Tire

Abstract

The present invention addresses the problem of improving the durability of a tire on which an electronic component is mounted during travel. [Solution] A tire having a tread section, a bead section comprising a bead apex and a bead core, a lap section provided on the outside of the bead section in the tire width direction and extending to a chafer section, and a carcass layer, an electronic component is arranged between the bead apex and the tire body layer; the complex elastic modulus of 70 DEG C E * BA (MPa) of the bead apex measured in a deformation mode under stretching under the conditions of the temperature of 70 DEG C, the frequency of 10 Hz, the initial strain of 5% and the dynamic strain rate of 1%, and the complex elastic modulus of 70 DEG C E * CA (MPa) of the lap joint measured in the deformation mode under stretching under the conditions of the temperature of 70 DEG C, the frequency of 10 Hz, the initial strain of 5% and the dynamic strain rate of 1%; and the length L (mm) of the electronic component in the circumferential direction of the tire satisfies the following formula (1). (70 DEG C E * BA + 70 DEG C E * CA) / Lgt; 0.4 (Formula 1).

Description

Technical Field

[0001] The present invention relates to a tire in which electronic components such as RFID are embedded. Background Art

[0002] In recent years, proposals have been made to embed electronic components such as RFID (Radio Frequency IDentification) transponders (hereinafter referred to as "RFID") in tires for the purpose of recording information at the time of tire manufacturing / shipment or information during driving and communicating with the outside (for example, Patent Documents 1 to 4). [Prior art literature] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-506676 [Patent Document 2] Japanese Patent Publication No. 2021-514891 [Patent Document 3] Japanese Patent Application Publication No. 2021-084510 [Patent Document 4] Japanese Patent Application Publication No. 2021-127114 Summary of the invention [Problems to be solved by the invention]

[0004] However, when electronic components are embedded in an unvulcanized tire and integrated with the tire, there is a possibility that the electronic components and rubber components may be separated due to impact loads during running, thereby reducing the durability of the tire.

[0005] Therefore, an object of the present invention is to improve the durability of a tire equipped with an electronic component during driving.

Methods for solving the problem

[0006] The present invention is a tire characterized by comprising a tread portion, a bead portion composed of a bead apex rubber and a bead core, a lap portion arranged outside the bead portion in the tire width direction and extending to a bead chafer portion, and a carcass layer. An electronic component is arranged between the bead apex rubber and the carcass layer. The complex elastic modulus of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension 70°C E * BA (MPa), and The complex elastic modulus of the overlapped portion measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is 70°C E * CA (MPa), and The tire circumferential length L (mm) of the electronic component satisfies the following (Formula 1). (70℃E * BA+70℃E * CA) / L>0.4 (Formula 1) [Effects of the Invention]

[0007] According to the present invention, the durability of a tire equipped with an electronic component during running can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

[0009] [1] Characteristics of the tire according to the present invention First, the characteristics of the tire according to the present invention will be described.

[0010] 1. Summary The tire of the present invention comprises a tread portion, a bead portion composed of a bead apex rubber and a bead core, a lap portion arranged outside the bead portion in the tire width direction and extending to the bead chafer portion, and a carcass layer; an electronic component is arranged between the bead apex rubber and the carcass layer. In addition, the complex elastic modulus 70°C E of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension * BA (MPa), and the complex elastic modulus of the overlapped portion measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension 70°C E * CA (MPa) and the tire circumferential length L (mm) of the electronic component satisfy the following (Formula 1). (70℃E * BA+70℃E * CA) / L>0.4 (Formula 1)

[0011] By having these features, as described later, the durability of the tire equipped with the electronic component during running can be improved.

[0012] 2. Effect manifestation mechanism in the tire of the present invention The mechanism by which the above-mentioned effects are achieved in the tire according to the present invention is considered to be as follows.

[0013] As described above, in the tire of the present invention, the electronic component is provided between the bead apex and the carcass layer.

[0014] The carcass layer is a tire component constituting the tire frame, and compared with other tire components, has a significantly high elastic modulus. In addition, since the carcass layer constituting the tire frame becomes the center during tire deformation, it can be considered that the deformation near the carcass layer is smaller than the surrounding when traveling.

[0015] On the other hand, since the bead portion composed of the bead apex rubber and the bead core is a portion fixed to the rim, it is considered that the bead apex rubber connected to the bead core fixed to the rim has a small amount of deformation during running.

[0016] Therefore, it can be considered that when electronic components are provided between the bead apex rubber and the carcass layer, the deformation around the electronic components during driving can be reduced and the peeling of the electronic components inside the tire can be suppressed. As a result, damage to the tire can be suppressed and the durability of the tire equipped with electronic components during driving can be improved.

[0017] At this time, since the electronic component has a larger tire circumferential length, the electronic component is in contact with the surroundings for a longer length, which is likely to cause stress concentration and easily generate a starting point for peeling. Therefore, in the present invention, the sum of the complex elastic modulus of the bead apex rubber and the lap portion, which is a rigidity parameter representing the rubber layer, is increased relative to the length L, thereby suppressing stress concentration.

[0018] Specifically, it can be considered that 70℃E * BA and 70℃E * The sum of CA (70℃E * BA+70℃E * Ratio of CA) to L (mm) (70℃E * BA+70℃E * If CA) / L) is greater than 0.4, the concentration of stress can be sufficiently suppressed, thereby improving the durability of the tire equipped with electronic components during driving.

[0019] As described above, in the tire of the present invention, by providing an electronic component between the bead apex rubber and the carcass layer, the 70°E * BA and 70℃E * The sum of CA (70℃E * BA+70℃E * Ratio of CA) to L (mm) (70℃E * BA+70℃E * When CA) / L) is greater than a certain value, the deformation around the electronic components during driving can be reduced, while the concentration of stress can be fully suppressed, and the peeling of the electronic components in the tire can be suppressed, thereby improving the durability of the tire equipped with electronic components during driving.

[0020] In addition, among the above, the complex elastic modulus (E * ) can be measured using a viscoelasticity measuring device such as "EPLEXOR (registered trademark)" manufactured by GABO.

[0021] [2] A more preferred embodiment of the tire according to the present invention The tire according to the present invention can obtain greater effects by adopting the following aspects.

[0022] 1. Loss tangent of the tread In the present invention, the loss tangent 30°C tanδTR of the tread portion measured under the conditions of temperature 30°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is preferably less than 0.25. The loss tangent tanδ is a viscoelastic parameter that indicates energy absorption performance. The larger the value, the more energy can be absorbed, the greater the heat generation, and the greater the deformation. Therefore, by setting the 30°C tanδTR to a smaller value, the heat generated by the tread portion during driving can be reduced, and the temperature rise of the entire tire can be suppressed, so the durability of the tire equipped with electronic components during driving can be further improved.

[0023] At this time, the loss tangent 0°C tanδTR of the tread portion measured under the conditions of temperature 0°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is more preferably greater than 0.50. In this way, by increasing the loss tangent tanδ at low temperatures, the vibration generated by the influence of the road surface during driving can be suppressed on the surface of the tread portion, so that the deformation of the bead portion caused by the vibration of the tread surface can be fully suppressed, and the durability of the tire equipped with electronic components during driving can be further improved.

[0024] In addition, the "tread portion" refers to a component forming the tire contact surface area, and refers to a portion that is closer to the tire radial outside than components including fiber materials such as the carcass, belt layer, and belt reinforcement layer. The tread portion can be formed by only one layer of crown rubber layer, or by providing a base rubber layer on the inner side of the crown rubber layer to form two layers, or three layers, or more than four layers. In this case, the thickness of the crown rubber layer in the entire tread portion is preferably 10% or more. In addition, the thickness of the crown rubber layer in the entire tread portion is more preferably 70% or more.

[0025] The thickness of the cap rubber layer and the thickness of the base rubber layer can be calculated as follows: the total thickness of the cap rubber layer and the base rubber layer in the tread portion thickness measured in a radially cut tire cross section with the bead portion aligned with the regular rim width.

[0026] Here, "regular rim" refers to a rim specified for each tire in a specification system including the specification to which the tire is based, for example, in JATMA (Japan Automobile Tire Association), it refers to a standard rim in the applicable size recorded in "JATMAYEAR BOOK", in ETRTO (The European Tyre and Rim Technical Organisation), it refers to a "measuring rim" recorded in "STANDARDS MANUAL", and in TRA (The Tire and Rim Association, Inc.), it refers to a "design rim" recorded in "YEAR BOOK". JATMA, ETRTO, and TRA are used in this order. If there is an applicable size when referring, the specification is followed. In addition, in the case of a tire not specified in the specification, it refers to a tire with the smallest rim diameter and the narrowest rim width among the rims that can be assembled and can maintain the internal pressure, that is, the rims that will not leak air from the rim / tire.

[0027] The loss tangent (tan δ) can be measured, similarly to the complex elastic modulus, using a viscoelasticity measuring apparatus such as “EPLEXOR (registered trademark)” manufactured by GABO Corporation.

[0028] 2. Tire weight and maximum load capacity In the present invention, the ratio of the tire weight (kg) to the maximum load capacity (kg) of the tire (tire weight / maximum load capacity) is preferably less than 0.0150. In this way, in a tire with a smaller tire weight than the maximum load capacity of the tire, since the thickness of the rubber is relatively thin, the temperature rise of the entire tire can be fully suppressed, and the durability of the tire equipped with electronic components during driving can be further improved.

[0029] In the above description, "tire weight (kg)" means the weight of the tire alone excluding the rim weight.

[0030] In addition, when the tire cross-sectional width measured under normal conditions is set to Wt (mm), the tire cross-sectional height is set to Ht (mm), and the tire outer diameter is set to Dt (mm), the "maximum load capacity (kg)" can be obtained as WL by the following formula. Here, under normal conditions, when there are patterns or text on the side of the tire, the tire cross-sectional width Wt is the maximum width between the outer surfaces of the sidewalls after removing these patterns or text. In addition, the tire cross-sectional height Ht is 1 / 2 of the difference between the outer diameter of the tire and the nominal diameter of the rim. V = {(Dt / 2) 2 -(Dt / 2-Ht) 2}×π×Wt WL=0.000011×V+100

[0031] In the above description, "normal state" means that the tire is mounted on a normal rim and filled with normal internal pressure, and is unloaded. In addition, "normal internal pressure" refers to the air pressure specified for each tire in the specification system including the specification to which the tire is based. In JATMA, it refers to "maximum air pressure", in ETRTO, it refers to "INFLATION PRESSURE", and in TRA, it refers to the maximum value recorded in the table "TIRE LOAD LIMITS AT VARIOUS COLDINFLATION PRESSURES". Reference is made in the order of JATMA, ETRTO, and TRA. If there is an applicable size when referring, it is in accordance with the standard. In the case of a tire not specified in the specification, it refers to the normal internal pressure (but above 250KPa) of other tire sizes (specified in the specification) that record the normal rim as a standard rim. In addition, in the case of multiple normal internal pressures above 250KPa, it refers to the minimum value among them.

