, the better the air barrier properties.

(Index of air barrier properties)=(air permeability of Comparative Example 1)/(air permeability of each rubber composition)×100

(Compounding Cost)

The compounding costs of the rubber compositions are expressed in indices where the compounding cost of Comparative Example 1 is 100. The higher the index, the lower the compounding cost, and, in turn, the better the performance.
The compounding costs of the compounding ingredients are shown below. Organic substances requiring complicated production processes and heavy metals such as zinc oxide are expensive. Moreover, the order from more to less expensive polymers is: halogenated butyl rubber, NR, and reclaimed butyl rubber. The order from more to less expensive fillers is: mica/flat talc, silicas, carbon blacks, and semi-reinforcing fillers other than the mica and flat talc. On the other hand, the mineral oil and stearic acid, which can be easily produced, are less expensive. The key point in cost reduction is to reduce the amount of expensive compounding ingredients.
A: mineral oil, stearic acid, and sulfur
A: tackifying resins (mixed resin) and bituminous coals
B: hard clay, common talc, and calcium carbonate
B: carbon blacks and antioxidant RD
B: reclaimed butyl rubber
C: NR and silicas
D: halogenated butyl rubber, antioxidant 6PPD, silane coupling agent, flat talc, vulcanization accelerator, and mica
E: zinc oxide and V200
Definition of Symbols
A: 100 yen/L or less
B: 250 yen/L or less
C: 400 yen/L or less
D: 550 yen/L or less
E: 551 yen/L or more









TABLE 1









Example

























1
2
3
4
5
6
7
8
9
10
11
12
13
14
15





Composition (part(s)
NR
20
20
20
20
20
20
20
20
20
30
5
20
15
20
20


by mass)
Chlorinated butyl rubber
70
70
70
70
75
50
50
70
70
60
85
70
75
70
70



Rubber reclaim (butyl rubber content)
20 (10)
20 (10)
20 (10)
20 (10)
10 (5)
40 (20)
60 (30)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)



Carbon black N762
—
—
—
—
—
—
—
—
—
—
—
—
—
50
—



Carbon black N660
40
40
40
40
43
33.5
40
40
40
40
40
43
40
—
25



Carbon black N550
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Silica Z1085
—
—
—
—
—
—
—
—
—
—
—
—
—
—
20



Silica Z115GR
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Silica VN3
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Silane coupling agent
—
—
—
—
—
—
—
—
—
—
—
—
—
—
1.2



Mixed resin
5
5
5
5
5
5
5
5
5
5
5
15
1
5
5



Mineral oil
6
6
6
6
7
4
6
6
6
6
12
6
10
6
6



Zinc oxide
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.0
1.5
1.5
1.5
1.5



Antioxidant 6PPD
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Antioxidant RD
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1



Finely ground
20
—
5
35
20
20
20
20
—
—
20
20
20
20
20



bituminous coal 1



Finely ground
—
20
—
—
—
—
—
—
—
—
—
—
—
—
—



bituminous coal 2



Finely ground
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



bituminous coal 3



Finely ground
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



bituminous coal 4



Talc
—
—
—
—
—
—
—
—
20
20
—
—
—
—
—



Mica
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Hard clay
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Calcium carbonate
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



5% Oil-containing sulfur
0.45
0.45
0.45
0.45
0.45
0.3
0.3
0.3
0.45
0.45
0.2
0.45
0.45
0.45
0.45



powder (a)



V200 (b)
—
—
—
—
—
0.5
0.5
0.5
—
—
1.0
—
—
—
—



Total sulfur content of
0.428
0.428
0.428
0.428
0.428
0.405
0.405
0.405
0.428
0.428
0.430
0.428
0.428
0.428
0.428



(a) and (b)



Vulcanization
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25



accelerator DM


Evaluation
E* (Target: 3.0 to 4.0)
3.55
3.51
3.51
3.72
3.61
3.40
3.59
3.59
3.89
3.77
3.38
3.12
3.42
3.89
3.22



tan δ (Target: <0.20)
0.191
0.187
0.187
0.198
0.182
0.177
0.165
0.165
0.191
0.174
0.190
0.189
0.191
0.184
0.172



EB (%) (Target: >550)
595
585
605
555
615
565
600
600
595
605
660
560
635
570
655



tan δ index
105
107
107
102
110
114
122
122
105
116
106
106
105
109
117



(Target: ≧102)



EB index
117
115
119
109
121
111
118
118
117
119
129
110
125
112
128



(Target: ≧105)



Sheet processability
100
100
95
110
100
90
90
90
105
100
100
103
100
100
95



index (Target: ≧90)



Index of air barrier
101
101
101
101
103
102
101
101
111
102
129
100
102
104
105



properties



(Target: ≧100)



Compounding cost index
110
110
105
113
107
120
105
105
102
114
102
116
107
115
103



(Target: ≧102)












Example

























16
17
18
19
20
21
22
23
24
25
26
27
28
29
30





Composition (part(s)
NR
20
20
20
20
20
20
20
20
20
20
20
20
—
20
20


by mass)
Chlorinated butyl rubber
70
70
70
70
70
70
70
70
70
70
70
70
85
65
70



Rubber reclaim (butyl rubber content)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)
30 (15)
30 (15)
20 (10)



