Tire innerliner composition

Abstract

To provide a tire innerliner composition and a method for preparing the same.SOLUTION: Disclosed is a tire innerliner composition (TILC) comprising (a) a rubber, (b) a filler, (c) a hydrogenated styrenic block copolymer (HSBC), and (d) optional additives. The HSBC comprises blocks "S" composed of vinyl aromatic units and blocks "R" composed of hydrogenated diene units. The HSBC has a general structure selected from S-R-S, (S-R) nX, and mixtures thereof, wherein X is a residue of a coupling agent and n is an integer from 2 to 30. The HSBC functions as a homogenizer and enables uniform dispersion of the filler within the TILC to enhance mechanical properties, crack resistance, and barrier performance.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to tire innerliner compositions and methods for preparing same. [Background technology]

[0002] Tubeless tires offer several advantages over tube-type tires, including reduced weight, improved fuel economy, and increased safety. One of the crucial components of a tubeless tire is the innermost layer, known as the innerliner, which helps retain air over the tire's lifespan. For optimal tire performance, the innerliner must provide excellent barrier and mechanical properties. Additionally, it should adhere well to the rest of the tire structure to prevent premature failure.

[0003] A typical tire innerliner composition includes a rubber component, such as bromobutyl rubber, chlorobutyl rubber, etc. Bromobutyl rubber provides high crosslinking efficiency, contributing to its low permeability to gases such as O, N, and CO. Tire innerliner compositions also typically contain high filler loadings to enhance performance and durability. However, uniformly dispersing these fillers within the rubber matrix remains challenging. To address this, filler dispersants (also known as homogenizers) containing aliphatic and / or aromatic hydrocarbon resins are commonly used in the art. Summary of the Invention [Problem to be solved by the invention]

[0004] There remains a need for improved tire innerliner compositions that incorporate hydrogenated styrene block copolymer (HSBC) based homogenizers that help disperse fillers to enhance overall performance. [Means for solving the problem]

[0005] (Summary of the Invention) In one aspect, the present disclosure relates to a tire innerliner composition (TILC) comprising, consisting essentially of, or consisting of: (a) 100 phr of rubber; (b) 30-80 phr of filler; (c) 3-25 phr of hydrogenated styrene block copolymer (HSBC); and (d) at least 0-40 phr of additives. The HSBC comprises a block "S" composed of vinyl aromatic units and a block "R" composed of hydrogenated diene units and optionally vinyl aromatic units. The HSBC is: SRS, (SR) n X, and mixtures thereof, where X is the residue of a coupling agent and n is an integer from 2 to 30. HSBCs have the following characteristics: (i) a vinyl aromatic unit content (VAC) of >50 wt.%, a molecular weight of the block "S" (M p ) <50 kg / mol, and the molecular weight of the block copolymer (M p ) 150 to 300 kg / mol; and (ii) vinyl aromatic unit content (VAC) < 50 wt.%, molecular weight of block "S" (M p ) <30 kg / mol, and the molecular weight of the block copolymer (M p ) 50 to 150 kg / mol. Each of the above transitional phrases (e.g., "comprising," "consisting essentially of," and "consisting of") shall convey its conventional meaning as understood or defined, where appropriate, in patent law.

[0006] In a second embodiment, the TILC has a dispersion value (G'10% / G'1%) of 0.50 to 0.90 after curing.

[0007] In a third embodiment, the rubber is a mixture of halobutyl rubber and a second rubber material in a weight ratio of 1:10 to 10:1.

[0008] In a fourth embodiment, the halobutyl rubber is a bromobutyl rubber. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following terms are used throughout this specification.

[0010] "Consisting essentially of" means that the composition comprises primarily the recited components and may additionally contain one or more components that do not materially affect the novel features or intended function of the invention. In embodiments, such additional components are present in an amount of <30 wt%, <20 wt%, or <10 wt%, based on the total weight of the composition.

[0011] "At least one of [a group such as A, B, and C]" or "any of [a group such as A, B, and C]" means a single element from the group, multiple elements from the group, or a combination of elements from the group. For example, at least one of A, B, and C includes, for example, A alone, B alone, or C alone, as well as A and B, A and C, B and C; or any other combination of A, B, and C, or A, B, and C.

[0012] A list of embodiments designated "A, B, or C" shall be interpreted as including embodiment A only, B only, C only, "A or B," "A or C," "B or C," or "A, B, or C."

[0013] "Either A, B, or C" refers to one choice from A, B, or C.

[0014] "Any of A, B and C" refers to one or more choices from A, B and C.

[0015] "Innerliner" and "tire innerliner" are used interchangeably.

[0016] "Elastomer" is used interchangeably with the term "rubber" and refers to any polymer or combination of polymers that meets the definition in ASTM D1566.

[0017] "Phr" refers to parts by weight per 100 parts of elastomer / rubber (of the total elastomers if several elastomers / rubbers are present).

[0018] The "vinyl aromatic unit content" or VAC of a block copolymer refers to the weight percentage of polymerized vinyl aromatic monomers, such as styrene, para-methylstyrene, etc., in the block copolymer. VAC is calculated by dividing the total molecular weight of all vinyl aromatic units by the total molecular weight of the block copolymer. VAC can be determined by proton nuclear magnetic resonance spectroscopy ( 1 H NMR) and 13 It can be determined using C NMR. VAC is sometimes used synonymously with PSC (polystyrene content).