[0032] 3. Tire radial distance from the upper end of the bead core to the electronic components (1) Since the tire radial distance D2 from the upper end of the bead core to the electronic component is larger, the bead apex rubber is more likely to deform and generate heat. Therefore, it is preferred to reduce the loss tangent of the bead apex rubber relative to the tire radial distance from the upper end of the bead core to the electronic component to suppress the heating of the bead apex rubber.

[0033] Specifically, it is believed that when the product of 70°C tanδBA and the tire radial distance D2 (mm) from the upper end of the bead core to the electronic component is 8.5 or less, heat generation can be appropriately suppressed and the durability of the tire equipped with electronic components during driving can be further improved.

[0034] In the above description, "the upper end of the bead core" refers to the outer edge of the bead core in the tire radial direction.

[0035] (2) In addition, it is also preferable to increase the complex elastic modulus of the bead apex rubber with respect to the tire radial distance from the upper end of the bead core to the electronic component.

[0036] Specifically, it can be considered that the complex elastic modulus of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is 70°C E * Ratio of BA (MPa) to the tire radial distance D2 (mm) from the upper end of the bead core to the electronic component (70°C E* When BA / D2) is greater than 0.85, the deformation of the bead apex rubber can be sufficiently suppressed, and the durability of the tire equipped with electronic components during driving can be further improved.

[0037] (3) In addition, it is preferred that the ratio (D2 / H) of D2 (mm) to the height of the bead apex, that is, the distance H (mm) from the upper end of the bead core to the front end top of the bead apex is greater than 0.2 and less than 0.8. By arranging the electronic components at this position, heat generation and peeling can be appropriately suppressed.

[0038] 4. Complex elastic modulus of bead apex rubber and overlap and circumferential length of electronic components As described above, it can be considered that the larger the circumferential length of the electronic component in the tire, the longer the length of contact between the electronic component and the surrounding area, and the easier it is to produce a starting point for peeling. However, by increasing the ratio of the complex elastic modulus of the bead apex rubber to the complex elastic modulus of the lap joint and simultaneously increasing this ratio relative to the circumferential length of the electronic component in the tire, it is easy to suppress the deformation of the contact portion between the electronic component and its surrounding area, thereby further improving the durability of the tire equipped with the electronic component during driving.

[0039] Specifically, it can be considered that 70℃E * BA relative to 70℃E * CA ratio (70℃E * BA / 70℃E * Ratio of CA) to L (mm) (70℃E * BA / 70℃E * When the ratio CA) / L) is 0.05 or more, the occurrence of deformation of the contact portion between the electronic component and its surroundings can be suppressed, and the durability of the tire equipped with the electronic component during driving can be further improved.

[0040] 5. Loss tangent of bead apex rubber and overlap and circumferential length of electronic components As mentioned above, since the bead apex is a part fixed to the rim, it can be considered that the deformation amount during driving is small, but despite this, it will deform and generate heat during the rolling of the tire. On the other hand, since the lap portion is also a part fixed to the rim, it can be considered that the deformation amount during driving is small, but despite this, it will deform and generate heat during the rolling of the tire.

[0041] Therefore, it can be considered that by controlling the product of the sum of the heat generation (loss tangent) of the bead apex rubber and the overlap portion and the circumferential length of the electronic component in the tire to below a certain value, the heat generation and heat accumulation around the electronic component can be suppressed, the occurrence of deformation can be suppressed, and the durability of the tire equipped with electronic components during driving can be further improved.

[0042] That is, as described above, the greater the loss tangent tanδ value, the greater the absorbed energy, the greater the heat generated, and the deformation. On the other hand, the smaller the tire circumferential length of the electronic component, the easier it is to dissipate heat and the more heat can be suppressed.

[0043] Specifically, it can be considered that if the product of the sum of 70℃tanδBA and 70℃tanδCA (70℃tanδBA+70℃tanδCA) and the tire circumferential length L (mm) of the electronic component ((70℃tanδBA+70℃tanδCA)×L) is controlled to be below 30, it is possible to suppress heat generation and heat accumulation around the electronic component, suppress deformation, and improve the durability of the tire equipped with electronic components during driving.

[0044] At this time, it can be considered that when the product of the loss tangent 70°C tanδBA of the bead apex rubber and the tire circumferential length L (mm) of the electronic component (70°C tanδBA×L) is 15 or less, the heating of the bead apex rubber and the peeling of the electronic component in the tire can be further suppressed, and the durability of the tire equipped with the electronic component during driving can be further improved. In addition, it is more preferably 13 or less.

[0045] 6. Electronic components In the present invention, RFID or a sensor is preferably used as an electronic component. Considering that a large amount of information can be stored and read in a non-contact manner, in addition to data such as pressure and temperature, tire manufacturing information, management information, customer information, etc. can also be stored. RFID is more preferred. In addition, as specific sensors, for example, pressure sensors, temperature sensors, acceleration sensors, magnetic sensors, groove depth sensors, etc. can be listed.

[0046] In addition, it is preferable to provide an adhesive layer or a plating layer on the surface of the electronic component to improve the adhesiveness with the rubber. This can sufficiently suppress the peeling of the electronic component.

[0047] As a specific adhesive layer, a known metal-rubber adhesive can be used, which can be purchased from LORD Corporation, etc. The plating layer preferably contains copper, and preferably forms an alloy with tin, nickel, iron, zinc, cobalt, aluminum, magnesium, etc.

[0048] In addition, it is preferred to provide an electronic component coating layer having a thickness of 0.5 mm or more on the surface of the electronic component. Thus, by providing an appropriate interval between the electronic component and the adjacent bead apex or carcass layer, it is less susceptible to interface deformation and can fully suppress the peeling of the electronic component.

[0049] As a specific electronic component covering layer, for example, a rubber composition or a thermoplastic elastomer composition can be used, and examples thereof include the rubber compositions described in this specification and rubber compositions known in the field of tires.

[0050] The product of the shortest distance D1 (mm) to the tire outer surface and the weight W (g) of the electronic component (D1×W) is preferably 2.5 or less. By controlling D1×W to such a value, deformation around the electronic component and peeling can be sufficiently suppressed.

[0051] In addition, in the present invention, the length L of the electronic component in the longitudinal direction (including the antenna) is preferably 80 mm or less, and more preferably 50 mm or less. By forming such a size, it is possible to suppress the generation of local stress concentration, and the electronic component can be properly attached to the tire component, so that peeling can be fully suppressed, and the durability of the tire equipped with the electronic component during driving can be further improved.

[0052] [3] Implementation Method Hereinafter, the present invention will be described in detail based on embodiments.

[0053] 1. Tire of this embodiment Figure 1 , Figure 2 Schematic cross-sectional view showing a tire structure according to one embodiment of the present invention. Figure 1 , Figure 2 In the figure, 1 is a tire, 2 is a bead portion, 3 is a sidewall portion, 4 is a tread portion, 31 is a sidewall portion, 32 is a carcass layer, 33 is an inner liner layer, and 34 is an electronic component. The carcass layer 32 is folded back from the inner side to the outer side in the tire width direction along the bead core 21 and the bead apex rubber 22 constituting the bead portion 2 at the lower end of the bead core 21, and is bonded to the inner carcass layer 32. In addition, a bead chafer 24 is provided on the inner side of the bead portion 2 in the tire width direction, and a lap portion 23 extending to the bead chafer 24 is provided on the outer side in the tire width direction.

[0054] like Figure 1 and Figure 2 As shown, in the present embodiment, the electronic component 34 is disposed between the bead apex 22 and the carcass layer 32. Here, "an electronic component is disposed between the bead apex and the carcass layer" means that the electronic component is disposed between the surfaces on the opposite sides of each surface in contact with the bead apex and the carcass layer, and also includes the case where the electronic component is buried in the bead apex or the carcass layer.

[0055] For example, in Figure 1 In the embodiment, the electronic component 34 is disposed between the bead apex rubber 22 and the carcass layer 32 on the inner side in the tire width direction. Figure 2 In the embodiment, the electronic component 34 is provided between the bead apex 22 and the carcass layer 32 on the outer side in the tire width direction.

[0056] Figure 3Schematic top views showing the electronic components used in this embodiment, with (a) and (b) being shown as examples. Figure 3 As shown in (a) and (b), the electronic component 34 is composed of a main body 34a composed of an IC chip and an antenna 34b.

[0057] Through this structure, the bead apex rubber 22, the overlap portion 23, and the tread portion 4 meet the above-mentioned parameters, which can fully reduce the deformation around the electronic components and inhibit the breakage and damage of the electronic components, thereby improving the durability of the tire equipped with electronic components during driving.

[0058] 2. Rubber composition In the present embodiment, the rubber compositions constituting the above-mentioned bead apex rubber, lap portion and tread (hereinafter respectively referred to as "rubber composition for bead apex rubber", "rubber composition for lap portion" and "rubber composition for tread") can be obtained by kneading various mixed materials such as rubber components, reinforcing materials, antioxidants, oils, resin materials, antioxidants and additives.

[0059] (1) Mixed materials (a) Rubber component In each rubber composition, the rubber component is not particularly limited, and for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR) and other diene rubbers can be used. These can be used alone or in combination of two or more. For example, in the rubber composition for bead apex rubber, it is preferred to use isoprene rubber and SBR in combination, in the rubber composition for clinch part, it is preferred to use isoprene rubber and BR in combination, and in the rubber composition for tread, it is preferred to use isoprene rubber, SBR, and BR in combination.

[0060] (①) Isoprene rubber Examples of the isoprene-based rubber include natural rubber (NR), isoprene rubber (IR), modified NR, modified NR, and modified IR. NR is preferred because of its excellent strength.

[0061] As NR, for example, SVR-L, SIR20, RSS#3, TSR20 and other NRs commonly used in the tire industry can be used. As IR, there is no particular limitation, and for example, IR2200 manufactured by Japan Zeon Co., Ltd. and other IRs commonly used in the tire industry can be used. As modified NR, deproteinized natural rubber (DPNR), high purity natural rubber (UPNR) and the like can be listed, as modified NR, epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), grafted natural rubber and the like can be listed, as modified IR, epoxidized isoprene rubber, hydrogenated isoprene rubber, grafted isoprene rubber and the like can be listed. These can be used alone or in combination of two or more.

[0062] In the rubber composition for bead apex, the content of isoprene-based rubber in 100 parts by mass of the rubber component is preferably 75 parts by mass or more, more preferably 80 parts by mass or more, and preferably 95 parts by mass or less, more preferably 90 parts by mass or less.

[0063] In the rubber composition for a clinch, the content of the isoprene-based rubber in 100 parts by mass of the rubber component is preferably 35 parts by mass or more, more preferably 55 parts by mass or more, and is preferably 70 parts by mass or less, more preferably 65 parts by mass or less.

[0064] In the rubber composition for tread, the content of the isoprene-based rubber in 100 parts by mass of the rubber component is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and is preferably 15 parts by mass or less, more preferably 12 parts by mass or less.

