RUBBER COMPOSITION AND TIRE

Abstract

A rubber composition and a tire that can ensure the balance between the vulcanization speed and the foaming speed are provided. A rubber composition comprises: a diene-based rubber component; a foaming agent generating carbon dioxide; a fatty acid metal salt; and urea, wherein a content of the foaming agent is 0.1 parts to 20 parts by mass with respect to 100 parts by mass the diene-based rubber component, a total content of the fatty acid metal salt and the urea is 0.1 parts to 20 parts by mass with respect to 100 parts by mass the diene-based rubber component, and a mass ratio of the fatty acid metal salt and the urea is 1:0.5 to 1:3.9.

Claims

1. A rubber composition for a tire comprising: a diene-based rubber component; a foaming agent generating carbon dioxide; a fatty acid metal salt; and urea, wherein a content of the foaming agent is 0.1 parts to 20 parts by mass with respect to 100 parts by mass the diene-based rubber component, a total content of the fatty acid metal salt and the urea is 0.1 parts to 20 parts by mass with respect to 100 parts by mass the diene-based rubber component, and a mass ratio of the fatty acid metal salt and the urea is 1:0.5 to 1:3.9.

2. The rubber composition for a tire according to claim 1, wherein the fatty acid metal salt is at least one selected from the group consisting of zinc stearate and magnesium stearate.

3. The rubber composition for a tire according to claim 1, wherein the foaming agent is baking soda.

4. The rubber composition for a tire according to claim 1, wherein a content of the urea is 3 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

5. The rubber composition for a tire according to claim 1, wherein the total content of the fatty acid metal salt and the urea is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

6. The rubber composition for a tire according to claim 1, wherein the content of the foaming agent is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

7. A tire comprising a tread in which the rubber composition for a tire according to claim 1 is used.

8. The rubber composition for a tire according to claim 2, wherein the foaming agent is baking soda.

9. The rubber composition for a tire according to claim 2, wherein a content of the urea is 3 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

10. The rubber composition for a tire according to claim 2, wherein the total content of the fatty acid metal salt and the urea is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

11. The rubber composition for a tire according to claim 2, wherein the content of the foaming agent is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

12. A tire comprising a tread in which the rubber composition for a tire according to claim 2 is used.

13. The rubber composition for a tire according to claim 3, wherein a content of the urea is 3 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

14. The rubber composition for a tire according to claim 3, wherein the total content of the fatty acid metal salt and the urea is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

15. The rubber composition for a tire according to claim 3, wherein the content of the foaming agent is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

16. A tire comprising a tread in which the rubber composition for a tire according to claim 3 is used.

17. The rubber composition for a tire according to claim 4, wherein the total content of the fatty acid metal salt and the urea is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

18. The rubber composition for a tire according to claim 4, wherein the content of the foaming agent is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

19. A tire comprising a tread in which the rubber composition for a tire according to claim 4 is used.

20. The rubber composition for a tire according to claim 5, wherein the content of the foaming agent is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component.

Description

DETAILED DESCRIPTION

[0009] A rubber composition and a tire according to one of the disclosed embodiments are described in detail below.

[0010] (Rubber Composition)

[0011] A rubber composition according to one of the disclosed embodiments (hereafter also referred to as exemplary rubber composition) includes at least a diene-based rubber component, a foaming agent, a fatty acid metal salt, and urea, and optionally includes other components.

[0012] In addition to the diene-based rubber component, the foaming agent, the fatty acid metal salt, and the urea, the exemplary rubber composition may further contain compounding agents typically used in the rubber industry, which may be selected as appropriate without affecting the object of the present disclosure. Commercially available products may be suitably used as these compounding agents. The rubber composition according to the embodiment can be produced by mixing a mixture of the diene-based rubber component, the foaming agent, the fatty acid metal salt, and the urea with compounding agents optionally selected as appropriate and subjecting the mixture to kneading, warming, extrusion, etc.

