Halobutyl rubber composition containing lignin-based fillers, free from or with reduced amounts of oil-based softeners.

Abstract

To provide a rubber composition. [Solution] The present invention relates to at least one halobutyl rubber that can be cured by at least one curing agent, at least one curing agent suitable for curing at least one halobutyl rubber, different from carbon black, 200m 2 A curable rubber composition comprising at least one lignin-based filler F1 having an STSA surface area up to / g, and at least one resin R1 selected from i) aromatic resins excluding phenolic resins, ii) aliphatic resins, and iii) mixtures thereof, wherein the total amount of phr of the at least one resin R1 exceeds the total amount of phr of any of paraffinic oil, naphthenic oil, and aromatic oil, each optionally present in the composition; a kit of parts comprising a spatially separated form of rubber composition; a curable rubber composition obtainable from the curable rubber composition; the use of the aforementioned products for producing articles, parts, and / or components; articles, parts, and / or components obtained thereby; and a method for preparing the articles, parts, and / or components.

Description

Technical Field

[0001] The present invention relates to a curable rubber composition containing halobutyl rubber, a kit of parts including the rubber composition in a spatially separated form, a cured rubber composition obtainable from the curable rubber composition, the use of the foregoing products for manufacturing articles, parts, and / or components, articles, parts, and / or components obtained thereby, and a method for preparing the articles, parts, and / or components.

Background Art

[0002] Typical modern tires, such as pneumatic tires, include a plurality of parts that are combined within the tire so that multi-directional forces affecting the tire are optimally addressed. In particular, most tires generally include at least a tread, at least one belt, a carcass ply, sidewalls, bead fillers, bead wires, and a so-called inner liner.

[0003] The inner liner is a layer disposed radially inward and is the innermost layer of the tire structure. Since the air pressure greatly affects the running characteristics and durability of the tire, the innermost layer plays a role in maintaining the internal air pressure. Further, the internal pressure also affects the rolling resistance of the tire. When the air pressure decreases, the dynamic deformation of the tire increases, whereby a part of the kinetic energy is unnecessarily converted into thermal energy. Further, the inner liner protects the carcass from the diffusion of air and moisture therein and prevents damage to the strength-imparting elements of the carcass and / or the belt. In order for the inner liner to maintain maximum airtightness, it must also have good tear resistance and fatigue resistance so that no tearing during running that affects airtightness occurs.

[0004] For this specific requirements profile, the rubber compound for the inner liner often has a completely different composition from the rubber compound used for other tire parts, in terms of the rubber and fillers used therein, and the mass ratio of the constituent components to each other. Nevertheless, compatibility with adjacent tire parts is still required, and in particular, good adhesion to them is necessary. In addition to the type of rubber, the minimum amount of different rubbers in the rubber compound can also play a role, as can the various specific parameters and properties of the available fillers.

[0005] Therefore, inner liners are typically based on butyl rubber or halobutyl rubber, typically bromobutyl rubber and / or chlorobutyl rubber, and occasionally blended with other rubbers. The airtightness of the inner liner can be further enhanced by adding low-activity or non-activity bulky fillers to the rubber compound. Fillers used to date include carbon black, particularly furnace carbon black.

[0006] For example, a carbon black filler of type N660 contains approximately 1.8 g / cm³ of this type. 3 The above-mentioned relatively high density is achieved. Therefore, rubber compositions containing such fillers also have a higher density, and thus a higher mass for the same volume. However, higher density of the filler leads to higher mass of the inner liner, and ultimately the tire, resulting in increased fuel consumption. Furthermore, industrial carbon black is petrochemically refined through the incomplete combustion or thermal decomposition of hydrocarbons. However, the use of fossil energy sources in the production of fillers must be avoided or minimized from an environmental perspective.

[0007] For example, it is known to use lignin-based fillers to replace carbon black in rubber compositions, at least partially. For instance, WO2020 / 140155 A1 discloses a lignin-reinforced vulcanized product prepared from halobutyl rubber, lignin, and a co-reinforcement comprising carbon black and / or silica. Furthermore, WO2022 / 063841 A1 and WO2023 / 180405 A1 disclose the use of lignin-based fillers that can substitute for industrial carbon black to prepare halobutyl rubber compositions also used in tire inner liners. Furthermore, WO2024 / 017455 A1 discloses a composition comprising an elastomer polymer containing halobutyl rubber and hydrothermally treated lignin with reduced gas permeability. These compositions can be used as membranes or gas barriers for tires. Finally, EP4 059 996 A1 also discloses the use of lignin-based fillers that can substitute for industrial carbon black in the preparation of rubber compositions, particularly for applications involving halobutyl rubber.

[0008] In tire manufacturing, the inner liner is in direct contact with the curing bladder and is therefore exposed to heat for the longest period compared to all other parts. Without countermeasures, this can cause the inner liner to over-curl, increasing its porosity and air permeability, and making it more susceptible to cracking. To achieve sufficient curing of the outer layers and parts while simultaneously preventing over-curing of the inner liner, retarders, such as dibenzothiazyl disulfide (MBTS), are widely used to optimize curing time in correlation with the curing of other rubber layers.

[0009] To prevent crack formation under dynamic load, the inner liner must have a balanced modulus and a matched hardness, which usually conflicts with a high proportion of inert fillers. Therefore, oil-based softeners, such as mineral oil-based softeners, are often added to rubber compositions. While this reduces the modulus and hardness of the composition, it also increases gas permeability, resulting in a relatively narrow optimal range for the amount of mineral oil-based softener and fillers used. Furthermore, the presence or use of oil-based softeners can adversely affect the mechanical properties of the resulting cured rubber composition. Nevertheless, such oil-based softeners are widely used, as exemplified by the aforementioned references WO2020 / 140155 A1, WO2022 / 063841 A1, WO2023 / 180405 A1, WO2024 / 017455 A1, and EP4 059 996 A1.

[0010] Therefore, there is a need to provide a rubber composition for curing a rubber composition containing halobutyl rubber, particularly for preparing a vulcanized product thereof, wherein the amount of carbon black used as a filler can be reduced as much as possible, or even completely avoided, and the amount of oil-based softener can be reduced as much as possible, or even completely avoided, but despite the reduction or avoidance of the oil-based softener, preferably the mechanical properties of the vulcanized product, such as elongation at break, are further improved, without adversely affecting the mechanical properties of the vulcanized product, such as elongation at break, but still an optimized curing time, particularly a sufficiently low t 90 Optimized curing time, etc. 90 The curing time can be achieved, unwanted over-curing can be prevented, and at the same time, sufficiently low air permeability can be provided and maintained. Therefore, the rubber composition can be effectively used for the manufacture of inner liners, for example, for the lightweight structure of suitable articles. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] WO2020 / 140155 A1 [Patent Document 2] WO2022 / 063841 A1 [Patent Document 3] WO2023 / 180405 A1 [Patent Document 4] WO2024 / 017455 A1 [Patent Document 5] and EP4 059 996 A1 [Overview of the Initiative] [Problems that the invention aims to solve]

[0012] Therefore, the fundamental objective of the present invention is to provide a rubber composition for curing a rubber composition containing halobutyl rubber, particularly for preparing a vulcanized product thereof, wherein the amount of carbon black used as a filler can be reduced as much as possible, or even completely avoided, and the amount of oil-based softener can be reduced as much as possible, or even completely avoided, but despite the reduction or avoidance of the oil-based softener, preferably the mechanical properties of the vulcanized product, such as elongation at break, are further improved, without adversely affecting the mechanical properties of the vulcanized product, such as elongation at break, but still an optimized curing time, particularly a sufficiently low t 90 Optimized curing time, etc. 90 The curing time can be achieved, unwanted over-curing can be prevented, and at the same time, sufficiently low air permeability can be provided and maintained. Therefore, the rubber composition can be effectively used for the manufacture of inner liners, for example, for the lightweight structure of suitable articles. [Means for solving the problem]

[0013] This objective has been addressed by the subject matter of the claims of this application, as well as by the preferred embodiments thereof disclosed herein, i.e., the subject matter described herein.