[0065] (②) SBR The weight average molecular weight of SBR is, for example, greater than 100,000 and less than 2,000,000. The styrene content of SBR is, for example, preferably greater than 5% by mass, more preferably greater than 10% by mass, and further preferably greater than 15% by mass. On the other hand, it is preferably less than 40% by mass, more preferably less than 35% by mass, and further preferably less than 30% by mass. The vinyl content (1,2-bonded butadiene unit amount) of SBR is, for example, preferably greater than 5% by mass, more preferably greater than 10% by mass, and further preferably greater than 15% by mass. On the other hand, it is preferably less than 70% by mass, more preferably less than 40% by mass, and further preferably less than 30% by mass. In addition, the structural identification of SBR (styrene content, determination of vinyl content) can be carried out using the device of the JNM-ECA series manufactured by JEOL Ltd., for example.

[0066] There is no particular limitation on SBR, and for example, emulsion polymerization styrene butadiene rubber (E-SBR), solution polymerization styrene butadiene rubber (S-SBR), etc. can be used. SBR can be any of non-modified SBR and modified SBR. In addition, hydrogenated SBR obtained by hydrogenating the butadiene part in SBR can also be used, and hydrogenated SBR can also be obtained by post-hydrogenation treatment of the BR part in SBR, and styrene, ethylene, and butadiene can also be copolymerized to obtain the same structure.

[0067] As the modified SBR, preferably an SBR having a functional group that interacts with a filler such as silica, for example, an end-modified SBR obtained by modifying at least one end of the SBR with a compound (modifier) ​​having the above functional group (end-modified SBR having the above functional group at the end); a main chain-modified SBR having the above functional group in the main chain; a main chain-end-modified SBR having the above functional group in the main chain and at the end (for example, a main chain-end-modified SBR having the above functional group in the main chain and at least one end modified with the above modifier); an end-modified SBR modified (coupled) by a polyfunctional compound having two or more epoxy groups in the molecule and having a hydroxyl group or epoxy group introduced therein, etc.

[0068] Examples of the functional group include amino, amide, silyl, alkoxysilyl, isocyanate, imino, imidazolyl, urea, ether, carbonyl, oxycarbonyl, mercapto, sulfhydryl, disulfide, sulfonyl, sulfinyl, thiocarbonyl, ammonium, imido, hydrazino, azo, diazo, carboxyl, cyano, pyridyl, alkoxy, hydroxyl, oxy, and epoxy groups. These functional groups may have substituents.

[0069] As the modified SBR, for example, SBR modified with a compound (modifier) ​​represented by the following formula can be used.

[0070]

Chemistry 1

[0071] In addition, in the formula, R 1 , R 2 and R 3 are the same or different and represent an alkyl group, an alkoxy group, a silyl group, an acetal group, a carboxyl group (-COOH), a mercapto group (-SH) or a derivative thereof. 4 and R 5 are the same or different and represent a hydrogen atom or an alkyl group. 4 and R 5 Can combine with nitrogen to form a ring structure. n represents an integer.

[0072] As the modified SBR modified with the compound (modifier) ​​represented by the above formula, there can be used SBR obtained by modifying the polymerization end (active end) of solution-polymerized styrene butadiene rubber (S-SBR) with the compound represented by the above formula (modified SBR described in Japanese Patent Application Laid-Open No. 2010-111753, etc.).

[0073] As R 1 , R 2 and R 3 , preferably an alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms). 4 and R 5 , preferably an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms). n is preferably 1 to 5, more preferably 2 to 4, and even more preferably 3. 4 and R 5 When combined with a nitrogen atom to form a ring structure, a 4- to 8-membered ring is preferred. In addition, the alkoxy group also includes a cycloalkoxy group (cyclohexyloxy group, etc.) and an aryloxy group (phenoxy group, benzyloxy group, etc.).

[0074] As the specific example of the above-mentioned modifier, 2-dimethylaminoethyl trimethoxysilane, 3-dimethylaminopropyl trimethoxysilane, 2-dimethylaminoethyl triethoxysilane, 3-dimethylaminopropyl triethoxysilane, 2-diethylaminoethyl trimethoxysilane, 3-diethylaminopropyl trimethoxysilane, 2-diethylaminoethyl triethoxysilane, 3-diethylaminopropyl triethoxysilane etc. can be listed. These can be used alone or in combination of two or more.

[0075] In addition, as modified SBR, modified SBR modified by the following compounds (modifiers) can also be used. Examples of the modifier include polyglycidyl ethers of polyols such as ethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, and trimethylolpropane triglycidyl ether; polyglycidyl ethers of aromatic compounds having two or more phenolic groups such as diglycidyl bisphenol A; polyepoxy compounds such as 1,4-diglycidylbenzene, 1,3,5-triglycidylbenzene, and polyepoxidized liquid polybutadiene; epoxy group-containing tertiary amines such as 4,4'-diglycidyl-diphenylmethylamine and 4,4'-diglycidyl-dibenzylmethylamine; diglycidylaniline, N,N'-diglycidyl Diglycidylamino compounds such as oleyl-4-glycidyloxyaniline, diglycidyl o-toluidine, tetraglycidyl m-xylene diamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane; amino-containing acyl chlorides such as bis-(1-methylpropyl)carbamoyl chloride, 4-morpholinecarbonyl chloride, 1-pyrrolidinecarbonyl chloride, N,N-dimethylcarbamoyl chloride, N,N-diethylcarbamoyl chloride; 1,3-bis-(glycidyloxypropyl)-tetramethyldisiloxane, (3-glycidyl) Silane compounds containing epoxy groups, such as (trimethylsilyl) [3-(trimethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(triethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(tripropoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(tributoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(methyldimethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(methyldiethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(tripropoxysilyl) propyl] sulfide, Sulfur-containing silane compounds such as (trimethylsilyl) [3-(methyldipropoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(methyldibutoxysilyl) propyl] sulfide; N-substituted aziridine compounds such as ethyleneimine and propyleneimine; alkoxysilanes such as methyltriethoxysilane, N,N-bis(trimethylsilyl)-3-aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)-3-aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminoethyltrimethoxysilane, and N,N-bis(trimethylsilyl)aminoethyltriethoxysilane;(thio)benzophenone compounds having an amino group and / or a substituted amino group, such as 4-N,N-dimethylaminobenzophenone, 4-N,N-di-tert-butylaminobenzophenone, 4-N,N-diphenylaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(diphenylamino)benzophenone, and N,N,N',N'-bis-(tetraethylamino)benzophenone; 4-N,N-dimethylaminobenzophenone, 4-N,N-di-tert-butylaminobenzophenone, 4-N,N-diphenylaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diphenylamino)benzophenone, and N,N,N',N'-bis-(tetraethylamino)benzophenone; Benzaldehyde compounds having an amino group and / or a substituted amino group, such as benzaldehyde, 4-N,N-diphenylaminobenzaldehyde, and 4-N,N-divinylaminobenzaldehyde; N-substituted pyrrolidones, such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, and N-methyl-5-methyl-2-pyrrolidone; N-methyl-2-piperidone, N-vinyl-2-piperidone, and N-phenyl-2-piperidone N-substituted piperidones; N-methyl-ε-caprolactam, N-phenyl-ε-caprolactam, N-methyl-ω-laurolactam, N-vinyl-ω-laurolactam, N-methyl-β-propiolactam, N-phenyl-β-propiolactam and other N-substituted lactams; and N,N-bis-(2,3-epoxypropoxy)-aniline, 4,4-methylene-bis-(N,N-glycidylaniline), tris-(2,3-epoxypropyl)-1,3,5-triazine-2 ,4,6-triones, N,N-diethylacetamide, N-methylmaleimide, N,N-diethylurea, 1,3-dimethylethyleneurea, 1,3-divinylethyleneurea, 1,3-diethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 4-N,N-dimethylaminoacetophenone, 4-N,N-diethylaminoacetophenone, 1,3-bis(diphenylamino)-2-propanone, 1,7-bis(methylethylamino)-4-heptanone, etc. In addition, the modification by the above-mentioned compounds (modifiers) can be carried out by a known method. ;

[0076] As the SBR, for example, SBR manufactured and sold by Sumitomo Chemical Co., Ltd., ENEOS Materials Co., Ltd., Asahi Kasei Corporation, Nippon Zeon Corporation, etc. can be used. The SBR may be used alone or in combination of two or more.

[0077] In the rubber composition for bead apex, the content of SBR in 100 parts by mass of the rubber component is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and is preferably 35 parts by mass or less, more preferably 25 parts by mass or less.

[0078] In the rubber composition for a clinch, the content of SBR in 100 parts by mass of the rubber component is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less.

[0079] In addition, in the rubber composition for tread, the content of SBR in 100 parts by mass of the rubber component is preferably 50 parts by mass or more, more preferably 60 parts by mass or more. The upper limit is not particularly limited, but is preferably 90 parts by mass or less, more preferably 70 parts by mass or less.

[0080] (③)BR The weight average molecular weight of BR is, for example, greater than 100,000 and less than 2,000,000. The vinyl content of BR is, for example, greater than 1% by mass and less than 30% by mass. The cis content of BR is, for example, greater than 1% by mass and less than 98% by mass. The trans content of BR is, for example, greater than 1% by mass and less than 60% by mass. In addition, the cis content can be measured by infrared absorption spectroscopy.

[0081] BR is not particularly limited, and BR with a high cis content (a cis content of 90% or more), BR with a low cis content, BR containing syndiotactic polybutadiene crystals, etc. can be used. BR can be either unmodified BR or modified BR. As modified BR, for example, BR modified by a compound (modifier) ​​represented by the following formula can be used.

[0082]

Chemistry 2

[0083] In addition, in the formula, R 1 , R 2 and R 3 are the same or different and represent an alkyl group, an alkoxy group, a silyl group, an acetal group, a carboxyl group (-COOH), a mercapto group (-SH) or a derivative thereof. 4 and R 5 are the same or different and represent a hydrogen atom or an alkyl group. 4 and R 5 Can combine with nitrogen to form a ring structure. n represents an integer.

[0084] Examples of the modified BR modified with the compound (modifying agent) represented by the above formula include BR in which the polymerization terminal (active terminal) is modified with the compound represented by the above formula.

[0085] As R 1 , R 2 and R 3 , preferably an alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms). 4 and R 5, preferably an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms). n is preferably 1 to 5, more preferably 2 to 4, and even more preferably 3. 4 and R 5 When combined with a nitrogen atom to form a ring structure, a 4- to 8-membered ring is preferred. In addition, the alkoxy group also includes a cycloalkoxy group (cyclohexyloxy group, etc.) and an aryloxy group (phenoxy group, benzyloxy group, etc.).

[0086] As the specific example of the above-mentioned modifier, 2-dimethylaminoethyl trimethoxysilane, 3-dimethylaminopropyl trimethoxysilane, 2-dimethylaminoethyl triethoxysilane, 3-dimethylaminopropyl triethoxysilane, 2-diethylaminoethyl trimethoxysilane, 3-diethylaminopropyl trimethoxysilane, 2-diethylaminoethyl triethoxysilane, 3-diethylaminopropyl triethoxysilane etc. can be listed. These can be used alone or in combination of two or more.

