Rubber composition and pneumatic tire

Abstract

The present technology provides a rubber composition having: from 30 to 50 parts by mass of carbon black having a nitrogen adsorption specific surface area of from 100 to 130 m.sup.2/g, from 25 to 40 parts by mass of carbon black having a nitrogen adsorption specific surface area of from 37 to 60 m.sup.2/g, from 1.5 to 2.2 parts by mass of sulfur as a pure sulfur content, and from 110 to 200 mass % of a sulfenamide-based vulcanization accelerator relative to the pure sulfur content compounded in 100 parts by mass of diene rubber containing from 30 to 60 parts by mass of isoprene rubber and from 40 to 70 parts by mass of butadiene rubber.

Claims

1. A tire rim cushion rubber composition comprising from 30 to 50 parts by mass of carbon black (1) having a nitrogen adsorption specific surface area of from 100 to 130 m.sup.2/g, from 25 to 40 parts by mass of carbon black (2) having a nitrogen adsorption specific surface area of from 37 to 60 m.sup.2/g, from 1.5 to 2.2 parts by mass of sulfur as a pure sulfur content, and from 110 to 200 mass % of a sulfenamide-based vulcanization accelerator relative to the pure sulfur content in 100 parts by mass of diene rubber containing from 30 to 60 parts by mass of isoprene rubber and from 40 to 70 parts by mass of polybutadiene homopolymer; wherein an elongation at break at room temperature of a vulcanized rubber obtained by vulcanizing the tire rim cushion rubber composition is from 100 to 120.

2. The tire rim cushion rubber composition according to claim 1, wherein a hardness Hs (170) when the tire rim cushion rubber composition is vulcanized for 10 minutes at 170° C. is from 68 to 72, a hardness Hs (180) when the tire rim cushion rubber composition is vulcanized for 10 minutes at 180° C. is from 67 to 71, and a difference between the Hs (170) and the Hs (180) is 3 or less.

3. The tire rim cushion rubber composition according to claim 1, which comprises from 40 to 60 parts by mass of the isoprene rubber and from 40 to 60 parts by mass of the polybutadiene homopolymer when a total amount of the diene rubber is 100 parts by mass.

4. The tire rim cushion rubber composition according to claim 1, wherein the nitrogen adsorption specific surface area of the carbon black (1) is from 115 to 125 m.sup.2/g.

5. The tire rim cushion rubber composition according to claim 1, wherein the nitrogen adsorption specific surface area of the carbon black (2) is from 40 to 49 m.sup.2/g.

6. The tire rim cushion rubber composition according to claim 1, wherein the sulfenamide-based vulcanization accelerator is N-cyclohexyl-2-benzothiazolyl sulfenamide, N-tert-butyl-2-benzothiazolyl sulfenamide, or N,N′-dicyclohexyl-2-benzothiazolyl sulfenamide.

7. The tire rim cushion rubber composition according to claim 1, comprising from 30 to 45 parts by mass of the carbon black (1) in 100 parts by mass of the diene rubber.

8. The tire rim cushion rubber composition according to claim 1, comprising from 25 to 35 parts by mass of the carbon black (2) in 100 parts by mass of the diene rubber.

9. A pneumatic tire comprising the tire rim cushion rubber composition described in claim 1 in a rim cushion.

10. A tire rim cushion rubber composition comprising from 30 to 50 parts by mass of carbon black (1) having a nitrogen adsorption specific surface area of from 100 to 130 m.sup.2/g, from 25 to 40 parts by mass of carbon black (2) having a nitrogen adsorption specific surface area of from 37 to 60 m.sup.2/g, from 1.5 to 2.2 parts by mass of sulfur as a pure sulfur content, and from 110 to 200 mass % of a sulfenamide-based vulcanization accelerator relative to the pure sulfur content in 100 parts by mass of diene rubber containing from 30 to 60 parts by mass of isoprene rubber and from 40 to 70 parts by mass of polybutadiene homopolymer; wherein a tan δ at 10% initial strain, +/−2% amplitude, 20 Hz frequency, and 60° C. temperature of a vulcanized rubber obtained by vulcanizing the tire rim cushion rubber composition is from 90 to 100.