[0014] The first subject of this invention is that the constituent components are different from each other, At least one type of halobutyl rubber that can be cured by at least one type of curing agent, At least one curing agent suitable for curing at least one type of halobutyl rubber, Different from carbon black, 200m 2 At least one lignin-based filler F1 having an STSA surface area up to / g, and i) aromatic resins excluding phenolic resins, ii) aliphatic resins, and iii) at least one resin R1 selected from mixtures thereof A curable rubber composition comprising the above, wherein the total amount of phr of at least one resin R1 present in the composition exceeds the total amount of phr of any of paraffin oil, naphthenic oil, and aromatic oil, each optionally present in the composition.

[0015] Further subject matter of the present invention is Part A) is at least a part of the rubber composition according to the present invention, however part A) is at least a part of the rubber composition that does not contain at least one curing agent. Optionally, as part B), the remaining portion of the rubber composition according to the present invention that is not present in part A), but part B) does not contain at least one curing agent, and Part C) at least one curing agent suitable for curing at least one type of halobutyl rubber. It is a kit of parts that includes these elements in a spatially separated form.

[0016] Further subject matter of the present invention is a curable rubber composition that can be obtained by curing a curable rubber composition available by curing a curable rubber composition available by mixing a combination of A), optionally B), and C) of the kit of parts according to the present invention.

[0017] Another subject of the present invention is the use of a curable rubber composition, a kit of parts, or a curable rubber composition according to the present invention for manufacturing articles, parts, and / or components that are preferably suitable for use in the automotive and / or aerospace and / or engineering industries and / or the pharmaceutical and / or consumer goods industries, and more preferably for rubber items requiring gas impermeability, particularly hoses, personal protective equipment, protective clothing, pharmaceutical closures, vacuum seals and membranes, tank linings, conveyor belts, consumer products, particularly ball bladders, and tires, especially when used as an inner liner for a tire, or at least as part of an inner liner for a tire, and even more preferably for the manufacture of pneumatic tires.

[0018] Further subject matter of the present invention is articles, parts and / or components, which in each case are available from the curable rubber composition according to the present invention, or from the kit of parts according to the present invention, or from the curable rubber composition according to the present invention, and are suitable for use in the automotive and / or aerospace and / or engineering industries and / or the pharmaceutical and / or consumer goods industries, and are preferably suitable for use in rubber items requiring gas impermeability, particularly hoses, personal protective equipment, protective clothing, pharmaceutical closures, vacuum seals and membranes, tank linings, conveyor belts, consumer products, particularly ball bladders, and tires, especially when used as an inner liner of a tire or at least as part of an inner liner of a tire, and more preferably for use in pneumatic tires.

[0019] A further subject of the present invention is a method for preparing articles, parts and / or components according to the present invention, the method comprising at least one step, wherein, according to this step, a curable rubber composition according to the present invention is formed into articles, parts and / or components, preferably before curing, by injection molding, compression molding, transfer molding, extrusion, co-extrusion by co-extrusion of at least two rubbers, extrusion coating, lamination, calendering, or a combination thereof, for example, a combination of extrusion or co-extrusion and calendering.

[0020] Particularly surprising, the rubber composition according to the present invention, comprising at least one type of halobutyl rubber, may be efficiently cured to produce a vulcanized product, i.e., a cured rubber composition, which has been found to be particularly suitable for use as an inner liner for tires, for example, for the lightweight construction of suitable articles.

[0021] In this regard, surprisingly, it was found that the amounts of paraffin oil, naphthenic oil, and aromatic oil as oil-based softeners could be reduced as much as possible, or even completely avoided, and yet the mechanical properties of the vulcanized product, such as elongation at break, were not adversely affected. In fact, it was even found that the mechanical properties of the vulcanized product, such as elongation at break, were improved despite the reduction or avoidance of oil-based softeners. In particular, this effect was found to be due to the presence of at least one type of resin R1.

[0022] Furthermore, remarkably, an optimized curing time, particularly a sufficiently low t, was achieved not only when compared to conventional carbon black-containing rubber compositions, especially those containing halobutyl rubber, but also when compared to rubber compositions that do not contain at least one resin R1, and instead contain an oil-based softener. 90 Optimized curing time, etc. 90 It has been found that the required curing time can be achieved while preventing unwanted over-curing.

[0023] Furthermore, and particularly surprisingly, the rubber composition according to the invention and vulcanizates obtainable therefrom not only show excellent (low) air permeability compared to conventional filler-containing rubber compositions, especially those containing halobutyl rubber, but also compared to rubber compositions containing an oil-based softening agent instead of at least one resin R1. Thus, it has been found that the rubber composition can be effectively used for the lightweight construction of suitable articles, for example for the production of inner liners. It was particularly surprising that the air permeability is improved (decreased) when using at least one resin R1 instead of oil.

[0024] Furthermore, and particularly surprisingly, the rubber composition according to the invention can be used as a filler and makes it possible to significantly reduce the amount of carbon black present therein or even completely avoid the use of carbon black as a filler, which has been found to be advantageous in terms of sustainability. In this context, it has been found that the reduction or avoidance in particular does not adversely affect, on the contrary, the curing time of the curable rubber composition, especially the t 90 time, and the air permeability of the cured rubber composition. Similarly, it has been found that the mechanical properties of the vulcanizate, such as elongation at break, are not adversely affected either.

Embodiments for Carrying Out the Invention

[0025] In the present invention, for example, the term "comprising" used in connection with the curable rubber composition according to the invention preferably has the meaning of "consisting of". In this context, for example, with respect to the curable rubber composition according to the invention, in addition to the constituents necessarily present therein, one or more further optionally contained constituents mentioned below may also be contained therein. All constituents may be present in each of their preferred embodiments mentioned below.

[0026] The total amount of all components described herein, including the components contained in the curable rubber composition according to the present invention (in each case, all essential components and further all optional components), is 100% by mass in each case.

[0027] The phr (parts per 100 parts by mass) standard used herein is a quantity standard commonly used in the rubber industry for rubber compositions. The dosage of parts by mass of individual components is always based on 100 parts by mass of the total mass of all rubber present in the composition.

[0028] Curable rubber composition The curable rubber composition includes at least one halobutyl rubber that can be cured by at least one curing agent, at least one curing agent suitable for curing at least one halobutyl rubber, and a 200m different from carbon black. 2 The composition comprises at least one lignin-based filler F1 having an STSA surface area of ​​up to / g, and at least one resin R1 selected from i) aromatic resins excluding phenolic resins, ii) aliphatic resins, and iii) mixtures thereof, wherein the total amount of phr of the at least one resin R1 present in the composition exceeds the total amount of phr of any of the paraffinic oils, naphthenic oils, and aromatic oils, each optionally present in the composition.

[0029] The components of the curable rubber composition are different from each other. In particular, at least one halobutyl rubber, at least one curing agent, at least one lignin-based filler F1, and at least one resin R1 are different from each other. Furthermore, each of these components, especially resin R1, is also different from paraffin oil, naphthenic oil, and aromatic oil, which may be optionally present in the composition but are preferably absent.

[0030] Halobutyl rubber At least one type of halobutyl rubber can be cured by at least one type of curing agent.

[0031] Those skilled in the art are aware of halobutyl rubber and methods for preparing such rubber. Halobutyl rubber is halogenated isobutene-isoprene rubber. These are available by halogenation, particularly bromination and / or chlorination, of butyl rubber.

[0032] In other words, butyl rubber is mainly composed of isobutene units, with the remainder being isoprene units. Particularly preferably, the proportion of isobutene units is 95-99.5 mol% and the proportion of isoprene units is 0.5-5 mol%, and more preferably, the proportion of isobutene units is 97-99.2 mol% and the proportion of isoprene units is 0.8-3 mol%, with the ratio of isobutene units to isoprene units preferably being 100 mol% of the monomers contained in the polymer and polymerized. Butyl rubber generally has low gas and moisture permeability.

[0033] Because isoprene units are polymerized, butyl rubber has carbon-carbon double bonds, which are useful for both vulcanization and modification with halogens such as chlorine and bromine.

