WO2018194063A1 - Composition de caoutchouc pour élément de couche interne de pneumatique, et pneumatique à usage intensif obtenu à l'aide de cette dernière - Google Patents

Composition de caoutchouc pour élément de couche interne de pneumatique, et pneumatique à usage intensif obtenu à l'aide de cette dernière Download PDF

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Publication number
WO2018194063A1
WO2018194063A1 PCT/JP2018/015886 JP2018015886W WO2018194063A1 WO 2018194063 A1 WO2018194063 A1 WO 2018194063A1 JP 2018015886 W JP2018015886 W JP 2018015886W WO 2018194063 A1 WO2018194063 A1 WO 2018194063A1
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WO
WIPO (PCT)
Prior art keywords
rubber composition
tire
rubber
layer member
mass
Prior art date
Application number
PCT/JP2018/015886
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English (en)
Japanese (ja)
Inventor
昇 齋藤
崇浩 齊藤
Original Assignee
株式会社ブリヂストン
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Filing date
Publication date
Application filed by 株式会社ブリヂストン filed Critical 株式会社ブリヂストン
Publication of WO2018194063A1 publication Critical patent/WO2018194063A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/40—Thiurams, i.e. compounds containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to a rubber composition for an inner layer member of a tire and a heavy duty pneumatic tire using the same (hereinafter, also simply referred to as “rubber composition” and “tire”, respectively).
  • the present invention relates to a rubber composition for an inner layer member of a tire that can achieve both high heat generation and crack growth resistance and a heavy-duty pneumatic tire using the same.
  • Patent Document 1 discloses a rubber composition for a tire tread that improves chipping resistance without deteriorating heat generation, and has high strength and elongation, and the performance can be maintained over a long period of time. Has been proposed.
  • the total amount of carbon black and silica having a nitrogen adsorption specific surface area (N 2 SA) of 90 m 2 / g or more with respect to 100 parts by weight of a diene rubber mainly composed of natural rubber and / or butadiene rubber is 30.
  • a rubber composition comprising ⁇ 70 parts by weight and less than 3 parts by weight of ultrahigh molecular weight polyethylene has been proposed. Although this rubber composition is a rubber composition for treads of heavy duty tires for icy and snowy roads, it is disclosed that deterioration of heat generation and fatigue resistance can be prevented.
  • the rubber used for the inner layer member of such a heavy duty pneumatic tire is required to have low heat generation and excellent wear resistance / cut resistance / tea resistance. From this point of view, the rubber compositions proposed in Patent Documents 1 and 2 are not necessarily sufficient in terms of low heat build-up and fracture resistance, which will be required for inner layer members of heavy duty pneumatic tires in the future. Absent.
  • an object of the present invention is to provide a rubber composition for an inner layer member of a tire and a heavy-duty pneumatic tire using the same, which can achieve both a low exothermic property and crack progress resistance at a higher level than before. There is.
  • a tire is manufactured by heating and vulcanizing an unvulcanized rubber composition.
  • the tire can reach the inside of the tire.
  • the vulcanization is performed under such a condition that the degree of vulcanization is larger than that of a tire for a general passenger car.
  • the present inventors have found that when vulcanization is performed under such conditions, the characteristics of the inner layer member such as low heat buildup and crack resistance are different from those of general passenger car tires. Based on such knowledge, the present inventors have made extensive studies to solve the above-mentioned problems. The present inventors have found that both can be achieved at a high level and have completed the present invention.
  • the rubber composition for an inner layer member of a tire according to the present invention is characterized in that silica, a thiuram compound, and a hydrazide compound are blended with a rubber component.
  • the rubber composition of the present invention 5 to 50 parts by mass of the silica, 0.1 to 2.0 parts by mass of the thiuram compound, and 0.1 to 2.0 parts of the hydrazide compound with respect to 100 parts by mass of the rubber component. It is preferably 5.0 parts by mass.
  • the nitrogen adsorption specific surface area of the said silica is 220 m ⁇ 2 > / g or more.
  • the rubber composition of the present invention preferably further contains carbon black.
  • the heavy duty pneumatic tire of the present invention is characterized in that the rubber composition for an inner layer member of the tire of the present invention is used for an inner layer member that is not in contact with an inner layer member other than rubber.
  • the gauge thickness of the tread portion is preferably 70 mm or more.