[0013] <Diene-Based Rubber Component>

[0014] The diene-based rubber component is not limited, and may be selected as appropriate depending on the purpose. Examples include natural rubber (NR), and diene-based synthetic rubber such as butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), and chloroprene rubber (CR). Diene-based rubber mentioned here also includes appropriately modified products of these rubbers. These may be used singly or in combination of two or more.

[0015] Of these, natural rubber (NR) and butadiene rubber (BR) are preferable in terms of ensuring the on-ice (low temperature) flexibility of the rubber composition or tire.

[0016] <Foaming Agent>

[0017] The foaming agent is not limited as long as it generates carbon dioxide, and may be selected as appropriate depending on the purpose. Examples include inorganic foaming agents such as baking soda, sodium carbonate, calcium hydrogen carbonate, calcium carbonate, ammonium hydrogen carbonate, and ammonium carbonate. These may be used singly or in combination of two or more.

[0018] Of these, baking soda is preferable in terms of the balance between the vulcanization speed and the foaming speed.

[0019] The content of the foaming agent with respect to 100 parts by mass the diene-based rubber component is not limited as long as it is in a range of 0.1 parts to 20 parts by mass, and may be selected as appropriate depending on the purpose. The content is preferably 5 parts by mass or more, and more preferably 5 parts to 15 parts by mass.

[0020] If the content is less than 0.1 parts by mass, foaming does not occur. If the content is more than 20 parts by mass, there is a possibility of a decrease in wear resistance. If the content is in the preferable range or the more preferable range, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0021] <Fatty Acid Metal Salt>

[0022] The fatty acid metal salt is not limited, and may be selected as appropriate depending on the purpose. For example, zinc stearate and magnesium stearate are preferable in terms of the balance between the vulcanization speed and the foaming speed. These may be used singly or in combination of two or more.

[0023] Of these, zinc stearate is particularly preferable.

[0024] <Urea>

[0025] The content of the urea with respect to 100 parts by mass the diene-based rubber component is not limited as long as the total content of the fatty acid metal salt and the urea is in a range of 0.1 parts to 20 parts by mass, and may be selected as appropriate depending on the purpose. The content is preferably 3 parts by mass or more.

[0026] If the content is in the preferable range or a more preferable range, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0027] In the case where the foaming agent is baking soda, the content of the urea is preferably ? times or more the content of the baking soda. If the content of the urea is ? times or more the content of the baking soda as the foaming agent, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0028] <Total Content of Fatty Acid Metal Salt and Urea>

[0029] The total content of the fatty acid metal salt and the urea with respect to 100 parts by mass the diene-based rubber component is not limited as long as it is in a range of 0.1 parts to 20 parts by mass, and may be selected as appropriate depending on the purpose. The total content is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.

[0030] If the total content is in the preferable range or the more preferable range, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0031] <Mass Ratio of Fatty Acid Metal Salt and Urea>

[0032] The mass ratio of the fatty acid metal salt and the urea is not limited as long as it is in a range of 1:0.5 to 1:3.9, and may be selected as appropriate depending on the purpose. The mass ratio is preferably 1:0.7 to 1:3.3, and more preferably 1:0.9 to 1:2.7.

[0033] If the mass ratio is less than 1:0.5, baking soda does not foam. If the mass ratio is more than 1:3.9, vulcanization is excessively fast, and foaming does not occur. If the mass ratio is in the preferable range or the more preferable range, the balance between the foaming speed and the vulcanization speed can be ensured.

[0034] <Other Components>

[0035] The other components are not limited, and may be selected as appropriate depending on the purpose. Examples include a filler, an age resistor, a softener, stearic acid, zinc oxide, a vulcanization accelerator, a vulcanizing agent, oil, and sulfur.

