TIRES

Abstract

A tire comprising an inner liner and insulation that contacts the inner liner on an outer surface of the inner liner in a tire radial direction, the insulation is made up of a rubber compound that includes recovered carbon black, where an air permeability coefficient of a rubber composition forming the inner liner is less than 18 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) is, where the thickness of the inner liner on a tire equator plane is 1.5 mm or less, and where the loss tangent at 70 °C, 70 °C tanδ, of a complex of the insulation and the inner liner is 0.22 or less.

Description

TECHNICAL AREA

[0001] The present invention relates to a tire. BACKGROUND OF THE INVENTION

[0002] The inner cavity of a tire is lined with an inner liner, a layer designed to suppress air permeability and maintain tire pressure. Recently, the need for improved fuel efficiency in cars has increased, and inner liners have been improved accordingly (JP 2018-165087 A). While thinning the inner liner and improving air permeability suppression have been considered as ways to achieve fuel efficiency, problems also exist for the inner liner and the insulation bonded to it (also known as a "binding layer"), such as warping or delamination at their interface. Therefore, further improvements have been required. SUMMARY OF THE INVENTION

[0003] One object of the present invention is to provide a tire that has improved performance in suppressing tire permeability.

[0004] The present invention relates to a tire comprising an inner liner and insulation contacting the inner liner on an outer surface of the inner liner in a tire radial direction, wherein the insulation is composed of a rubber composition comprising recovered carbon black, wherein the air permeability coefficient of a rubber composition forming the inner liner is less than 18 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) is, wherein the thickness of the inner liner on a tire equatorial plane is 1.5 mm or less, and wherein the loss tangent at 70 °C, 70 °C tanδ, of a complex of the insulation and the inner liner is 0.22 or less.

[0005] According to the present invention, a tire can be provided which improves in terms of its performance in suppressing air permeability.

[0006] Although not intended to be a theoretical framework, the reason why air permeability suppression performance can be improved is assumed to be as follows. That is, the tanδ, which relates to the insulation and inner liner complex, is reduced, and the thickness of the complex is made thinner, making it more difficult for the entire tire to generate heat and thus making it more difficult for air to pass through. It is assumed that, due to the synergistic effect between this aspect and an improved air permeability coefficient of the inner liner, the tire contributes to improved air permeability suppression performance while driving. BRIEF DESCRIPTION OF THE FIGURES Fig.Figure 1 is a schematic view showing part of a cross-section of a tire according to an embodiment of the present invention along a tire meridian line (the part of the cross-section at the top right). DETAILED DESCRIPTION

[0007] The tire according to one embodiment of the present invention is a tire comprising an inner liner and insulation that contacts the inner liner on an outer surface of the inner liner in a tire radial direction, wherein the insulation is composed of a rubber composition comprising recovered carbon black, wherein an air permeability coefficient of a rubber composition forming the inner liner is less than 18 × 10⁻⁶ 11 cm 3 · cm / (cm 2· s · cmHg) is, wherein the thickness of the inner liner on a tire equatorial plane is 1.5 mm or less, and wherein the loss tangent at 70 °C, 70 °C tanδ, of a complex of the insulation and the inner liner is 0.22 or less.

[0008] The thickness of the inner liner at the tire equator plane is preferably 1.4 mm or less, more preferably 1.2 mm or less, and even more preferably 1.1 mm or less.

[0009] Stress on the inner liner is reduced, heat generation is suppressed, and the performance of suppressing air permeability is believed to be improved.

[0010] The air permeability coefficient of the rubber composition forming the inner liner is 17 × 10- 11 cm 3 · cm / (cm 2 · s · cmHg) or less, preferably 16 × 10- 11 cm 3 · cm / (cm 2 · s · cmHg) or less, preferably less than 15 × 10-11 cm 3 · cm / (cm 2 · s · cmHg) and even more preferably 14.0 × 10- 11 cm 3 • cm / (cm 2 · s · cmHg) or less.

[0011] Heat generation is suppressed when air is retained, shape stability is improved, and rolling resistance is reduced, with the further improvement of air permeability suppression being assumed to result.

[0012] It is preferred that a rubber composition forming the insulation comprises a rubber component comprising more than 20 wt% of an isoprene-based rubber and that the rubber composition forming the inner liner comprises a rubber component comprising more than 70 wt% of a butyl-based rubber.

[0013] It is preferred that a statistical thickness surface area (STSA) be given in m². 2 / g of the recovered soot is greater than 37 and less than 77 and an ash content in mass % of the recovered soot is greater than 11 and less than 27. <definitionen>

[0014] A “standardized condition” is a condition in which a tire is mounted on a standardized rim, filled with air at a standardized internal pressure, and is not subjected to any load.

[0015] Unless otherwise specified, a “dimension of each part of a tire” is a value specified in a standardized state for one appearing on the outer surface of the tire, while for one present inside the tire, or for one on a tire cut surface, it is a value specified in a state in which, for example, the tire is cut along a plane containing a tire axis of rotation and the cut piece of tire is held to a rim width of a standardized rim.

[0016] A “tire weight” is represented by G in kg and refers to the weight of a single tire, excluding the weight of a rim. On the other hand, if an element consisting of a sponge and sealant, a sensor element, or the like is provided within a tire lumen, G is a weight that includes the weight of such an element.

[0017] A "standardized rim" is a rim within a standard system that includes a standard on which the tire is based, and which is defined by the standard for each tire. For example, "standardized rim" refers to a standard rim of an applicable size described in the "Jatma Year Book" of JATMA (The Japan Automobile Tire Manufacturers Association, Inc.), a "Measuring Rim" described in the "STANDARDS MANUAL" of ETRTO (The European Tyre and Rim Technical Organisation), or a "Design Rim" described in the "YEAR BOOK" of TRA (The Tire and Rim Association, Inc.), referenced in that order, and if an applicable size exists at the time of reference, the rim conforms to its standard.Furthermore, if the tire is not defined in the standard described above, the “standardized rim” refers to a rim that has the narrowest rim width, among rims that can be mounted on the tire and maintain internal pressure (i.e., cause no air leakage between the rim and the tire), and each of which has the smallest diameter.

[0018] A “standardized internal pressure” is an air pressure in a standard system containing a standard on which the tire is based, defined by the standard for each tire. It refers, for example, to a “MAXIMUM AIR PRESSURE” in JATMA, “INFLATION PRESSURE” in ETRTO, or a maximum value described in the “TIRE LOAD LIMITS AT VARIOUS COLD INFLATION PRESSURES” table in TRA, to which reference is made in that order, as in the case of the standardized rim, and if there is an applicable size at the time of reference, the standardized internal pressure conforms to its standard.Furthermore, in the case of tires not defined by the standard, the standardized internal pressure should refer to a standardized internal pressure (250 kPa or more) of another tire size (specified in the standard) for which the standardized rim is described as a standard rim, and if several standardized internal pressures of 250 kPa or more are described, it should refer to a minimum value below that.

[0019] A "standardized load" is a load within a standard system that includes a standard on which the tire is based, defined by the standard for each tire. For example, a "MAXIMUM LOAD CAPACITY" for JATMA, a "LOAD CAPACITY" for ETRTO, or a maximum value described in the "TIRE LOAD LIMITS AT VARIOUS COLD INFLATION PRESSURES" table for TRA. Reference is made to this load in that order, as in cases of a standardized rim and standardized inflation pressure. If an applicable size exists at the time of reference, the load conforms to its standard. Then, in the case of tires not defined by the standard, a maximum load capacity W is specified. L , which is obtained through a different calculation than a standardized load defined.

[0020] A "maximum load capacity W" L The volume is calculated using the following equation. "V" represents a virtual volume in mm³. 3 The dimensions of a tire are represented as follows: "Dt" represents the tire's outer diameter in mm in a standardized state, "Ht" represents the tire's cross-sectional height in mm in a radial direction in a cross-section of the tire on a plane containing a tire axis of rotation, and "Wt" represents the tire's cross-sectional width in mm in the standardized state. If R represents the tire's rim diameter, Ht can be calculated using the following equation: (Dt - R) / 2. Wt is a value obtained by excluding any patterns, letters, or the like on the tire's sidewall. Furthermore, the maximum load capacity has the same meaning as the standardized load described above. WL=0.000011×V+175 V={(Dt / 2)2−(Dt / 2−Ht)2}×π×Wt

[0021] "Recovered carbon black" refers to carbon black obtained through the pyrolysis process of a product, such as a used tire or similar material, containing carbon black, where, when the product is subjected to oxidative combustion by heating in air using a thermal weight measurement method according to JIS K 6226-2:2003, the mass of ash (ash content), which is a component that does not combust, is greater than 11% by mass. That is, the mass (amount of carbon) of the weight loss content due to oxidative combustion is less than 89% by mass. Recovered carbon black is also referred to as "recycled carbon" or "recycled soot" and can be expressed as rCB.

[0022] An “inner liner thickness” is a thickness in a tire radial direction on an equator in a cross-section of a tire along a plane containing a tire axis of rotation, and corresponds to L, which is in Fig. Figure 1 shows that the “thickness of an inner liner” is defined as an average of measurements taken at five points along the plane containing the tire's axis of rotation in tire cross-sections, rotated in 72-degree increments. Alternatively, the measurement can be performed by preparing a cross-sectional piece of the tire cut along the plane containing the tire's axis of rotation and holding the cross-sectional piece in a state where the space between its beads is adjusted to match the width of a standardized rim.

[0023] A "loss tangent of a rubber compound" is a loss tangent (tanδ) measured using a dynamic viscoelasticity measuring device (for example, the EPLEXOR series, manufactured by gabo Systemtechnik GmbH) with a strain mode under any given condition. A sample used for measuring dynamic viscoelasticity is a vulcanized rubber compound with a length of 20 mm, a width of 4 mm, and a thickness of 1 mm. In a case where the sample is prepared by cutting it from a tire, the length direction of the sample is aligned with the tire's circumferential direction, and the thickness direction of the sample is aligned with the tire's radial direction.When collecting a sample of a complex consisting of insulation and an inner liner, the sample is cut out so that the thickness of the complex, encompassing the entire thickness of the insulation, becomes 1 mm by appropriately adjusting the thickness of the inner liner.

[0024] Furthermore, “70 °C-tanδ” is a loss tangent (tanδ) measured under a condition of a temperature of 70 °C, a frequency of 10 Hz, an initial strain of 10%, a dynamic strain of ± 1%, and a strain mode. <messverfahren>

[0025] The “styrene content” is calculated by pyrolysis gas chromatography.

[0026] A “vinyl bond quantity (1,2-bonded butadiene unit quantity)” is measured by infrared absorption spectrometry.

[0027] A “cis content (cis-1,4-bound butadiene unit amount)” is measured by infrared absorption spectrometry.