[0034] Halobutyl rubbers, available through halogen modification (halogenation), are more reactive than butyl rubber and therefore have a wider range of vulcanization possibilities, particularly with other rubbers such as polybutadiene, 3,4-polyisoprene, cis-1,4-polyisoprene, natural rubber (NR), epoxidized natural rubber, butyl rubber (IIR; isobuteneisoprene rubber), styrene-isoprene rubber, styrene-butadiene rubber (SBR), and styrene-isoprene-butadiene rubber.

[0035] Preferably, at least one halobutyl rubber is selected from the group consisting of chlorobutyl rubber (CIIR; chloro-isobutene-isoprene rubber), bromobutyl rubber (BIIR; bromo-isobutene-isoprene rubber), and mixtures thereof.

[0036] Among halobutyl rubbers, bromobutyl rubber has weaker carbon-bromide bonds, making it more reactive than chlorobutyl rubber, which has carbon-chlorine bonds. This expands the range of vulcanization systems for bromobutyl rubber. Bromobutyl rubber vulcanizes more quickly and generally has better adhesion to diene rubbers.

[0037] Among halobutyl rubbers, bromobutyl rubber is particularly preferred in the context of the present invention. More preferably, the bromobutyl rubber is derived from isobutene and para-bromomethylstyrene, and particularly preferably contains 40-60 mol%, most preferably about 50 mol%, of para-bromomethylstyrene based on the total composition of the bromobutyl rubber. A suitable commercially available example of bromobutyl rubber is Exxpro® 3563 manufactured by Exxon Mobil.

[0038] However, it is also possible to use a compound of one or more types of bromobutyl rubber and one or more types of chlorobutyl rubber as the halobutyl rubber component.

[0039] In the context of the present invention, suitable chlorobutyl rubber (CIIR) preferably contains chlorine between 1.1 and 1.3 wt.%, and bromobutyl rubber (BIIR) preferably contains bromine between 1.9 and 2.1 wt.%. This corresponds to a reaction site ratio of about 2 mol%.

[0040] The viscosity of the halobutyl rubber is preferably between 35 and 55 Mooney units (ML(1+8), 125°C). Similar to butyl rubber, the product contains very few secondary components (rubber proportion > 98.5%). The halobutyl rubber preferably contains stabilizers, particularly sterically hindered phenols.

[0041] The rubber composition according to the present invention may contain, in addition to halobutyl rubber, one or more further rubbers different from halobutyl rubber. If present, particularly preferred further rubbers different from halobutyl rubber are polybutadiene, 3,4-polyisoprene, cis-1,4-polyisoprene, natural rubber (NR), epoxidized natural rubber, butyl rubber (IIR; isobuteneisoprene rubber), styrene-isoprene rubber, styrene-butadiene rubber (SBR), and styrene-isoprene-butadiene rubber.

[0042] Therefore, for example, by blending natural rubber with halobutyl rubber, adhesion to other rubber-based tire components can be improved, especially compared to general-purpose rubber. Crosslinking different rubbers can create a synergistic effect with respect to tensile strength, and thus it may even be possible to exceed the tensile strength of the individual rubbers. The gas and moisture permeability of the vulcanized final product is usually increased by the blending of natural rubber.

[0043] The adsorption of styrene-butadiene rubber into halobutyl rubber may be carried out in the same way as the adsorption of natural rubber, but there is usually no particular advantage to the latter, and therefore, the use of natural rubber is generally preferred over the use of styrene-butadiene rubber, especially in terms of the use of renewable resources. For example, typical natural rubber is available under the names SMR ("Standard Malaysian Rubber"), TSR ("Technically Specified Rubber"), and RSS ("Ribbed Smoked Sheets").

[0044] The adsorption of butyl rubber to halobutyl rubber up to 30 phr, preferably up to 20 phr, usually has little effect on the gas and moisture permeability of the final vulcanized product. However, if desired, this can reduce the vulcanization rate and increase heat resistance.

[0045] The phr (parts per 100 parts by mass) standard used herein is a quantity standard commonly used in the rubber industry for rubber compositions. The dosage of parts by mass of individual components is always based on 100 parts by mass of the total mass of all rubber present in the composition.

[0046] The total amount of halobutyl rubber is 30 to 100 phr, preferably 40 to 100 phr, more preferably 50 to 100 phr, even more preferably 60 to 100 phr, particularly preferably 65 or 70 to 100 phr, even more preferably 75 or 80 to 100 phr, even more particularly preferably 85 or 90 to 100 phr, for example 95 to 100 phr, and most preferably 100 phr.

[0047] If the rubber compound contains less than 100 phr of halobutyl rubber, at least one other rubber, preferably one of the above rubbers, and more preferably natural rubber, is included in the rubber composition such that the total amount of rubber included is 100 phr.

[0048] This means that the amount of other rubbers different from halobutyl rubber is 0-40 phr, preferably 0-35 phr, particularly preferably 0-30 phr, even more preferably 0-20 or 25 phr, and even more preferably 0-10 or 15 phr, for example 0-5 phr or 0 phr.

[0049] hardening agent At least one curing agent is suitable for curing at least one type of halobutyl rubber.

[0050] Those skilled in the art will recognize suitable curing agents that can be used to cure halobutyl rubber. The selection of the curing agent depends, in particular, on the type of application and / or, for example, whether or not it has functional groups, what kind of functional groups they are, and the types of halogen atoms present, as well as the type of halobutyl rubber used.

[0051] Preferably, at least one curing agent is present in the composition in an amount ranging from 0.05 to 30 phr, more preferably 0.2 to 20 phr, even more preferably 0.5 to 12 phr, even more preferably 0.9 to 8.0 phr, and most preferably 1.0 or 1.5 to 7.5 or 7.0 phr.

[0052] Preferably, at least one curing agent is at least one of sulfur, amine, phenol resin, hydroquinone, metal oxide, and peroxide.

[0053] Suitable amines as curing agents include amine derivatives. The amines and amine derivatives are preferably diamines and / or diamine derivatives, more preferably organic diamines and / or organic diamine derivatives, even more preferably aliphatic and / or aromatic diamines and / or diamine derivatives, and most preferably aliphatic diamines and / or diamine derivatives. Examples of suitable amines are diamines such as alkylenediamines like C1-C8 alkylenediamines. Specific examples include methylenediamine, hexamethylenediamine, and hexamethylenediamine carbamate (HMDA), where one amino group is converted to a carbamate group. Suitable amines as curing agents preferably do not contain guanidines such as biguanidine.

[0054] Exemplary phenolic resins are phenol-aldehyde resins, such as phenol-formaldehyde resins and phenol-acetylene resins. The phenolic resin is preferably selected from alkylated phenolic resins, such as alkylated phenol-formaldehyde resins. An example of an alkylated phenol-formaldehyde resin is octylphenol-formaldehyde resin. Preferably, the phenolic resin used as a curing agent is used in combination with zinc oxide.

[0055] Examples of peroxide curing agents include organic peroxides such as dialkyl peroxides, alkylaryl peroxides, diaryl peroxides, alkyl peroxide esters, aryl peroxide esters, diacyl peroxides, polyvalent peroxides, and mixtures thereof. Specific examples of organic peroxides include di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, tert-butylcumyl peroxide, tert-butylperoxybenzoate, dibenzoyl peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and bis-(tert-butylperoxy)-diisopropylbenzene and mixtures thereof.

[0056] Examples of hydroquinones include substituted or modified hydroquinones such as 2,5-diorgano-hydroquinone. Preferably, the hydroquinone is selected from 2,5-ditterallyalkyl-hydroquinones, with the most preferred being 2,5-ditterallyamyl-hydroquinone.

[0057] Preferably, at least one curing agent contains at least sulfur. Preferably, elemental sulfur in the form of an S8 ring is used for sulfur curing. The S8 ring is opened thermally or by an alkaline substance. Sulfur may be present in the curable rubber composition as soluble or insoluble sulfur. Preferably, no sulfur donor is used as a curing agent. In other words, sulfur donors are preferably not included by the term "sulfur" and / or are not used as sulfur curing agents.