  • 1 is a schematic cross-sectional view in the width direction of a heavy duty pneumatic tire according to a preferred embodiment of the present invention. It is a general
  • the rubber composition for an inner layer member of a tire of the present invention is obtained by blending silica, a thiuram compound, and a hydrazide compound with a rubber component.
  • the type of rubber is not particularly limited.
  • natural rubber synthetic polyisoprene rubber (IR), polybutadiene (BR), styrene-butadiene copolymer (SBR), butyl rubber (IIR), ethylene-propylene-diene copolymer (EPDM), acrylonitrile-butadiene copolymer (NBR), rubbers combining these, and the like.
  • NR natural rubber
  • IR synthetic polyisoprene rubber
  • BR polybutadiene
  • SBR styrene-butadiene copolymer
  • IIR butyl rubber
  • EPDM ethylene-propylene-diene copolymer
  • NBR acrylonitrile-butadiene copolymer
  • the amount of silica is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the rubber component. If the addition amount of silica is less than 5 parts by mass, a sufficient decrease in exothermic property may not be observed. On the other hand, if it exceeds 50 parts by mass, the crack propagation resistance is excellent, but the low heat build-up may be inferior. More preferably, it is 10 to 20 parts by mass.
  • the silica used for the rubber composition of this invention there is no restriction
  • the silica preferably has a nitrogen adsorption specific surface area (BET specific surface area) of 80 m 2 / g or more, more preferably 220 m 2 / g or more. By using such silica, the effect of the present invention can be favorably obtained.
  • the nitrogen adsorption specific surface area is measured by a single point value of the BET method defined by a method based on ISO 5794/1.
  • silica may be used alone or in combination of two or more.
  • the amount of the thiuram compound is preferably 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount of thiuram is less than 0.1 parts by mass, the effect of improving low heat build-up and crack resistance may not be seen. On the other hand, if blending more than 2.0 parts by mass, the scorch of rubber It may be difficult to process due to deterioration of the properties. More preferably, it is 0.2 to 1.0 part by mass.
  • the blending amount of the hydrazide compound is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount of the hydrazide compound is less than 0.1 parts by mass, the low heat build-up may be insufficient. Is not preferable. More preferred is 0.5 to 2.0 parts by mass.
  • Examples of the hydrazide compound used in the rubber composition of the present invention include isophthalic acid dihydrazide, adipic acid dihydrazide, isophthalic acid di (1,3-dimethylpropylidene) hydrazide, and 2-naphthalic acid-3-hydroxy (1,3- Dimethylpropylidene) hydrazide, 2-naphthalenic acid-3-hydroxy (1,3-dimethylbutylidene) hydrazide, salicylic acid (1,3-dimethylpropylidene) hydrazide, isonicotinic acid hydrazide, isonicotinic acid (1,3- Dimethylpropylidene) hydrazide, salicylic acid hydrazide, 2-naphthalenic acid-3-hydroxyhydrazide, salicylic acid (1-methylethylidene) hydrazide, 2-naphthalenic acid-3-hydroxyhydrazide, salicylic acid (1-methylethy
  • the rubber composition of the present invention preferably further contains carbon black.
  • the amount of carbon black added is preferably such that the total of silica and carbon black is 30 to 55 parts by mass. If the total of silica and carbon black is less than 30 parts by mass, the specific exothermic deterioration may not be observed. On the other hand, if the total of silica and carbon black exceeds 55 parts by mass, the crack resistance is improved. However, low exothermic properties may deteriorate.
  • the carbon black is not particularly limited.
  • high, medium or low structure SAF, ISAF, IISAF, N339, HAF, FEF, GPF, SRF grade carbon Black can be used.
  • those having an iodine absorption of 35 to 90 g / kg can be preferably used.
  • the iodine absorption is less than 35 g / kg, the low heat build-up property is excellent, but the crack resistance may be poor.
  • the iodine absorption exceeds 90 g / kg, the crack growth resistance is excellent, but the low heat build-up may be deteriorated.
  • the iodine adsorption amount is a value measured according to JIS K 62177-1: 2001.
  • the rubber composition of the present invention it is important only that silica, a thiuram compound and a hydrazide compound are used in combination in the rubber, and there is no particular limitation other than that.
  • various chemicals usually used in the rubber industry for example, a vulcanizing agent, a vulcanization accelerator, a softening agent, and an anti-aging agent, as long as the object of the present invention is not impaired.