[0028] The “ash content of recovered soot” is measured using a thermal weight measurement method according to JIS K 6226-2:2003.

[0029] A “statistical thickness surface area (STSA) of recovered carbon black” is a value calculated according to JIS K 6217-7:2017. Furthermore, a “specific nitrogen adsorption surface area (N2SA) of recovered carbon black” is a value calculated according to JIS K 6217-2:2017.

[0030] An “average primary particle size of soot” and an “average primary particle size of recovered soot” are values ​​calculated by taking the arithmetic mean of the particle sizes of 400 particles photographed with a transmission or scanning electron microscope. In cases where the particle is spherical, a diameter of the sphere is defined as a particle size, and in cases of shapes other than spherical, an equivalent circle diameter (positive square root of “4 × (area of ​​particle) / π”) calculated from a microscope image is defined as a particle size.

[0031] A “specific nitrogen adsorption surface (N2SA) of silicon dioxide” is a value measured by a BET method according to ASTM D3037-93.

[0032] An “air permeability coefficient” is a value measured according to Annex 2 of JIS K 7126-1 (a test method for gas permeability by a method of gas chromatography). <reifen>

[0033] The tire according to one embodiment of the present invention is suitably described below with reference to the drawings. However, the drawings are merely examples for illustrative purposes.

[0034] Fig. Figure 1 is a schematic view showing part of a cross-section of a tire according to an embodiment of the present invention along a tire meridian line (the part of the cross-section at the top right). Fig. An inner liner 3 forms an inner surface of a tire 1 and maintains internal pressure within the tire 1. An insulation 2 lies against the outside of the inner liner in one direction relative to the tire's axis of rotation, and the inner liner is joined to another element, such as a carcass, via the insulation. The thickness of the inner liner along a tire centerline is represented by L.

[0035] The thickness L in mm of the inner liner on a tire equator plane is 1.5 mm or less, preferably 1.4 mm or less, more preferably 1.2 mm or less, and even more preferably 1.1 mm or less. Its lower limit is not particularly restricted and is, for example, 0.01 mm or more. Stress along with heat generation by the inner liner is suppressed, and thus it is assumed that air permeability resistance is improved.

[0036] Furthermore, since the rubber composition for the inner liner, according to one embodiment of the present invention, is shaped to form an inner cavity surface of the tire, and is used for the inner liner with the function of reducing air permeability to maintain the tire's internal pressure, excellent air permeability resistance is required. Because the excellent air permeability suppression required for the inner liner can be obtained, the air permeability coefficient of the rubber composition is less than 18 × 10⁻⁶. 11 cm 3 · cm / (cm 2 · s · cmHg) , preferably 17 × 10- 11 cm 3 · cm / (cm 2 · s · cmHg) or less, preferably 16 × 10- 11 cm 3 · cm / (cm 2 · s · cmHg) or less, preferably 15 × 10- 11 cm 3 · cm / (cm 2 · s · cmHg) or less and even more preferably 14.0 × 10- 11 cm 3 · cm / (cm 2 · s · cmHg) or less. Its lower limit is not particularly restricted and is, for example, 1.0 × 10 -13 cm 3 · cm / (cm 2 · s · cmHg) or more.

[0037] The air permeability coefficient can be changed by altering the type or content of a rubber component, filler, resin component, or the like in the rubber composition. In particular, for example, the air permeability coefficient can be decreased by increasing the amount of filler or by decreasing its particle size.

[0038] The loss tangent at 70 °C, 70 °C-tanδ, of a complex of the inner liner and the insulation is 0.22 or less, preferably 0.21 or less, and more preferably 0.20 or less. Its lower limit is not particularly restricted and is, for example, 0.01 or more. Suppression of heat generation is improved, and thus, it is assumed that air permeability resistance is improved. 70 °C-tanδ can be suitably adjusted depending on the type or quantity of a polymer component, filler, oil, resin component, and the like, as described below. For example, 70 °C-tanδ can tend to be increased by increasing the quantity of a filler, reducing its particle size, decreasing the quantities of a vulcanizing agent and vulcanization accelerator, or the like, and 70 °C-tanδ can tend to be decreased by the reverse processes.

[0039] Furthermore, the loss tangent at 70 °C of a rubber composition forming the insulation is, for example, less than 0.185, preferably 0.18 or less, more preferably 0.17 or less, and still more preferably 0.15 or less. If it lies within these ranges, the air permeability resistance is assumed to be further improved.

[0040] Furthermore, the loss tangent at 70 °C of the rubber composition forming the inner liner is, for example, less than 0.25, preferably 0.24 or less, more preferably 0.22 or less, and even more preferably 0.21 or less. If it lies within these ranges, the air permeability resistance is assumed to be further improved. <kautschukzusammensetzung>

[0041] A rubber composition for insulation and a rubber composition for inner liners are described below. [Rubber composition for insulation]

[0042] Each component of the rubber compound for insulation is described. The rubber compound that forms the insulation includes recovered carbon black. <kautschukkomponente>

[0043] The rubber composition forming the insulation comprises a rubber component consisting of an isoprene-based rubber (IR-based rubber) and a styrene-butadiene rubber (SBR). In this case, the rubber component may include a different rubber component than the IR-based rubber and the SBR. Furthermore, the rubber component may be one consisting of the IR-based rubber and the SBR. An explanation of each of the rubbers capable of forming the rubber component is as follows. (Isoprene-based rubber)

[0044] Examples of isoprene-based rubber include natural rubber (NR), isoprene rubber (IR), refined NR, modified NR, modified IR, and the like. For example, those commonly used in the rubber industry, such as SIR20, RSS#3, TSR20, SVR-L, and the like, can be used as NR. IR is not particularly restricted, and those commonly used in the rubber industry, such as IR2200, can be used.Examples of refined NR include deproteinized natural rubber (DPNR) and ultrapure natural rubber (UPNR), and the like; examples of modified NR include epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), and grafted natural rubber, and the like; and examples of modified IR include epoxidized isoprene rubber, hydrogenated isoprene rubber, grafted isoprene rubber, and the like. Isoprene-based rubbers can be used alone, or two or more can be used in combination.

[0045] For example, the content of an IR-based rubber in 100 wt% of the rubber component is more than 20 wt%, preferably more than 30 wt%, further preferably more than 40 wt%, and even more preferably 50 wt% or more. On the other hand, the content is, for example, 100 wt% or less, preferably less than 90 wt%, and further preferably less than 80 wt%. (SBR)

[0046] Styrene-butadiene rubber (SBR) is not particularly restricted; examples include unmodified emulsion-polymerized styrene-butadiene rubber (E-SBR), unmodified solution-polymerized styrene-butadiene rubber (S-SBR), and modified SBRs obtained by modifying these SBRs, such as modified emulsion-polymerized styrene-butadiene rubber (modified E-SBR) and modified solution-polymerized styrene-butadiene rubber (modified S-SBR), and the like. Examples of modified SBR include SBR modified at its end and / or main chain, SBR coupled with tin, a silicon compound, etc. (a modified condensate SBR or one with a branched structure, etc.), and the like.Furthermore, SBR types include an oil-extended type, whose flexibility is adjusted by adding an extender oil, and a non-oil-extended type, to which no extender oil is added; either type can be used. Examples of such SBRs include products from JSR Corporation, Asahi Chemicals Co., Ltd., Zeon Corporation, ZS Elastomer Co., Ltd., etc. SBRs can be used alone, or two or more can be used in combination.

[0047] The styrene content of an SBR is preferably more than 15 wt%, more preferably more than 20 wt%, and even more preferably more than 23 wt%. Furthermore, from the perspective of fuel efficiency, the styrene content is preferably less than 40 wt%, more preferably less than 30 wt%, and even more preferably less than 25 wt%. Moreover, the styrene content of an SBR is a value determined by the 1 H-NMR measurement is calculated.

[0048] The vinyl content (unit amount of 1,2-bonded butadiene) of an SBR is preferably greater than 10 wt%, and more preferably greater than 15 wt%. Furthermore, the vinyl content is preferably less than 80 wt%, more preferably less than 50 wt%, and even more preferably less than 30 wt%. The vinyl content of the SBR is also a value measured by infrared absorption spectrometry.

[0049] For example, the content of an SBR-based rubber in 100 wt% of the rubber component is greater than 5 wt%, preferably greater than 10 wt%, more preferably greater than 20 wt%, and even more preferably greater than 25 wt%. On the other hand, the content is, for example, 100 wt% or less, preferably less than 90 wt%, and more preferably less than 80 wt%.

[0050] Furthermore, the total content of an IR-based rubber and an SBR in 100 wt% of the rubber component is preferably greater than 80 wt%, more preferably greater than 90 wt%, even more preferably greater than 95 wt% or may be 100 wt%. (Other rubbers)

[0051] Other usable rubbers besides those described above are not particularly restricted, and rubbers used in the tire industry and similar applications may be used as such. Examples of other usable rubbers include diene-based rubbers such as butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), styrene isoprene butadiene copolymer rubber (SIBR), and the like. These other rubbers may be used alone, or two or more of them may be used in combination. (BR)

[0052] Butadiene rubber (BR) is not particularly restricted, and examples include those commonly used in the tire industry, such as a high-cis BR, a BR containing a 1,2-syndiotactic polybutadiene crystal (SPB-containing BR), a butadiene rubber synthesized using a rare-earth-based catalyst (rare-earth-based BR), a tin-modified butadiene rubber modified by a thin compound (tin-modified BR), a modified butadiene rubber other than these (modified BR), and the like. Commercially available BR products include those from UBE Corporation, JSR Corporation, Asahi Kasei Corporation, Ltd., Zeon Corporation, etc. Modified BR can be a BR containing a filler, such as silicon dioxide, etc.interacting functional group. Examples of modified BR include, for example, an end-modified BR obtained by modifying at least one end of an SBR with a compound (a modifier) ​​having the functional group described above (end-modified BR having the functional group described above at its end), a main-chain-modified BR whose main chain has the functional group described above, a main-chain / end-modified BR having the functional group described above on its main chain and at its end (for example, a main-chain / end-modified BR whose main chain has the functional group described above and at least one end of it is modified with the modifier described above), an end-modified BR obtained with a polyfunctional compound having two or more epoxy groups in one molecule,is modified (coupled) and into which a hydroxyl group or an epoxy group has been introduced, and the like. Examples of the functional group described above include, for example, an amino group, an amido group, a silyl group, an alkoxysilyl group, an isocyanate group, an imino group, an imidazole group, a urea group, an ether group, a carbonyl group, an oxycarbonyl group, a mercapto group, a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, an ammonium group, an imide group, a hydrazo group, an azo group, a diazo group, a carboxyl group, a nitrile group, a pyridyl group, an alkoxy group, a hydroxyl group, an oxy group, an epoxy group, and the like. Furthermore, these functional groups may contain a substituent. Among these are an amino group (preferably an amino group,whose hydrogen atom is substituted by an alkyl group with 1 to 6 carbon atoms), an alkoxy group (preferably an alkoxy group with 1 to 6 carbon atoms) and an alkoxysilyl group (preferably an alkoxysilyl group with 1 to 6 carbon atoms).