[0058] Examples of metal oxides include divalent metal oxides, more preferably at least one divalent metal oxide selected from magnesium oxide, zinc oxide, lead oxide, and mixtures thereof, and even more preferably at least one divalent metal oxide selected from magnesium oxide, zinc oxide, and mixtures thereof. However, preferably, when at least one metal oxide such as zinc oxide is used, it is not used as a curing agent alone, but in combination with at least one of the aforementioned curing agents such as sulfur.

[0059] Preferably, the curable rubber composition further contains zinc oxide.

[0060] Delaying agents are available as an option. Optionally, at least one retarder is present in the composition, distinct from any other required and optional components present in the composition. The proportion of at least one retarder in the curable rubber composition according to the present invention is preferably 0 or 0.1 to 10 phr, more preferably 0 or 0.2 to 8 phr, even more preferably 0 or 0.2 to 6 phr, and most preferably 0 or 0.2 to 3 phr. The retarder is preferably in the sense of the term “retarder” as defined in DIN ISO 1382:2023-08, and is a retarder in the curable rubber composition. 90 It is suitable for delaying the curing time. Preferably, at least one of the retarders is an organic component.

[0061] Suitable organic components as retarders may be selected from diamino-2,4,6-triazinyl, guanidine, biguanidine, and organic sulfur-containing components including sulfur donors, particularly components having at least one SN bond. Such components are preferably selected from thiazoles, thiols, sulfenamides, thiram, dithiocarbamates, xanthogenetes, alkylphenol disulfides, thioureas, alkoxythiocarbamates, alkoxythiocarbonates, dialkylthiophosphonates, and mixtures thereof.

[0062] Preferably, suitable organic components as retarders include 2-mercaptobenzothiazole, 2,2'-dibenzothiazolyl disulfide, N-tert-butyl-2-benzothiazole sulfenamide, zinc dialkyldithiophosphate, benzothiazole disulfide, zinc butyl xanthoate, N-dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, thyram, tetrabenzyl thiuram disulfide, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, poly-tert-amylphenol disulfide, and dithiocarbamic acid. Selected from zinc, zinc diethyldithiocarbamate, 2-morpholinothiobenzothiazole, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N-diphenylthiourea, dithiocarbamyl sulfenamide, N,N-diisopropylbenzothioazole-2-sulfenamide, zinc-2-mercaptolimidazole, dithiobis(N-methylpiperazine), dithiobis(N-beta-hydroxyethylpiperazine), dithiobis(dibenzylamine), OTBG (o-tolylbiguanidine), DOTG (di-o-tolylguanidine), DPG (diphenylguanidine), and mixtures thereof.

[0063] Filler The curable composition contains at least one lignin-based filler F1.

[0064] Lignin-based filler F1 At least one lignin-based filler F1 is different from carbon black, 200m 2 It has an STSA surface area up to / g. A method for determining the STSA surface area (statistical thickness surface area) is disclosed in the “Method” section below. The above at least one lignin-based filler F1 and its preferred embodiments are also referred to as “at least one filler F1” as described below.

[0065] The terms filler and organic filler are known to those skilled in the art. Preferably, the filler F1 used in accordance with the present invention is a reinforcing filler, i.e., an active filler. Reinforcing or active fillers are characterized by a higher specific surface area than inert fillers and, in contrast to inert (unreinforcing) fillers, can alter the viscoelasticity of the rubber by interacting with the rubber in the rubber composition.

[0066] Preferably, at least one type of filler F1 is 2.5 to 200 m 2 / g, more preferably 5.0~<200m 2 / g, more preferably 7.5~175m 2 / g, more preferably 10.0~150m 2 It has an STSA surface area in the range of / g.

[0067] Preferably, at least one type of filler F1 is >40.5m 2 / g, more preferably >42.0m 2 / g, more preferably >45.0m 2 It has an STSA surface area of ​​ / g.

[0068] Therefore, more preferably, at least one type of filler F1 is >40.5~200m 2 / g, especially more preferably >42.0~175m 2 / g, most preferably >45.0~150m 2 It has an STSA surface area in the range of / g.

[0069] Preferably, at least one type of filler F1 is 200m 2 It has a BET surface area up to / g. More preferably, at least one filler F1 is 3.0 to 200m 2 / g, more preferably 6.0~<200m 2 / g, more preferably 8.0~175m 2 / g, more preferably 12.0 to 150m 2It has a BET surface area in the range of / g. A method for determining the BET surface area (specific total surface area according to Brunauer, Emmett, and Teller) is disclosed in the "Method" section below.

[0070] Preferably, at least one filler F1 has a d99 value of <25 μm, more preferably <20 μm, even more preferably <18 μm, still more preferably <15 μm, and still more preferably <10 μm. The method for determining the d99 value is described below in the "Method" section and is carried out by laser diffraction in accordance with ISO 13320:2009.

[0071] Preferably, at least one filler F1 has a mass-average molecular weight in the range of 1000 to 4000 Da, more preferably 1300 to 3700 Da, even more preferably 1700 to 3200 Da, still more preferably 2500 to 3000 Da, still more preferably 2600 to 2900 Da, and most preferably 2650 to 2850 Da, as determined in each case based on the soluble fraction of filler F1. A method for determining the mass-average molecular weight is described below in the "Method" section.

[0072] Preferably, at least one filler F1 has a polydispersity index (PDI) in the range of 1.5 to 5.0, more preferably 1.8 to 4.5, even more preferably 1.9 to 4.3, still more preferably 2.1 to 4.0, still more preferably 2.4 to 3.5, and most preferably 2.6 to 3.2, as determined based on the soluble fraction of the lignin-based filler. The polydispersity index can be determined by the same method used to determine the mass-average molecular weight. The PDI is calculated by dividing the mass-average molecular weight by the number-average molecular weight.

[0073] Preferably, at least one filler F1 has an ash content in the range of 0.1 to 3.0 wt.%, more preferably 0.1 to 2.5 wt.%, even more preferably 0.2 to 2.0 wt.%, still more preferably 0.3 to 1.5 wt.%, and still more preferably 0.4 to 1.0 wt.%.

[0074] Preferably, at least one filler F1 has a solubility in 0.1 M NaOH in the range of 1 to 40 wt.%, more preferably 3 to 35 wt.%, and even more preferably 5 to 30 wt.%. A method for determining the solubility is disclosed in the following "Method" section.

[0075] Preferably, at least one type of filler F1 is at most 1.50 g / cm³. 3 It has a density of . More preferably, at least one filler F1 is 1.00 to 1.50 g / cm³ 3 More preferably 1.15 to 1.35 g / cm³ 3 More preferably, 1.10 to 1.40 g / cm³ 3 It has a density of . A method for determining the density is disclosed in the following "Method" section.

[0076] Preferably, at least one filler F1 has a carbon content in the range of >60% to <90% by mass, more preferably >60% to <85% by mass, and even more preferably >60% to ≤80% by mass. A method for determining the carbon content is disclosed in the following "Method" section.

[0077] Preferably, at least one type of filler F1 has an oxygen content in the range of >8% to <30% by mass, more preferably >10% to <30% by mass, and even more preferably >15% to <30% by mass, relative to the ashless and anhydrous fillers. The oxygen content can be determined by high-temperature pyrolysis using, for example, a EuroEA3000 CHNS-O Analyzer from EuroVector SpA.

[0078] Preferably, at least one filler F1 has at least one functional group selected from phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups, and mixtures thereof.

[0079] Preferably, at least one filler F1 has a pH value in the range of 6 to 10, more preferably in the range of 6 to 9, even more preferably in the range of 7 to 9, and still more preferably in the range of 7 to < 9.

[0080] In the sense of the present invention, the term "lignin-based" preferably means that one or more lignin moieties and / or one or more lignin scaffolds are present in the filler F1. Lignin is a solid biopolymer incorporated into plant cell walls, thus resulting in the lignification of plant cells. Therefore, they are present in biomass, particularly in biologically renewable raw materials, and thus serve as an environmentally friendly alternative to fillers such as carbon black, which are available from fossil materials, especially in hydrothermally treated forms.

[0081] In the sense of the present invention, the term "lignin-based filler" preferably means that the filler F1 exists in a form obtainable by hydrothermal treatment of at least one lignin-containing biomass, such as at least one lignin-containing phytomass, and the hydrothermal treatment is preferably carried out at a temperature in the range of >100°C to <300°C, more preferably >150°C to <250°C. Preferably, at least one lignin-based filler F1 is hydrothermally treated lignin.