[0019] "Butylene unit content" refers to the content, in weight percent, of butylene units ("B") relative to all diene-based units in a given polymer (e.g., a hydrogenated block copolymer). Butylene units are formed through the polymerization of 1,3-butadiene monomers via 1,2-addition, followed by hydrogenation. 1,3-butadiene monomers can also be polymerized via 1,4-addition, which upon hydrogenation results in ethylene units ("E"). Both butylene and ethylene units can be present in a hydrogenated block copolymer, which may also contain other units derived from vinyl aromatic units and / or conjugated diene monomers, arranged in any order. The butylene unit content can be expressed as: 1 H NMR and 13 It can be measured by C NMR. The butylene unit ("B") content is sometimes used synonymously with the "vinyl content" before hydrogenation.

[0020] "HSBC" refers to hydrogenated styrene block copolymers derived from the polymerization of 1,3-butadiene and / or isoprene monomers with vinyl aromatic monomers. In HSBC, a significant percentage of the double bonds originating from the 1,3-butadiene and / or isoprene units are hydrogenated to achieve hydrogenation levels of greater than 95% or even 99%. However, aromatic bonds are hydrogenated to levels ranging from 0% to 15%.

[0021] "Molecular weight" or M wrefers to the polystyrene equivalent molecular weight of the polymer block or block copolymer in kg / mol. M w can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, as performed by ASTM 5296-19. The GPC detector can be an ultraviolet or refractive index detector, or a combination of these. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The M of a polymer measured using such a calibrated GPC is w is the polystyrene equivalent molecular weight or apparent molecular weight. w is measured by the peak in the GPC trace and is generally p This is called the polystyrene equivalent "peak molecular weight."

[0022] "Hydrogenation level" refers to the level of saturation of double bonds (e.g., olefinic, aromatic, etc.) in the block copolymer (in %); 1 It can be measured by 1 H NMR.

[0023] "Residual unsaturation" or RU refers to the level of olefinic unsaturation, i.e., the level of carbon-carbon double bonds in a block copolymer, and is expressed in milliequivalents per gram (meq / g), where 1 equivalent is 1 mole of olefinic double bonds. RU is 1 It can be measured using 1 H NMR or ozonolysis titration.

[0024] "Unit" refers to a structural building block derived from one monomer after its polymerization and represents a repeating entity that forms part of a polymer or copolymer chain. Unlike "monomers," which are individual molecules before polymerization, "units" are transformed forms of monomers after undergoing a polymerization process. Polymerized units can be further transformed into hydrogenated or functionalized units.

[0025] "Coupling efficiency" or CE refers to the weight of coupled polymer molecules divided by the total weight of both coupled and uncoupled polymer molecules, expressed as a percentage (%). CE can be used to determine the amount of diblock or, more generally, "uncoupled arm" content in an overall block copolymer. For example, if the coupling efficiency is 80%, the polymer will contain 20% by weight of diblock or uncoupled arms and 80% by weight of triblock and multiarm species.

[0026] "Polydispersity Index" or "PDI" is the weight average molecular weight (M w ) and number average molecular weight (M n ), and is sometimes called the molecular weight distribution. PDI is used to indicate the distribution of polymer chain molecular weights in a given polymer. PDI can be calculated over the entire GPC or over a portion of the GPC, for example, as the peak between two extreme apparent molecular weight values.

[0027] "Cured," or crosslinked, or vulcanized, are used interchangeably to refer to a state in which a tire innerliner composition has undergone chemical crosslinking, typically through a vulcanization process involving heat and curatives (e.g., sulfur, peroxides, etc.), resulting in a reticulated polymer structure with high mechanical integrity.

[0028] "Dispersion" refers to the ratio of the elastic storage modulus G' measured at a strain amplitude of 10% (G'10) to the elastic storage modulus G' measured at a strain amplitude of 1% (G'1), i.e., dispersion = G'10% / G'1%. This value indicates the microdispersion of materials (e.g., fillers) in a composition, such as a rubber compound, after curing. Dispersion corresponds to better filler dispersion and enhanced filler-filler interactions in the cured composition. The elastic storage modulus (G'), which represents the recoverable (elastic) portion of the mechanical response of a material, can be measured using dynamic mechanical analysis (DMA) on the cured material.

[0029] "Payne effect test" refers to the characterization of the change in elastic storage modulus (G') as a function of strain amplitude. This test is performed on cured materials and utilizes DMA. G' reflects the elastic (recoverable) response of the cured material under cyclic loading and is a relevant parameter for assessing the Payne effect. As used herein, dispersion values ​​are determined via the Payne effect test performed at 70°C and a frequency of 1 Hz according to ASTM D8059 using carbon black as the filler.

[0030] The present disclosure relates to a tire innerliner composition (TILC) containing: (a) rubber, (b) filler, (c) hydrogenated styrene block copolymer (HSBC), and (d) optional additives. The HSBC acts as a homogenizer, allowing for uniform dispersion of the filler in the TILC composition to enhance mechanical properties, crack resistance, and barrier performance.

[0031] (Rubber): The rubber is a halobutyl rubber selected from the group consisting of chlorobutyl rubber, bromobutyl rubber, fluorobutyl rubber, iodobutyl rubber, copolymers thereof, and mixtures thereof. In embodiments, the halobutyl rubber is a copolymer of isobutylene and a diene-based monomer (e.g., isoprene, para-methylstyrene monomer, etc.), commonly referred to as haloisobutylene-isoprene rubber. The halobutyl rubber may contain >90 wt% isobutylene and <10 wt% isoprene or para-methylstyrene, or 90-99.5 wt% isobutylene and 0.5-10 wt% isoprene or para-methylstyrene.