[0053] The cis content of a BR is preferably more than 90 wt%, more preferably more than 93 wt%, still more preferably more than 95 wt%, and even more preferably 97 wt% or more. The cis content of the BR can be measured by infrared absorption spectrometry.

[0054] The BR can be used, for example, with products from UBE Corporation, JSR Corporation, Asahi Kasei Corporation, Ltd., Zeon Corporation, etc. The BR can be used alone, or two or more can be used in combination. (Rubber component synthesized from recycled / biomass-derived raw material)

[0055] A monomer that is a structural unit of a synthetic rubber, such as IR, SBR, BR, and the like, can be one derived from earth resources, such as petroleum, natural gas, and the like, or one recycled from a rubber product, such as a tire, and the like, or from a non-rubber product, such as polystyrene, and the like. Examples of monomers obtained through recycling (recycled monomers) include, but are not limited to, polyisoprene, butadiene, and aromatic vinyl compounds. Examples of butadiene, as described above, include 1,2-butadiene and 1,3-butadiene. Examples of aromatic vinyl compounds include, but are not limited to, styrene and the like.Among these, polyisoprene obtained from recycling (recycled isoprene), butadiene obtained from recycling (recycled butadiene), and / or styrene obtained from recycling (recycled styrene) are preferably used as raw materials.

[0056] A process for producing a recycled monomer is not particularly restricted; examples include, for instance, the synthesis of a recycled monomer from recycled naphtha obtained by decomposing a rubber product, such as a tire. Furthermore, a process for producing recycled naphtha is not particularly restricted and can be carried out, for example, by decomposing a rubber product, such as a tire, under high temperature and high pressure, by decomposing it using microwaves, or by extracting it after mechanical pulverization.

[0057] Furthermore, a monomer that is a structural unit of a polymer, such as an IR, SBR, BR, and the like, can be one derived from biomass. In this description, "biomass" refers to a material derived from natural resources, such as plants and the like. Examples of biomass include, but are not limited to, agricultural, forestry, and fishery products; sugar; wood waste; plant residues after the capture of a useful component; plant-derived ethanol; biomass naphtha. Examples of biomass-derived monomers include biomass-derived butadiene, biomass-derived aromatic vinyl compounds, and the like. Examples of butadiene, as described above, include 1,2-butadiene and 1,3-butadiene.Examples of the aromatic vinyl compound described above include, but are not limited to, styrene and the like. Furthermore, a process for producing a biomass monomer is not particularly restricted; examples include, for instance, a process by biological and / or chemical and / or physical conversion of an animal or plant. Microbial fermentation is representative of biological conversion, and examples of chemical and physical conversion include a process using a catalyst, a process using high heat, a process using high pressure, a process using an electromagnetic wave, a process using a critical fluid, and combinations thereof.

[0058] Examples of a polymer synthesized from a biomass monomer component (biomass polymer) include a polybutadiene rubber synthesized from biomass-derived butadiene, an aromatic vinyl / butadiene copolymer synthesized from biomass-derived butadiene and / or a biomass-derived aromatic vinyl compound, and the like, but they are not particularly limited. Examples of aromatic vinyl butadiene copolymers include, for example, a styrene-butadiene rubber synthesized from biomass-derived butadiene and / or biomass-derived styrene, and the like.

[0059] Whether a polymer's raw material is derived from biomass or not can be determined by pMC (percent modern carbon), measured according to ASTM D6866-10.

[0060] Here, "pMC" means a ratio of 14 C concentration of a sample to 14 The carbon concentration of a modern standard reference carbon (modern standard reference) is a value used as an index indicating the biomass ratio of a compound. The meaning of this value is mentioned below.

[0061] In 1 mol of carbon atoms (approx. 6.02 × 10 23 There are approximately 6.02 × 10 11 14 C, which are about one trillionth the number of normal carbon atoms. A half-life of 14 C is 5730 years, and 14 Carbon decreases regularly. Therefore, in fossil fuels such as coal, oil, natural gas, and the like, where it is assumed that 226,000 years or more have passed since carbon dioxide was absorbed into the atmosphere by plants to be fixed, all the carbon dioxide decomposes. 14 Carbon elements, which were present at the beginning of the fixation. Therefore, fossil fuels, such as coal, oil, natural gas and the like, do not contain any carbon in the current 21st century. 14 Carbon element. Accordingly, the chemical substances produced using these fossil fuels as raw materials also contain no carbon. 14 C-element.

[0062] on the other hand 14 C is constantly produced by cosmic rays that cause nuclear reactions in the atmosphere. Thus, a decrease of 14 C due to radioactive decay and the production of 14 C is balanced due to nuclear reactions and is the amount of 14 The temperature C in the Earth's atmospheric environment is constant. Therefore, the 14 Carbon concentration of substances derived from biomass resources that have circulated in the current environment to a value of approximately 1 × 10 -12 Molar percentages, based on total carbon atoms, as described above. Accordingly, by using the difference between these values, a biomass ratio in a given compound can be calculated.

[0063] This 14 C is generally measured as follows. Using accelerator mass spectrometry based on a tandem accelerator, a 13 C concentration ( 13 C / 12 C) and a 14 C concentration ( 14 C / 12 C) measured. During the measurements, a 14 Carbon concentration in a circulating carbon in nature from 1950 as the modern standard reference for the 14 C concentration is used. A standard oxalic acid body provided by the National Institute of Standards and Technology (NIST) is used as a specific reference material. A specific radioactivity of carbon in this oxalic acid (radioactivity intensity of 14 C per gram of carbon) is sorted for each carbon isotope. 13 C is corrected to a constant value, and a value corrected for attenuation correction from 1950 to the measurement date is considered a standard. 14 A carbon concentration value (100%) is used. A ratio of this value to an actual measured value for a sample is called a pMC value.

[0064] Thus, when a rubber is produced from a material derived 100% from biomass, the 14 The carbon concentration typically has a value of approximately 110 pMC; currently, under normal conditions, it is often not equal to 100, although there are regional differences and the like. On the other hand, it shows when this 14 When the carbon concentration of a chemical substance derived from a fossil fuel, such as petroleum, is measured, it will be approximately 0 pMC (for example, 0.3 pMC). This value corresponds to a biomass ratio of 0%, as mentioned above.

[0065] Based on the above, it is suitable in terms of environmental protection to use a material, such as rubber, that has a high pMC value, i.e. a material, such as rubber, that has a high biomass ratio, for a rubber composition. <Füllstoff>

[0066] The rubber composition for insulation according to one embodiment of the present invention comprises a filler comprising recovered carbon black (rCB). Furthermore, the filler may comprise carbon black, silicon dioxide, or another reinforcing filler used in the tire industry. Preferably, the filler comprises recovered carbon black and a carbon black other than recovered carbon black. In a case where the filler comprises silicon dioxide, the filler may further comprise a silane coupling agent. (Recovered soot)

[0067] In the present invention, recovered carbon black refers to carbon black obtained by a pyrolysis process of a product, such as a used tire or the like, comprising carbon black, wherein, when the product is subjected to oxidative combustion by heating in air using a thermal weight measurement method according to JIS K 6226-2:2003, the ratio of mass to ash (ash content), which is a non-combustible component, is greater than 11% by mass. The ash content of recovered carbon black is preferably 13% by mass or more, more preferably 15% by mass or more, still more preferably 16% by mass or more, and even more preferably 17% by mass or more. Furthermore, the ash content is preferably less than 27% by mass, more preferably less than 26% by mass, and even more preferably less than 25% by mass.

[0068] Recovered carbon black can be obtained from a pyrolysis process of a used pneumatic tire. EP 3427975 A1, for example, refers to “Rubber Chemistry and Technology”, Vol. 85, No. 3, pp. 408-449 (2012), in particular pages 438, 440 and 442, and describes how recovered carbon black can be obtained by pyrolysis of an organic material at 550 to 800 °C under an oxygen-free environment or by vacuum pyrolysis at a relatively low temperature (

[0027] ). As described in

[0004] of JP 6856781 B2, such carbon black obtained by the pyrolysis process normally lacks a functional group on its surface (A Comparison of Surface Morphology and Chemistry of Pyrolytic Carbon Blacks with Commercial Carbon Blacks, Powder Technology 160 (2005) 190-193).As described above, since recovered carbon black has few surface functional groups, its interaction with the rubber component is low, and heat generation due to friction with a rubber is assumed to be reduced.

[0069] The recovered carbon black can be carbon black lacking a functional group on its surface, or it can be carbon black treated to contain a functional group on its surface. This treatment can be carried out using a conventional method. For example, in EP 3173251 A1, carbon black obtained from a pyrolysis process is treated with potassium permanganate under acidic conditions, yielding carbon black containing a hydroxyl group and / or a carboxyl group on its surface. Furthermore, in JP 6856781 B1, carbon black obtained from a pyrolysis process is treated with an amino acid compound containing at least one thiol group or disulfide group, yielding carbon black with an activated surface.Examples of recovered carbon black according to an embodiment of the present invention also include carbon black that has been treated to contain a functional group on its surface.

[0070] The average primary particle size of recovered carbon black is preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, and particularly preferably 35 nm or more. When the average primary particle size of carbon black is within the ranges described above, the number of rubber molecules bound by the carbon black is minimized, and the rubber molecules are more easily able to move flexibly. Accordingly, it is assumed that stress can be mitigated when applying a force, even through polymer molecule chains. On the other hand, the average primary particle size is preferably 90 nm or less, more preferably 75 nm or less, and still more preferably 60 nm or less. Furthermore, the average primary particle size of carbon black is measured using the measurement method described above.

[0071] A specific nitrogen adsorption surface area (N2SA) of recovered carbon black is preferably greater than 30 m², in order to obtain sufficient reinforcing properties and good abrasion resistance. 2 / g, preferably larger than 40 m 2 / g, preferably larger than 50 m 2 / g, preferably larger than 60 m 2 / g and preferably larger than 70 m 2 / g, but it is not particularly limited to that. Furthermore, the N2SA is preferably less than 300 m, considering that the recovered carbon black has excellent dispersibility and is less likely to generate heat. 2 / g, preferably less than 200 m 2 / g, preferably less than 150 m 2 / g, preferably less than 120 m 2 / g, preferably less than 110 m 2 / g, preferably less than 100 m 2 / g, preferably less than 90 m 2 / g. Furthermore, the N2SA of the recovered carbon black in the present description is a value measured in accordance with JIS K 6217-2:2017.