[0082] Preferred methods for the hydrothermal treatment of lignin in particular are described, for example, in WO 2017 / 085278 A1, WO 2017 / 194346 A1, and EP 3 470 457 A1. Hydrothermal treatment in the sense of the present invention preferably means hydrothermal carbonization (HTC), which may also be referred to as "aqueous carbonization at high temperature and pressure." Hydrothermal treatment preferably refers to hydrothermal carbonization of a lignin-containing material, which is a thermochemical conversion method of a lignin-containing material in an aqueous suspension. The lignin-containing material is preferably selected from the group consisting of Kraft lignin, steam explosion lignin, biorefinery lignin, supercritical separation lignin, hydrolyzed lignin, flash precipitated lignin, biomass-derived lignin, lignin from alkali pulping, lignin from soda process, lignin from organosolve pulping, lignin from alkali process, lignin from enzymatic hydrolysis, and any combination thereof. Preferably, the lignin is wood-based lignin, which may be derived from coniferous and / or broad-leaved trees, and / or from annual plants.

[0083] "Kraft lignin" is understood to originate from Kraft black liquor, an alkaline aqueous solution of lignin residue, hemicellulose, and inorganic chemicals used in the Kraft pulping process. Black liquor from pulping contains components derived from different species of coniferous and deciduous trees in varying proportions. Lignin can be separated from the black liquor by various techniques, including precipitation and filtration. Precipitated lignin can be purified from inorganic impurities, hemicellulose, and wood extracts using an acidic washing process. Further purification can be achieved by filtration. "Flash-precipitated lignin" is understood to be lignin precipitated from the black liquor in a continuous process by using a carbon dioxide-based acidifying agent, preferably carbon dioxide, to lower the pH of the black liquor stream to the lignin precipitation level under the influence of an overpressure of 200-1000 kPa, and then suddenly releasing the pressure to precipitate the lignin. Lignin may also be derived from the alkaline process. The "alkaline process" may begin with liquefying biomass with a strong alkali, followed by a neutralization process. After alkali treatment, lignin may be precipitated as described above. Lignin may be derived from steam explosion. Steam explosion is a pulping and extraction technique applicable to wood and other fibrous organic materials. "Biorefinery lignin" is understood to mean lignin that can be recovered from refining facilities or methods in which biomass is converted into fuel, chemicals, and other materials. "Supercritical separation lignin" is understood to be lignin that can be recovered from biomass using supercritical fluid separation or extraction techniques. Lignin may be derived from "hydrolysis methods". Lignin derived from hydrolysis methods can be recovered from paper pulp or wood chemical methods. Lignin may originate from "organosolve methods". Organosolve is a pulping technique that uses organic solvents to solubilize lignin and hemicellulose. "Enzymatic hydrolysis methods" is understood to include enzymatic hydrolysis of plant-based feedstocks such as wood-based feedstocks, such as enzymatic hydrolysis of cellulose. Enzymatic hydrolysis is a method in which enzymes assist in cleaving molecular bonds by adding water as an element.

[0084] The lignin-containing material may first be dissolved in an alkaline solution such as NaOH before hydrothermal treatment. Dissolution can be achieved by heating the mixture of lignin and the alkaline solution to about 80°C, adjusting the pH to a value greater than 7, for example, 9-11, and mixing the mixture of lignin and the alkaline solution for a predetermined time. The mixing time may be continued for about 2-3 hours. The dissolved lignin material can then be subjected to hydrothermal treatment such as hydrothermal carbonization. Hydrothermal carbonization may be carried out in a reactor or, if necessary, in multiple parallel reactors operating in a batch manner. The dissolved lignin material may be preheated before entering the reactor. The reactor temperature may be 150-300°C or 250°C, and the pressure may be 20-30 bar. The residence time in the reactor may be about 3-6 hours. In the reactor, the lignin is carbonized, thereby precipitating a stabilized lignin derivative having a high specific surface area. The formed slurry containing the carbonized lignin may then be removed and cooled. As a result, a slurry containing lignin-based packing agent F1 is formed. The slurry containing lignin-based packing agent F1 may be fed into a separation unit such as a filter press, where the settled lignin-based packing agent F1 may be separated from the slurry, for example, in the form of a filter cake. The separated lignin-based packing agent F1, which may exist in the form of a filter cake, may be crushed and dried. Before crushing or drying, the lignin-based packing agent F1 may be washed as necessary. The crushed lignin particles may be dried and used as is as a lignin-based packing agent. However, preferably, after drying, the obtained lignin particles are subsequently subjected to a grinding step to obtain lignin particles with smaller particle sizes.

[0085] Optionally, the starting material used for hydrothermal treatment, i.e., the lignin-containing material, may be reacted with at least one crosslinking agent before the hydrothermal treatment is carried out. The crosslinking agent preferably has at least one functional group that can react with the crosslinkable groups of lignin. Preferably, the crosslinking agent has at least one functional group selected from aldehyde groups, carboxylic acid anhydride groups, epoxide groups, hydroxyl groups, and isocyanate groups, or combinations thereof. Preferably, the crosslinking agent is selected from aldehydes, epoxides, acid anhydrides, polyisocyanates and / or polyols, particularly from aldehydes such as formaldehyde, furfural and / or sugar aldehydes. The crosslinking agent can react with the free ortho and para positions of the phenol ring, aromatic and aliphatic OH groups, and / or the carboxyl groups of lignin.

[0086] The biomass as defined herein is any biomass, and the term “biomass” as used herein includes phytomass, i.e., biomass derived from plants; zoomass, i.e., biomass derived from animals; and microbial biomass, i.e., biomass derived from microorganisms, including fungi. The biomass particularly preferred herein for the production of fillers is phytomass, preferably dead phytomass.

[0087] Preferably, at least one filler F1 contains carbon in the range of 0.20 to 0.45 Bq / g, more preferably 0.23 to 0.42 Bq / g. 14 It contains C. The necessary information cited above. 14 The carbon content is achieved by organic fillers available from biomass. Therefore, fillers obtained from fossil materials, particularly fossil fuels, are the corresponding 14 It does not contain carbon. For example, carbon black fillers available from fossil materials are the corresponding 14 It does not contain C.

[0088] Preferably, at least one filler F1 is present in the composition in an amount ranging from 0.25 to 150 phr, more preferably 0.75 to 125 phr, even more preferably 1.00 to 100 phr, still more preferably 1.50 to 85 phr, still more preferably 1.75 to 70 phr, and most preferably 2.0 to 60 phr.

[0089] Preferably, at least one filler F1 is present in the composition in an amount exceeding the amount of further fillers, including optional fillers F2 and F3, which are different from the at least one filler F1 and are also optionally present therein. However, preferably, no fillers other than the at least one filler F1 are present in the curable rubber composition.

[0090] Optional filler F2 The composition may further include at least one additional filler F2, which, unlike filler F1, is at least one organic filler, if present. Examples of organic fillers different from filler F1 are carbon black and other organic fillers, which, although different from lignin-based filler F1, can be obtained from biomass and / or renewable and / or recycled raw materials, for example, by hydrothermal treatment or thermal decomposition. Preferably, filler F2 is carbon black. Further examples of at least one additional filler F2 are graphite including expanded graphite, and / or graphene, and / or carbon nanotube materials including single-walled and multi-walled nanotubes.

[0091] The optional carbon black used as filler F2 may be carbon black available from biomass and / or renewable and / or recycled raw materials, but may also be industrial carbon black available from fossil materials, such as furnace carbon black, which is classified as general-purpose carbon black under ASTM code N772, ASTM code N660, or ASTM code N550.

[0092] Those skilled in the art will recognize that carbon black has a high carbon content of at least 95 wt.% based on the total mass of the filler. Therefore, an optional carbon black filler preferably has a higher carbon content than filler F1.