[0087] In addition, as modified BR, modified BR modified by the following compounds (modifiers) can also be used. Examples of the modifier include polyglycidyl ethers of polyols such as ethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, and trimethylolpropane triglycidyl ether; polyglycidyl ethers of aromatic compounds having two or more phenolic groups such as diglycidyl bisphenol A; polyepoxy compounds such as 1,4-diglycidylbenzene, 1,3,5-triglycidylbenzene, and polyepoxidized liquid polybutadiene; tertiary amines containing epoxy groups such as 4,4'-diglycidyl-diphenylmethylamine and 4,4'-diglycidyl-dibenzylmethylamine; diglycidylaniline, N,N'-diglycidyl Diglycidylamino compounds such as oleyl-4-glycidyloxyaniline, diglycidyl o-toluidine, tetraglycidyl m-xylene diamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane; amino-containing acyl chlorides such as bis-(1-methylpropyl)carbamoyl chloride, 4-morpholinecarbonyl chloride, 1-pyrrolidinecarbonyl chloride, N,N-dimethylcarbamoyl chloride, N,N-diethylcarbamoyl chloride; 1,3-bis-(glycidyloxypropyl)-tetramethyldisiloxane, (3-glycidyl) Silane compounds containing epoxy groups, such as (trimethylsilyl) [3-(trimethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(triethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(tripropoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(tributoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(methyldimethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(methyldiethoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(tripropoxysilyl) propyl] sulfide, Sulfur-containing silane compounds such as (trimethylsilyl) [3-(methyldipropoxysilyl) propyl] sulfide, (trimethylsilyl) [3-(methyldibutoxysilyl) propyl] sulfide; N-substituted aziridine compounds such as ethyleneimine and propyleneimine; alkoxysilanes such as methyltriethoxysilane, N,N-bis(trimethylsilyl)-3-aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)-3-aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminoethyltrimethoxysilane, and N,N-bis(trimethylsilyl)aminoethyltriethoxysilane;(thio)benzophenone compounds having an amino group and / or a substituted amino group, such as 4-N,N-dimethylaminobenzophenone, 4-N,N-di-tert-butylaminobenzophenone, 4-N,N-diphenylaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(diphenylamino)benzophenone, and N,N,N',N'-bis-(tetraethylamino)benzophenone; 4-N,N-dimethylaminobenzophenone, 4-N,N-di-tert-butylaminobenzophenone, 4-N,N-diphenylaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diphenylamino)benzophenone, and N,N,N',N'-bis-(tetraethylamino)benzophenone; Benzaldehyde compounds having an amino group and / or a substituted amino group, such as benzaldehyde, 4-N,N-diphenylaminobenzaldehyde, and 4-N,N-divinylaminobenzaldehyde; N-substituted pyrrolidones, such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, and N-methyl-5-methyl-2-pyrrolidone; N-methyl-2-piperidone, N-vinyl-2-piperidone, and N-phenyl-2-piperidone N-substituted piperidones; N-methyl-ε-caprolactam, N-phenyl-ε-caprolactam, N-methyl-ω-laurolactam, N-vinyl-ω-laurolactam, N-methyl-β-propiolactam, N-phenyl-β-propiolactam and other N-substituted lactams; and N,N-bis-(2,3-epoxypropoxy)-aniline, 4,4-methylene-bis-(N,N-glycidylaniline), tris-(2,3-epoxypropyl)-1,3,5-triazine-2 ,4,6-triones, N,N-diethylacetamide, N-methylmaleimide, N,N-diethylurea, 1,3-dimethylethyleneurea, 1,3-divinylethyleneurea, 1,3-diethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 4-N,N-dimethylaminoacetophenone, 4-N,N-diethylaminoacetophenone, 1,3-bis(diphenylamino)-2-propanone, 1,7-bis(methylethylamino)-4-heptanone, etc. In addition, the modification by the above-mentioned compounds (modifiers) can be implemented by a known method. In addition, these modified BRs can be used alone or in combination of two or more. ;

[0088] As BR, for example, products of Ube Industries, Ltd., ENEOS Materials Co., Ltd., Asahi Kasei Corporation, Nippon Zeon Corporation, etc. can be used.

[0089] In the rubber composition for a tread, the content of BR in 100 parts by mass of the rubber component is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

[0090] In addition, the rubber composition for bead apex and the rubber composition for clinch may contain 1 part by mass or more and less than 10 parts by mass of BR based on 100 parts by mass of the rubber component, as required.

[0091] (④) Other rubber components In the present embodiment, each rubber composition may contain a rubber (polymer) commonly used in the production of tires such as nitrile rubber (NBR) as other rubber components as necessary.

[0092] (b) Compounding materials other than rubber components (①) Fillers In this embodiment, it is preferred that each rubber composition contains a reinforcing agent such as carbon black or silica as a filler. In addition, as fillers, in addition to the above-mentioned carbon black and silica, calcium carbonate, talc, alumina, clay, aluminum hydroxide, mica, etc. can also be cited. In addition, when silica is used, it is preferably used in combination with a silane coupling agent.

[0093] The total amount of fillers mixed in any rubber composition is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the rubber component. On the other hand, from the viewpoint of dispersibility in the rubber composition, it is preferably 150 parts by mass or less, more preferably 100 parts by mass or less.

[0094] (i) Carbon black Carbon black is used to improve the crack growth resistance, durability, resistance to ultraviolet degradation, etc. of the tire.

[0095] From the viewpoint of reinforcement of rubber, the nitrogen adsorption specific surface area (N2SA) of carbon black is preferably 30 m 2 / g or more, more preferably 50m 2 / g or more, more preferably 60m 2 / g or more. On the other hand, from the viewpoint of heat generation, 250 m 2 / g or less, more preferably 150m 2 / g or less, more preferably 120m 2 / g or less. From the viewpoint of the rigidity of the rubber, the absorption of dibutyl phthalate (DBP) of carbon black is, for example, preferably 50 ml / 100 g or more, and more preferably 100 ml / 100 g or more. On the other hand, from the viewpoint of the followability to the deformation of the rubber, it is preferably 250 ml / 100 g or less, and more preferably 150 ml / 100 g or less. In addition, the nitrogen adsorption specific surface area of ​​carbon black is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93.

[0096] The carbon black is not particularly limited, and examples thereof include furnace blacks such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF, and ECF; acetylene black; thermal carbon blacks such as FT and MT; channel carbon blacks such as EPC, MPC, and CC, etc. These may be used alone or in combination of two or more.

[0097] In addition to carbon black made from mineral oil or the like as raw materials, carbon black from biomass obtained by burning lignin or the like, or recycled carbon black obtained by thermally decomposing and purifying rubber products containing carbon black, such as tires, may be appropriately substituted in equal amounts.

[0098] Specific carbon black is not particularly limited, and examples include N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, and N762. Commercially available products include, for example, products of Asahi Carbon Co., Ltd., Cabot Japan Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Corporation, Lion Corporation, Shinjyo Carbon Co., Ltd., and Columbia Carbon Co., Ltd. These may be used alone or in combination of two or more.

[0099] In the rubber composition for bead apex, the content of carbon black per 100 parts by mass of the rubber component is, for example, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and preferably 90 parts by mass or less, more preferably 80 parts by mass or less.

[0100] In the rubber composition for a clinch, the content of carbon black per 100 parts by mass of the rubber component is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.

[0101] In the rubber composition for tread, the content of carbon black per 100 parts by mass of the rubber component is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

[0102] (ii) Silicon dioxide Since silica is not conductive, it can reduce the dielectric constant and expand the reading range of electronic components when used as a reinforcing material. In addition, since the hydrated water or surface functional groups contained in silica can capture ozone, it can improve ozone resistance and improve the durability of tires.

[0103] As silica, if the average primary particle size is too small, the processability deteriorates, so it is preferred to use silica larger than 8 nm. It is more preferably 9 nm or more, and even more preferably 10 nm or more. On the other hand, from the viewpoint of ensuring the reinforcement of the rubber and ensuring the handling stability on wet roads during driving, it is preferably 25 nm or less, more preferably 20 nm or less, and even more preferably 17 nm or less.

[0104] The average primary particle size of silica refers to the average value of the values ​​obtained by observing the smallest particle unit of silica constituting the agglomerated structure as a circle and measuring the absolute maximum length of the smallest particle as the diameter of the circle. It can be obtained by observing with a transmission or scanning electron microscope, measuring 400 or more primary particles of silica observed in the field of view, and using the average value.

[0105] From the viewpoint of obtaining good durability, the BET specific surface area of ​​silica is preferably greater than 100 m 2 / g, more preferably greater than 130m 2 / g. On the other hand, it is preferably less than 250m 2 / g, more preferably less than 200m 2 / g. The above-mentioned BET specific surface area is a value of N2SA measured by the BET method according to ASTM D3037-93.

[0106] As silica, for example, dry-process silica (anhydrous silica), wet-process silica (hydrous silica), colloidal silica, etc. can be cited. Among them, wet-process silica containing hydrated water, a large amount of silanol groups, and being able to effectively capture ozone is preferred. In addition, silica made of water-containing glass or the like, silica made of biomass materials such as rice husks or the like can also be used.

[0107] As silica, products of Evonik Industries, Rhodia, Tosoh Silicone Chemical Co., Ltd., Solvay Japan K.K., Tokuyama Co., Ltd., and the like can be used.

[0108] In the rubber composition for tread, the content of silica is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of the rubber component. On the other hand, from the viewpoint of dispersibility in the rubber composition, it is preferably 110 parts by mass or less, more preferably 100 parts by mass or less.

[0109] In addition, the rubber composition for bead apex rubber and the rubber composition for lap joint may also contain silica as required. In this case, considering sufficient extrusion processability and ozone resistance, the content of silica relative to 100 parts by mass of the rubber component is preferably 5 parts by mass or more, more preferably 10 parts by mass or more. In addition, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. With such an amount of silica, sufficient extrusion processability and ozone resistance can be obtained.

[0110] (iii) Silane coupling agent When silica is used as a filler, it is preferred to use a silane coupling agent in combination in order to improve the dispersibility of silica and improve mechanical properties, moldability, etc. by reacting with silica.

[0111] The silane coupling agent is not particularly limited, and examples thereof include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-trimethoxysilylbutyl)tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) disulfide, bis(4-triethoxysilylbutyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(2-trimethoxysilylethyl) disulfide, bis(4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthio Sulfide-based silanes such as carbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, and 3-triethoxysilylpropyl methacrylate monosulfide; mercapto-based silanes such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and NXT and NXT-Z manufactured by Momentive; vinyl-based silanes such as vinyltriethoxysilane and vinyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and NXT and NXT-Z manufactured by Momentive; vinyl-based silanes such as vinyltriethoxysilane and vinyltrimethoxysilane; The silane coupling agents include amino-based silanes such as 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane; glycidoxy-based silanes such as γ-glycidoxypropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane; nitro-based silanes such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; chlorine-based silanes such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane, etc. Among them, silane coupling agents having thiocarbonyl groups such as the above-mentioned NXT are preferred. These may be used alone or in combination of two or more.

[0112] As the silane coupling agent, for example, products of Evonik Industries, Momentive, Shin-Etsu Silicone Co., Ltd., Tokyo Chemical Industry Co., Ltd., AZmax Co., Ltd., Dow Corning Toray Industries, Ltd., etc. can be used.