  • Viscosity reducing agents, zinc white, stearic acid, and the like can be used as appropriate.
  • the vulcanizing agent examples include sulfur, and the amount of the vulcanizing agent is preferably 0.1 to 10.0 parts by mass, more preferably 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component. Part. If the amount is less than 0.1 parts by mass, the fracture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. If the amount exceeds 10.0 parts by mass, rubber elasticity will be lost.
  • the vulcanization accelerator is not particularly limited.
  • M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide) And guanidine vulcanization accelerators such as DPG (diphenylguanidine).
  • the blending amount is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass with respect to 100 parts by mass of the rubber component.
  • process oil can be used, and examples thereof include paraffinic, naphthenic, and aromatic process oils.
  • an aromatic system is used for applications where importance is placed on tensile strength and wear resistance
  • a naphthenic system or paraffin system is used for applications where importance is placed on hysteresis loss and low temperature characteristics.
  • the blending amount is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it is 100 parts by mass or less, the deterioration of the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber is suppressed. can do.
  • antioxidants examples include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine), AW ( 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), a high-temperature condensate of diphenylamine and acetone, etc.
  • the blending amount is about 0.
  • the amount is preferably 1 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass.
  • the rubber composition of the present invention is obtained by kneading using a kneading machine such as an open kneading machine such as a roll or a closed kneading machine such as a Banbury mixer. Applicable to products. Although there is no restriction
  • FIG. 1 is a schematic cross-sectional view in the width direction of a heavy duty pneumatic tire according to a preferred embodiment of the present invention.
  • the illustrated tire 20 includes a pair of bead portions 1, a pair of side portions 2, and a tread portion 3, and a carcass 5 that extends in a toroid shape between bead cores 4 embedded in the bead portions 1.
  • the belt 6 includes a plurality of belt layers arranged on the outer side in the tire radial direction at the crown portion of the carcass 5, and the bead filler 7 on the outer side in the tire radial direction of the bead core 4.
  • the tire 20 of the present invention is used as an inner layer member that is not in contact with an inner layer member other than rubber of a heavy duty pneumatic tire, that is, the rubber composition of the present invention is used as a material other than a coating rubber.
  • FIG. 2 is a schematic enlarged cross-sectional view of the vicinity of the belt end portion of the heavy duty pneumatic tire according to one preferred embodiment of the present invention.
  • the rubber composition of the present invention includes, for example, each belt. It can be suitably used for the belt end rubbers 8a to 8e covering the ends of the layers 6a to 6e and the end cushion rubber 9 disposed in the gap between the upper and lower belt layers at the end of the belt layer.
  • the rubber composition of the present invention is, for example, a carcass. It can be suitably used as the soft stiffener 10 disposed between the main body 5a and the folded portion 5b of the carcass 5 or the sidewall filler 11 disposed on the outer side in the tire width direction of the carcass folded portion 5b.
  • the rubber composition of the present invention can also be used as a base rubber for the tread portion.
  • the rubber composition of the present invention is more effective in an inner layer member of a tire that is excessively vulcanized such that the gauge thickness of the tread portion is 70 mm or more.
  • the gauge thickness of the tread is as large as 70 mm or more.
  • vulcanization is performed excessively as compared with a general passenger car tire or the like, and vulcanization is performed under such a condition that the degree of vulcanization is increased.
  • the rubber composition for an inner layer member of the present invention contains a rubber component, silica, a hydrazide compound, and a thiuram compound, so that the inner layer member rubber excellent in low heat buildup and crack resistance is obtained. can get.
  • the gauge thickness of the tread portion is the thickness of the outermost layer reinforcing layer from the outer surface in the tire radial direction to the outer surface of the tire, and means the value at the thinnest position.
  • members other than these are not particularly limited, and known members can be used.
  • an inert gas such as nitrogen, argon, helium, etc. can be used in addition to normal or air with adjusted oxygen partial pressure.
  • Examples 1 to 6 and Comparative Examples 1 to 11 Rubber compositions were prepared with the formulations shown in Tables 1 to 3 below. The resulting rubber composition was vulcanized under vulcanization conditions at 160 ° C. for 20 minutes to prepare a predetermined test piece, and then the crack resistance and low heat build-up were evaluated by the following procedures. In addition, the unit of the compounding quantity in a table
  • surface is a mass part.