[0072] A statistical surface area (STSA) of recovered carbon black is preferably greater than 37 m², from the perspective that sufficient reinforcing properties and good abrasion resistance can be obtained. 2 / g, preferably larger than 40 m 2 / g and preferably larger than 45 m 2 / g, but it is not particularly limited to that. Furthermore, the STSA is preferably less than 77 m, considering that the recovered carbon black has excellent dispersibility and is less likely to generate heat. 2 / g, preferably less than 75 m 2 / g and even more preferably less than 73 m 2 / g. Furthermore, the STSA of the recovered carbon black in the present description is a value measured in accordance with JIS K 6217-7:2017.

[0073] For example, the content of recovered carbon black based on 100 parts by mass of the rubber component is, from the point of view of reinforcing properties, more than 10 parts by mass, preferably more than 20 parts by mass, further preferably 30 parts by mass or more and even more preferably more than 50 parts by mass. (soot that is different from rCB)

[0074] Examples of carbon black, other than recycled carbon black, include N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, N762, and the like, but are not specifically limited to these. A raw material for carbon black can be a biomass material, such as lignin, vegetable oil, and the like, or it can be pyrolysis oil obtained by pyrolyzing a used tire. Furthermore, a process for producing carbon black can be a combustion process, such as a furnace process, a process using hydrothermal carbonization (HTC), or a process using the pyrolysis of methane via a thermal carbon black process, and the like. Products from ASAHI CARBON CO., LTD., Cabot Japan KK, TOKAI CARBON CO., LTD., Mitsubishi Chemical Corporation, Lion Corporation, NIPPON STEEL Carbon Co., Ltd., Columbia Carbon Corporation, etc., can be used as commercially available products.They can be used alone, or two or more of them can be used in combination.

[0075] An average primary particle size of carbon black is preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, and particularly preferably 35 nm or more. When the average primary particle size of carbon black is within the ranges described above, the number of rubber molecules bound by carbon black is minimized, and it becomes easier for the rubber molecules to move flexibly. Accordingly, it is assumed that stress can be mitigated for force transmission, even through polymer molecule chains. On the other hand, the average primary particle size is preferably 90 nm or less, more preferably 75 nm or less, and still more preferably 60 nm or less. Furthermore, the average primary particle size of carbon black is measured by the measurement method described above.

[0076] A specific nitrogen adsorption surface area (N2SA) of carbon black is preferably greater than 30 m², in order to obtain sufficient reinforcing properties and good abrasion resistance. 2 / g, preferably larger than 40 m 2 / g, preferably larger than 50 m 2 / g, preferably larger than 60 m 2 / g and preferably larger than 70 m 2 / g, but it is not particularly limited to that. Furthermore, the N2SA is preferably less than 300 m, considering that carbon black is excellent in terms of dispersibility and is less likely to generate heat. 2 / g, preferably less than 200 m 2 / g, preferably less than 150 m 2 / g, preferably less than 120 m 2 / g, preferably less than 110 m 2 / g, preferably less than 100 m 2 / g, preferably less than 90 m 2 / g. Furthermore, the N2SA of soot in the present description is a value measured according to JIS K 6217-2:2017.

[0077] A statistical surface area (STSA) of carbon black is preferably greater than 37 m², considering that sufficient reinforcing properties and good abrasion resistance can be obtained. 2 / g, preferably larger than 40 m 2 / g and preferably larger than 45 m 2 / g, but it is not particularly limited to that. Furthermore, the STSA, considering that carbon black is excellent in terms of dispersibility and is less likely to generate heat, is preferably less than 77 m. 2 / g, preferably less than 75 m 2 / g and even more preferably less than 73 m 2 / g. Furthermore, the STSA of carbon black in the present description is a value measured in accordance with JIS K 6217-7:2017. (Soot content)

[0078] The carbon black content, when combined, based on 100 parts by mass of the rubber component, is, for example, more than 10 parts by mass, preferably more than 20 parts by mass, and further preferably 30 parts by mass or more. The total carbon black content, including recovered carbon black, based on 100 parts by mass of the rubber component, is, for example, more than 20 parts by mass, preferably more than 30 parts by mass, further preferably more than 40 parts by mass, even more preferably more than 50 parts by mass, and even more preferably 60 parts by mass or more. On the other hand, the total content is preferably less than 100 parts by mass, more preferably less than 90 parts by mass, and even more preferably less than 80 parts by mass.If the carbon black content is within the ranges described above, sufficient reinforcing properties and good dispersion in the rubber are obtained, so that sufficient rubber strength and sufficient crack growth resistance tend to be achieved. (Silicon dioxide)

[0079] Silicon dioxide is not particularly restricted, and those commonly used in the tire industry can be employed, such as silicon dioxide produced by a dry process (anhydrous silicon dioxide), silicon dioxide produced by a wet process (hydrous silicon dioxide), and the like. The source of silicon dioxide is not particularly restricted and can be, for example, a raw material derived from a mineral, such as quartz, or a raw material derived from a biological substance, such as rice husks (e.g., silicon dioxide from a biomass material, such as rice husks, and the like), or silicon dioxide recycled from a silicon dioxide-containing product. Among these, hydrous silicon dioxide produced by a wet process is preferred because it contains many silanol groups.Silicon dioxide can be used alone, or two or more of them can be used in combination.

[0080] Silicon dioxide from a biomass material can be obtained, for example, by burning rice husks to obtain rice husk ash, extracting silicate from the rice husk ash using a sodium hydroxide solution, producing silicon dioxide by reacting the silicate with sulfuric acid in the same way as for conventional wet silicon dioxide, and filtering, washing with water, drying, and pulverizing the silicon dioxide precipitates.

[0081] Silicon dioxide recycled from a product containing silicon dioxide can include, for example, silicon dioxide recovered from an electronic component, such as a semiconductor, a tire, a product containing silicon dioxide, such as a desiccant, a filter material, such as diatomaceous earth, and the like. Furthermore, the recovery method is not particularly restricted; examples include pyrolysis, decomposition by electromagnetic waves, and the like. Silicon dioxide recovered from an electronic component, such as a semiconductor, or from a tire is preferred.

[0082] When silicon dioxide crystallizes, it is insoluble in water, and silicic acid, a component of it, cannot be used. Crystallization of silicon dioxide in rice hull ash can be suppressed by controlling the firing temperature and duration (see JP 2009-2594 A, Akita Prefectural University Web Journal B / 2019, vol. 6, pp. 216-222 etc.).

[0083] Amorphous silicon dioxide extracted from rice husks can be used, including those commercially available from Wilmar, etc.

[0084] A specific nitrogen adsorption surface area (N2SA) of silicon dioxide is preferably greater than 50 m² from the perspective of its amplification properties. 2 / g, preferably larger than 100 m 2 / g, preferably larger than 150 m 2 / g and especially preferably larger than 170 m 2 / g. Furthermore, an upper limit for the N2SA of silicon dioxide is not particularly restricted, but it is preferably less than 350 m. 2 / g, preferably smaller than 250 m 2 / g and preferably smaller than 200 m 2 / g. If the content is within the ranges described above, cutting strength tends to be improved. Furthermore, the N₂SA of silicon dioxide is a value measured by a BET method according to ASTM D3037-93. (Silicon dioxide content)

[0085] The silicon dioxide content, when combined, based on 100 parts by mass of the rubber component, is preferably more than 1 part by mass, more preferably more than 5 parts by mass, more preferably more than 10 parts by mass, and more preferably more than 20 parts by mass, from the perspective of ensuring fuel efficiency and driving comfort, but is not specifically limited to these values. Furthermore, from the perspective of silicon dioxide dispersibility and processability, the content is preferably less than 150 parts by mass, more preferably less than 100 parts by mass, more preferably less than 50 parts by mass, and more preferably less than 30 parts by mass. (Silane coupling agent)

[0086] In a case where silicon dioxide is used as a filler, a rubber composition preferably further comprises a silane coupling agent. Examples of silane coupling agents include, for example, those based on sulfides, such as bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(2-triethoxysilylethyl)trisulfide, bis(4-trimethoxysilylbutyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(4-triethoxysilylbutyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(2-trimethoxysilylethyl)disulfide, bis(4-trimethoxysilylbutyl)disulfide, and 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide. 2-Triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-Triethoxysilylpropylmethacrylate monosulfide and the like;Those based on mercapto, such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, NXT and NXT-Z 100, manufactured by Momentive Performance Materials, and the like; those based on vinyl, such as vinyltriethoxysilane and vinyltrimethoxysilane; those based on amino, such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and the like; those based on glycidoxy, such as γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like; those based on nitro, such as 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, and the like;and those based on chlorine, such as 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and the like, are not particularly restricted. Commercially available products from Evonik Industries AG, Momentive Performance Materials, Shin-Etsu Chemical Co., Ltd., Tokyo Chemical Industry Co., Ltd., AZmax.co, Dow Corning Toray Co., Ltd., etc., can be used. These silane coupling agents can be used alone, or two or more of them can be used in combination. (Content of silane coupling agent)

[0087] The content of a silane coupling agent, when combined, based on 100 parts by mass of silicon dioxide, is preferably greater than 1 part by mass, more preferably greater than 3 parts by mass, still more preferably greater than 5 parts by mass, and still more preferably greater than 7 parts by mass. Conversely, the content is preferably less than 20 parts by mass, more preferably less than 18 parts by mass, still more preferably less than 16 parts by mass, and still more preferably less than 14 parts by mass. If the content is within the ranges described above, the dispersibility of the silicon dioxide tends to be improved. (Other fillers)

[0088] Other fillers are not particularly restricted, and materials known in the tire industry can be used as alternative fillers. Examples of such alternative fillers include inorganic fillers such as calcium carbonate, talc, aluminum oxide (alumina), clay, aluminum hydroxide, aluminum oxide, and mica, among others. They can be used alone, or two or more of them can be used in combination. <Andere Verbindungsmittel>

[0089] In addition to the rubber component and filler, the rubber composition may appropriately include bonding agents that are conventionally and commonly used in the tire industry, such as a plasticizer, processing aid, vulcanized rubber particles, wax, stearic acid, zinc oxide, an antioxidant, a vulcanizing agent, a vulcanization accelerator, and the like. (Plasticizing agent)

[0090] A plasticizer is a material that imparts plasticity to a rubber component. The term encompasses both liquid plasticizers (in a liquid state) and solid plasticizers (solids) at normal temperature (25°C). Examples of plasticizers include resins, oils, liquid polymers, ester-based plasticizers, and the like. These plasticizers can be derived from petroleum, biomass, or naphtha recycled from rubber or non-rubber products. Additionally, low molecular weight hydrocarbons obtained by pyrolyzing and extracting them from end-of-life tires or products containing various components can also be used as plasticizers.The plasticizing agents can be used alone, or two or more of them can be used in combination. <<Oil>>

[0091] Examples of oils include mineral oils, vegetable oils, animal oils, and the like. Furthermore, from a life cycle assessment perspective, one can be used that is obtained by refining used oil after use in a rubber mixer or engine, or used cooking oil from a restaurant. These oils can be used individually, or two or more of them can be used in combination.