[0113] The content of the silane coupling agent is preferably, for example, greater than 3 parts by mass, more preferably 5 parts by mass or more, and preferably less than 15 parts by mass, more preferably 10 parts by mass or less, relative to 100 parts by mass of silica.

[0114] (iv) Other fillers In addition to the above-mentioned carbon black and silica, each rubber composition may contain fillers commonly used in the tire industry, such as graphite, calcium carbonate, talc, alumina, clay, aluminum hydroxide, mica, magnesium sulfate, etc. The content of these fillers is, for example, greater than 0.1 parts by mass and less than 150 parts by mass relative to 100 parts by mass of the rubber component.

[0115] (②) Plasticizer ingredients In each rubber composition, considering the appropriate dispersion of powder materials during kneading, it is preferred to use a plasticizer component as required. In addition, the plasticizer component here refers to a component that plasticizes the rubber composition, such as a diffusion oil of an operating oil or rubber component, liquid rubber, or a resin component.

[0116] In this case, in each rubber composition, the content of the plasticizer component per 100 parts by mass of the rubber component is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and on the other hand, is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

[0117] In addition, the content of the plasticizer also includes the amount of oil contained in rubber (oil-extended rubber) or the like.

[0118] (i)Oil Examples of the oil include mineral oil, synthetic oil, vegetable oil, animal oil, and mixtures thereof.

[0119] As the mineral oil, for example, paraffinic, aromatic, naphthenic, etc. oils can be cited, and for example, products of Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo Co., Ltd., ENEOS Co., Ltd., Orisoy Co., Ltd., H&R Co., Ltd., Toyokuni Oil Refining Co., Ltd., Showa Shell Sekiyu Co., Ltd., Fuji Kosan Co., Ltd., etc. can be used. These can be used alone or in combination of two or more.

[0120] In addition, from the viewpoint of life cycle assessment, lubricating oil used in agitators of rubber mixers, engines, etc., or waste cooking oil used in restaurants, etc., may be appropriately purified and used as these oils.

[0121] Examples of the vegetable oil include linseed oil, rapeseed oil, safflower oil, soybean oil, corn oil, cottonseed oil, rice oil, tall oil, sesame oil, sesame oil, castor oil, tung oil, pine oil, pine tar, sunflower oil, coconut oil, palm oil, palm kernel oil, olive oil, camellia oil, jojoba oil, macadamia nut oil, peanut oil, grape seed oil, and wood wax.

[0122] In addition, as vegetable oils, there can be cited refined oils (salad oils, etc.) obtained by refining the above-mentioned oils, esterified oils after transesterification, solidified oils after hydrogenation, thermally polymerized oils after thermal polymerization, oxidatively polymerized oils after oxidation, and waste edible oils recovered after use as edible oils, etc. In addition, the vegetable oils may be liquid or solid at room temperature (25° C.), and these may be used alone or in combination of two or more.

[0123] As the vegetable oil, acylglycerol is preferred, and triacylglycerol is more preferred. In addition, acylglycerol refers to a compound in which the hydroxyl group of glycerol forms an ester bond with a carboxylic acid. As acylglycerol, there is no particular limitation, and it can be 1-monoacylglycerol, 2-monoacylglycerol, 1,2-diacylglycerol, 1,3-diacylglycerol, or triacylglycerol. In addition, acylglycerol can be a monomer, a dimer, or a multimer of a trimer or more. In addition, acylglycerols of dimers or more can be obtained by thermal polymerization or oxidative polymerization. In addition, acylglycerols can be liquid or solid at room temperature (25°C).

[0124] The method for confirming whether or not the rubber composition contains acylglycerols is not particularly limited, and the method can be performed by 1 For example, a rubber composition mixed with triacylglycerol is immersed in deuterated chloroform at room temperature (25°C) for 24 hours, and after removing the rubber composition, the rubber composition is measured at room temperature. 1 H-NMR, when the signal of tetramethylsilane (TMS) was set to 0.00 ppm, signals were observed near 5.26 ppm, near 4.28 ppm, and near 4.15 ppm. It is presumed that these signals are derived from hydrogen atoms bonded to carbon atoms adjacent to the oxygen atom of the ester group, and thus it was confirmed that acylglycerol was contained. In addition, "nearby" here means the range of ±0.10 ppm.

[0125] The carboxylic acid is not particularly limited and may be an unsaturated fatty acid or a saturated fatty acid. Examples of the unsaturated fatty acid include monounsaturated fatty acids such as oleic acid, and polyunsaturated fatty acids such as linoleic acid and linolenic acid.

[0126] As the vegetable oil, for example, commercially available products from Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo Co., Ltd., ENEOS Co., Ltd., Orisoy Co., Ltd., H&R Co., Ltd., Toyokuni Oil Manufacturing Co., Ltd., Fuji Kosan Co., Ltd., Nissin Oillio Group Co., Ltd., etc. can be used.

[0127] (ii) Liquid Rubber Liquid rubber refers to a polymer that is in a liquid state at room temperature (25° C.) and is a rubber component that can be extracted from a vulcanized tire by acetone extraction. Examples of liquid rubber include farnesene polymers, liquid diene polymers, and hydrogenated products thereof.

[0128] Farnesene polymers are polymers obtained by polymerizing farnesene, and have a farnesene-based structural unit. Farnesene includes isomers such as α-farnesene ((3E,7E)-3,7,11-trimethyl-1,3,6,10-dodecatetraene) and β-farnesene (7,11-dimethyl-3-methylene-1,6,10-dodecatriene).

[0129] The farnesene polymer may be a homopolymer of farnesene (farnesene homopolymer) or a copolymer of farnesene and a vinyl monomer (farnesene-vinyl monomer copolymer).

[0130] Examples of the liquid diene polymer include liquid styrene butadiene copolymers (liquid SBR), liquid butadiene polymers (liquid BR), liquid isoprene polymers (liquid IR), and liquid styrene isoprene copolymers (liquid SIR).

[0131] The weight average molecular weight (Mw) of the liquid diene polymer measured by gel permeation chromatography (GPC) in terms of polystyrene is, for example, greater than 1.0×10 3 , less than 2.0×10 5 Here, the Mw of the liquid diene polymer is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0132] In each rubber composition, the content of the liquid rubber (the total content of the liquid farnesene polymer, the liquid diene polymer, etc.) is preferably, for example, greater than 1 part by mass and less than 100 parts by mass relative to 100 parts by mass of the rubber component.

[0133] As the liquid rubber, for example, products of Kuraray Co., Ltd., Cray Valley Corporation, etc. can be used.

[0134] (iii) Resin component The resin component also functions as a component that imparts adhesiveness, and may be solid or liquid at room temperature. Specific examples of the resin component include rosin resins, styrene resins, coumarone resins, terpene resins, C5 resins, C9 resins, C5C9 resins, acrylic resins, and the like, and two or more of these resin components may be used in combination. In each rubber composition, the content of the resin component is greater than 2 parts by mass, preferably less than 45 parts by mass, and more preferably less than 30 parts by mass, relative to 100 parts by mass of the rubber component.

[0135] Rosin-based resin is a resin with rosin acid as the main component obtained by processing rosin. The rosin-based resin (rosin) can be classified according to whether it is modified or not, and can be classified into unmodified rosin (unmodified rosin) and rosin modified products (rosin derivatives). As unmodified rosin, floating oil rosin (also known as tall oil rosin), gum rosin, wood rosin, disproportionated rosin, polymerized rosin, hydrogenated rosin, rosin modified by other chemicals, etc. can be listed. Rosin modified products are modified products of unmodified rosin, and rosin esters, unsaturated carboxylic acid modified rosins, unsaturated carboxylic acid modified rosin esters, amide compounds of rosin, amine salts of rosin, etc. can be listed.

[0136] Styrene resins are polymers using styrene monomers as constituent monomers, and examples thereof include polymers obtained by polymerizing styrene monomers as main components (50% by mass or more). Specifically, in addition to homopolymers obtained by homopolymerizing styrene monomers (styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc.), copolymers obtained by copolymerizing two or more styrene monomers, copolymers of styrene monomers and other monomers copolymerizable therewith may also be mentioned.

[0137] Examples of the other monomers include acrylonitriles such as acrylonitrile and methacrylonitrile, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, unsaturated carboxylic acid esters such as methyl acrylate and methyl methacrylate, dienes such as chloroprene, butadiene and isoprene, olefins such as 1-butene and 1-pentene; α,β-unsaturated carboxylic acids such as maleic anhydride or their anhydrides, etc.

[0138] Among the benzofuran resins, benzofuran indene resins are preferred. Benzene indene resins are resins containing benzofuran and indene as monomer components constituting the backbone (main chain) of the resin. Examples of monomer components contained in the backbone other than benzofuran and indene include styrene, α-methylstyrene, methyl indene, vinyl toluene, and the like.

[0139] In each rubber composition, the content of the coumarone indene resin relative to 100 parts by mass of the rubber component is preferably, for example, greater than 1.0 part by mass and less than 50.0 parts by mass.

[0140] The hydroxyl value (OH value) of the coumarone indene resin is, for example, greater than 15 mgKOH / g and less than 150 mgKOH / g. The OH value refers to the amount of potassium hydroxide required to neutralize acetic acid bound to hydroxyl groups when 1 g of the resin is acetylated, expressed in milligrams, and is a value measured by potentiometric titration (JIS K 0070: 1992).

[0141] The softening point of the coumarone indene resin is, for example, higher than 30° C. and lower than 160° C. The softening point is a softening point specified in JIS K 6220-1:2001 measured by a ring and ball softening point measuring apparatus, and is a temperature at which a ball falls.

[0142] Examples of terpene resins include polyterpene, terpene phenol, and aromatic modified terpene resins. Polyterpene is a resin obtained by polymerizing terpene compounds and their hydrogenated products. Terpene compounds are composed of (C5H8) n The hydrocarbons and their oxygenated derivatives are classified as monoterpenes (C 10 H 16 ), sesquiterpenes (C 15 H 24 ), diterpenes (C 20 H 32 ) as the basic skeleton, for example, α-pinene, β-pinene, dipentene, limonene, myrcene, alloocimene, ocimene, α-phellandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole, α-terpineol, β-terpineol, γ-terpineol, etc.

[0143] As polyterpenes, in addition to terpene resins such as α-pinene resin, β-pinene resin, limonene resin, dipentene resin, β-pinene / limonene resin, etc., which are made from the above-mentioned terpene compounds, hydrogenated terpene resins that have been hydrogenated can also be listed. As terpene phenols, resins obtained by copolymerizing the above-mentioned terpene compounds with phenolic compounds, and resins obtained by hydrogenating the resins can be listed. Specifically, resins obtained by condensing the above-mentioned terpene compounds, phenolic compounds, and formalin can be listed. In addition, as phenolic compounds, for example, phenol, bisphenol A, cresol, xylenol, etc. can be listed. As aromatic modified terpene resins, resins obtained by modifying terpene resins using aromatic compounds, and resins obtained by hydrogenating the resins can be listed. In addition, the aromatic compound is not particularly limited as long as it is a compound having an aromatic ring, and examples thereof include phenol compounds such as phenol, alkylphenol, alkoxyphenol, and phenol containing an unsaturated hydrocarbon group; naphthol compounds such as naphthol, alkylnaphthol, alkoxynaphthol, and naphthol containing an unsaturated hydrocarbon group; styrene derivatives such as styrene, alkylstyrene, alkoxystyrene, and styrene containing an unsaturated hydrocarbon group; benzofuran, indene, etc.