11. A tire rim cushion rubber composition comprising from 30 to 50 parts by mass of carbon black (1) having a nitrogen adsorption specific surface area of from 100 to 130 m.sup.2/g, from 25 to 40 parts by mass of carbon black (2) having a nitrogen adsorption specific surface area of from 37 to 60 m.sup.2/g, from 1.5 to 2.2 parts by mass of sulfur as a pure sulfur content, and from 110 to 200 mass % of a sulfenamide-based vulcanization accelerator relative to the pure sulfur content in 100 parts by mass of diene rubber containing from 30 to 60 parts by mass of isoprene rubber and from 40 to 70 parts by mass of polybutadiene homopolymer; wherein a rolling resistance of the tire rim cushion rubber composition expressed as an index value with respect to a reference index value of 100, tested at 80 km/h in accordance with JIS D4324:2009 and conditions for a passenger vehicle, is from 97-99, wherein the reference index value is based on a reference rubber obtained from a reference rubber composition comprising: 20 parts by mass of a first reference carbon black having a nitrogen adsorption specific surface area of 71 m.sup.2/g, 60 parts by mass of a second reference carbon black having a nitrogen adsorption specific surface area of 42 m.sup.2/g, 2.4 parts by mass of sulfur as a reference pure sulfur content, and 50 mass % of a reference sulfenamide-based vulcanization accelerator relative to the reference pure sulfur content in 100 parts by mass of a reference diene rubber containing 50 parts by mass of a reference isoprene rubber and 50 parts by mass of a reference polybutadiene homopolymer.

Description

DETAILED DESCRIPTION

(1) The present technology will be described in further detail below.

(2) Diene Rubber

(3) The diene rubber used in an embodiment of the present technology includes isoprene rubber and butadiene rubber (BR) as essential components. Examples of the isoprene rubber include various natural rubbers (NR), epoxidized natural rubber, and various synthetic polyisoprene rubbers (IR).

(4) In an embodiment of the present technology, when the total amount of the diene rubber is 100 parts by mass, it must contain from 30 to 60 parts by mass of isoprene rubber and from 40 to 70 parts by mass of butadiene rubber. If the amount of the isoprene rubber is less than 30 parts by mass, elongation at break and heat build-up will deteriorate, while the amount is greater than 60 parts by mass, the vulcanization temperature dependency of physical properties of rubber will deteriorate.

(5) In an embodiment of the present technology, when the total amount of the diene rubber is 100 parts by mass, the compounded amount of the isoprene rubber is preferably from 40 to 60 parts by mass, and the compounded amount of the butadiene rubber is preferably from 40 to 60 parts by mass.

(6) (Carbon Black CB)

(7) The rubber composition according to an embodiment of the present technology must include both carbon black (1) having a nitrogen adsorption specific surface area (N.sub.2SA) of from 100 to 130 m.sup.2/g and carbon black (2) having a nitrogen adsorption specific surface area (N.sub.2SA) of from 37 to 60 m.sup.2/g, thereby exhibiting its effect.

(8) The nitrogen adsorption specific surface area (N.sub.2SA) of the carbon black (1) is more preferably from 115 to 125 m.sup.2/g from the perspective of improving the effect of the present technology.

(9) Furthermore, the nitrogen adsorption specific surface area (N.sub.2SA) of the carbon black (2) is more preferably from 40 to 49 m.sup.2/g from the perspective of improving the effect of the present technology.

(10) The nitrogen adsorption specific surface area (N.sub.2SA) is a value calculated in accordance with JIS (Japanese Industrial Standard) K6217-2.

(11) (Sulfenamide-Based Vulcanization Accelerator)

(12) The sulfenamide-based vulcanization accelerator used in an embodiment of the present technology may be commercially available and known compounds, and specific examples include N-cyclohexyl-2-benzothiazolyl sulfenamide, N-tert-butyl-2-benzothiazolyl sulfenamide, and N, N′-dicyclohexyl-2-benzothiazolyl sulfenamide. N-cyclohexyl-2-benzothiazolyl sulfenamide is available from Ouchi Shinko Chemical Industrial Co., Ltd. under the trade name NOCCELER CZ-G, and N-tert-butyl-2-benzothiazolyl sulfenamide is available from Ouchi Shinko Chemical Industrial Co., Ltd. under the trade name NOCCELER NS-P.