[0036] In the rubber composition according to this embodiment, preferably, the fatty acid metal salt is at least one selected from the group consisting of zinc stearate and magnesium stearate. With this structure, the balance between the vulcanization speed and the foaming speed can be ensured reliably.

[0037] In the rubber composition according to this embodiment, further preferably, the foaming agent is baking soda. With this structure, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0038] In the rubber composition according to this embodiment, further preferably, the content of the urea is 3 parts by mass or more with respect to 100 parts by mass the diene-based rubber component. With this structure, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0039] In the rubber composition according to this embodiment, further preferably, the total content of the fatty acid metal salt and the urea is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component. With this structure, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0040] In the rubber composition according to this embodiment, further preferably, the content of the foaming agent is 5 parts by mass or more with respect to 100 parts by mass the diene-based rubber component. With this structure, the balance between the vulcanization speed and the foaming speed can be ensured more reliably.

[0041] (Tire)

[0042] A tire according to one of the disclosed embodiments (hereafter also referred to as exemplary tire) includes a tread in which the rubber composition according to this embodiment is used.

[0043] The method of producing the exemplary tire may be a conventional method. For example, members typically used for tire production, such as a carcass layer, a belt layer, and a tread layer containing unvulcanized rubber, are successively laminated on a drum for forming a tire. The drum is then removed to obtain a green tire. The green tire is then heated and vulcanized according to an ordinary method, to obtain a desired tire (e.g. pneumatic tire). Thus, the method of producing the exemplary tire includes, for example, (i) a lamination step and (ii) a heating and vulcanization step.

[0044] The tire according to this embodiment includes the tread in which the rubber composition according to this embodiment is used.

[0045] The tire according to this embodiment can ensure the balance between the vulcanization speed and the foaming speed. Hence, for example, a water drainage effect can be produced to thus improve on-ice performance, i.e. performance on ice (around 0? C.) which is most slippery.

EXAMPLES

[0046] The disclosed techniques are described in more detail below using examples, although the present disclosure is not limited to these examples.

Examples 1 to 13 and Comparative Examples 1 to 10

[0047] Rubber compositions of Examples 1 to 13 and Comparative Examples 1 to 10 were produced according to an ordinary method, based on the respective compounding recipes listed in Tables 1 and 2. In Tables 1 and 2, the unit is parts by mass unless otherwise indicated.

[0048] Each obtained rubber composition was vulcanized as a tread (foamed rubber layer), and a test passenger vehicle radial tire with tire size 185/70R15 was produced according to an ordinary method.

[0049] <Measurement of Foaming Ratio>

[0050] The foaming ratio Vs denotes the total foaming ratio in the tread, and was calculated according to the following formula using samples (n=10) collected from each tread:

Vs=((?.sub.0/?.sub.1)?1)?100(%)

[0051] where ?.sub.1 is the density (g/cm.sup.3) of the rubber (foamed rubber) after the vulcanization, and ?.sub.0 is the density (g/cm.sup.3) of a solid phase portion in the rubber (foamed rubber) after the vulcanization. For example, the density of the rubber (foamed rubber) after the vulcanization and the density of the solid phase portion in the rubber (foamed rubber) after the vulcanization were calculated by measuring the mass in ethanol and the mass in air. The measurement results and the evaluation results are listed in Tables 1 and 2. The evaluation criteria of the foaming ratio are as follows.

<Evaluation Criteria of Foaming Ratio>

[0052] Excellent: 95% or more and less than 105% in comparison with current foaming agent

[0053] Good: 50% or more and less than 95% in comparison with current foaming agent, 105% or more in comparison with current foaming agent

[0054] Poor: less than 50% in comparison with current foaming agent

[0055] <Measurement of Vulcanization Speed>

[0056] Measurement was taken using a typical rheometer, and quantified in vulcanization speed T0.9. The measurement results and the evaluation results are listed in Tables 1 and 2. The evaluation criteria of the vulcanization speed are as follows.