[0093] Preferably, the filler F2 present in the form of at least one optional type is 200m 2 Up to / g, more convenient 2.5~200m 2 / g range, more preferably 5.0 to <200m 2 / g, more preferably 7.5 to 175m 2 Up to / g, more preferably 10.0~150m 2 It has an STSA surface area of ​​ / g.

[0094] Preferably, the filler F2, which is present in the composition in an amount ranging from 0 or 0.25 to 150 phr, more preferably 0 or 0.75 to 125 phr, even more preferably 0 or 1.00 to 100 phr, even more preferably 0 or 1.50 to 85 phr, even more preferably 0 or 1.75 to 70 phr, and most preferably 0 or 2.0 to 60 phr, 50 phr, 40 phr, or 30 phr.

[0095] Optional filler F3 The composition may further contain at least one inorganic filler F3, unlike filler F1. Examples of inorganic fillers include clay minerals, such as phyllosilicates such as talc; carbonates such as calcium carbonate, such as silicates such as calcium, magnesium, and aluminum silicate; and oxides such as magnesium oxide, such as silica including rice husk silica; and / or silicic acid.

[0096] Preferably, at least one optionally selected inorganic filler F3 is a silicate, more preferably aluminum silicate or zeolite. Examples of aluminum silicates include andalusite, kyanite, sillimanite, metakaolinite, mullite, halloysite, pyrophyllite, donbasite, and kaolin (also known as kaolinite), so that at least one filler F3 is most preferably kaolin.

[0097] At least one optionally selected inorganic filler F3 enhances the processability of the cured vulcanized product, i.e., the cured rubber composition, and improves (decreases) the air permeability of the resulting vulcanized product.

[0098] Preferably, the curable rubber composition contains at least one filler F3 in an amount in the range of preferably 0 or 1.0 to 120 phr, more preferably 0 or 5.0 to 100 phr, even more preferably 0 or 10 to 85 phr, still more preferably 0 or 15 to 70 phr, still more preferably 0 or 20 to 60 phr, and most preferably 0 or 25 to 55 phr.

[0099] Resin R1 At least one resin R1 is selected from i) aromatic resins excluding phenolic resins, ii) aliphatic resins, and iii) mixtures thereof. The total amount of phr of the at least one resin R1 present in the composition exceeds the total amount of phr of any of the paraffinic oil, naphthenic oil, and aromatic oil, each optionally present in the composition. The term "aliphatic resin" includes cycloaliphatic resins.

[0100] Preferably, the total amount of phr of the at least one resin R1 present in the composition is at least 1.05 times, more preferably at least 1.15 times, even more preferably at least 1.25 times, even more preferably at least 1.50 times, even more preferably at least 2.00 times, even more preferably at least 2.50 times, and most preferably at least 5.00 times, the total amount of phr of the paraffin oil, naphthenic oil, and aromatic oil, each optionally present in the composition.

[0101] Preferably, the total amount of at least one type of resin R1 is in the range of 0.1 to 30.0 phr, more preferably 0.5 to 27.5 phr, even more preferably 1.0 to 25.0 phr, even more preferably 2.0 to 22.5 phr, even more preferably 3.0 to 20.0 phr, and most preferably 5.0 to 17.5 phr.

[0102] Preferably, at least one resin R1 is made from unsaturated aliphatic and / or aromatic hydrocarbons, more preferably unsaturated C5 or C8-C5. 30 Aliphatic and / or C5 or C8~C 30 The oligomer or polymer resin available from aromatic hydrocarbons, more preferably oligomerized or polymerized products. The term "aliphatic hydrocarbon" includes cycloaliphatic hydrocarbons. Most preferably, at least one resin R1 is made from unsaturated aliphatic and / or aromatic hydrocarbons, and more preferably from unsaturated C8-C 30 Aliphatic and / or C8-C 30 These are oligomeric resins, particularly oligomerized products, that can be obtained from aromatic hydrocarbons. The oligomeric resins preferably contain dimer and more preferably trimer structures. Preferably, at least one resin R1 is a non-monomer resin, more preferably in contrast to optionally present paraffinic oil, naphthenic oil, and aromatic oil, each of which is preferably monomeric.

[0103] Preferably, at least one resin R1 is selected from hydrogenated resins, partially hydrogenated resins, non-hydrogenated resins, and mixtures thereof.

[0104] Preferably, at least one resin R1 can be obtained by polymerization, more preferably by oligomerization, which involves copolymerizing or oligomerizing one or more of the following: terpenes and unsaturated aliphatic monomers such as 1,3-pentadiene, unsaturated cycloaliphatic monomers such as rosinic acid and dicyclopentadiene, unsaturated fatty acids, (meth)acrylic monomers, indene, styrene, vinyltoluene, coumarone, alpha-methylstyrene, and aromatic monomers such as diisopropylbenzene.

[0105] Preferably, at least one resin R1 is a terpene resin, terpene phenol resin, terpene styrene resin, rosin acid ester resin, rosin alcohol resin, modified rosin acid ester resin, modified rosin alcohol resin, indene-coumarone (IC) resin, or dicyclopentadiene (DCPD) resin, wherein each of the aforementioned resins is selected from copolymers of at least two monomers selected from resins, styrene, alpha-methylstyrene, vinyltoluene, para-methylstyrene, indene, methylindene, and mixtures thereof, which preferably exist in a partially or fully hydrogenated form.

[0106] As stated above, the presence of a phenolic resin as resin R1 is excluded. However, such a resin may nevertheless be present in the composition in addition to resin R1. The phenolic resin is discussed herein in relation to the curing agent present in the composition.

[0107] Paraffinic oils, naphthenic oils, and aromatic oils, as well as oils in general, are optional. Paraffin oil, naphthenic oil, and aromatic oil may be optionally present in the curable rubber composition. However, the total amount of phr of at least one resin R1 present in the composition exceeds the total amount of phr of any one of the paraffin oil, naphthenic oil, and aromatic oil.

[0108] Those skilled in the art will recognize the terms “paraffin oil” and / or “naphthenic oil.” In the sense of the present invention, paraffin oil is preferably a substantially saturated chain hydrocarbon, and therefore particularly an aliphatic alicyclic C8-C18 hydrocarbon. 30 It includes aliphatic alicyclic hydrocarbons such as hydrocarbons, and consequently aliphatic alicyclic C9-C 20 Contains hydrocarbons. Naphthenic oil in the sense of the present invention is preferably substantially saturated cyclic hydrocarbons, and therefore particularly cyclic C8-C 30 This includes cyclic hydrocarbons such as hydrocarbons, and by extension, cyclic C9-C 20 Contains hydrocarbons. Paraffin oil and naphthenic oil are examples of mineral oils. Those skilled in the art will also recognize the term “aromatic oil.” Aromatic oils in the sense of the present invention are preferably substantially aromatic hydrocarbons, and therefore particularly aromatic C8-C. 30 It contains hydrocarbons, and consequently aromatic C9-C 20 These contain hydrocarbons. While the use of such aromatic oils is possible, it is not very advantageous because it exhibits inferior dissolution behavior with halobutyl rubber compared to mineral oils. Paraffinic oils, naphthenic oils, and aromatic oils are preferably monomers in each case, and therefore monomeric oils.

[0109] Both mineral oils and aromatic oils, particularly mineral oils, are preferably considered "process oils" or "plasticizer oils" in the sense of the present invention. Such oils, especially mineral oils, have traditionally been used as softeners. The use of such softeners can affect not only the properties of uncured rubber compositions, such as processability, but also the properties of cured rubber compositions, such as flexibility, particularly at low temperatures. Examples of mineral oils and aromatic oils include MES (Mild Extract Solvates), RAE (Residual Aromatic Extracts), TDAE (Treated Distilled Aromatic Extracts), Rubber to Liquid Oil (RTL), and Biomass to Liquid Oil (BTL).

[0110] Preferably, the curable rubber composition does not contain any paraffin oil, naphthenic oil, or aromatic oil, or substantially does not contain any paraffin oil, naphthenic oil, or aromatic oil, where "substantially contained" in this context means that none of the paraffin oil, naphthenic oil, or aromatic oil are intentionally added to the composition. More preferably, it does not contain any kind of mineral oil and aromatic oil, or substantially does not contain any kind of mineral oil and aromatic oil, where "substantially contained" in this context means that none of the mineral oil and aromatic oil are intentionally added to the composition.