[0144] "C5 resin" refers to a resin obtained by polymerizing a C5 fraction. Examples of the C5 fraction include petroleum fractions corresponding to 4 to 5 carbon atoms, such as cyclopentadiene, pentene, pentadiene, and isoprene. As a C5-based petroleum resin, dicyclopentadiene resin (DCPD resin) is preferably used.

[0145] "C9 resin" refers to a resin obtained by polymerizing a C9 fraction, and may also be a product after hydrogenation or modification. As the C9 fraction, for example, petroleum fractions equivalent to 8 to 10 carbon atoms, such as vinyltoluene, alkylstyrene, indene, and methylindene, can be cited. As specific examples, for example, benzofuran indene resin, benzofuran resin, indene resin, and aromatic vinyl resins are suitable. As aromatic vinyl resins, based on the reasons of economy, easy processing, and good heat generation, α-methylstyrene (AMS resin) or a homopolymer of styrene or a copolymer of α-methylstyrene and styrene is preferred, and a copolymer of α-methylstyrene and styrene is more preferred. As aromatic vinyl resins, commercial products such as KRATON and Eastman Chemical can be used.

[0146] "C5C9 resin" refers to a resin obtained by copolymerizing the above-mentioned C5 fraction and the above-mentioned C9 fraction, and may also be a product obtained by hydrogenating or modifying them. Examples of the C5 fraction and the C9 fraction include the above-mentioned petroleum fractions. As the C5C9 resin, commercial products such as those of Tosoh Corporation and LUHUA Corporation may be used.

[0147] The acrylic resin is not particularly limited, and for example, a solvent-free acrylic resin can be used.

[0148] Examples of solvent-free acrylic resins include (meth) acrylic resins (polymers) synthesized by a high temperature continuous polymerization method (high temperature continuous bulk polymerization method) (methods described in U.S. Patent No. 4,414,370, Japanese Patent Laid-Open No. 59-6207, Japanese Patent No. 5-58005, Japanese Patent Laid-Open No. 1-313522, U.S. Patent No. 5,010,166, East Asia Synthesis Research Annual Report TREND 2000 No. 3, p. 42-45, etc.) without using a polymerization initiator, a chain transfer agent, an organic solvent, etc. as secondary raw materials as much as possible. In addition, in the present invention, (meth) acrylic acid refers to methacrylic acid and acrylic acid.

[0149] Examples of the monomer components constituting the acrylic resin include (meth)acrylic acid, (meth)acrylic acid esters (alkyl esters, aryl esters, arylalkyl esters, etc.), (meth)acrylamide, and (meth)acrylic acid derivatives such as (meth)acrylamide derivatives.

[0150] As monomer components constituting the acrylic resin, aromatic vinyl groups such as styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene and divinylnaphthalene may be used together with (meth)acrylic acid or a (meth)acrylic acid derivative.

[0151] The acrylic resin may be a resin composed only of a (meth)acrylic acid component or a resin containing components other than the (meth)acrylic acid component as constituent elements. In addition, the acrylic resin may have a hydroxyl group, a carboxyl group, a silanol group, or the like.

[0152] As the resin component, for example, products of Maruzen Petrochemical Co., Ltd., Sumitomo Bakelite Co., Ltd., Yasuhara Chemical Co., Ltd., Tosoh Corporation, Rutgers Chemicals, BASF, KRATON, Nippon Paint Chemicals Co., Ltd., Nippon Shokubai Co., Ltd., ENEOS Co., Ltd., Arakawa Chemical Industries, Ltd., and Taoka Chemical Industries, Ltd. can be used.

[0153] (③) Curable resin component In each rubber composition, in order to suppress E * It is preferable to contain a curable resin component such as a modified resorcinol resin or a modified phenolic resin as a heat resistance improver.

[0154] Specific examples of the modified resorcinol resin include SUMIKANOL 620 (modified resorcinol resin) manufactured by Taoka Chemical Industry Co., Ltd., and examples of the modified phenolic resin include PR12686 (cashew nut oil-modified phenolic resin) manufactured by Sumitomo Bakelite Co., Ltd.

[0155] For example, from the viewpoint of sufficiently improving the complex elastic modulus and obtaining a large reaction force during deformation, the content of the curable resin component is preferably 1 part by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the rubber component. On the other hand, from the viewpoint of maintaining the breaking strength, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less.

[0156] When using modified resorcinol resin, preferably contain methylene donor as curing agent simultaneously.As methylene donor, for example hexamethylenetetramine (HMT), hexamethoxymethyl melamine (HMMM) or hexamethylol melamine pentamethyl ether (HMMPME) etc. can be listed, relative to curable resin component 100 mass parts, preferably contain for example more than 5 mass parts, about 15 mass parts.If too little, then may not obtain sufficient complex elastic modulus.On the other hand, if too much, then the viscosity of rubber increases, processability is likely to deteriorate.

[0157] As a specific methylene donor, for example, SUMIKANOL 507 manufactured by Taoka Chemical Industry Co., Ltd. can be used.

[0158] (④) Lubricant (stearic acid) Each rubber composition may contain a lubricant. As the lubricant, a lubricant based on a fatty acid derivative such as stearic acid is preferably used. As stearic acid, conventionally known stearic acid can be used, and specifically, products such as those of NOF Corporation, NOF Corporation, Kao Corporation, Fujifilm Co., Ltd., Wako Pure Chemical Industries, Ltd., Chiba Fatty Acid Co., Ltd., etc. can be used. In addition, Struktol WB16 manufactured by Struktol Corporation, etc. can also be used.

[0159] The content of stearic acid is preferably, for example, greater than 0.5 parts by mass and less than 10.0 parts by mass relative to 100 parts by mass of the rubber component.

[0160] (⑤) Anti-aging agent Each rubber composition may contain an antioxidant. The content of the antioxidant is, for example, greater than 1 part by mass and less than 10 parts by mass relative to 100 parts by mass of the rubber component.

[0161] Examples of antioxidants include naphthylamine antioxidants such as phenyl-α-naphthylamine; diphenylamine antioxidants such as octylated diphenylamine and 4,4'-bis(α,α'-dimethylbenzyl)diphenylamine; p-phenylenediamine antioxidants such as N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and N,N'-di-2-naphthyl-p-phenylenediamine; quinoline antioxidants such as polymers of 2,2,4-trimethyl-1,2-dihydroquinoline; monophenol antioxidants such as 2,6-di-tert-butyl-4-methylphenol and styrenated phenol; bisphenol, triphenol and polyphenol antioxidants such as tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, etc. These antioxidants may be used alone or in combination of two or more.

[0162] As specific antioxidants, for example, products of Seiko Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., Ouchi Shinko Chemical Co., Ltd., Flexis Corporation, etc. can be used.

[0163] (⑥) Zinc oxide Each rubber composition may contain zinc oxide. The content of zinc oxide is, for example, greater than 0.5 parts by mass and less than 10 parts by mass relative to 100 parts by mass of the rubber component. As zinc oxide, conventionally known zinc oxide may be used, for example, products of Mitsui Mining & Smelting Co., Ltd., Toho Asia Lead Co., Ltd., Shiromizu Chemical Co., Ltd., Shodo Chemical Co., Ltd., Sakai Chemical Industry Co., Ltd., etc. may be used.

[0164] (⑦) Wax Each rubber composition may contain wax. The content of the wax is, for example, preferably 0.5 to 20 parts by mass, more preferably 1.0 to 15 parts by mass, and even more preferably 1.5 to 10 parts by mass, relative to 100 parts by mass of the rubber component.

[0165] The wax is not particularly limited, and examples thereof include petroleum waxes such as paraffin wax and microcrystalline wax, natural waxes such as plant wax and animal wax, and synthetic waxes such as polymers of ethylene and propylene, etc. These may be used alone or in combination of two or more.

[0166] In addition, as the wax, for example, products of Ouchi Shinko Chemical Industry Co., Ltd., Nippon Seiro Co., Ltd., Seiko Chemical Co., Ltd., etc. can be used.

[0167] (⑧) Cross-linking agent and vulcanization accelerator Each rubber composition preferably contains a crosslinking agent such as sulfur. The content of the crosslinking agent is, for example, greater than 0.1 parts by mass and less than 10.0 parts by mass relative to 100 parts by mass of the rubber component. In addition, the sulfur content is the pure sulfur content, and when insoluble sulfur is used, it is the content after removing the oil content.

[0168] Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, and soluble sulfur commonly used in the rubber industry. These may be used alone or in combination of two or more.

[0169] As sulfur, for example, products of Tsurumi Chemical Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Chemical Industry Co., Ltd., Flexis Co., Ltd., Nippon Kanryu Kogyo Co., Ltd., Hosoi Chemical Co., Ltd., and the like can be used.

[0170] Cross-linking agents other than sulfur may also be used. Specifically, for example, vulcanizing agents containing sulfur atoms such as TACKIROL V200 manufactured by Taoka Chemical Industry Co., Ltd., DURALINK HTS (1,6-hexamethylene-sodium dithiosulfate dihydrate) manufactured by Flexis, and KA9188 (1,6-bis(N,N'-dibenzylthiocarbamoyl disulfide) hexane: mixed cross-linking agent) manufactured by Lanxess, or organic peroxides such as dicumyl peroxide may be used.

[0171] In addition, each rubber composition preferably contains a vulcanization accelerator. The content of the vulcanization accelerator is, for example, greater than 0.3 parts by mass and less than 10.0 parts by mass relative to 100 parts by mass of the rubber component.

[0172] Examples of the vulcanization accelerator include thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, and N-cyclohexyl-2-benzothiazole sulfenamide; thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), and tetrakis(2-ethylhexyl)thiuram disulfide (TOT-N); sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, and N,N'-diisopropyl-2-benzothiazole sulfenamide; and guanidine-based vulcanization accelerators such as diphenylguanidine, di-o-tolylguanidine, and o-tolylbiguanide. These may be used alone or in combination of two or more.

[0173] (⑨) Others In addition to the above-mentioned components, each rubber composition may also contain additives commonly used in the tire industry, such as organic fillers such as cellulose fibers, organic peroxides, etc. The content of these additives is, for example, greater than 0.1 parts by mass and less than 50 parts by mass relative to 100 parts by mass of the rubber component.

[0174] In each rubber composition, the loss tangent (tan δ) can be adjusted by adjusting the amount of carbon black or sulfur, and thereby, a target loss tangent (tan δ) can be achieved without excessive trial and error.