<Evaluation Criteria of Vulcanization Speed>

[0057] Excellent: 90% or more in comparison with current

[0058] Good: 50% or more and less than 90% in comparison with current

[0059] Poor: less than 50% in comparison with current

<Evaluation of On-Ice Performance>

[0060] Four tires corresponding to each of the above-mentioned test tires (tire size 185/70R15) were attached to a domestic 1600CC class passenger vehicle, and on-ice braking performance at freezing temperature ?1? C. was examined. The result was expressed by an index according to the following formula, using the tire of Comparative Example 1 as a control. A higher value indicates better on-ice performance. The evaluation results are listed in Tables 1 and 2.

On-ice performance=((braking distance of tire of Comparative Example 1)/(braking distance of sample tire))?100

TABLE-US-00001 TABLE 1 Example Comparative Example Comparative Example 1 Example 1 2 Example 2 3 Diene-based rubber component Natural Rubber (NR)*1 45 45 45 45 45 Butadiene rubber (BR)*2 55 55 55 55 55 Carbon black (CB)*3 35 35 35 35 35 Silica*4 41.86 41.86 41.86 41.86 41.86 Silane coupling agent*5 3.36 3.36 3.36 3.36 3.36 Oil*6 20 20 20 20 20 Wax*7 1.5 1.5 1.5 1.5 1.5 Age resistor 6C*8 1.5 1.5 1.5 1.5 1.5 Antioxidant RD*9 0.3 0.3 0.3 0.3 0.3 Vulcanization accelerator CZ*10 0.5 0.5 0.5 0.5 0.5 Sulfur 2 2 2 2 2 Stearic acid 0.75 2.75 2.75 3.25 0.75 Zinc oxide 1.5 2 2 2 1.5 Fatty acid metal salt Zinc stearate 2.2 0 0.5 0 3.3 Magnesium stearate 1 1 1 1 1 Fatty acid metal salt*11 0 0 0 0 0 Urea 4 4 4 4 4 Total of fatty acid metal salt and urea 7.2 5 5.5 5 8.3 Urea/fatty acid metal salt (mass ratio) 1.3 4.0 2.7 4.0 0.9 Foaming agent Baking soda*12 9 9 9 9 9 Organic foaming agent (DPT)*13 0 0 0 0 0 Organic foaming agent (ADCA)*14 0 0 0 0 0 Rubber composition Foaming ratio evaluation Excellent Poor Good Poor Excellent evaluation result Vulcanization speed evaluation Excellent Excellent Excellent Excellent Excellent Balance between vulcanization No No Low foaming No No and foaming problem foaming ratio foaming problem Tire evaluation result On-ice performance 100 70 90 70 100 Example Comparative Comparative Comparative Comparative 4 Example 3 Example 4 Example 5 Example 6 Diene-based rubber component Natural Rubber (NR)*1 45 45 45 45 45 Butadiene rubber (BR)*2 55 55 55 55 55 Carbon black (CB)*3 35 35 35 35 35 Silica*4 41.86 41.86 41.86 41.86 41.86 Silane coupling agent*5 3.36 3.36 3.36 3.36 3.36 Oil*6 20 20 20 20 20 Wax*7 1.5 1.5 1.5 1.5 1.5 Age resistor 6C*8 1.5 1.5 1.5 1.5 1.5 Antioxidant RD*9 0.3 0.3 0.3 0.3 0.3 Vulcanization accelerator CZ*10 0.5 0.5 0.5 0.5 0.5 Sulfur 2 2 2 2 2 Stearic acid 0.75 0.75 2.75 0.75 2.75 Zinc oxide 1.5 1.5 2 1.5 2 Fatty acid metal salt Zinc stearate 1.1 2.2 0 2.2 0 Magnesium stearate 1 0 0 0 0 Fatty acid metal salt*11 0 0 0 0 0 Urea 4 4 4 4 4 Total of fatty acid metal salt and urea 6.1 6.2 4 6.2 4 Urea/fatty acid metal salt (mass ratio) 1.9 1.8 1.8 Foaming agent Baking soda*12 9 0 0 0 0 Organic foaming agent (DPT)*13 0 5 5 0 0 Organic foaming agent (ADCA)*14 0 0 0 5 5 Rubber composition Foaming ratio evaluation Good Excellent Good Excellent Good evaluation result Vulcanization speed evaluation Excellent Excellent Excellent Excellent Excellent Balance between vulcanization Low foaming No Low foaming No Low foaming and foaming ratio problem ratio problem ratio Tire evaluation result On-ice performance 90 100 90 100 90