[0092] In this patent specification, "mineral oil" refers to oil derived from mineral resources such as petroleum, natural gas, and the like. Examples of mineral oil include paraffinic oils (mineral oils), naphthenic oils, aromatic oils, and the like. Specific examples of mineral oils include, for example, Mild Extracted Solvated (MES), Distillate Aromatic Extract (DAE), Treated Distillate Aromatic Extract (TDAE), Treated Residual Aromatic Extract (TRAE), Residual Aromatic Extract (RAE), and the like. Furthermore, as an environmental measure, oils that each have a low content of a polycyclic aromatic compound (PCA) may also be used. Examples of oils that each have a low content of a PCA include MES, TDAE, heavy naphthenic oil, and the like.

[0093] In this description, examples of vegetable oils include, for instance, linseed oil, rapeseed oil, safflower oil, soybean oil, corn oil, cottonseed oil, rice bran oil, tall oil, sesame oil, perilla oil, castor oil, tung oil, pine oil, pine tar oil, sunflower oil, coconut oil, palm oil, palm kernel oil, olive oil, camellia oil, jojoba oil, macadamia nut oil, peanut oil, grapeseed oil, Japan wax, and the like. Furthermore, examples of vegetable oil also include refined oils obtained by refining the oils described above (cooking oils, etc.).), a transesterified oil obtained by transesterifying the oil described above, a hydrogenated oil obtained by hydrogenating the oil described above, a thermally polymerized oil obtained by thermally polymerizing the oil described above, an oxidized polymerized oil obtained by oxidizing the oils described above, a used cooking oil obtained by restoring what was previously used as an edible oil, etc., and the like. Furthermore, the vegetable oil may be liquid or solid at room temperature (25°C). These vegetable oils may be used individually, or two or more of them may be used in combination.

[0094] The vegetable oil according to the present embodiment preferably comprises acylglycerol and further preferably triacylglycerol. In this description, acylglycerol also refers to a compound in which a hydroxyl group of glycerol and a fatty acid are ester-bound. The acylglycerol is not particularly restricted and can be 1-monoacylglycerol, 2-monoacylglycerol, 1,2-diacylglycerol, 1,3-diacylglycerol, or triacylglycerol. Furthermore, the acylglycerol can be a monomer, a dimer, or a multimer that is a trimer or higher. Acylglycerol that is a dimer or higher can also be obtained by thermal polymerization, oxidative polymerization, or the like. In addition, acylglycerol can be liquid or solid at room temperature (25 °C).

[0095] Whether the rubber composition includes the acylglycerol described above can be determined by 1 The range of applications can be verified by H-NMR measurement, but is not particularly limited. For example, a heavy chloroform into which a rubber composition containing triacylglycerol is immersed at room temperature (25 °C) for 24 hours and then removed will be tested by a 1 Subjected to ¹H NMR measurements at room temperature, signals near 5.26 ppm, near 4.28 ppm, and near 4.15 ppm were observed under the condition that a signal from tetramethylsilane (TMS) was set to 0.00 ppm. It is suggested that these signals are derived from hydrogen atoms bonded to carbon atoms adjacent to oxygen atoms of an ester group. Furthermore, "near" in this paragraph refers to a range of ±0.10 ppm.

[0096] The fatty acid described above is not particularly restricted and can be either an unsaturated or a saturated fatty acid. Examples of unsaturated fatty acids include monounsaturated fatty acids, such as oleic acid, and the like; and polyunsaturated fatty acids, such as linoleic acid, linolenic acid, and the like. Furthermore, examples of saturated fatty acids include butyric acid, lauric acid, and the like.

[0097] The desired fatty acid, as described above, is one with few double bonds, meaning a saturated or monounsaturated fatty acid, and oleic acid is preferred. A vegetable oil containing such a fatty acid could be, for example, a vegetable oil containing a saturated or monounsaturated fatty acid, or a vegetable oil refined by transesterification or similar processes. Furthermore, to produce a vegetable oil containing such a fatty acid, a plant can be improved through selective breeding, gene combination, genome editing, or similar methods.

[0098] Suitable vegetable oils include, for example, those commercially available from Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo KK, ENEOS Corporation, Olisoy, H&R Group, HOKOKU Corporation, Fuji Kosan Co., Ltd., The Nisshin Oillio Group, etc.

[0099] An oil content based on 100 parts by mass of the rubber component is preferably greater than 1 part by mass, more preferably greater than 3 parts by mass, and even more preferably greater than 5 parts by mass. Furthermore, the content is preferably less than 20 parts by mass, more preferably less than 15 parts by mass, and even more preferably less than 10 parts by mass. The oil content also includes an amount of oil contained as an extender in a rubber component or oil contained in another component, such as sulfur. <<Flüssiges Polymer> >

[0100] A liquid polymer is a polymer in a liquid state at normal temperature (25 °C), and examples include, for instance, liquid diene-based polymers and the like. Examples of liquid diene-based polymers include liquid styrene-butadiene copolymer (liquid SBR), liquid butadiene polymer (liquid BR), liquid isoprene polymer (liquid IR), liquid styrene-isoprene copolymer (liquid SIR), and the like. The number-mean molecular weight (Mn) of the liquid diene-based polymer, measured by gel permeation chromatography (GPC) and calculated with respect to polystyrene, is preferably greater than 1000 and more preferably greater than 3000. On the other hand, the Mn is preferably less than 100,000 and more preferably less than 15,000. The Mn of the liquid polymer is a value measured by gel permeation chromatography (GPC) and calculated with respect to polystyrene.Suitable liquid diene-based polymers include products from Sartomer, Kuraray Co., Ltd., etc. The liquid polymer can be used alone, or two or more can be used in combination. (resin component)

[0101] The rubber composition according to the present embodiment may include a resin component. The resin component that may be used in the present embodiment is not particularly restricted, and any resin commonly used in the tire industry may be used. Examples include, for instance, a C9-based resin, a C5-based resin, a C5 / C9-based resin, a dicyclopentadiene-based resin, an aromatic vinyl-based resin, a coumaron-based resin, an indene-based resin, a terpene-based resin, a rosin-based resin, a phenol-based resin, and the like. These resin components may be used individually, or two or more of them may be used in combination. Each resin component may also be used individually, or two or more of them may be used in combination. <<Harz auf C9-Basis> >

[0102] A "C9-based resin" refers to a resin obtained by polymerizing C9 fractions and can be a polymer obtained by polymerizing a C9 fraction alone, or a copolymer obtained by copolymerizing a C9 fraction with other components. For example, a resin obtained by copolymerizing dicyclopentadiene (DCPD) with a C9 fraction is called a DCPD / C9 resin. Furthermore, a C9-based resin can be one obtained by hydrogenating or modifying it. Examples of C9 fractions include petroleum fractions with 8 to 10 carbon atoms, such as vinyltoluene, alkylstyrene, coumaron, indene, methylindene, dicyclopentadiene, and the like. Examples of C9-based resins include those commercially available from BASF, Zeon Corporation, ENEOS Corporation, etc. <<Harz auf C5-Basis> >

[0103] A "C5-based resin" refers to a resin obtained by polymerizing C5 fractions, and can be one obtained by hydrogenating or modifying them. Examples of C5 fractions other than dicyclopentadiene include petroleum fractions with 4 to 5 carbon atoms, such as cyclopentadiene, isoprene, piperylene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, and the like. Examples of C5-based resins that can be used include those commercially available from STRUKTOL, Zeon Corporation, ENEOS Corporation, etc. <<Harz auf C5 / C9-Basis> >

[0104] A "C5 / C9-based resin" refers to a resin obtained by copolymerizing the C5 and C9 fractions, and can be one obtained by hydrogenation or modification thereof. For example, suitable C5 / C9-based petroleum resins include those commercially available from Tosoh Corporation, Zibo Luhua Hongjin New Material Group Co., Ltd. <<Harz auf Dicyclopentadien-Basis> >

[0105] A "dicyclopentadiene-based resin" refers to a resin that contains cyclopentadiene (CPD) and / or dicyclopentadiene (DCPD) as the predominant monomer component and may be one obtained by hydrogenation or modification thereof. Examples of dicyclopentadiene-based resins include polymers obtained by polymerizing only dicyclopentadiene as a monomer, copolymers obtained by copolymerizing dicyclopentadiene with the C9 fraction (DCPD / C9 resin), and similar formulations. Examples of dicyclopentadiene-based resins that can be used include those commercially available from Exxon Mobil Corporation, ENEOS Corporation, Zeon Corporation, Maruzen Petrochemical Co., Ltd., etc. <<Harz auf aromatischer Vinyl-Basis> >

[0106] An "aromatic vinyl-based resin" refers to a resin that incorporates an aromatic vinyl compound, such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, and the like, as a monomer component with the highest concentration, and may be one obtained by hydrogenation or modification thereof. A homopolymer of α-methylstyrene or styrene, or a copolymer of α-methylstyrene and styrene, is preferred as the aromatic vinyl-based resin, and a copolymer of α-methylstyrene and styrene is further preferred because it is economical, easy to process, and has excellent heat generation properties. Examples of aromatic vinyl-based resins that can be used include those commercially available from Kraton Corporation, Eastman Chemical Company, Mitsui Chemicals, Inc., etc. <<Harz auf Cumaron-Basis> >

[0107] A "coumaron-based resin" refers to a resin that includes coumaron as a monomer component and can be one obtained by hydrogenating or modifying it. Examples of resins suitable for use as coumaron-based resins include a coumaron resin that is a polymer containing only coumaron as a monomer component, a coumaron-indene resin that is a copolymer containing coumaron and indene as monomer components, a coumaron-indene-styrene resin that is a copolymer containing coumaron, indene, and styrene as monomer components, and similar formulations. Examples of suitable coumaron-based resins include those commercially available from Rutgers Chemicals, Nitto Chemical Co., Ltd., Mitsui Chemicals, Inc., etc. <<Harz auf Inden-Basis> >

[0108] An "indene-based resin" refers to a resin that includes indene as a monomer component and can be one obtained by hydrogenating or modifying it. Examples of indene-based resins include a coumaron-indene resin, which is a copolymer containing coumaron and indene as monomer components; a coumaron-indene-styrene resin, which is a copolymer containing coumaron, indene, and styrene as monomer components; and similar resins. Examples of indene-based resins that can be used include those commercially available from Rutgers Chemicals, Nitto Chemical Co., Ltd., Mitsui Chemicals, Inc., etc. <<Harz auf Terpen-Basis> >