[0175] In addition, the complex elastic modulus (E * ) can be adjusted by adjusting the amount of curable resin component. In addition, by adjusting the amount of carbon black or sulfur, the complex elastic modulus (E * Specifically, the complex elastic modulus (E * However, if carbon black is increased, the heat generation increases, and if sulfur is increased, the heat generation decreases. Therefore, the preferred method is to first determine whether a curable resin component is used and the mixing amount, then adjust the sulfur amount, and finally adjust the carbon black amount. In this way, the target complex elastic modulus (E * ).

[0176] (2) Preparation of various rubber compositions Each rubber composition can be produced by a general method, for example, a production method comprising a basic kneading step of kneading a rubber component and a filler such as carbon black, and a finishing kneading step of kneading the kneaded product obtained in the basic kneading step with a crosslinking agent.

[0177] Kneading can be performed using a known (closed type) kneading machine such as a Banbury mixer, a kneader, or an open roll mill.

[0178] The kneading temperature of the basic kneading step is, for example, greater than 50° C. and less than 200° C., and the kneading time is, for example, greater than 30 seconds and less than 30 minutes. In the basic kneading step, in addition to the above-mentioned components, admixtures used in the conventional rubber industry, such as softeners such as oil, stearic acid, zinc oxide, antioxidants, waxes, vulcanization accelerators, etc., may be appropriately added and kneaded as needed.

[0179] In the refining and kneading step, the kneaded product obtained in the above-mentioned basic kneading step and the crosslinking agent are kneaded. The kneading temperature of the refining and kneading step is, for example, higher than room temperature and lower than 80° C., and the kneading time is, for example, higher than 1 minute and lower than 15 minutes. In the refining and kneading step, in addition to the above-mentioned components, a vulcanization accelerator, zinc oxide, etc. may be appropriately added and kneaded as needed.

[0180] By extruding the rubber composition for bead apex, the rubber composition for clinch, and the rubber composition for tread obtained above into a predetermined shape, they can be molded into bead apex, clinch, and tread, respectively.

[0181] 3. Tire manufacturing The tire involved in this embodiment can be manufactured by a common method except that electronic components are embedded in the molding process. First, the rubber compositions obtained above are molded into a predetermined shape to manufacture bead apex rubber, clinch portion, and tread. Then, they are combined with other rubber components on a tire molding machine to manufacture an unvulcanized tire.

[0182] Specifically, on a drum forming machine, an inner liner for ensuring the airtightness of the tire, a carcass for bearing the load, impact, and filling pressure of the tire, a belt for strongly clamping the carcass and improving the rigidity of the tread, etc. are wound, and while fixing both ends of the carcass on the edge portions on both sides, a bead portion for fixing the tire on the rim is arranged, and after being formed into a ring shape, the tread is attached to the center of the outer circumference, and the sidewall is attached to the radially outer side to form the sidewall portion, thereby manufacturing an unvulcanized tire. In this unvulcanized tire manufacturing process, electronic components are embedded in a predetermined position.

[0183] Then, the unvulcanized tire prepared as above is heated and pressurized in a vulcanizer to obtain a tire. The vulcanization step can be implemented by applying a known vulcanization method. The vulcanization temperature is, for example, greater than 120° C. and less than 200° C., and the vulcanization time is, for example, greater than 5 minutes and less than 15 minutes.

[0184] In the tire obtained above, as described above, the electronic components are arranged between the bead apex rubber and the carcass layer, and the 70°E * BA and 70℃E *The sum of CA (70℃E * BA+70℃E * Ratio of CA) to L (mm) (70℃E * BA+70℃E * When CA) / L) is greater than a certain value, the deformation around the electronic components during driving can be reduced and stress concentration can be fully suppressed, thereby suppressing the peeling of the electronic components in the tire, thereby improving the durability of the tire equipped with electronic components during driving.

[0185] In addition, the tires of the present invention can be suitably used as tires for passenger cars, large passenger cars, large SUVs, truck / bus tires, two-wheeled vehicle tires, racing tires, studless tires (winter tires), all-season tires, run-flat tires, etc., and are particularly preferably tires for passenger cars. [Example]

[0186] The following are examples (embodiments) that are considered to be preferable in practice, but the scope of the present invention is not limited to these examples.

[0187] A study was conducted on tires (tire sizes 205 / 55R16 (Study 1), 195 / 65R15 (Study 2), and 155 / 60R16 (Study 3)) consisting of bead apex rubber, clinch rubber composition, tread and other rubber components molded based on the various mixed materials shown below and the rubber compositions for bead apex rubber, clinch rubber composition, and tread rubber composition in Tables 1 to 3. The results are shown in Tables 4 to 9.

[0188] 1. Preparation of various rubber compositions The rubber composition for bead apex, the rubber composition for clinch portion, and the rubber composition for tread were prepared using the various mixed materials shown below.

[0189] (1) Mixed materials (a) Rubber component (①)NR:TSR20 (②) SBR: SBR1502 manufactured by ENEOS Materials (Styrene content: 23.5% by mass, vinyl bond content: 16% by mass, non-oil-extended) (③) BR: UBEPOL BR150B (high-cis BR) manufactured by Ube Industries (Mw: 440,000, cis-1,4 bond content: 96 mass%)

[0190] (b) Mixed materials other than rubber components (①) Carbon black-1: DIABLACK N330 manufactured by Mitsubishi Chemical Corporation (Average particle size: 31nm, CTAB: 78nm 2 / g, N2SA: 79m 2 / g) (②) Carbon black-2: DIABLACK N351H manufactured by Mitsubishi Chemical Corporation (Average particle size: 31nm, CTAB: 78nm 2 / g, N2SA: 79m 2 / g) (③) Silica: ULTRASIL VN3 manufactured by Evonik Industries (N2SA: 175m 2 / g, average primary particle size: 17nm) (④) Silane coupling agent: Si266 manufactured by Evonik Industries (Bis(3-triethoxysilylpropyl) disulfide) (⑤) Oil: VivaTec 500 (TDAE oil) manufactured by H&R (⑥) Thermosetting resin: PR12686 manufactured by Sumitomo Bakelite Co., Ltd. (Cashew nut oil modified phenolic resin) (⑦) Resin-1: SP-1068 (alkylphenol / formaldehyde polycondensation resin) manufactured by Schenectady International Co., Ltd. (⑧) Resin-2: PETROTACK 100V manufactured by Tosoh Corporation (C5C9 series petroleum resin, softening point 96℃) (⑨) Stearic acid: Beaded stearic acid "Tsubaki" manufactured by NOF Corporation (⑩) Antioxidant-1: NOCRAC 6C manufactured by Ouchi Shinko Chemical Industry Co., Ltd. (N-(1,3-dimethylbutyl)N'-phenyl-p-phenylenediamine) Antioxidant-2: NOCRAC RD manufactured by Ouchi Shinko Chemical Industry Co., Ltd. (Poly(2,2,4-trimethyl-1,2-dihydroquinoline)) Zinc oxide: Zinc oxide No. 2 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powdered sulfur manufactured by Karuizawa Sulfur Co., Ltd. Accelerator-1: NOCRAC-NS manufactured by Ouchi Shinko Chemical Industry Co., Ltd. (N-tert-Butyl-2-benzothiazolesulfenamide (TBBS)) Accelerator-2: NOCCELER H manufactured by Ouchi Shinko Chemical Industry Co., Ltd. (Hexamethylenetetramine (HMT))

[0191] (2) Preparation of rubber composition for bead apex rubber According to the mixtures (blendings) shown in Table 1, materials other than sulfur and the vulcanization accelerator were kneaded at 150° C. for 5 minutes using a Banbury mixer to obtain a kneaded product. The respective mixing amounts are parts by mass.

[0192] Next, sulfur and a vulcanization accelerator were added to the kneaded product, and kneaded for 5 minutes at 80° C. using an open roll mill to obtain rubber compositions for bead apex of BA-1 to BA-8.

[0193]

Table 1

[0194] (3) Preparation of rubber composition for clinch At the same time, according to the respective mixing (blending) shown in Table 2, rubber compositions for clinch portions CA-1 to CA-4 were obtained in the same manner as the rubber composition for bead apex.

[0195]

Table 2

[0196] (4) Preparation of rubber composition for tread At the same time, according to the mixing (blending) shown in Table 3, rubber compositions for treads TR-1 to TR-3 were obtained in the same manner as the rubber composition for bead apex.

[0197]

Table 3

[0198] 2. Forming of bead apex, lap joint and tread Next, each rubber composition obtained as described above was used to form a bead apex, a clinch portion, and a tread of a predetermined shape.

[0199] In addition, tanδ at 70°C, tanδ at 30°C, and tanδ at 0°C among the physical properties listed in Tables 1 to 3 are obtained by cutting out test pieces of 20 mm in length × 4 mm in width × 1 mm in thickness from each tire, and measuring them under the conditions of frequency of 10 Hz, initial strain of 5%, dynamic strain rate of 1%, and deformation mode: tension, with the temperatures set to 70°C, 30°C, and 0°C, respectively, using "EPLEXOR (registered trademark)" manufactured by GABO.

[0200] In addition, for 70℃E *The test pieces prepared in the same manner were measured at a temperature of 70°C, a frequency of 10 Hz, an initial strain of 5%, a dynamic strain rate of 1%, and a deformation mode of tension using "EPLEXOR (registered trademark)" manufactured by GABO.

[0201] In addition, when making the test piece, make the length direction of the test piece consistent with the circumferential direction. Furthermore, the thickness direction of the test piece is consistent with the radial direction of the tire in the case of the tread, and is consistent with the width direction of the tire in the case of the bead apex and the overlap. In addition, when the thickness of each component is less than 1mm, a test piece of a certain thickness is collected at the thickest part of the tire equatorial plane of the component. For example, when the thickness on the equatorial plane of the tire is measured to be 0.5mm, the measurement is performed using a test piece of 20mm long×4mm wide×0.5mm thick.

[0202] 3. Tire manufacturing Next, the bead apex rubber, clinch portion, and tread obtained above were bonded together with other tire components in the combination shown in Tables 4 to 9 to form an unvulcanized tire, and press-vulcanized at 170° C. for 10 minutes to manufacture the test tires shown in Tables 4 to 9.

[0203] In addition, when forming an unvulcanized tire, an electronic component (RFID) having the dimensions (weight W (g), tire circumferential length L (mm), and longitudinal length (mm)) shown in Tables 4 to 9 was embedded at the embedding position shown in Tables 4 to 9. At this time, a plating layer containing copper and nickel was formed in advance on the surface of the electronic component, and a rubber coating layer with a thickness of 0.5 mm was provided.

[0204] In Tables 4 to 9, embedding position 1 indicates that the electronic component is embedded between the bead apex rubber and the carcass layer on the inner side in the tire width direction (see Figure 1 ), embedding position 2 means that the electronic component is embedded between the bead apex rubber and the carcass layer on the outer side in the tire width direction (refer to Figure 2 ), embedding position 3 means that the electronic component is embedded outside the carcass layer in the tire width direction (refer to Figure 4 ), embedding position 4 indicates that the electronic component is embedded between the carcass layer and the sidewall portion on the outer side of the tire width direction (refer to Figure 5 ).