Carbon black N762
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Carbon black N660
25
40
40
40
40
40
40
40
40
45
40
40
40
40
40



Carbon black N550
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Silica Z1085
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Silica Z115GR
20
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Silica VN3
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Silane coupling agent
1.2
—
—
—
—
—
—
—
—
—
—
—
—
—
—



Mixed resin
5
5
5
5
5
5
5
5
—
22
5
5
5
5
5



Mineral oil
6
6
6
6
6
6
6
6
11
—
6
6
12
6
6



Zinc oxide
1.5
1.5
1.5
0.6
5
1.5
1.5
1.5
1.5
1.5
0.8
2.9
1.5
1.5
1.5



Stearic acid
1.5
0.5
2.7
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.0
1.5
1.5



Antioxidant 6PPD
—
—
—
—
—
—
1
—
—
—
—
—
—
—
—



Antioxidant RD
1
1
1
1
1
3
—
1
1
1
1
1
1
1
1



Finely ground
20
—
—
—
—
20
20
—
20
20
—
—
20
—
—



bituminous coal 1



Finely ground
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



bituminous coal 2



Finely ground
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



bituminous coal 3



Finely ground
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—



bituminous coal 4



Talc
—
20
20
20
20
—
—
—
—
—
20
20
—
—
—



Mica
—
—
—
—
—
—
—
—
—
—
—
—
—
40
25



Hard clay
—
—
—
—
—
—
—
15
—
—
—
—
—
—
—



Calcium carbonate
—
—
—
—
—
—
—
—
—
—
—
—
—
—
20



5% Oil-containing sulfur
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.20
0.45
0.45



powder (a)



V200 (b)
—
—
—
—
—
—
—
—
—
—
—
—
1
—
—



Total sulfur content of
0.428
0.428
0.428
0.428
0.428
0.428
0.428
0.428
0.428
0.428
0.428
0.428
0.430
0.428
0.428



(a) and (b)



Vulcanization
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25



accelerator DM


Evaluation
E* (Target: 3.0 to 4.0)
3.55
3.57
3.95
3.65
3.87
3.42
3.59
3.97
3.41
3.08
3.67
3.81
3.30
3.58
3.51



tan δ (Target: <0.20)
0.188
0.191
0.198
0.186
0.171
0.191
0.191
0.191
0.190
0.195
0.182
0.173
0.199
0.192
0.198



EB (%) (Target: >550)
670
555
580
615
625
555
575
555
640
540
615
620
665
605
605



tan δ index
107
105
102
108
118
105
105
105
106
103
110
116
101
105
102



(Target: ≧102)



EB index
131
109
114
121
123
109
113
109
125
106
121
122
130
119
119



(Target: ≧105)



Sheet processability
90
90
105
90
105
95
90
110
100
90
92
103
100
105
105



index (Target: ≧90)



Index of air barrier
101
100
100
101
100
100
100
100
100
100
101
100
134
120
113



properties



(Target: ≧100)



Compounding cost index
104
111
116
115
105
113
108
106
107
120
114
103
102
102
110



(Target: ≧102)


















TABLE 2









Comparative Example


















1
2
3
4
5
6
7
8
9
10






















Composition
NR
20
20
20
35
20
20
20
20
20
20


(part(s)
Chlorinated butyl rubber
80
80
40
65
80
70
70
70
70
70


by mass)
Rubber reclaim
—
—
80 (40)
—
—
20 (10)
20 (10)
20 (10)
20 (10)
20 (10)



(butyl rubber content)



Carbon black N762
—
—
—
—
—
—
65
—
—
—



Carbon black N660
46.5
46.5
20.3
40
46.5
—
—
15
40
40



Carbon black N550
—
—
—
—
—
30
—
—
—
—



Silica Z1085
—
—
—
—
—
—
—
—
—
—



Silica Z115GR
—
—
—
—
—
—
—
—
—
—



Silica VN3
—
—
—
—
—
—
—
30
—
—



Silane coupling agent
—
—
—
—
—
—
—
2.4
—
—



Mixed resin
0
5
5
5
5
5
5
5
5
5



Mineral oil
9
6
0
6
6
6
6
6
6
6



Zinc oxide
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Antioxidant 6PPD
—
—
—
—
—
—
—
—
—
—



Antioxidant RD
1
1
1
1
1
1
1
1
1
1



Finely ground
—
20
20
20
20
20
20
20
—
—



bituminous coal 1



Finely ground
—
—
—
—
—
—
—
—
—
—



bituminous coal 2



Finely ground
—
—
—
—
—
—
—
—
20
—



bituminous coal 3



Finely ground
—
—
—
—
—
—
—
—
—
20



bituminous coal 4



Talc
—
—
—
—
—
—
—
—
—
—



Mica
—
—
—
—
—
—
—
—
—
—



Hard clay
—
—
—
—
—
—
—
—
—
—



Calcium carbonate
30
—
—
—
—
—
—
—
—
—



5% Oil-containing sulfur
0.45
0.45
0.45
0.45
0.45
0.45
0.4
0.45
0.45
0.45



powder (a)