[0032] In embodiments, the halobutyl rubber has a viscosity of 0.87 to 0.96, or 0.89 to 0.94, or 0.90 to 0.94 g / cm, measured according to ASTM D297. 3 The bromobutyl rubber may contain bromine in an amount ranging from 0.5 to 5, or 1 to 4, or 1.5 to 3.5 wt %, based on the total weight of the bromobutyl rubber.

[0033] In an embodiment, the rubber further comprises an additional rubber material (second rubber material) in a weight ratio of halobutyl rubber to the second rubber material of 1:10 to 10:1, or 1:8 to 8:1, or 1:5 to 5:1, or 1:3 to 3:1. Examples of the second rubber material include ethylene propylene diene monomer rubber (EPDM), styrene-butadiene rubber (SBR), hydrogenated SBR, butadiene rubber (BR), synthetic polyisoprene rubber, natural rubber (NR), brominated NR, chlorinated NR, epoxidized NR, nitrile-hydrogenated butadiene rubber (HNBR), ethylene propylene rubber, maleated ethylene propylene rubber, isobutylene-aromatic vinyl or diene monomer copolymer, brominated isobutylene p-methylstyrene copolymer, chloroprene rubber, epichlorohydrin homopolymer rubber. , epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubber, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber, fluorinated silicone rubber, fluorinated phosphagen rubber, and mixtures thereof.

[0034] In an embodiment, the second rubber material is natural rubber (NR), including Hevea NR, non-Hevea NR (e.g., guayule shrub, dandelion (Taraxacum kok-saghys (TKS)), and mixtures thereof).

[0035] The halobutyl rubber and / or the second rubber material can be coupled, star-branched, and / or functionalized using a coupling, star-branching, or functionalizing agent. In embodiments, the halobutyl rubber and / or the second rubber material is end-functionalized with a functional group to enhance its affinity for fillers such as carbon black and / or silica. Examples of functional groups include C-Sn bonds, amine functional groups (e.g., benzophenone), silanol or polysiloxane functional groups with silanol end groups, alkoxysilane groups, polyether groups, and the like.

[0036] (Filler): The filler is selected from the group consisting of sand, talc, dolomite, calcium carbonate, carbon nanotubes, carbon black, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, titanium dioxide, zinc oxide, ceramic microspheres, thermoplastic microspheres, barytes, wood flour, wood fiber, carbon fiber, and mixtures thereof. The filler can be surface treated before being added to the TILC.

[0037] In embodiments, the filler has an average particle size of <500 nm, or <300 nm, or 10-200 nm, or 20-150 nm, or 30-100 nm, or 10-50 nm.

[0038] In embodiments, the filler is carbon black selected from the 100, 200, 300, 600, 700, or 900 series, as designated by ASTM D-1765-82a, such as N110, N115, N134, N220, N234, N326, N330, N339, N347, N351, N375, N550, N660, N683, N772, N990, etc. The carbon black can be in recycled form and can be provided as pelletized material or as non-palletized flocculant. In embodiments, the carbon black has a viscosity of 1.5 to 2.1, or 1.55 to 2.0, or 1.6 to 1.95 g / cm, as measured according to ASTM D4894. 3The nitrogen surface area of ​​the carbon black is 10 to 60, or 15 to 55, or 20 to 0, or 25 to 55, or 30 to 60 m2 as measured by ASTM D6556. 2 / g.

[0039] In embodiments, the filler is added in an amount of 30 to 80, or 35 to 75, or 40 to 70, or 50 to 80, or 30 to 70 phr per 100 phr of rubber.

[0040] Hydrogenated Styrenic Block Copolymers (HSBCs): HSBCs are either linear, branched, or radial block copolymers containing at least one block "S" composed of vinyl aromatic units and at least one rubbery block "R" (block "R") composed of hydrogenated diene units and optionally vinyl aromatic units. The vinyl aromatic units are derived from polymerized vinyl aromatic monomers, while the hydrogenated diene units are derived from polymerized conjugated diene monomers prior to hydrogenation.

[0041] In embodiments, the HSBC is functionalized with at least one functional group, such as a hydroxyl group, an amino group, a carboxyl group, an anhydride group, an epoxy group, an isocyanate group, a silanol group, a silane group, and the like.

[0042] In an embodiment, the HSBC is: SR, (SR) n X, SRS, SRSR, RSRSR, (RSR) n X, SRSRS, (SRS) n X, and mixtures thereof; n is an integer from 2 to 30, and X is the residue of a coupling agent.

[0043] In an embodiment, each block "R" is a block selected from E / B, E / B / S, EP / MB, EP / MB / S, E / B / EP / MB, and combinations thereof.

[0044] In embodiments, the block "R" is of the form E / B composed of ethylene ("E") and butylene ("B") units, which are hydrogenated 1,4-butadiene and hydrogenated 1,2-butadiene units, respectively.

[0045] In embodiments, the block "R" takes the form E / B / S, which is composed of ethylene ("E") units, butylene ("B") units, and vinyl aromatic units.

[0046] In an embodiment, the block "R" is in the form of an EP / MB block consisting of ethylene-propylene (EP) and methyl-butylene (MB) units, each EP unit being a hydrogenated 1,4-isoprene unit and each MB unit being a hydrogenated 3,4-isoprene unit and a hydrogenated 1,2-isoprene unit.