[0205] 4. Calculation parameters Next, for each test tire (different from the tire from which the test piece was collected), the tire weight (kg), cross-sectional height H (mm), and outer diameter Dt (mm) were measured, and the maximum load capacity (kg) was calculated based on these. At the same time, the shortest distance D1 (mm) from the electronic component to the outer surface of the tire and the tire radial distance D2 (mm) from the upper end of the bead core to the electronic component were measured, and (D2 / H) was calculated.

[0206] Then, calculate (70℃E * BA+70℃E * CA) / L, tire weight / maximum load capacity, 70℃tanδBA×D2, 70℃E * BA / D2, (70℃E * BA / 70℃E * CA) / L, (70℃tanδBA+70℃tanδCA)×L, 70℃tanδBA×L, D1×W.

[0207] 5. Performance evaluation test (durability evaluation of tires during driving) Each test tire was installed on all wheels of a vehicle (domestic FF car, displacement 2000cc), filled with air to an internal pressure of 230kPa, and then driven on the test field in an overloaded state. During the test, the vehicle repeatedly crossed the bumps set on the road surface and drove normally. The driving speed started at 50km / h, and the speed was gradually increased each time it was repeated, and the driving speed before the driver felt abnormal was recorded.

[0208] Next, the results of each comparative example 1 (Comparative Example 1-1, Comparative Example 2-1, Comparative Example 3-1) were taken as 100, and indexed based on the following formula to evaluate the durability of the tire during running. A larger value indicates better durability of the tire during running. Durability of tires while driving =[(result of test tire) / (result of comparative example 1)]×100

[0209]

Table 4

[0210]

Table 5

[0211]

Table 6

[0212]

Table 7

[0213]

Table 8

[0214]

Table 9

[0215] As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to said embodiment. Various changes can be made to said embodiment within the range of the sameness and equality with this invention.

[0216] The present invention (1) is a tire having a tread portion, a bead portion consisting of a bead apex rubber and a bead core, a lap portion provided on the outer side of the bead portion in the tire width direction and extending to a bead chafer portion, and a carcass layer. An electronic component is arranged between the bead apex rubber and the carcass layer. The complex elastic modulus of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension 70°C E * BA (MPa), and The complex elastic modulus of the overlapped portion measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is 70°C E * CA (MPa), and The tire circumferential length L (mm) of the electronic component satisfies the following (Formula 1). (70℃E * BA+70℃E * CA) / L>0.4 (Formula 1)

[0217] The present invention (2) is a tire according to the present invention (1), characterized in that the loss tangent 30°C tanδTR of the tread portion measured under the conditions of temperature 30°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is less than 0.25.

[0218] The present invention (3) is a tire according to the present invention (1) or (2), characterized in that the loss tangent of the tread portion measured under the conditions of temperature 0°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is 0°C tanδTR greater than 0.50.

[0219] The present invention (4) is a tire according to any combination of any one of the present inventions (1) to (3), characterized in that the tire weight (kg) and the maximum load capacity (kg) of the tire satisfy the following (Formula 2). Tire weight / maximum load capacity < 0.0150 (Formula 2)

[0220] The present invention (5) is a tire according to any combination of any one of the present inventions (1) to (4), characterized in that the loss tangent 70°C tanδBA of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is A tire radial distance D2 (mm) from the upper end of the bead core to the electronic component satisfies the following (Formula 3). 70℃tanδBA×D2≤8.5 (Formula 3)

[0221] The present invention (6) is a tire according to any combination of any one of the present inventions (1) to (5), characterized in that the 70°E * BA (MPa), and A tire radial distance D2 (mm) from the upper end of the bead core to the electronic component satisfies the following (Formula 4). 70℃E * BA / D2>0.85 (Formula 4)

[0222] The present invention (7) is a tire according to any combination of any one of the present inventions (1) to (6), characterized in that the 70°E * BA (MPa), with the 70℃E * CA (MPa) and the above L (mm) satisfy the following (Formula 5). (70℃E * BA / CA70℃E * CA) / L≥0.05 (Formula 5)

[0223] The present invention (8) is a tire according to any combination of any one of the present inventions (1) to (7), characterized in that the loss tangent 70°C tanδBA of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is The loss tangent 70°C tanδCA of the overlapped portion measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is The L (mm) satisfies the following (Formula 6). (70℃tanδBA+70℃tanδCA)×L≤30 (Formula 6)

[0224] The tire of the present invention (9) is a tire according to any combination of any one of the present inventions (1) to (8), characterized in that the loss tangent 70°C tanδBA of the bead filler measured under the conditions of a temperature of 70°C, a frequency of 10 Hz, an initial strain of 5%, a dynamic strain rate of 1%, and in a deformation mode: tension, and the L (mm) satisfies the following (Equation 7). 70°C tanδBA × L ≤ 15 (Equation 7)

[0225] The tire of the present invention (10) is a tire according to the tire of the present invention (9), characterized in that the loss tangent 70°C tanδBA of the bead filler measured under the conditions of a temperature of 70°C, a frequency of 10 Hz, an initial strain of 5%, a dynamic strain rate of 1%, and in a deformation mode: tension, and the L (mm) satisfies the following (Equation 8). 70°C tanδBA × L ≤ 13 (Equation 8)

[0226] The tire of the present invention (11) is a tire according to any combination of any one of the present inventions (1) to (10), characterized in that the electronic component is an RFID tag or a sensor.

[0227] The tire of the present invention (12) is a tire according to any combination of any one of the present inventions (1) to (11), characterized in that on the surface of the electronic component, an adhesive layer or a plating layer for improving the adhesiveness to rubber is provided.

[0228] The tire of the present invention (13) is a tire according to any combination of any one of the present inventions (1) to (12), characterized in that an electronic component coating layer with a thickness of 0.5 mm or more covering the electronic component is provided.

[0229] The tire of the present invention (14) is a tire according to any combination of any one of the present inventions (1) to (13), characterized in that the distance H (mm) from the upper end of the bead core to the front top of the bead filler, and the radial distance D2 (mm) of the tire from the upper end of the bead core to the electronic component satisfies the following (Equation 9). 0.2 < D2 / H < 0.8 (Equation 9)

[0230] The tire of the present invention (15) is a tire according to any combination of any one of the present inventions (1) to (14), characterized in that the weight W (g) of the electronic component and the shortest distance D1 (mm) from the electronic component to the outer surface of the tire satisfy the following (Equation 10). D1 × W ≤ 2.5 (Equation 10)

[0231] The present invention (16) is a tire according to any combination of any one of the present inventions (1) to (15), characterized in that the length of the electronic component in the longitudinal direction is 80 mm or less.

[0232] The present invention (17) is the tire according to the present invention (16), characterized in that the length of the electronic component in the longitudinal direction is 50 mm or less.

Claims

1. A tire comprising a tread portion, a bead portion consisting of a bead apex rubber and a bead core, a lap portion provided on the outer side of the bead portion in the tire width direction and extending to a chafer portion, and a carcass layer, An electronic component is arranged between the bead apex rubber and the carcass layer. The complex elastic modulus of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension 70°C E * BA, with The complex elastic modulus of the overlapped portion measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is 70°C E * CA, with The tire circumferential length L of the electronic component satisfies the following (Formula 1): (70℃E * BA + 70℃E * (CA) / L > 0.4 (Equation 1) In the above formula, 70℃E * BA and 70℃E * The unit of CA is MPa, and the unit of L is mm.

2. The tire according to claim 1, characterized in that The loss tangent 30°C tanδTR of the tread portion measured under the conditions of a temperature of 30°C, a frequency of 10 Hz, an initial strain of 5%, a dynamic strain rate of 1%, and a deformation mode: tension is 0.25 or less.

3. The tire according to claim 1 or 2, characterized in that: The loss tangent 0°C tanδTR of the tread portion measured under the conditions of temperature 0°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is greater than 0.

50.

4. The tire according to any one of claims 1 to 3, characterized in that: The tire weight and the maximum load capacity of the tire satisfy the following (Formula 2): Tire weight / maximum load capacity < 0.0150 (Formula 2) In the above formula, the unit of tire weight and maximum load capacity is kg.

5. The tire according to any one of claims 1 to 4, characterized in that: The loss tangent 70°C tanδBA of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is The tire radial distance D2 from the upper end of the bead core to the electronic component satisfies the following (Formula 3): 70℃tanδBA×D2≤8.5 (Formula 3) In the above formula, the unit of D2 is mm.

6. The tire according to any one of claims 1 to 5, characterized in that: 70℃E stated * BA, given The tire radial distance D2 from the upper end of the bead core to the electronic component satisfies the following (Formula 4): 70°C E * BA / D2>0.85 (Equation 4) In the above formula, 70℃E * The unit of BA is MPa, and the unit of D2 is mm.

7. The tire according to any one of claims 1 to 6, characterized in that: 70°C E * BA, with the 70°C E * CA, and L satisfy the following (Formula 5): (70℃ * BA / CA70℃E * CA) / L≥0.05 (Equation 5) In the above formula, 70℃E * BA and 70℃E * The unit of CA is MPa, and the unit of L is mm.

8. The tire according to any one of claims 1 to 7, characterized in that: The loss tangent 70°C tanδBA of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is The loss tangent 70°C tanδCA of the overlapped portion measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension is The L satisfies the following (Formula 6), (70℃tanδBA+70℃tanδCA)×L≤30 (Formula 6) In the above formula, the unit of L is mm.

9. The tire according to any one of claims 1 to 8, characterized in that The loss tangent 70°C tanδBA of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension, satisfies the following (Formula 7) with L: 70℃tanδBA×L≤15 (Formula 7) In the above formula, the unit of L is mm.

10. The tire according to claim 9, characterized in that The loss tangent 70°C tanδBA of the bead apex rubber measured under the conditions of temperature 70°C, frequency 10 Hz, initial strain 5%, dynamic strain rate 1%, and deformation mode: tension, satisfies the following (Formula 8) with L: 70℃tanδBA×L≤13 (Formula 8) In the above formula, the unit of L is mm.

11. The tire according to any one of claims 1 to 10, characterized in that: The electronic component is an RFID tag or a sensor.

12. The tire according to any one of claims 1 to 11, characterized in that: An adhesive layer or a plating layer is provided on the surface of the electronic component to improve adhesion with rubber.

13. The tire according to any one of claims 1 to 12, characterized in that: An electronic component covering layer having a thickness of 0.5 mm or more is provided to cover the electronic component.

14. The tire according to any one of claims 1 to 13, characterized in that: The distance H from the upper end of the bead core to the top of the front end of the bead filler, and the radial tire distance D2 from the upper end of the bead core to the electronic component satisfy the following (Equation 9), 0.2 < D2 / H < 0.8 (Equation 9) In the above equation, the units of D2 and H are mm.

15. The tire according to any one of claims 1 to 14, characterized in that: The weight W of the electronic component and the shortest distance D1 from the electronic component to the outer surface of the tire satisfy the following (Equation 10), D1 × W ≤ 2.5 (Equation 10) In the above equation, the unit of W is g and the unit of D1 is mm.

16. The tire according to any one of claims 1 to 15, characterized in that: The length of the electronic component in the length direction is 80 mm or less.

17. The tire according to claim 16, characterized in that The length of the electronic component in the length direction is 50 mm or less.

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