[0111] Preferably, the total amount of any one of the paraffin oil, naphthenic oil, and aromatic oil is ≤6 phr, more preferably ≤5 phr, even more preferably ≤4 phr, even more preferably ≤3 phr, even more preferably ≤2 phr, and most preferably ≤1 phr.

[0112] Preferably, the composition contains no or substantially no oils of any kind, and the term “substantially no” in this context means that no oils of any kind are intentionally added to the composition.

[0113] Dispersants available at will At least one dispersant is optionally present in the composition, and this dispersant is different from any of the other required and optional components present in the composition. The proportion of the at least one dispersant in the curable rubber composition according to the present invention is preferably 0 or 0.1 to 10 phr, more preferably 0 or 0.5 to 8 phr, and most preferably 0 or 1 to 5 phr.

[0114] Examples of such dispersants include saturated fatty acids having preferably 12 to 24 carbon atoms, more preferably 14 to 20, and most preferably 16 to 18 carbon atoms, such as stearic acid and zinc salts of the aforementioned fatty acids.

[0115] Further optional components Optionally, the curable rubber composition comprises at least one organosilane selected from at least one organosilane, more preferably an organosilane comprising at least one hydrolyzable group and at least one non-hydrolyzable group, and even more preferably an organosilane comprising at least one hydrolyzable group and at least one sulfur-containing non-hydrolyzable group. Examples include 4-mercaptobutyltrialkoxysilane and / or 6-mercaptohexyltrialkoxysilane and / or 3-mercaptopropyltrialkoxysilane, where the alkoxy groups more preferably independently mean methoxy groups or ethoxy groups. Further examples include bis(dimethylethoxysilylpropyl)tetrasulfide (DMESPT), bis(dimethylethoxysilylpropyl)-disulfide (DMESPD), 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyl-trimethoxysilane, 3-octanoylthiopropyltriethoxysilane, bis(triethoxysilylpropyl)-polysulfides containing 2 to 8 sulfur atoms in particular, such as bis(triethoxysilylpropyl)tetrasulfide (TESPT) and bis(triethoxysilylpropyl)disulfide (TESPD), and mixtures thereof, where TESPD is preferred.

[0116] Preferably, at least one organosilane is present in the curable rubber composition in an amount ranging from 0 or 0.05 to 40 phr, more preferably 0 or 0.20 to 30 phr, even more preferably 0 or 0.40 to 20 phr, still more preferably 0 or 0.80 to 15 phr, particularly more preferably 0 or 1.30 to 12 phr, and most preferably 0 or 1.80 to 10 phr.

[0117] The rubber composition may further contain optional components such as degradation inhibitors and / or anti-ozone agents and / or light-stabilizing additives and / or pigments and / or processing aid additives and / or softeners, which are different from oils such as paraffin oil, naphthenic oil, and aromatic oil. Such softeners are, for example, esters of aliphatic dicarboxylic acids such as adipic acid or sebacic acid, paraffin wax and polyethylene wax. Preferably, such softeners are used in an amount of 0 or 1 to 20 phr, more preferably 0 or 2 to 15 phr, and even more preferably 0 or 5 to 12 phr.

[0118] Preferably, t for obtaining a cured rubber composition from a cured rubber composition 90 The values ​​are preferably in each case at temperatures in the range of 155°C to 180°C, including 140°C to 220°C, more preferably 150°C to 200°C, and even more preferably 170°C, and / or preferably in the range of 3 to 80 minutes, more preferably 4 to 60 minutes, even more preferably 5 to 50 minutes, particularly preferably 5 to 45 minutes, still more preferably 5 to 30 minutes or 5 to 20 minutes or 5 to 15 minutes, particularly preferably 7 to 15 minutes or 9 to 15 minutes, when the sample used has a thickness in the range of 1.5 to 4 mm, including a sample thickness of 0.1 to 10 mm, more preferably 0.5 to 8 mm, even more preferably 1.0 to 6 mm, and even more preferably 2.7 mm. 90 The value is according to ASTM D5289-19a, minimum torque M L Starting from that point, the torque reaches the maximum torque M H This refers to the period during which 90% of the total is reached.

[0119] Kit of Parts Further subject matter of the present invention is Part A) is at least a part of the rubber composition according to the present invention, however Part A) is at least a part of the rubber composition that does not contain at least one curing agent. Optionally, as part B), the remaining portion of the rubber composition according to the present invention that is not present in part A), but part B) does not contain at least one curing agent, and Part C) at least one curing agent suitable for curing at least one type of halobutyl rubber. It is a kit of parts that includes these elements in a spatially separated form.

[0120] Preferably, part A) contains more or less a portion of any curing agent that, when present in part of part A), would prevent the rubber composition from curing. The same applies to part B), which is optionally present. The portion of any curing agent that is optional, which is part of part A) or optional, which is optional, part B), that would prevent the rubber composition from curing may contain a metal oxide, preferably a metal oxide, and more preferably zinc oxide. More preferably, if part A) contains a portion of such curing agent that would prevent the rubber composition from curing, then part A) also contains at least a portion of the filler F1.

[0121] Preferably, part A) represents a rubber composition that is not yet curable on its own and therefore, at this point, preferably not yet curable by at least one curing agent. The same applies to part B), which is optionally present. Curing is only possible after parts A) and optionally B) are mixed with C).

[0122] Preferably, the rubber and fillers of the rubber composition, which on the one hand cannot cure the rubber composition on its own, and optionally a portion of the curing agent, and on the other hand, at least one curing agent or the remainder of at least one curing agent, are spatially separated from each other in the kit of parts and can therefore be stored. The kit of parts is useful for preparing a curable rubber composition. For example, a rubber composition constituting a portion of the kit of parts, which includes rubber and fillers and optionally other components including at least one fatty acid or metal oxide such as stearic acid, can be used as part A) in the first step for preparing a curable rubber composition, and a second part of the kit of parts, i.e., part C), which includes at least one curing agent or the remainder thereof, can be used in the second step of the method.

[0123] For example, part A) may contain the complete rubber composition according to the present invention, excluding the curing agent. In this case, part B) is not required. Alternatively, part A) may contain only a portion of the rubber composition according to the present invention, excluding the curing agent, for example, only a portion of filler F1 and / or only a portion of at least one type of halobutyl rubber. Another rubber different from halobutyl rubber, and / or the remaining portion of halobutyl rubber not present in part A), and / or another filler F2 and / or F3 different from filler F1, and / or the remaining portion of filler F1, and / or additional components of any choice can be used as part B).

[0124] All preferred embodiments described herein in relation to the curable rubber composition according to the present invention are also preferred embodiments with respect to the kit of parts according to the present invention.

[0125] Hardened rubber composition A further subject of the present invention is a curable rubber composition that can be obtained by curing a curable rubber composition available by curing a curable rubber composition available by curing a curable rubber composition available by mixing parts A), optionally B), and C) of the kit of parts according to the present invention.

[0126] All preferred embodiments described herein in relation to the curable rubber composition and the kit of parts according to the present invention are also preferred embodiments with respect to the curable rubber composition according to the present invention.

[0127] The preparation of the cured rubber composition according to the present invention is preferably carried out in two steps, namely steps 1 and 2. The steps may be further specified in terms of which step at which at least one curing agent or fraction thereof is added, namely steps 1a and 2a of the first modified example V1 and steps 1b and 2b of the second modified example V2.

[0128] In the first step (V1, step 1a) of the first modification, a rubber composition as a base mixture (masterbatch) is first prepared by mixing all the components used for preparing the rubber composition according to the present invention with each other, but without including at least one curing agent. In the second step (step 2a), at least one curing agent and optionally further components such as optionally present retarders are mixed into the rubber composition obtained after step 1a.

[0129] In the first step of the second modification (V2, step 1b), the base mixture of the rubber composition is prepared in the same manner as in the first step of the first modification (step 1a), except that a portion of at least one curing agent has already been added to the base mixture. In the second step (2b), the remainder of at least one curing agent and optionally further components, such as optionally present retarders, are mixed into the rubber composition obtained after step 1b. Preferably, the portion of at least one curing agent added in step 1a cannot cure the base mixture on its own.