[0109] A "terpene-based resin" refers to a resin that incorporates a terpene compound, such as α-pinene, β-pinene, limonene, dipentene, and the like, as a monomer component, and may be one obtained by hydrogenation or modification thereof. Preferred examples of terpene-based resins include a polyterpene resin, which is a polymer comprising only one or more of the terpene compounds as monomer components; an aromatically modified terpene resin, which is a copolymer comprising the terpene compound and an aromatic compound as monomer components; a terpenophenolic resin, which is a copolymer comprising the terpene compound and a phenolic compound as monomer components; and the like. Examples of aromatic compounds used as monomer components for aromatically modified terpene resins include styrene, α-methylstyrene, vinyltoluene, divinyltoluene, and the like.Examples of phenolic compounds used as monomer components for terpene phenolic resin include phenol, bisphenol A, cresol, xylenol, and the like. Terpene-based resins that can be used include those commercially available from companies such as Yasuhara Chemical Co., Ltd., Arakawa Chemical Industries, Ltd., and Nippon Terpene Chemicals, Inc. <<Harz auf Kolophonium-Basis> >

[0110] A "rosin-based resin" refers to a resin containing a rosin acid compound, such as abietic acid, neoabietic acid, palustric acid, isopimaric acid, and the like, and may be one obtained by hydrogenation or modification thereof. Examples of rosin-based resins include, for instance, natural resin rosin and rosin-modified resins obtained by modifying natural resin rosin through hydrogenation, disproportionation, dimerization, esterification, etc., but are not particularly limited. Examples of rosin-based resins include those commercially available from Harima Chemicals Group, Inc., Arakawa Chemical Industries, Ltd., IREC Co., Ltd., etc. <<Harz auf Phenol-Basis> >

[0111] A "phenol-based resin" refers to a resin that incorporates a phenolic compound, such as phenol, cresol, and the like, as a monomer component, and may be one obtained by hydrogenation or modification thereof. Examples of phenol-based resins include, but are not limited to, phenol-formaldehyde resins, alkylphenol-formaldehyde resins, alkylphenol-acetylene resins, oil-modified phenol-formaldehyde resins, terpene phenol resins, and the like. Examples of phenol-based resins include those commercially available from Sumitomo Bakelite Co., Ltd., DIC Corporation, ASAHI YUKIZAI CORPORATION, etc.

[0112] The content of a resin component, when combined, based on 100 parts by mass of the rubber component, is preferably more than 2 parts by mass, further preferably more than 3 parts by mass, and even more preferably more than 4 parts by mass. Conversely, the content is preferably less than 20 parts by mass, further preferably less than 15 parts by mass, and even more preferably less than 10 parts by mass. <<Plastifizierungsmittel auf Ester-Basis> >

[0113] Examples of ester-based plasticizers include dibutyl adipate (DBA), diisobutyl adipate (DIBA), dioctyl adipate (DOA), di(2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), diisononyl adipate (DINA), diethyl phthalate (DEP), dioctyl phthalate (DOP), diundecyl phthalate (DUP), dibutyl phthalate (DBP), dioctyl sebacate (DOS), tributyl phosphate (TBP), trioctyl phosphate (TOP), triethyl phosphate (TEP), trimethyl phosphate (TMP), thymidine triphosphate (TTP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), and the like. These ester-based plasticizers can be used alone, or two or more of them can be used in combination. (Antioxidants)

[0114] Examples of the antioxidant include, but are not limited to, a naphthylamine-based antioxidant such as phenyl-α-naphthylamine and the like; a diphenylamine-based antioxidant such as an octylated diphenylamine, 4,4'-bis(α,α'-dimethylbenzyl)diphenylamine and the like; an antioxidant based on p-phenylenediamine, such as N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N,N'-di-2-naphthyl-p-phenylenediamine (DNPD) and the like; an antioxidant based on quinoline, such as a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline and the like;A monophenol-based antioxidant, such as 2,6-di-t-butyl-4-methylphenol, a styrenized phenol, and the like; and bisphenol-based, trisphenol-based, and polyphenol-based antioxidants, such as tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane and the like. Among these, the p-phenylenediamine-based and the quinoline-based antioxidants are preferred, and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline are further preferred. Commercially available products such as those from Seiko Chemical Co., Ltd., Sumitomo Chemical Co., Ouchi Shinko Chemical Industry Co., Flexsys, etc., may be used. The antioxidants can be used alone, or two or more of them can be used in combination.

[0115] The content of an antioxidant, when combined, based on 100 parts by mass of the rubber component, is preferably more than 0.5 parts by mass, further preferably more than 0.8 parts by mass, and even more preferably more than 1.0 parts by mass. On the other hand, the content is preferably less than 7.0 parts by mass, further preferably less than 5.0 parts by mass, and even more preferably 3.0 parts by mass or less. (Vulcanized rubber particle)

[0116] Vulcanized rubber particles are particles made from vulcanized rubber. Specifically, rubber powder as specified in JIS K 6316:2017, and similar materials, can be used. Recycled rubber powder produced from a powdered end-of-life tire or similar material is preferred from an environmental and cost perspective. These particles can be used individually, or two or more can be used in combination.

[0117] The vulcanized rubber particle is not particularly restricted and can be an unmodified vulcanized rubber particle or a modified vulcanized rubber particle.

[0118] Examples of commercially available vulcanized rubber products include those from Lehigh Technologies, Muraoka Rubber Reclaiming Co., Ltd., etc. (Processing aids)

[0119] Examples of processing aids include, for example, a fatty acid metal salt, a fatty acid amide, an amide ester, a silicon dioxide surfactant, a mixture of a fatty acid metal salt and an amide ester, a mixture of a fatty acid metal salt and a fatty acid amide, and the like. The processing aid can be used alone, or two or more can be used in combination. Examples of processing aids that can be used include those commercially available from Schill+Seilacher GmbH, Performance Additives, etc.

[0120] The amount of processing aids, when combined, based on 100 parts by mass of the rubber component, is preferably greater than 0.5 parts by mass, more preferably greater than 1 part by mass, and still more preferably greater than 1.5 parts by mass, in order to demonstrate an effect of improving processability. Furthermore, in order to improve abrasion resistance and fracture toughness, it is preferably less than 10 parts by mass, more preferably less than 8.0 parts by mass, and still more preferably less than 5.0 parts by mass. (Wax)

[0121] The type of wax is not particularly restricted, and any wax commonly used in the tire industry may be suitable. Examples include mineral-based waxes, plant-derived waxes, and the like. Mineral-based waxes refer to waxes derived from mineral resources such as oil, natural gas, and the like. Plant-derived waxes refer to waxes derived from natural resources such as plants. Mineral-based waxes are preferred. Examples of plant-derived waxes include rice bran wax, carnauba wax, candelilla wax, and the like. Examples of mineral-based waxes include paraffin wax, microcrystalline wax, a specially selected wax of these, and the like, with paraffin wax being preferred.Furthermore, the wax relating to the present embodiment should not contain stearic acid. Examples of waxes that can be used include those commercially available from Ouchi Shinko Chemical Industry Co., Nippon Seiro Co., Ltd., PARAMELT, etc. The wax can be used alone, or two or more can be used in combination.

[0122] The wax content, when combined, based on 100 parts by mass of the rubber component, is preferably more than 0.3 parts by mass, more preferably more than 0.7 parts by mass, and even more preferably more than 1.0 parts by mass. Conversely, the content is preferably less than 4.0 parts by mass, more preferably less than 3.0 parts by mass, and even more preferably less than 2.5 parts by mass. (Stearic acid)

[0123] The stearic acid content, when combined, based on 100 parts by mass of the rubber component, is preferably more than 0.5 parts by mass, more preferably more than 0.7 parts by mass, and even more preferably 1.0 parts by mass or more, from the point of view of processability. On the other hand, from the point of view of vulcanization rate, the content is preferably less than 10 parts by mass, more preferably less than 5 parts by mass, and even more preferably less than 3 parts by mass. (Zinc oxide)

[0124] The zinc oxide content, when combined, based on 100 parts by mass of the rubber component, is preferably more than 0.5 parts by mass, more preferably more than 0.7 parts by mass, and even more preferably more than 1 part by mass, from the point of view of processability. On the other hand, from the point of view of abrasion resistance, the content is preferably 10 parts by mass or less, more preferably less than 7 parts by mass, and even more preferably 5 parts by mass or less. (Vulcanizing agent)

[0125] The choice of vulcanizing agent is not particularly restricted, and known vulcanizing agents may be used, examples of which include organic peroxide, a sulfur-based vulcanizing agent, a resin vulcanizing agent, metal oxide such as magnesium oxide, and the like. Among these, a sulfur-based vulcanizing agent is preferred. Sulfur donors such as sulfur, morpholine disulfide, and the like may be used as the sulfur-based vulcanizing agent. Sulfur is preferred. The vulcanizing agent may be used alone, or two or more may be used in combination.

[0126] Examples of sulfur include sulfur powder, precipitated sulfur, colloidal sulfur, surface-treated sulfur (oil-processing sulfur, special sulfur treated with a dispersant, masterbatch-type sulfur, and the like), insoluble sulfur (oil-processing insoluble sulfur, and the like), and any of these may be used appropriately. Among these, sulfur powder is preferred. Examples of sulfur that may be used include those manufactured and sold by Tsurumi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Chemicals Corporation, Flexsys, Nippon Kanryu Industry Co., Ltd., Hosoi Chemical Industry Co., Ltd., and the like.

[0127] A well-known organic crosslinking agent can also be used as a vulcanizing agent. While the choice of organic crosslinking agent is not particularly limited, as long as it can form a crosslinking chain other than a polysulfide bond, examples of organic crosslinking agents include alkylphenol sulfur chloride condensate, sodium hexamethylene 1,6-bisthiosulfate dihydrate, 1,6-bis(N,N'-dibenzylthiocarbamoyldithio)hexane, dicumyl peroxide, and the like, with 1,6-bis(N,N'-dibenzylthiocarbamoyldithio)hexane being preferred. These organic crosslinking agents can include those commercially available from Taoka Chemical Co., Ltd., LANXESS, Flexsys, etc.