[0047] In embodiments, the block "R" is of the form EP / MB / S, which is composed of EP units, MB units, and vinyl aromatic units.

[0048] In embodiments, the block "R" is of the form E / B / EP / MB, composed of ethylene ("E"), butylene ("B"), EP and MB units.

[0049] Examples of coupling agents X include di- or polyfunctional compounds such as divinylbenzene, halides of aliphatic or araliphatic hydrocarbons such as 1,2-dibromomethane, bis(chloromethyl)benzene, silicon tetrachloride, dialkyl or diaryl silicon dichlorides, alkyl or aryl silicon trichlorides, tin tetrachloride, alkyl silicon methoxides, alkyl silicon ethoxides, polyfunctional aldehydes such as terephthalic dialdehyde, ketones, esters, anhydrides, or epoxides. In embodiments, the coupling agent is selected from methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, dimethyl adipate, gamma-glycidoxypropyltrimethoxysilane, and mixtures thereof. In embodiments, the HSBC has a coupling efficiency (CE) of >65%, or >70%, or 60-98%, or 65-95%, or 75-95%.

[0050] Examples of vinyl aromatic monomers include styrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, ortho-substituted styrenes, meta-substituted styrenes, alpha-methylstyrene, 1,1-diphenylethylene, and mixtures thereof.

[0051] In embodiments, the conjugated diene monomer is selected from the group consisting of isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, farnesene, myrcene, piperylene, cyclohexadiene, and mixtures thereof.

[0052] In embodiments, each block "S" has a hydrogenation level of <30%, or <20%, or <10%, or <5% of the total double bonds present in block "S". In embodiments, the diene units in each block "R" have a hydrogenation level of >80%, or >90%, or >95%, or >98%, or up to 100%, or 80-99%, or 90-98%.

[0053] In embodiments, the HSBC comprises a mixture of at least two block copolymers selected from (i) diblock copolymers and (ii) multiblock copolymers having more than two blocks (e.g., triblock, tetrablock, pentablock, etc.). In embodiments, based on the total weight of the HSBC, the diblocks comprise 2-20, or 3-15, or 4-12, or >2, or <20 wt. %; and the species with more than two blocks comprise 80-98, or 85-97, or 88-96, or >80, or <98 wt. %.

[0054] Examples of HSBC include styrene-ethylene / butylene-styrene (SE / BS), styrene-ethylene-propylene / methylene-butylene-styrene (S-EP / MB-S), styrene-ethylene / butylene / ethylene-propylene / methylene-butylene-styrene (SE / B / EP / MB-S), styrene-ethylene / butylene / styrene-styrene (SE / B / SS), styrene-ethylene-propylene / methylene-butylene-styrene-styrene (S-EP / MB / SS), and mixtures thereof.

[0055] In embodiments, the HSBC has the general structure SRS, where: a) the vinyl aromatic unit content (VAC) is >50, or >52, or >55, or <70, or 50-70, or 52-68, or 55-65 wt. % based on the total weight of the HSBC; b) the molecular weight of the block "S" (M p) is <50, or <40, or <35, or >10, or 10-50, or 15-45, or 20-40, or 15-35 kg / mol; c) the melt flow rate (MFR) is <5, or <3, or <2, or <1, ​​or >0.001, or 0.001-5, or 0.01-3 g / 10 min, measured at 230°C under a 5 kg load according to ASTM D1238; d) the butylene ("B") unit content is <50, or <45, or <40, or >20, or 20-50, or 25-45, or 30-40, or 30-50 wt. %, based on the total weight of hydrogenated diene units in the HSBC; and e) the molecular weight (M p ) is 150 to 300, or 170 to 290, or 200 to 280, or 220 to 300 kg / mol.

[0056] In embodiments, HSBC has the general structure (SR) n X, having: a) a vinyl aromatic unit content (VAC) of <50, or <45, or <40, or <35, or >10, or 10-50, or 15-45, or 18-40 wt. % based on the total weight of the SBC; b) a molecular weight of the block "S" (M p )<30, or <25, or <20, or <15, or >2, or 2-30, or 3-25, or 4-20, or 3-10 kg / mol; c) ASTM a melt flow rate (MFR) of >5, or >10, or >20, or >30, or <300, or 10-300, or 20-280, or 25-260, or 30-240, or 20-50, or 30-55, or 190-240, or 200-230, measured at 230°C under a load of 2.16 kg in accordance with D1238; d) a butylene ("B") unit content of >50, or >60, or >70, or <90, or 50-90, or 55-85, or 60-80, or 65-85 wt. %, based on the total weight of hydrogenated diene units in the HSBC; and e) a molecular weight (M p ) 50 to 150, or 60 to 140, or 70 to 130, or 75 to 150, or 50 to 130 kg / mol.

[0057] In embodiments, the HSBC is added in an amount of 3 to 25, or 4 to 20, or 5 to 15, or 6 to 25, or 3 to 12 phr per 100 phr of rubber.

[0058] (Curing Agent): In embodiments, the TILC comprises a curing agent selected from the group consisting of sulfur-based compounds, peroxides, bismaleimides, and mixtures thereof.

[0059] In embodiments, the curative comprises a vulcanizing agent and at least one of a vulcanization accelerator, a vulcanization activator, a vulcanization inhibitor, an anti-scorching agent, and mixtures thereof.

[0060] In embodiments, the vulcanizing agent is a sulfur-based compound selected from the group consisting of sulfur; sulfur donors, such as amine disulfide, polymeric polysulfides, or sulfur olefin adducts; insoluble polymeric sulfur; and mixtures thereof.