  • tan ⁇ was measured at a temperature of 60 ° C., a dynamic strain of 5%, and a frequency of 15 Hz. A smaller index value indicates a lower exothermic property and a smaller hysteresis loss.
  • the rubber composition of the present invention can achieve both low heat buildup and crack growth resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne : une composition de caoutchouc pour un élément de couche interne d'un pneumatique, la composition de résine permettant au pneumatique d'associer des propriétés de faible accumulation de chaleur et une résistance à la propagation des fissures d'un niveau supérieur à celui des pneumatiques classiques ; et un pneumatique à usage intensif obtenu à l'aide de la composition de caoutchouc. La composition de caoutchouc est obtenue par incorporation de silice, d'un composé de thirame, et d'un composé d'hydrazide dans un ingrédient de caoutchouc.
PCT/JP2018/015886 2017-04-18 2018-04-17 Composition de caoutchouc pour élément de couche interne de pneumatique, et pneumatique à usage intensif obtenu à l'aide de cette dernière WO2018194063A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-081984 2017-04-18
JP2017081984 2017-04-18

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WO2018194063A1 true WO2018194063A1 (fr) 2018-10-25

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08192608A (ja) * 1995-01-17 1996-07-30 Bridgestone Corp 空気入りタイヤのビード部構造
JP2007023070A (ja) * 2005-07-12 2007-02-01 Bridgestone Corp 高速高荷重用空気入りラジアルタイヤ
JP2009001682A (ja) * 2007-06-21 2009-01-08 Sumitomo Rubber Ind Ltd サイド補強層用ゴム組成物、およびこれを用いたランフラットタイヤ
JP2009101920A (ja) * 2007-10-24 2009-05-14 Bridgestone Corp タイヤ
JP2010285472A (ja) * 2009-06-09 2010-12-24 Bridgestone Corp 空気入りタイヤ
WO2014148453A1 (fr) * 2013-03-22 2014-09-25 株式会社ブリヂストン Composition de caoutchouc pour pneus et pneu
JP2015025093A (ja) * 2013-07-29 2015-02-05 東洋ゴム工業株式会社 ゴム組成物の製造方法
JP2015083639A (ja) * 2013-10-25 2015-04-30 東洋ゴム工業株式会社 ゴム組成物
JP2015093879A (ja) * 2013-11-08 2015-05-18 東洋ゴム工業株式会社 ゴム組成物の製造方法
JP2016041779A (ja) * 2014-08-15 2016-03-31 株式会社ブリヂストン タイヤ用ゴム組成物及びタイヤ
WO2016056219A1 (fr) * 2014-10-07 2016-04-14 株式会社ブリヂストン Composition de caoutchouc pour transporteur à courroie, et transporteur à courroie

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08192608A (ja) * 1995-01-17 1996-07-30 Bridgestone Corp 空気入りタイヤのビード部構造
JP2007023070A (ja) * 2005-07-12 2007-02-01 Bridgestone Corp 高速高荷重用空気入りラジアルタイヤ
JP2009001682A (ja) * 2007-06-21 2009-01-08 Sumitomo Rubber Ind Ltd サイド補強層用ゴム組成物、およびこれを用いたランフラットタイヤ
JP2009101920A (ja) * 2007-10-24 2009-05-14 Bridgestone Corp タイヤ
JP2010285472A (ja) * 2009-06-09 2010-12-24 Bridgestone Corp 空気入りタイヤ
WO2014148453A1 (fr) * 2013-03-22 2014-09-25 株式会社ブリヂストン Composition de caoutchouc pour pneus et pneu
JP2015025093A (ja) * 2013-07-29 2015-02-05 東洋ゴム工業株式会社 ゴム組成物の製造方法
JP2015083639A (ja) * 2013-10-25 2015-04-30 東洋ゴム工業株式会社 ゴム組成物
JP2015093879A (ja) * 2013-11-08 2015-05-18 東洋ゴム工業株式会社 ゴム組成物の製造方法
JP2016041779A (ja) * 2014-08-15 2016-03-31 株式会社ブリヂストン タイヤ用ゴム組成物及びタイヤ
WO2016056219A1 (fr) * 2014-10-07 2016-04-14 株式会社ブリヂストン Composition de caoutchouc pour transporteur à courroie, et transporteur à courroie

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