[0128] The content of a vulcanizing agent, when combined, based on 100 parts by mass of the rubber component, is preferably more than 0.4 parts by mass, more preferably more than 0.5 parts by mass, more preferably more than 1.0 parts by mass, and more preferably more than 1.5 parts by mass. Conversely, the content is preferably less than 6.0 parts by mass, more preferably 5.0 parts by mass or less, and more preferably less than 4.0 parts by mass. If the content of the vulcanizing agent is within the ranges described above, a suitable strengthening effect is generally achieved. Furthermore, in a case where the vulcanizing agent contains a component other than sulfur, such as oil-processing sulfur and the like, the content of the vulcanizing agent means the content of the sulfur component itself. (Vulcanization accelerator)

[0129] The choice of vulcanization accelerator is not particularly restricted, and known vulcanization accelerators may be used, examples of which include sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based, aldehyde-amine-based, aldehyde-ammonia-based, imidazoline-based, and xanthate-based vulcanization accelerators. Among these, the sulfenamide-based, thiuram-based, and guanidine-based vulcanization accelerators are preferred, with the sulfenamide-based vulcanization accelerator being further preferred. Examples of suitable vulcanization accelerators include those manufactured and sold by Ouchi Shinko Chemical Industry Co., Ltd., Sanshin Chemical Industry Co., Ltd., and the like.These vulcanization accelerators can be used alone, or two or more of them can be used in combination.

[0130] Examples of sulfenamide-based vulcanization accelerators include, for example, N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N,N'-dicyclohexyl-2-benzothiazolylsulfenamide (DZ), and the like. Examples of thiuram-based vulcanization accelerators include, for example, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetrabenzylthiuram disulfide (TBzTD), and the like. Examples of guanidine-based vulcanization accelerators include, for example, 1,3-diphenylguanidine (DPG), diorthotrilguanidine, orthotrilbiguanidine, and the like.

[0131] The content of a vulcanization accelerator, based on 100 parts by mass of the rubber component, is preferably greater than 0.3 parts by mass, more preferably greater than 0.4 parts by mass, and even more preferably greater than 0.5 parts by mass. Conversely, the content is preferably less than 4.0 parts by mass, more preferably less than 3.0 parts by mass, and even more preferably less than 2.0 parts by mass. If the content of the vulcanization accelerator is within the ranges described above, fracture toughness and elongation can generally be ensured. [Rubber composition for inner liner]

[0132] Each component of the rubber composition for inner liners is described. (Rubber component)

[0133] An explanation of a rubber component is not only as described below, but also as described in the explanation of the rubber composition for insulation. A rubber composition for inner liners includes a rubber component that comprises a butyl-based rubber. In this case, the rubber component may comprise a rubber component other than butyl-based rubbers. A rubber component described in the explanation of the rubber composition for insulation can be used as such a rubber component that differs from butyl-based rubbers. Furthermore, the rubber component may be one that consists of a butyl-based rubber. An explanation of a butyl-based rubber is as follows. <<Kautschuk auf Butyl-Basis> >

[0134] The butyl-based rubbers are preferably a polymer having an isobutylene unit and an isoprene unit as repeating units, and a derivative thereof. Examples of such butyl-based rubbers include a butyl rubber (IIR); a halogenated butyl rubber, such as a brominated butyl rubber (Br-IIR), a chlorinated butyl rubber (Cl-IIR), and the like. Among these, a halogenated butyl rubber is preferred, and a brominated butyl rubber and a chlorinated butyl rubber are further preferred because they allow for a good balance between sheet processability and air barrier properties. They can be used individually, or two or more of them can be used in combination.

[0135] In addition to conventional butyl rubber (non-recycled butyl rubber), recycled butyl rubber can be used in combination with other butyl rubbers. Since the content of non-halogenated butyl rubber (regular butyl rubber) in recycled butyl rubber is typically high, good air barrier properties and vulcanization rates can be ensured by using recycled butyl rubber in combination with halogenated butyl rubber. These recycled butyl rubbers can be used alone, or two or more can be used in combination.

[0136] The rubber component may include rubber components other than butyl-based rubbers. Examples of such other rubber components include diene-based rubbers, such as isoprene-based rubber (IR-based rubber), butadiene rubber (BR), styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber (SIBR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and the like. The explanation given for the rubber composition for insulation can be similarly applied to these other rubber components. These other rubber components may be used alone, or two or more of them may be used in combination.

[0137] From the perspective of sufficient air barrier properties, the content of a butyl-based rubber in 100 wt% of the rubber component is preferably more than 70 wt%, further preferably more than 75 wt%, even more preferably 80 wt% or more and particularly preferably 90 wt% or more. (Filler)

[0138] A filler may comprise carbon black. Furthermore, the filler may comprise recycled carbon black (rCB) or silicon dioxide. In the case where the filler comprises silicon dioxide, the filler may further comprise a silane coupling agent. The filler may also comprise a filler other than carbon black and silicon dioxide. The filler preferably comprises carbon black and recycled carbon black. An explanation of each component capable of forming the filler is as described in the section on rubber composition for insulation. <<Gehalt an Ruß> >

[0139] A total carbon black content, including recovered carbon black when combined, based on 100 parts by mass of the rubber component, is, for example, more than 20 parts by mass, preferably more than 40 parts by mass, further preferably 50 parts by mass or more, and still more preferably 60 parts by mass or more. Conversely, the total content is preferably less than 150 parts by mass, further preferably less than 110 parts by mass, and still more preferably less than 80 parts by mass. If the carbon black content is within the ranges described above, sufficient reinforcing properties and good dispersion in the rubber are obtained, and thus sufficient rubber strength and sufficient crack growth resistance are tended to be achieved.

[0140] In a case where the filler comprises recovered carbon black, the proportion of recovered carbon black in the total carbon black content is, for example, from the point of view of reinforcing properties, preferably more than 10 wt%, more preferably more than 20 wt%, still more preferably more than 30 wt% and more preferably 40 wt% or more.

[0141] The explanation given for the rubber composition used for insulation can be similarly applied to these other carbon blacks (including recovered carbon black). (Other connecting means)

[0142] The explanation given for the rubber composition for insulation can be applied similarly to descriptions other than those described above. <Andere Kautschukelemente, die Reifen bilden>

[0143] In the present description, the tire may include rubber elements other than those described above. Such other rubber elements are not particularly restricted, and a variety of rubber elements commonly used in a tire may be employed.

[0144] In the present description, various materials, each comprising a single carbon atom (for example, rubber, oil, a resin component, a vulcanization accelerator, an antioxidant, a surfactant, and the like), can be derived from atmospheric carbon dioxide. These various materials, which are compound substances, can be obtained either by directly converting carbon dioxide or by converting methane, which is obtained via a methanation process by which methane is synthesized from carbon dioxide. <anwendung>

[0145] In this description, the tire, although it may be a pneumatic or a deflated tire, can be used as a suitable pneumatic tire. Furthermore, in this description, the tire can be used for various applications, such as a tire for a passenger car, a heavy-duty tire for a truck / bus, a motorcycle tire, a high-performance tire, and the like. <produktionsverfahren>

[0146] The tire according to the present embodiment can be produced by a known method. (Production of rubber compound)

[0147] Each of the rubber compositions described above can be produced by a known process. They can be produced, for example, by kneading the respective components described above using a rubber kneading machine, such as an open roller, a closed-type kneader (a Banbury mixer, a kneader, etc.), and the like. A kneading step includes, for example, a basic kneading step of kneading bonding agents and additives other than a vulcanizing agent and a vulcanization accelerator, and a final kneading step (F-kneading) of adding the vulcanizing agent and the vulcanization accelerator to the kneaded product obtained in the basic kneading step and kneading it. Furthermore, the basic kneading step can also be subdivided into several steps if necessary.Examples of kneading conditions include, for instance, a process of kneading at a delivery temperature of 150 °C to 170 °C for 3 to 10 minutes for the basic kneading step and kneading at 50 °C to 110 °C for 1 to 5 minutes for the final kneading step, but they are not particularly limited to these. (Production of tires)

[0148] Each rubber composition obtained as described above is extruded into the desired shape of each tire element at an unvulcanized stage, producing an unvulcanized insulation and an unvulcanized inner liner. The insulation and inner liner thus obtained are formed together with other tire elements on a tire forming machine by a conventional process, producing an unvulcanized tire according to the present embodiment. The tire can be obtained by heating and pressurizing (vulcanizing) this unvulcanized tire in a vulcanizing machine. Examples of vulcanization conditions include, but are not limited to, a process of vulcanizing at 150 to 200 °C for 5 to 30 minutes. EXAMPLES

[0149] Examples considered preferred in implementing the present invention (examples) are described below, although the scope of protection of the present invention is not limited to these examples. Results calculated on the basis of evaluation methods described below, taking into account a rubber composition and a tire obtained in accordance with each table using various chemicals described below, are shown as a durability index and an air permeability resistance index in the lower part of each table. <materialien>

[0150] Materials used in examples and comparisons are shown collectively below. Natural rubber: SVR-L SBR: SBR1502 (manufactured by JSR Corporation (styrene content: 23.5 wt%, vinyl content: 18 wt%, Mw: 500000) Butyl-based rubber 1: BB2222 (manufactured by Exxon Mobil Corporation, bromobutyl rubber) Butyl-based rubber 2: Chlorobutyl HT1066 (manufactured by Exxon Mobil Corporation, Chlorobutyl rubber) Carbon black: SHOW BLACK N660 (manufactured by Cabot Japan KK, N2SA: 35 m 2 / G; Ash content: 0.5% by mass Recovered carbon black (rCB): Carbon black obtained from a tire pyrolysis process (ash content: 17% by mass). Oil 1: Diana process NH-70S (manufactured by Idemitsu Kosan Co., Ltd., aromatic process oil) Oil 2: PS-32 (manufactured by Idemitsu Kosan Co., Ltd., mineral oil) Zinc oxide: Zinc oxide No. 2 (manufactured by Mitsui Mining & Smelting Co., Ltd.) Stearic acid: Stearic acid “CAMELLIA” (manufactured by NOF CORPORATION) Sulfur: HK-200-5 (manufactured by Hosoi Chemical Industry Co., Ltd., sulfur powder, oil content: 5 wt%) Vulcanization accelerator 1: Nocceler CZ (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., N,N-Dicyclohexyl-2-benzothiazolylsulfenamide) Vulcanization accelerator 2: Nocceler DM (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., Di-2-benzothiazolyl disulfide) <Kautschukzusammensetzung für Isolierung>

[0151] According to the compound formulations shown in Tables 1 and 2, all chemicals except sulfur and a vulcanization accelerator are kneaded for 5 minutes at a discharge temperature of 150 °C using a closed 1.7-liter Banbury mixer. Next, using an open roller, the sulfur and the vulcanization accelerator are added to the resulting kneaded product, and the mixture is kneaded for 4 minutes until the temperature reaches 105 °C to obtain an unvulcanized rubber composition for insulation. <Kautschukzusammensetzung für Innerliner>