[0061] Examples of vulcanization accelerators include thiazoles such as 2-mercaptobenzothiazole, 2,2'-dithiobis(benzothiazole), N-cyclohexyl-2-benzothiazole-sulfenamide, N-tert-butyl-2-benzothiazole-sulfenamide; guanidine vulcanization accelerators such as diphenylguanidine (DPG); thiuram vulcanization accelerators such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, tetraethylthiuram disulfide, tetraisobutylthiuram disulfide, tetrabenzylthiuram disulfide, and zinc thiuram; carbamate vulcanization accelerators; and mixtures thereof.

[0062] The vulcanization activator may be selected from the group consisting of inorganic components, organic components, and mixtures thereof. In embodiments, the inorganic vulcanization activator may include zinc oxide. In embodiments, the organic vulcanization activator includes stearic acid, palmitic acid, lauric acid, zinc salts of each of the foregoing, or mixtures thereof. In embodiments, the vulcanization activator is one or more thiourea compounds selected from N,N'-diphenylthiourea, trimethylthiourea, N,N'-diethylthiourea, N,N'-dimethylthiourea, N,N'-dibutylthiourea, ethylenethiourea, N,N'-diisopropylthiourea, N,N'-dicyclohexylthiourea, 1,3-di(o-tolyl)thiourea, 1,3-di(p-tolyl)thiourea, 1,1-diphenyl-2-thiourea, 2,5-dithiobiurea, guanylthiourea, 1-(1-naphthyl)-2-thiourea, 1-phenyl-2-thiourea, p-tolylthiourea, o-tolylthiourea, and mixtures thereof. Examples of other vulcanization activators include zinc stearate, magnesium stearate, calcium stearate, and mixtures thereof.

[0063] Examples of vulcanization inhibitors include alumina, aluminum hydrate, aluminum hydroxide, aluminum carbonate, aluminum nitride, magnesium aluminum oxide, pyrophyllite, bentonite, boron nitride, silicon nitride, aluminum nitride, mica, kaolin, glass balloons, glass beads, calcium oxide, calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium oxide, magnesium dioxide, magnesium carbonate, titanium oxide, titanium dioxide, potassium titanate, barium sulfate, zirconium oxide, zirconium hydroxide, zirconium carbonate, crystalline aluminosilicate, calcium silicate, starch, gypsum (calcium sulfate hydrate), fly ash, and mixtures thereof. In embodiments, the amount of vulcanization inhibitor added is 0.01 to 1, or 0.02 to 0.8, or 0.05 to 0.5 phr per 100 phr of rubber.

[0064] In embodiments, the curative is added in an amount of up to 30 phr, or 0.5 to 30, or 1 to 20, or 3 to 15, or 5 to 12, or 0.5 to 15 phr per 100 phr of rubber.

[0065] (Optional Additives): In embodiments, the TILC further comprises additives selected from the group consisting of stabilizers, antioxidants, antiozonants, plasticizers, fillers, other resins, adhesion promoters, lubricants, processing aids, anti-fatigue agents, and mixtures thereof.

[0066] Examples of plasticizers include liquid diene polymers, aliphatic acid esters, hydrocarbon processed oils, tall oil pitch, modified tall oil pitch, polyolefin oils, naphthenic oils, paraffin oils, distillate aromatic extract oils, intermediate extract solvent oils, treated distillate aromatic extract oils, residual aromatic extract oils, treated residual aromatic extract oils, safe residual aromatic extract oils, mineral oils, vegetable oils, plasticizing ethers, plasticizing esters, plasticizing phosphates, plasticizing sulfonates, terpene derivatives, and mixtures thereof. Examples of vegetable oils include linseed oil, safflower oil, soybean oil, corn oil, cottonseed oil, turnip seed oil, castor oil, tung oil, pine oil, sunflower oil, palm oil, olive oil, coconut oil, peanut oil, grapeseed oil, and mixtures thereof. The modified tall oil pitch can be selected from the group consisting of pitch esters, decarbonated tall oil pitch, tall oil pitch soap, heat-treated tall oil pitch, heat- and catalyst-treated tall oil pitch, and mixtures thereof.

[0067] In embodiments, additives, if used, are added in an amount of up to 40 phr, or <35, or 1-30, or 3-25, or 5-20, or 1-15 phr per 100 phr of rubber.

[0068] (Optional Tackifying Resin): In embodiments, the TILC further comprises a tackifying resin selected from the group consisting of C5-C9 hydrocarbon resins, hydrogenated C5-C9 hydrocarbon resins, styrenated C5-C9 hydrocarbon resins, terpenes, styrene-modified terpenes, vinyltoluene-terpenes, phenolic resins, phenol-modified terpene resins, fully hydrogenated or partially hydrogenated terpene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, rosin esters, rosin derivatives, and mixtures thereof.

[0069] In embodiments, the tackifying resin has a softening point of >70°C, or >75°C, or 70-150°C, or 75-130°C, or 80-120°C, as measured according to ASTM E-28.

[0070] In embodiments, the tackifying resin has an acid number of >20, or <50, or from 20 to 50 mg KOH / g, as measured according to ASTM D465.

[0071] In embodiments, the tackifying resin is an octylphenol resin.

[0072] In embodiments, tackifying resins, if used, are added in amounts up to 25 phr, or 1 to 20, or 3 to 15, or 1 to 10 phr per 100 phr of rubber.