(13) (Compounding Ratio of Rubber Composition)

(14) The rubber composition according to an embodiment of the present technology includes from 30 to 50 parts by mass of carbon black (1) having a nitrogen adsorption specific surface area of from 100 to 130 m.sup.2/g, from 25 to 40 parts by mass of carbon black (2) having a nitrogen adsorption specific surface area of 37 to 60 m.sup.2/g, from 1.5 to 2.2 parts by mass of sulfur as a pure sulfur content, and from 110 to 200 mass % of a sulfenamide-based vulcanization accelerator relative to the pure sulfur content in 100 parts by mass of the diene rubber.

(15) If the compounded amount of the carbon black (1) is less than 30 parts by mass, the hardness decreases. On the other hand, if the compounded amount is greater than 50 parts by mass, the heat build-up and physical breakage properties deteriorate.

(16) If the compounded amount of the carbon black (2) is less than 25 parts by mass, the heat build-up and physical breakage properties deteriorate. On the other hand, if the compounded amount is greater than 40 parts by mass, the hardness decreases.

(17) When the compounded amount of the pure sulfur content is less than 1.5 parts by mass, the heat build-up deteriorates. On the other hand, if the compounded amount is greater than 2.2 parts by mass, the physical breakage properties deteriorate.

(18) If the compounded amount of the sulfenamide-based vulcanization accelerator relative to the pure sulfur content is less than 110 mass %, the heat build-up deteriorates. On the other hand, if the compounded amount is greater than 200 mass %, the physical breakage properties deteriorate.

(19) The compounded amount of the carbon black (1) is more preferably from 30 to 45 parts by mass relative to 100 parts by mass of the diene rubber.

(20) The compounded amount of the carbon black (2) is more preferably from 25 to 35 parts by mass relative to 100 parts by mass of the diene rubber.

(21) The compounded amount of sulfur is more preferably from 1.7 to 2.2 parts by mass as the pure sulfur content.

(22) The compounded amount of the sulfenamide-based vulcanization accelerator is more preferably from 120 to 150 mass % relative to the pure sulfur content.

(23) In addition to the aforementioned components, the rubber composition according to an embodiment of the present technology can also contain various kinds of additives that are commonly added for other rubber compositions, such as vulcanizing or crosslinking agents, vulcanizing or crosslinking accelerators, various kinds of fillers, various kinds of oils, anti-aging agents, plasticizers, and the like. The additives may be kneaded in according to a common method and used in vulcanizing or crosslinking. Compounded amounts of these additives may be any known standard compounded amount, so long as the object of the present technology is not hindered.

(24) The rubber composition according to an embodiment of the present technology can suppress the vulcanization temperature dependency of the physical properties of rubber.

(25) For example, the hardness Hs (170) when the rubber composition is vulcanized for 10 minutes at 170° C. can be from 68 to 72, and the hardness Hs (180) when the rubber composition is vulcanized for 10 minutes at 180° C. can be from 67 to 71. Additionally, the difference between the Hs (170) and the Hs (180) can be 3 or less, so that the vulcanization temperature dependency of the physical properties of rubber is remarkably suppressed. The hardness Hs in the present technology is measured at 20° C. in accordance with JIS K6253.

(26) Furthermore, a wide range of vulcanization conditions can be employed for the rubber composition according to an embodiment of the present technology. For example, vulcanization conditions at a temperature of from 140 to 190° C. and a vulcanization time of from 5 minutes to 60 minutes can be employed.

(27) Additionally, the rubber composition according to an embodiment of the present technology can improve the hardness, heat build-up, and physical breakage properties at the same time, and thus is preferably used as a rubber composition for use in tire applications, particularly for tire rim cushions. Additionally, the rubber composition according to an embodiment of the present technology can be used to manufacture a pneumatic tire according to a known method for manufacturing pneumatic tires.

Example

(28) The present technology will be described in further detail by way of examples and comparative examples, but the present technology is not limited by these examples.