[0152] According to the compound formulations shown in Tables 1 and 2, using a closed 1.7-liter Banbury mixer, all chemicals except sulfur and a vulcanization accelerator are kneaded for 4 minutes until a discharge temperature of 130 °C is reached to obtain a kneaded product. Next, using an open twin-screw mixer, sulfur and the vulcanization accelerator are added to the resulting kneaded product, and the mixture is kneaded for 4 minutes until the temperature reaches 80 °C to obtain an unvulcanized rubber composition for inner liners. <reifen>

[0153] According to the descriptions in Tables 1 and 2, the unvulcanized rubber composition for insulation and the unvulcanized rubber composition for inner liner are accordingly formed into a mold of insulation (thickness: 0.4 mm) and a mold of inner liner, and further joined with other elements to produce an unvulcanized tire, and the unvulcanized tire is press-vulcanized under a condition at 170 °C for 12 minutes, thereby producing each test tire (size: 195 / 65R15). <bewertungen>

[0154] Results of evaluations of the respective test tires using the evaluation procedures described below are described in the corresponding columns in each of the tables. <70 °C-tanδ>

[0155] The 70 °C tanδ is measured using a dynamic viscoelasticity measuring device at a temperature of 70 °C, a frequency of 10 Hz, an initial strain of 10%, a dynamic strain of ± 1%, and in a strain mode. A sample is cut from a tire such that a complex of insulation and inner liner has a length of 20 mm, a width of 4 mm, and a thickness of 1 mm. The longitudinal direction of the sample is aligned with the tire's circumferential direction, and the thickness direction is aligned with the tire's radial direction. During sample collection, the sample is cut such that the thickness of the complex encompassing the entire thickness of the insulation is adjusted to 1 mm by appropriately modifying the thickness of the inner liner. <Luftdurchlässigkeitskoeffizient>

[0156] An air permeability coefficient at 20 °C in cm 3 · cm / (cm 2 The air permeability coefficient (· s · cmHg) is calculated from a measurement result of an inner liner according to Annex 2 of JIS K 7126-1 (a test method for gas permeability by a gas chromatography procedure) using a gas permeability measuring device (GTR-11A / 31A, manufactured by GTR TEC Corporation). The results show that the smaller the air permeability coefficient, the lower the amount of air permeability, resulting in excellent air barrier properties. <Luftdurchlässigkeitswiderstand>

[0157] Each test tire is mounted on a standardized 15 × 6.0 JJ rim and inflated to an internal pressure of 230 kPa. This tire is mounted on a drum-type tire tester, and a standardized load is applied. The tire is then run for 30,000 km on the drum at a constant speed of 80 km / h, and the air pressure is measured. An index of air permeability resistance is assigned, where the air pressure of the reference example (Comparison Example 2) after running is 100. The results show that the higher the numerical value of the index, the better the air permeability resistance after prolonged driving. <reifenhaltbarkeit>

[0158] Each test tire is mounted on a standardized 15 × 6.0 JJ rim and inflated to an internal pressure of 230 kPa. This tire is mounted on a drum-type tire tester, and a standardized load is applied. The tire is then run on the drum at a speed of 80 km / h, and the distance traveled until an inner liner or insulation is ruptured is measured. Results are indicated by indices, where the distance traveled for the reference comparison example (Comparison Example 2) is 100. The higher the numerical value of the index, the better the tire's durability.

[0159] The sum of an air permeability resistance index and a tire durability index is defined as an overall performance index. Table 1 Example 1 2 3 4 5 6 7 Connection for insulation (mass-produced parts) natural rubber 70 70 70 70 70 70 70 SBR 30 30 30 30 30 30 30 soot 30 - - 30 30 - 30 Recovered soot 30 60 60 30 30 60 30 Öl 1 10 10 10 10 10 10 10 zinc oxide 5,0 5,0 5,0 5,0 5,0 5,0 5,0 Stearic acid 1,0 1,0 1,0 1,0 1,0 1,0 1,0 sulfur 2,0 2,0 2,0 2,0 2,0 2,0 2,0 Vulcanization accelerator 1 1,0 1,0 1,0 1,0 1,0 1,0 1,0 Vulcanization accelerator 2 0,5 0,5 0,5 0,5 0,5 0,5 0,5 Connection for inner liners (mass-produced parts) Butyl-based rubber 1 100 100 100 100 100 100 100 Butyl-based rubber 2 - - - - - - - soot 50 50 50 50 60 60 25 Recovered soot - - - - - - 25 Öl 2 5,0 5,0 5,0 10,0 10,0 10,0 5,0 zinc oxide 10 10 10 10 10 10 10 Stearic acid 1,01,0 1,01,0 1,0 1,01,0 1,01,0 1,01,0 1,0 sulfur 1,0 1,0 1,0 1,0 1,0 1,0 1,0 Vulcanization accelerator 2 1,0 1,0 1,0 1,0 1,0 1,0 1,0 70 °C-tanδ 0,22 0,21 0,21 0,20 0,21 0,20 0,20 1 2 3 4 5 6 7 Inner liner thickness (mm) 1,4 1,4 1,1 1,1 1,1 1,1 1,4 air permeability coefficient (× 10 -11 cm 3 · cm / (cm 2 · s ·cmHg)) 17, 0 17, 0 17, 0 17, 0 14, 0 14,0 17,0 Index of air permeability resistance 115 123 123 123 135 142 131 Tire durability index 105 126 126 120 115 138 120 Total Performance Index 220 249 249 243 250 280 251 Table 2 Comparative example 1 2 3 4 5 Connection for insulation (mass-produced parts) natural rubber 70 70 70 70 70 SBR 30 30 30 30 30 soot 50 30 30 30 50 Recovered soot 10 30 30 30 10 Öl 1 10 10 10 10 10 zinc oxide 5,0 5,0 5,0 5,0 5,0 Stearic acid 1,0 1,0 1,0 1,0 1,0 sulfur 2,0 2,0 2,0 2,0 2,0 Vulcanization accelerator 1 1,0 1,0 1,0 1,0 1,0 Vulcanization accelerator 2 0,5 0,5 0,5 0,5 0,5 Connection for inner liners (mass-produced parts) Butyl-based rubber 1 100 100 100 100 - Butyl-based rubber 2 - - - - 100 soot 50 50 70 40 70 Recovered soot - - - - - Öl 2 5,0 5,0 5,0 5,0 5,0 zinc oxide 1,0 1,0 1,0 1,0 1,0 Stearic acid 1,0 1,0 1,0 1,0 1,0 sulfur 1,0 1,0 1,0 1,0 1,0 Vulcanization accelerator 2 1,0 1,0 1,0 1,0 1,0 70 °C-tanδ 0,23 0,22 0,24 0,21 0,25 1 2 3 4 5 Inner liner thickness (mm) 1, 4 1, 6 1, 4 1, 4 1, 6 air permeability coefficient (× 10 -11 cm 3 · cm / (cm 2 · s ·cmHg)) 17, 0 17, 0 17, 0 19,0 20,0 Index of air permeability resistance 92 100 92 77 62 Tire durability index 95 100 94 100 84 Total Performance Index 187 200 186 177 146 <Ausführungsformen>

[0160] Preferred embodiments are described below. [1] A tire comprising an inner liner and insulation that contacts the inner liner on an outside side of the inner liner in a tire radial direction, the insulation is made up of a rubber compound that includes recovered carbon black, where an air permeability coefficient of a rubber composition forming the inner liner is less than 18 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) is, wherein the thickness of the inner liner on a tire equator plane is 1.5 mm or less and preferably 1.4 mm or less, and wherein a loss tangent at 70 °C, 70 °C-tanδ, of a complex of the insulation and the inner liner is 0.22 or less, preferably 0.21 or less and more preferably 0.20 or less. [2] The tire of [1] above, wherein the thickness of the inner liner on the tire equator plane is 1.2 mm or less and more preferably 1.1 mm or less. [3] The tire of [1] or [2] above, wherein the air permeability coefficient of the rubber composition forming the inner liner is 17 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) or less, preferably 16 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) or less, preferably less than 15 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) and even more preferably 14.0 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) or less. [4] The tire from one of [1] to [3] above, comprising a rubber composition forming the insulation, comprising a rubber component comprising more than 20 wt%, preferably more than 30 wt%, further preferably more than 40 wt% and even more preferably 50 wt% or more of an isoprene-based rubber, and the rubber composition forming the inner liner comprising a rubber component comprising more than 70 wt%, preferably more than 75 wt%, further preferably 80 wt% or more and even more preferably 90 wt% or more of a butyl-based rubber. [5] The tire from one of [1] to [4] above, where a statistical thickness surface (STSA) in m 2 / g of recovered soot greater than 37, preferably greater than 40 m 2 / g and preferably larger than 45 m 2 / g and smaller than 77 and STSA prefers smaller than 75 m 2 / g, preferably smaller than 73 m 2 / g and wherein the ash content in mass % of the recovered soot is greater than 11 mass %, preferably 13 mass % or more, further preferably 15 mass % or more, even more preferably 16 mass % or more and even more preferably 17 mass % or more and the ash content is less than 27 mass %, preferably less than 26 mass % and further preferably less than 25 REFERENCE MARK LIST 1 tire 2 Insulating rubber 3 Inner liner rubber CL tire equator plane L Thickness of inner liner rubber at tire equator level R rim< / reifenhaltbarkeit> < / bewertungen> < / reifen> < / materialien> < / produktionsverfahren> < / anwendung> < / kautschukkomponente> < / kautschukzusammensetzung> < / reifen> < / messverfahren> < / definitionen>

Claims

[1] Tire comprising an inner liner and insulation that contacts the inner liner on an outside of the inner liner in a tire radial direction, the insulation is made up of a rubber compound that includes recovered carbon black, where an air permeability coefficient of a rubber composition forming the inner liner is less than 18 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) is, where the thickness of the inner liner on a tire equator plane is 1.5 mm or less, and where the loss tangent at 70 °C, 70 °C tanδ, of a complex of the insulation and the inner liner is 0.22 or less. [2] Tire according to claim 1, wherein the thickness of the inner liner on the tire equator plane is 1.2 mm or less. [3] Tires according to claim 1 or 2, wherein the air permeability coefficient of the rubber composition forming the inner liner is less than 15 × 10 -11 cm 3 · cm / (cm 2 · s · cmHg) is. [4] Tires according to any one of claims 1 to 3, wherein a rubber composition forming the insulation comprises a rubber component comprising more than 20 wt% of an isoprene-based rubber and the rubber composition forming the inner liner comprises a rubber component comprising more than 70 wt% of a butyl-based rubber. [5] Tires according to any one of claims 1 to 4, wherein a statistical thickness surface area (STSA) in m² 2 / g of the recovered soot is greater than 37 and less than 77 and an ash content in mass % of the recovered soot is greater than 11 and less than 27.

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