[0073] (Methods of preparing TILCs): TILCs can be prepared by using conventional mixing techniques, including kneading, roller milling, extruder mixing, internal mixing (e.g., Banbury mixer), etc. The mixing sequences and temperatures used are known in the art.

[0074] In embodiments, the TILC composition is prepared by mixing the ingredients in at least one non-productive masterbatch stage and a final production mix stage. The term non-productive masterbatch stage is known in the art and is generally understood to be a mix stage(s) in which no curing agent is added. The term final production mix stage is also known in the art and is generally understood to be a mix stage in which a curing agent is added to the TILC. The TILC can be prepared by a process that includes multiple non-productive masterbatch mix stages.

[0075] In embodiments, the TILC is prepared by adding the rubber, HSBC, filler, and optional additives in a non-productive masterbatch mix stage(s). The non-productive mix can be carried out at a temperature of 70-200°C, or 75-180°C, or 80-150°C. In embodiments, the curative is added in a final or productive mix stage, and mixing is carried out until the temperature is raised to 50-145°C, or 55-135°C, or 60-125°C to obtain the TILC. The final productive mix stage can be carried out at a temperature below the cure temperature (e.g., <150°C) to avoid undesirable pre-curing of the TILC.

[0076] In embodiments, the TILC is cured at a temperature ranging from 150 to 200°C, or from 155 to 195°C, or from 160 to 190°C, for 1 to 60 minutes, or from 3 to 40 minutes, or from 5 to 35 minutes, or from 10 to 30 minutes.

[0077] (Preparation of TILC): HSBC helps to enhance the dispersion of fillers in TILC, providing balanced air tightness, shorter setting time, improved hardness, and other mechanical properties.

[0078] The properties of both the cured and uncured TILC compositions are described for formulations containing, for the uncured compositions, 100 phr rubber, 30-80 phr filler, 3-25 phr hydrogenated styrene block copolymer, and optional additives. The cured TILC compositions (or compositions after curing) further contain a curative in an amount of 0.5-30 phr per 100 phr rubber.

[0079] In embodiments, the TILC has adhesive performance prior to cure as indicated by a peel force of >45 N, or >50 N, or >53 N, or 48-75 N, or 50-70 N, or 52-68 N as measured by ZDT (Zero Degree Tack) testing.

[0080] In embodiments, the cure performance (cure state) of the TILC is measured according to ASTM D5289 at 90% of the maximum torque (T c 90). c 90 hours indicates faster cure. In embodiments, the TILC may have a T c 90<4.0 minutes, or <3.8 minutes, or <3.6 minutes, or <3.5 minutes, or <3.3 minutes, or <3.0 minutes, or >0.5 minutes, or 0.5 to 3.5 minutes.

[0081] In an embodiment, the TILC has, after curing, a dispersion value (G'10% / G'1%) measured according to the Payne effect test of 0.50 to 0.90, or 0.52 to 0.88, or 0.55 to 0.85, or 0.60 to 0.82, or 0.65 to 0.80.

[0082] In embodiments, the TILC, after curing, has an increase in dispersion (G'10% / G'1%) of at least 10%, or >12%, or >15%, or <60% relative to the dispersion of the cured TILC without HSBC.

[0083] In embodiments, the TILC, after curing, has a Shore A hardness of 40 to 55, or 42 to 52, or 44 to 50, measured according to ASTM D2240.

[0084] In embodiments, the TILC, after curing, has a tensile strength measured according to ASTM D412 of 5 to 30, or 7 to 25, or 8 to 20, or 8 to 30, or 5 to 15 MPa.

[0085] In embodiments, the TILC, after curing, has an ultimate elongation measured according to ASTM D412 of 500 to 800%, or 520 to 780%, or 540 to 750%, or 530 to 640%.

[0086] In embodiments, the TILC, after curing, has a 100% modulus measured according to ASTM D412 of 0.5 to 5, or 0.7 to 4, or 0.9 to 3.5, or 1 to 2.5, or 1.1 to 2.2 MPa.

[0087] In embodiments, the TILC, after curing, has a 300% modulus measured according to ASTM D412 of 1 to 12, or 1.5 to 10, or 2 to 8, or 2.5 to 7, or 3.5 to 8 MPa.

[0088] In embodiments, the TILC, after curing, is subjected to cyclic deformation until crack initiation, and the number of cycles it can withstand is measured according to ASTM D 430. In embodiments, the TILC, after curing, withstands >400,000, >430,000, >450,000, or >480,000 deformation cycles before the first crack appears.

[0089] In embodiments, the TILC, after cure, is <220, or <210, or <200, or 100-220, or 150-210, or 160-200 cc / (m 2 / day) air permeability (O2 permeability).

[0090] Application Examples: In embodiments, the TILC is formed into a sheet by processes known in the art. The sheet can be placed adjacent to an intermediate layer (e.g., carcass layer) of an uncured tire, which can be formed on a tire building drum. Tires are generally built on the drum from at least three layers: an outer layer, an intermediate layer, and an inner layer (e.g., innerliner).

[0091] Tires containing innerliners can be intended for passenger motor vehicles, including two-wheeled vehicles (e.g., motorcycles), three-wheeled vehicles, four-wheeled vehicles, and industrial vehicles selected from heavy vehicles such as vans and buses, heavy road transport vehicles such as lorries, agricultural or civil engineering vehicles.