Examples 1 to 9 and Comparative Examples 1 to 13

(29) According to the composition (part by mass) shown in Tables 1 and 2, the components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes in a 1.7-L sealed Banbury Mixer. The vulcanization accelerator and sulfur were then added to the mixture and further kneaded to obtain a rubber composition. Next, the rubber composition thus obtained was pressure vulcanized in a predetermined mold at 170° C. for 10 minutes to obtain a vulcanized rubber test sample, and then the test methods shown below were used to measure the physical properties thereof.

(30) Hardness Hs: Measured at 20° C. in accordance with JIS K6253. The hardness Hs (170) when the rubber composition was vulcanized for 10 minutes at 170° C. and the hardness Hs (180) when the rubber composition was vulcanized for 10 minutes at 180° C. were measured. In addition, the difference between the Hs (170) and the Hs (180) was determined.

(31) Elongation at break: The elongation at break was tested at room temperature in accordance with JIS K 6251. The results are shown as an index with the value of Comparative Example 2 being 100. Larger values indicate superior elongation at break.

(32) tan δ (60° C.): The tan δ (60° C.) was measured using a viscoelasticity spectrometer (available from Toyo Seiki Seisaku-sho, Ltd.) under the following conditions: 10% initial strain, +/−2% amplitude, 20 Hz frequency, and 60° C. temperature. The results are shown as an index with the value of Comparative Example 2 being 100. Smaller index values indicate lower heat build-up.

(33) Tire rolling resistance (RRC): The tire rolling resistance was tested at 80 km/h in accordance with JIS D4324:2009 and conditions for a passenger vehicle. The results are expressed as index values with Comparative Example 2 being assigned the index value of 100. A smaller index value indicates lower rolling resistance.

(34) The results are shown in Tables 1 and 2.

(35) TABLE-US-00001 TABLE 1 Comparative Comparative Example Example Example Example 1 Example 2 1 2 3 NR 50 50 50 50 30 BR1 70 BR2 50 50 BR3 50 50 CB1 50 40 40 40 CB2 20 CB3 30 CB4 60 30 30 30 Oil 10 1 5 5 5 Anti-aging agent 1 2 2 2 2 2 Anti-aging agent 2 1 1 1 1 1 Wax 1 1 1 1 1 Stearic acid 2 2 2 2 2 Zinc oxide 3 3 3 3 3 Vulcanization accelerator 1 1.2 1.2 2.4 2.4 2.4 Vulcanization accelerator 2 Insoluble sulfur 3 3 2.2 2.2 2.2 Total 203.2 194.2 188.6 188.6 188.6 Pure sulfur content 2.4 2.4 1.76 1.76 1.76 Accelerator/ 50 50 136 136 136 pure sulfur content (%) Hs (170) 72 70 70 70 70 Hs (180) 68 65 68 68 69 Hs (170) - Hs (180) 4 5 2 2 1 Elongation at break 120 100 120 110 105 tan δ (60° C.) 190 100 95 95 100 RRC 105 100 98 98 99 Example Comparative Example Comparative Comparative 4 Example 3 5 Example 4 Example 5 NR 50 70 50 50 50 BR1 50 30 50 50 50 BR2 BR3 CB1 40 40 35 20 55 CB2 CB3 CB4 30 30 30 50 20 Oil 5 5 1 5 5 Anti-aging agent 1 2 2 2 2 2 Anti-aging agent 2 1 1 1 1 1 Wax 1 1 1 1 1 Stearic acid 2 2 2 2 2 Zinc oxide 3 3 3 3 3 Vulcanization 2.4 2.4 2.4 2.4 accelerator 1 Vulcanization 2.4 accelerator 2 Insoluble sulfur 2.2 2.2 2.2 2.2 2.2 Total 188.6 188.6 179.5 188.6 193.6 Pure sulfur content 1.76 1.76 1.76 1.76 1.76 Accelerator/ 136 136 136 136 136 pure sulfur content (%) Hs (170) 70 71 70 67 74 Hs (180) 68 67 69 65 71 Hs (170) - Hs (180) 2 4 1 2 3 Elongation at break 110 115 115 120 95 tan δ (60° C.) 95 90 90 80 115 RRC 98 97 97 96 101