TABLE-US-00002 TABLE 2 Com- Com- Com- parative parative parative Ex- Ex- Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample ample ample 7 5 6 8 9 7 8 Diene-based Natural Rubber 45 45 45 45 45 45 45 rubber component (NR)*1 Butadiene rubber 55 55 55 55 55 55 55 (BR)*2 Carbon black (CB)*3 35 35 35 35 35 35 35 Silica*4 41.86 41.86 41.86 41.86 41.86 41.86 41.86 Silane coupling agent*5 3.36 3.36 3.36 3.36 3.36 3.36 3.36 Oil*6 20 20 20 20 20 20 20 Wax*7 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Age resistor 6C*8 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Antioxidant RD*9 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Vulcanization CZ*10 0.5 0.5 0.5 0.5 0.5 0.5 0.5 accelerator Sulfur 2 2 2 2 2 2 2 Stearic acid 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Zinc oxide 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Fatty acid metal salt Zinc stearate 0.03 1.7 6 7 2.2 2.2 2.2 Magnesium stearate 0 0 0 0 1 1 1 Fatty acid metal salt*11 0 0 0 0 0 0 0 Urea 0.06 3.4 12 14 1.3 1.6 12.4 Total of fatty acid metal salt and urea 0.09 5.1 18 21 4.5 4.8 15.6 Urea/fatty acid metal salt (mass ratio) 2.0 2.0 2.0 2.0 0.4 0.5 3.9 Foaming agent Baking soda*12 9 9 9 9 9 9 9 Organic foaming agent 0 0 0 0 0 0 0 (DPT)*13 Organic foaming agent 0 0 0 0 0 0 0 (ADCA)*14 Rubber composition Foaming ratio Poor Excel- Excel- Excel- Good Excel- Excel- evaluation result evaluation lent lent lent lent lent Vulcanization Excel- Excel- Good Poor Excel- Excel- Good speed evaluation lent lent lent lent Balance between Low No No No Low No No vulcanization and foaming prob- prob- foam- foaming prob- prob- foaming ratio lem lem ing ratio lem lem Tire evaluation On-ice 90 100 95 70 90 100 95 result performance Com- parative Ex- Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample ample 9 10 11 12 10 13 Diene-based Natural Rubber 45 45 45 45 45 45 rubber component (NR)*1 Butadiene rubber 55 55 55 55 55 55 (BR)*2 Carbon black (CB)*3 35 35 35 35 35 35 Silica*4 41.86 41.86 41.86 41.86 41.86 41.86 Silane coupling agent*5 3.36 3.36 3.36 3.36 3.36 3.36 Oil*6 20 20 20 20 20 20 Wax*7 1.5 1.5 1.5 1.5 1.5 1.5 Age resistor 6C*8 1.5 1.5 1.5 1.5 1.5 1.5 Antioxidant RD*9 0.3 0.3 0.3 0.3 0.3 0.3 Vulcanization CZ*10 0.5 0.5 0.5 0.5 0.5 0.5 accelerator Sulfur 2 2 2 2 2 2 Stearic acid 0.75 0.75 0.75 0.75 0.75 0.75 Zinc oxide 1.5 1.5 1.5 1.5 1.5 1.5 Fatty acid metal salt Zinc stearate 2.2 2.2 2.2 2.2 2.2 0 Magnesium stearate 1 1 1 1 1 0 Fatty acid metal salt*11 0 0 0 0 0 3.2 Urea 3 4 4 4 4 4 Total of fatty acid metal salt and urea 6.2 7.2 7.2 7.2 7.2 7.2 Urea/fatty acid metal salt (mass ratio) 0.9 1.3 1.3 1.3 1.3 1.3 Foaming agent Baking soda*12 9 0.1 5 20 21 9 Organic foaming agent 0 0 0 0 0 0 (DPT)*13 Organic foaming agent 0 0 0 0 0 0 (ADCA)*14 Rubber composition Foaming ratio Excel- Excel- Excel- Excel- Good Excel- evaluation result evaluation lent lent lent lent lent Vulcanization Excel- Excel- Excel- Excel- Excel- Excel- speed evaluation lent lent lent lent lent lent Balance between No No No No High No vulcanization and prob- prob- prob- prob- foaming prob- foaming lem lem lem lem ratio lem Tire evaluation On-ice 100 100 100 100 105 100 result performance