[0092] (Analysis method): HSBC in tire inner liner compositions was analyzed by Fourier transform infrared spectroscopy (FTIR), 1 H NMR, 13 It can be detected using a combination of C NMR and GPC techniques. 1 H NMR and 13 C NMR can be used to reveal the presence of vinyl aromatic units and hydrogenated diene units within the polymer. NMR provides direct evidence of the level of hydrogenation, as seen through the disappearance or strong reduction of olefinic proton signals, and allows for the assessment of vinyl aromatic unit content (VAC) by integrating aromatic versus aliphatic proton or carbon signals. GPC, especially when combined with multi-angle light scattering (MALS) or refractive index (RI) detection, can provide information on the molecular weight (M) of both the block "S" and the total HSBC polymer. p ) can be used to measure

[0093] To determine the structure of HSBC, SRS, or (SR)nX, small-angle X-ray scattering (SAXS) or transmission electron microscopy (TEM) can be used to assess its microphase-separated morphology. Additionally, matrix-assisted laser desorption / ionization time-of-flight (MALDI-TOF) mass spectrometry can be used to detect coupling structures, such as the presence of X residues, and to confirm the polymer architecture in coupled (SR)nX configurations.

[0094] Rubber in tire innerliners can be detected using FTIR, which provides a spectral fingerprint specific to the type of rubber, such as characteristic C=C, C-Cl, or C-Br signals, allowing for rapid identification of the base polymer. 1 H NMR can further confirm the microstructure of the rubber (e.g., methyl or methylene signals, unsaturation levels). Pyrolysis-Gas Chromatography / Mass Spectrometry (Py-GC / MS) can be used to break the rubber into volatile fragments and then analyze their mass spectra, providing a detailed chemical fingerprint.

[0095] Fillers can be detected by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), which can image filler particles dispersed in the matrix and identify their elemental composition (e.g., Si for silica, C for carbon black, Mg / Si for talc). X-ray diffraction (XRD) can reveal crystalline phases present, which is useful for identifying mineral fillers such as clay and silica. Ash content analysis (via TGA or muffle furnace) can quantify the total inorganic content by burning off the organic matrix and weighing the residue, which directly correlates to filler content. [Example]

[0096] The following examples are intended to be non-limiting.

[0097] The following test methods are used:

[0098] The crack resistance, which indicates the toughness of the cured TILC material, is evaluated by subjecting an unperforated specimen to cyclic deformation until a crack forms, and then observing the crack growth. This test is performed in accordance with ASTM D430 and is also known as the DeMattia flexural fatigue test.

[0099] Zero Degree Adhesion (ZDT) Test: The adhesion of uncured TILC to carcass compound is measured using the ZDT test with an Instron tensile tester. In this setup, the ZDT tester is attached to the crosshead of the Instron tensile tester. Two test specimens, one uncured TILC and the other carcass compound, are placed one on top of the other in a holder. The tester is then moved downward and a force of 20 N is applied at a rate of 2 N / sec. This force is held for 0.5 seconds, after which the crosshead is moved upward at a rate of 300 mm / min, separating the specimens. The load cell and crosshead displacement are used to measure the peel force and separation distance.

[0100] Ingredients used in the examples include: HSBC-1 has 58 wt% VAC and 29 kg / mol of M of block "S". p , M of block copolymer of 265 kg / mol p , a linear hydrogenated triblock copolymer (SE / B / SS) with a butylene ("B") unit content of 38 wt. % and an MFR of <1 g / 10 min at 230°C / 5 kg.

[0101] HSBC-2 has 34 wt% VAC and 7 kg / mol of block "S" M. p , M of block copolymer of 125 kg / mol p , a linear hydrogenated triblock copolymer (SE / B / SS) having a butylene ("B") unit content of 78 wt%, a CE of 93%, an MFR of 43 g / 10 min at 230°C / 2.16 kg, and a diblock content of 7 wt%.

[0102] HSBC-3 is a 20 wt% VAC, 5 kg / mol M of block "S". p , M of block copolymer of 83 kg / mol p , a linear hydrogenated triblock copolymer (SE / BS) having a butylene ("B") unit content of 78 wt%, a CE of 93%, an MFR of 220 g / 10 min at 230°C / 2.16 kg, and a diblock content of 7 wt%.

[0103] BBR-1 is 0.93g / cm 3 and 2% by weight of bromine.

[0104] NR-1 is a natural rubber manufactured by Harwick Standard.

[0105] TR-1 is an octylphenol resin (tackifying resin) manufactured by Akrochem, with a softening point of 85-95° C. and an acid value of 25-42 mg KOH / g.

[0106] C-HydR-1 is a copolymeric hydrocarbon resin containing aromatic, naphthenic, and aliphatic components.

[0107] (Examples 1 to 3): The TILCs were prepared by mixing the ingredients listed in Table 1 using an internal mixer. BBR-1, NR-1, and HSBC were first mixed for 30 minutes at a temperature of 90–95°C. Next, carbon black, TR-1, and paraffin oil were added, and mixing continued until the temperature reached 125–130°C. Mixing continued until the temperature reached 145–150°C, after which the mixture was cooled to ambient temperature to obtain the masterbatch. The masterbatch was then reintroduced into the mixer, its initial temperature set between 70–75°C. At this stage, the curing agents (stearic acid, magnesium oxide, zinc oxide, sulfur, and 2-mercaptobenzothiazole) were added, and mixing continued until the temperature reached 100–105°C to obtain the TILCs. C-Ex is a control example prepared using the same procedure, except that HSBC was replaced with C-HydR-1.