(36) TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Example Example Example 2 Example 6 Example 7 6 7 NR 50 50 50 50 50 BR1 50 50 50 50 50 BR2 BR3 50 CB1 40 40 CB2 20 40 CB3 40 CB4 60 30 30 30 30 CB5 Oil 1 5 5 5 5 Anti-aging agent 1 2 2 2 2 2 Anti-aging agent 2 1 1 1 1 1 Wax 1 1 1 1 1 Stearic acid 2 2 2 2 2 Zinc oxide 3 3 3 3 3 Vulcanization 1.2 2.4 2.4 2.4 2.4 accelerator 1 Vulcanization accelerator 2 Insoluble sulfur 3 2.2 2.2 2 2.7 Total 194.2 188.6 188.6 188.4 189.1 Pure sulfur content 2.4 1.76 1.76 1.6 2.16 Accelerator/pure sulfur 50 136 136 150 111 content (%) Hs (170) 70 70 68 69 72 Hs (180) 65 66 64 67 71 Hs (170)-Hs (180) 5 4 4 2 1 Elongation at break 100 115 120 115 100 tan δ (60° C.) 100 85 75 100 90 RRC 100 97 96 99 97 Comparative Comparative Example Example Example 8 Example 9 8 9 NR 50 50 50 50 BR1 50 50 50 50 BR2 BR3 CB1 40 40 40 40 CB2 CB3 CB4 30 30 30 30 CB5 Oil 5 5 5 5 Anti-aging agent 1 2 2 2 2 Anti-aging agent 2 1 1 1 Wax 1 1 1 1 Stearic acid 2 2 2 2 Zinc oxide 3 3 3 3 Vulcanization accelerator 1 2.4 2.4 2 3.5 Vulcanization accelerator 2 Insoluble sulfur 1.7 3 2.2 2.2 Total 188.1 189.4 188.2 189.7 Pure sulfur content 1.36 2.4 1.76 1.76 Accelerator/pure sulfur content (%) 176 100 114 199 Hs (170) 68 73 69 71 Hs (180) 66 72 67 71 Hs (170)-Hs (180) 2 1 2 0 Elongation at break 120 90 113 100 tan δ (60° C.) 105 85 100 85 RRC 101 97 100 97 Comparative Comparative Comparative Comparative Example 10 Example 11 Example 12 Example 13 NR 50 50 50 50 BR1 50 50 50 50 BR2 BR3 CB1 40 40 40 40 CB2 CB3 CB4 30 30 CB5 30 30 Oil 5 5 5 5 Anti-aging agent 1 2 2 2 2 Anti-aging agent 2 1 1 1 1 Wax 1 1 1 1 Stearic acid 2 2 2 2 Zinc oxide 3 3 3 3 Vulcanization accelerator 1 1.8 4 2.4 2 Vulcanization accelerator 2 Insoluble sulfur 2.2 2.2 2 2.2 Total 188 190.2 188.4 188.2 Pure sulfur content 1.76 1.76 1.6 1.76 Accelerator/pure sulfur 100 227 150 114 content (%) Hs (170) 68 73 68 68 Hs (180) 65 73 66 66 Hs (170)-Hs (180) 3 0 2 2 Elongation at break 120 90 124 122 tan δ (60° C.) 105 80 90 91 RRC 101 97 98 99 NR: STR20 BR1: Nipol BR1220, available from Zeon Corporation BR2: UBEPOL BR130B, available from Ube Industries, Ltd. BR3: UBEPOL BR360, available from Ube-made by Ube Industries, Ltd. CB1: Show Black N234, available from Cabot Japan, nitrogen adsorption specific surface area (N2SA) = 123 m2/g) CB2: Show Black N330T, available from Cabot Japan, nitrogen adsorption specific surface area (N2SA) = 71 m2/g) CB3: Show Black N339, available from Cabot Japan, nitrogen adsorption specific surface area (N2SA) = 88 m2/g) CB4: Show Black N550, available from Cabot Japan nitrogen adsorption specific surface area (N2SA) = 42 m2/g) CB5: STERLING-V, available from Cabot Corporation, nitrogen adsorption specific surface area (N2SA) = 35 m2/g Oil: Extract No. 4S, available from Showa Shell Sekiyu K.K. Anti-aging agent 1: VULKANOX 4020, available from LANXESS K.K. Anti-aging agent 1: VULKANOX HS/LG, available from LANXESS K.K. Wax: OZOACE-0015A, available from Nippon Seiro Co., Ltd. Stearic acid: Stearic acid 50S, available from New Japan Chemical Co., Ltd. Zinc oxide: Zinc Oxide III, available from Seido Chemical Industry Co., Ltd. Vulcanization accelerator 1: NOCCELER NS-P, available from Ouchi Shinko Chemical Industrial Co., Ltd. Vulcanization accelerator 2: NOCCELER CZ-G, available from Ouchi Shinko Chemical Industrial Co., Ltd. Insoluble sulfur: Crystex HS OT 20 (pure sulfur content: 80 mass %), available from FlexSys Inc.