[0061] *1. Natural rubber (NR)

[0062] *2. Butadiene rubber (BR): (manufacturer name: JSR Corporation, trade name: Polybutadiene Rubber BR01)

[0063] *3. Carbon black (CB): (made by Asahi Carbon Co., Ltd., [N134 (N.sub.2SA: 146 m.sup.2/g)])

[0064] *4. Silica: (made by Tosoh Silica Corporation, trade name Nipsil AQ)

[0065] *5. Silane coupling agent: (made by Evonik Degussa Japan Co., Ltd., trade name Si69)

[0066] *6. Oil: naphthenic process oil: (made by Idemitsu Kosan Co., Ltd., trade name Diana Process Oil NS-24, pour point: ?30? C.)

[0067] *7. Wax

[0068] *8. Age resistor 6C: (N-phenyl-N-(1,3-dimethylbutyl)-p-phenylenediamine, made by Ouchi Shinko Chemical Industrial Co., Ltd., NOCRAC NS-6)

[0069] *9. Antioxidant RD: (made by Seiko Chemical Co., Ltd., NONFLEX RD)

[0070] *10. Vulcanization accelerator CZ: (made by Sanshin Chemical Industry Co., Ltd., Sanceler CZ)

[0071] *11. Fatty acid metal salt: zinc stearate: (made by NOF Corporation, Zinc Stearate G)

[0072] *12. Inorganic foaming agent: baking soda: (made by Otsuka Chemical Co., Ltd., P-5): foaming agent generating carbon dioxide

[0073] *13. Organic foaming agent: dinitrosopentamethylenetetramine (DPT): foaming agent not generating carbon dioxide

[0074] *14. Organic foaming agent: azodicarbonamide (ADCA): foaming agent not generating carbon dioxide

[0075] As shown in Tables 1 and 2, the rubber compositions of Examples 1 to 13 in which (i) the content of the foaming agent is 0.1 parts to 20 parts by mass with respect to 100 parts by mass the diene-based rubber component, (ii) the total content of the fatty acid metal salt and the urea is 0.1 parts to 20 parts by mass with respect to 100 parts by mass the diene-based rubber component, and (iii) the mass ratio of the fatty acid metal salt and the urea is 1:0.5 to 1:3.9 can ensure the balance between the vulcanization speed and the foaming speed, as compared with the rubber compositions of Comparative Examples 1 to 10 not satisfying at least one of (i) to (iii).

[0076] Moreover, as shown in Tables 1 and 2, the tires produced from the rubber compositions of Examples 1 to 13 satisfying all of (i) to (iii) have improved on-ice performance and can be produced in a predetermined range of vulcanization time, as compared with the tires produced from the rubber compositions of Comparative Examples 1 to 10 not satisfying at least one of (i) to (iii).