[0108] [Table 1]

[0109] (Example 4): The cure of the TILC was monitored by measuring torque as a function of time using a moving disc rheometer (MDR) according to ASTM D5289. The compositions (test specimens) were cured in a compression mold at 177°C for 15 minutes. 90% of the maximum torque (T c The time required to reach a temperature of 90°C was used as the curing time. The curing details are provided in Table 2. The cured TILC was subsequently used for further testing.

[0110] [Table 2]

[0111] The ZDT test performance and filler dispersion in the composition are presented in Table 3. The hardness and other mechanical properties of the cured TILC are presented in Table 4. The crack resistance and air permeability of the cured TILC samples are presented in Table 5.

[0112] [Table 3]

[0113] [Table 4]

[0114] [Table 5]

Claims

1. (a) 100 phr of rubber; (b) 30 to 80 phr of a filler; (c) a block "S" composed of vinyl aromatic units, and a block "R" composed of hydrogenated diene units and optionally vinyl aromatic units; A hydrogenated styrene block copolymer comprising: S—R—S, (S—R) ｎ X, where X is the residue of a coupling agent and n is an integer from 2 to 30, and mixtures thereof; The hydrogenated styrene block copolymer may be: (i) vinyl aromatic unit content (VAC) >50 wt.%; The molecular weight of the block "S" (M ｐ ) < 50 kg / mol, and The molecular weight (M ｐ ) 150 to 300 kg / mol, and (ii) a vinyl aromatic unit content (VAC) of <50 wt.%; The molecular weight of the block "S" (M ｐ ) < 30 kg / mol, and The molecular weight (M ｐ )50-150kg / mol At least one of the following is satisfied: 3 to 25 phr of a hydrogenated styrene block copolymer; (d) at least 0 to 40 phr of additives; 1. A tire innerliner composition comprising:

2. 10. The tire innerliner composition of claim 1, having a dispersion value (G'10% / G'1%) of 0.50 to 0.90 after curing.

3. 3. The tire innerliner composition according to claim 1, wherein the rubber is a mixture of halobutyl rubber and a second rubber material in a weight ratio of 1:10 to 10:

1.

4. the halobutyl rubber is a bromobutyl rubber, the second rubber material is selected from the group consisting of ethylene propylene diene monomer rubber (EPDM), styrene-butadiene rubber (SBR), hydrogenated SBR, butadiene rubber (BR), synthetic polyisoprene rubber, natural rubber (NR), maleic acid modified ethylene propylene rubber, chloroprene rubber, epichlorohydrin homopolymer rubber, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber, fluorinated silicone rubber, and mixtures thereof; The tire innerliner composition of claim 3.

5. the hydrogenated styrene block copolymer vinyl aromatic unit content (VAC) of 50 to 70% by weight; The molecular weight of the block "S" (M ｐ ) 10 to 50 kg / mol, and The molecular weight (M ｐ )200-280kg / mol The tire innerliner composition according to any one of claims 1 to 2, comprising:

6. 6. The tire innerliner composition of claim 5, wherein said hydrogenated styrenic block copolymer has a butylene ("B") unit content of <50 wt. % based on the total weight of hydrogenated diene units in said hydrogenated styrenic block copolymer.

7. the hydrogenated styrene block copolymer vinyl aromatic unit content (VAC) of 10 to 50 wt. %; The molecular weight of the block "S" (M ｐ ) 2 to 30 kg / mol, and The molecular weight (M ｐ )60-140kg / mol The tire innerliner composition according to any one of claims 1 to 2, comprising:

8. 8. The tire innerliner composition of claim 7, wherein said hydrogenated styrenic block copolymer has a butylene ("B") unit content >50 wt.%, based on the total weight of hydrogenated diene units in said hydrogenated styrenic block copolymer.

9. 8. The tire innerliner composition of claim 7, wherein said hydrogenated styrenic block copolymer has a diblock content of 2 to 20 weight percent, based on the total weight of said hydrogenated styrenic block copolymer.

10. further comprising 1 to 20 phr of a tackifying resin; The tackifying resin is C ５ ~C ９ Hydrocarbon resin, hydrogenated C ５ ~C ９ Hydrocarbon resin, styrenated C ５ ~C ９ selected from the group consisting of hydrocarbon resins, terpenes, styrene-modified terpenes, vinyltoluene-terpenes, phenolic resins, phenol-modified terpene resins, fully hydrogenated or partially hydrogenated terpene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, rosin esters, rosin derivatives, and mixtures thereof; The tire innerliner composition according to any one of claims 1 and 2.

11. The phenolic resin is a softening point of >70°C, measured according to ASTM E-28, and Acid number >20 mg KOH / g measured according to ASTM D465 11. The tire innerliner composition of claim 10, wherein the octylphenol resin has at least one of the following:

12. 3. The tire innerliner composition of any of claims 1 to 2, having a peel force of >45 N as measured by the ZDT (Zero Degree Tack) test.

13. 3. The tire innerliner composition according to claim 1, which after curing has a Shore A hardness of 40 to 55 as measured according to ASTM D2240.

14. After cure, <220 cc / (m) measured according to ASTM D3985 ２ 3. The tire innerliner composition according to claim 1, wherein the tire innerliner composition has an air permeability of 1000 psi / day.

15. After curing, all measurements were performed according to ASTM D412. Tensile strength of 5 to 30 MPa, Ultimate elongation of 500-800%, a 100% modulus of 0.5 to 5 MPa, and 300% modulus of 1 to 12 MPa The tire innerliner composition according to any one of claims 1 to 2, comprising at least one of the following:

Images