V200 (b)
—
—
—
—
—
—
—
—
—
—



Total sulfur content of
0.428
0.428
0.428
0.428
0.428
0.428
0.380
0.428
0.428
0.428



(a) and (b)



Vulcanization
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25



accelerator DM


Evaluation
E* (Target: 3.0 to 4.0)
3.99
3.67
3.52
3.67
3.67
3.59
3.92
3.37
3.52
3.49



tan δ (Target: <0.20)
0.201
0.185
0.255
0.184
0.185
0.218
0.227
0.204
0.189
0.187



EB (%) (Target: >550)
510
585
505
580
610
600
505
635
545
525



tan δ index
100
109
79
109
109
92
89
99
106
107



(Target: ≧102)



EB index
100
115
99
114
120
118
99
125
107
103



(Target: ≧105)



Sheet processability
100
95
100
103
95
100
85
80
100
105



index (Target: ≧90)



Index of air barrier
100
101
89
85
101
92
100
91
98
96



properties



(Target: ≧100)



Compounding cost
100
90
135
112
90
101
110
93
110
110



index (Target: ≧102)









The rubber compositions of the examples, each of which contained predetermined amounts of a reclaimed butyl rubber, a halogenated butyl rubber, a specific semi-reinforcing filler, and a specific carbon black and/or a specific silica, were more improved in handling stability, fuel economy, elongation at break, sheet processability, air barrier properties, and compounding cost in a balanced manner, compared with the rubber composition of Comparative Example 1.
The air barrier properties of the rubber compositions of the following examples were better by 10% or more than those of the rubber composition of Comparative Example 1: Examples 11 and 28, in which the reclaimed butyl rubber and the halogenated butyl rubber were contained in large amounts; Example 9, in which the combined content of the reclaimed butyl rubber and the halogenated butyl rubber was 80 parts by mass and talc was also used; and Examples 29 and 30, in which the combined content of the reclaimed butyl rubber and the halogenated butyl rubber was 80 parts by mass and mica was also used.
In the rubber composition of Example 21 containing 3 parts by mass of antioxidant RD, the elongation at break and the sheet processability were in acceptable levels, but were inferior to those in Example 1 since the filler dispersibility was reduced.
In the rubber composition of Example 22 containing the antioxidant 6PPD, the extrudate partially scorched; therefore, the sheet processability was inferior to that of Example 1 although it was in acceptable levels.
In the rubber composition of Example 17 containing a small amount of stearic acid, the zinc oxide dispersibility was reduced; therefore, the elongation at break and the sheet processability were inferior to those of Example 1 although they were in acceptable levels.
In the rubber composition of Example 18 containing a large amount of stearic acid, the lubricity during kneading was too high, which caused reduced filler dispersibility. Therefore, the fuel economy was inferior to that of Example 1 although it was in acceptable levels.

## Claims

1. An inner liner rubber composition, comprising:
a rubber component containing a reclaimed butyl rubber and a halogenated butyl rubber other than the reclaimed butyl rubber;
at least one semi-reinforcing filler selected from the group consisting of finely ground bituminous coal having an average particle size of 50 μm or less, talc, mica, and hard clay;
at least one of a carbon black having a nitrogen adsorption specific surface area of 20 to 35 m2/g and a silica having a nitrogen adsorption specific surface area of 40 to 120 m2/g; and zinc oxide,
wherein

the inner liner rubber composition has a reclaimed butyl rubber content of 5 to 30 mass % and a combined content of the reclaimed butyl rubber and the halogenated butyl rubber of 70 to 100 mass %, each based on 100 mass % of the rubber component,
the inner liner rubber composition has a total semi-reinforcing filler content of 3 to 45 parts by mass, a combined content of the carbon black and the silica of 20 to 60 parts by mass, and a content of zinc oxide of 0.8 to 1.8 parts by mass, each per 100 parts by mass of the rubber component.

2. The inner liner rubber composition according to claim 1, which has a tan δ at 70° C. of 0.20 or lower.

3. The inner liner rubber composition according to claim 1, wherein said at least one semi-reinforcing filler is finely ground bituminous coal.

4. The inner liner rubber composition according to claim 1, which contains a quinoline antioxidant.

5. The inner liner rubber composition according to claim 1, which has a phenylenediamine antioxidant content of 0.5 parts by mass or less per 100 parts by mass of the rubber component.

6. The inner liner rubber composition according to claim 1, comprising, per 100 parts by mass of the rubber component:
1 to 20 parts by mass of a mixed resin and
1.0 to 1.8 parts by mass of zinc oxide.

7. The inner liner rubber composition according to claim 1, comprising, per 100 parts by mass of the rubber component, 0.1 to 3 parts by mass of an alkylphenol-sulfur chloride condensate represented by the following formula (1):



wherein R1, R2 and R3 are the same as or different from one another and each represent a C5 to C12 alkyl group; x and y are the same as or different from each other and each represent an integer of 1 to 3; and t represents an integer of 0 to 250.

8. A pneumatic tire, comprising an inner liner formed from the rubber composition according to claim 1.