(37) As is evident from Table 1, since the rubber compositions prepared in Examples 1 to 9 each included two kinds of carbon black having specific nitrogen adsorption specific surface areas (N.sub.2SA), sulfur, and a sulfenamide-based vulcanization accelerator in specific amounts in diene rubber having a specific composition, the vulcanization temperature dependency of physical properties of rubber was suppressed without deteriorating the heat build-up, and the hardness and the physical breakage properties improved at the same time, compared to the composition of Comparative Example 2.

(38) In contrast, in Comparative Example 1, since the carbon black (2) was not included, the compounded amount of the pure sulfur content of Comparative Example 1 was greater than the upper limit specified in the present technology, and the compounded amount of the sulfenamide-based vulcanization accelerator relative to the pure sulfur content was less than the lower limit specified in the present technology, the temperature dependency of physical properties of rubber, heat build-up, and rolling resistance deteriorated.

(39) In Comparative Example 2, since the carbon black (1) was not included, the compounded amount of the pure sulfur content was greater than the upper limit specified in the present technology, and the compounded amount of the sulfenamide-based vulcanization accelerator relative to the pure sulfur content was less than the lower limit specified in the present technology, the temperature dependency of the physical properties of rubber deteriorated, and neither the heat build-up nor physical breakage properties improved as much as in Examples.

(40) In Comparative Example 3, since the compounded amount of the isoprene rubber was greater than the upper limit specified in the present technology, the temperature dependency of the physical properties of rubber deteriorated.

(41) In Comparative Example 4, since the compounded amount of the carbon black (1) was less than the lower limit specified in the present technology, and the compounded amount of the carbon black (2) was greater than the upper limit specified in the present technology, the hardness decreased.

(42) In Comparative Example 5, since the compounded amount of the carbon black (1) was greater than the upper limit specified in the present technology, and the compounded amount of the carbon black (2) was less than the lower limit specified in the present technology, the physical breakage properties and heat build-up deteriorated.

(43) In Comparative Examples 6 and 7, since the carbon black (1) was not included, the temperature dependency of the physical properties of rubber deteriorated.

(44) In Comparative Example 8, since the compounded amount of the pure sulfur component was less than the lower limit specified in the present technology, the heat build-up deteriorated.

(45) In Comparative Example 9, since the compounded amount of the pure sulfur content was greater than the upper limit specified in the present technology, and the compounded amount of the sulfenamide-based vulcanization accelerator relative to the pure sulfur content was less than the lower limit specified in the present technology, the physical breakage properties deteriorated.

(46) In Comparative Example 10, since the compounded amount of the sulfenamide-based vulcanization accelerator relative to the pure sulfur content was less than the lower limit specified in the present technology, the heat build-up deteriorated.

(47) In Comparative Example 11, since the compounded amount of the sulfenamide-based vulcanization accelerator relative to the pure sulfur content was greater than the upper limit specified in the present technology, the physical breakage properties deteriorated.

(48) In Comparative Examples 12 and 13, since the nitrogen adsorption specific surface area (N.sub.2SA) of the carbon black (2) was less than the lower limit specified in the present technology, the hardness Hs (180) decreased.