[0130] Alternatively, the preparation of the cured rubber composition according to the present invention is preferably carried out in only one mixing step in which all parts of the rubber composition, including the curing agent, are mixed together. For example, the step may be carried out by first adding and mixing at least one type of halobutyl rubber in a suitable mixing chamber, then adding only a portion of the remaining components of the composition, for example, only 50 wt.% of the total remaining components including the curing agent, mixing, and then adding the remaining portion of the total components and mixing further.

[0131] Before curing, the curable rubber composition thus prepared may preferably undergo a customized or modified process for the final article. The rubber composition may preferably be formed into a suitable shape required for the curing process by extrusion, co-extrusion, compression molding, transfer molding, injection molding, calendering, extrusion coating, lamination, or a combination thereof, for example, by co-extrusion of at least two rubbers, or by using a combination of extrusion and calendering. Curing may be carried out by pressure and temperature in a vulcanizing mold, or without pressure in a temperature-controlled channel where air or liquid material provides heat transfer, or curing may be carried out in an autoclave.

[0132] Preferably, t for obtaining a cured rubber composition from a cured rubber composition 90 The values ​​are preferably in each case at temperatures in the range of 155°C to 180°C, including 140°C to 220°C, more preferably 150°C to 200°C, and even more preferably 170°C, and / or preferably at temperatures in the range of 155°C to 180°C, and / or preferably at temperatures in the range of 0.1 to 10 mm, more preferably 0.5 to 8 mm, with an outer sample thickness of about 6.8 mm and a central gap thickness of about 0.5 mm, and an average sample thickness of about 2.7 mm across the entire sample area, in the range of 3 to 80 minutes, more preferably 4 to 60 minutes, even more preferably 5 to 50 minutes, particularly preferably 5 to 45 minutes, still more preferably 5 to 30 minutes or 5 to 20 minutes or 5 to 15 minutes, particularly preferably 7 to 15 minutes or 9 to 15 minutes. 90 The value is according to ASTM D5289-19a, minimum torque M L Starting from that point, the torque reaches the maximum torque M H This refers to the period during which 90% of the total is reached.

[0133] Preferably, the cured rubber composition is 3.50·10 -17 m 2 Less than / (Pa·s), preferably 3.25·10 -17 m 2Less than / (Pa·s), more preferably 3.00·10 -17 m 2 Less than / (Pa·s), more preferably 2.75·10 -17 m 2 Less than / (Pa·s), more preferably 2.50·10 -17 m 2 Less than / (Pa·s), more preferably 2.30·10 -17 m 2 It has air permeability in the range of less than / (Pa·s).

[0134] Curable materials and curable compositions, and use of kits of parts A further subject of the present invention is the use of each of the curable rubber compositions, kits of parts, or curable rubber compositions according to the present invention for manufacturing articles, parts and / or components that are preferably suitable for use in the automotive and / or aerospace and / or engineering industries and / or the pharmaceutical and / or consumer goods industries, more preferably for rubber items requiring gas impermeability, particularly hoses, personal protective equipment, protective clothing, pharmaceutical closures, vacuum seals and membranes, tank linings, conveyor belts, consumer products, particularly ball bladders, and tires, especially when used as inner liners for tires or at least as part of inner liners for tires, and even more preferably for the manufacture of pneumatic tires.

[0135] All preferred embodiments described herein relating to curable rubber compositions, kits of parts, and curable rubber compositions are also preferred embodiments relating to the use of curable rubber compositions, kits of parts, or curable rubber compositions according to the present invention.

[0136] Articles, parts, and / or components Further subject matter of the present invention is articles, parts and / or components that, in each case, are available from the curable rubber composition or kit of parts or curable rubber composition according to the present invention, and are suitable for use in the automotive and / or aerospace and / or engineering industry and / or pharmaceutical industry and / or consumer goods industry, preferably for use in rubber items requiring gas impermeability, particularly hoses, personal protective equipment, protective clothing, pharmaceutical closures, vacuum seals and membranes, tank linings, conveyor belts, consumer products, particularly ball bladders, and tires, especially for use as an inner liner of a tire or in at least a portion of an inner liner of a tire, and more preferably for use in pneumatic tires.

[0137] All preferred embodiments described herein in relation to curable rubber compositions, kits of parts, curable rubber compositions, and the use of curable rubber compositions, kits of parts, or curable rubber compositions according to the present invention are also preferred embodiments with respect to articles, parts, and / or components available from curable rubber compositions, kits of parts, or curable rubber compositions according to the present invention.

[0138] Method for preparing articles, parts, and / or components. A further subject of the present invention is a method for preparing articles, parts and / or components according to the present invention, the method comprising at least one step, wherein a curable rubber composition according to the present invention is formed into articles, parts and / or components, preferably before curing, by injection molding, compression molding, transfer molding, extrusion, co-extrusion by co-extrusion of at least two rubbers, extrusion coating, lamination, calendering, or a combination thereof, for example, at least one of extrusion or a combination of co-extrusion and calendering.

[0139] All preferred embodiments described herein relating to the use of curable rubber compositions, kits of parts, or curable rubber compositions, and articles, parts and / or components obtainable from curable rubber compositions, kits of parts, or curable rubber compositions according to the present invention are also preferred embodiments relating to methods for preparing articles, parts and / or components according to the present invention.

[0140] method 1. STSA and BET surface area The STSA and BET surface areas were determined according to standard ASTM D6556-21, respectively.

[0141] 2. Carbon content The carbon content was determined by elemental analysis according to DIN 51732:2014-07.

[0142] 3.Particle size distribution The particle size distribution was determined by laser diffraction of the material under investigation (1% by mass in water) dispersed in water, in accordance with ISO 13320:2020. The volume fraction is defined, for example, in μm units as d99 (the diameter of 99% of the sample's volume of particles is less than this value). The values ​​for d90 and d25 (in μm units) can be determined in the same way.

[0143] 4. 14 C content 14 The 1C content (biological base carbon content) was determined by radiocarbon dating in accordance with DIN EN 16640:2017-08.

[0144] 5.Ash content The ash content was determined according to standard DIN 51719:1997-07.

[0145] 6. Density Density was determined according to ASTM D297-15 (2019).

[0146] 7. Solubility in NaOH aqueous solution Solubility was measured using the following method. First, the sample was dried at 60°C for 4 hours. 0.5 g of the sample was weighed and suspended in 50 ml of 1% 0.1 M NaOH at 22°C. After mixing for 1 hour, the sample was placed on glass microfiber paper (1.6 μm), and the filter paper on which the sample was placed was dried at 60°C for 2 hours. Subsequently, the portion of the dissolved sample could be determined by gravimetric method.

[0147] 8.Average molecular weight The mass-average molecular weight was determined by size exclusion chromatography (SEC) using 0.1 M NaOH as the eluent and approximately 1 mg / ml of the sample dissolved in 0.1 M NaOH. The mass-average molecular weight relative to a polystyrene sulfonic acid standard was measured using a 280 nm UV detector. The number-average molecular weight and polydispersity index were also determined by this method.

[0148] 9. Shore A hardness Shore A hardness was tested according to ASTM D2240-15 (2021).

[0149] 10. Tensile properties The tensile properties (tensile strength and elongation at fracture) were determined according to ASTM D412-16(2021).

[0150] 11.Curing properties and t 90 curing time A moving direometer (MDR) was used to evaluate the hardening properties of a conical thickness sample, ensuring that the strain was equal along the radius, with an outer sample thickness of approximately 6.8 mm, a central gap thickness of approximately 0.5 mm, and an average sample thickness of approximately 2.7 mm across the entire sample area. The test was conducted at 170°C for 30 minutes according to ASTM D5289-19a. Minimum and maximum torque (M L M H It can measure the minimum torque M. L Starting from that point, the torque reaches the maximum torque M H The period during which 90% of the total was reached was determined for each case.90 Specify this.

[0151] 12. Air permeability The air permeability of the cured rubber composition was determined according to ISO 15105:2007-10. Measurements were performed at 70°C. The air permeability shown is the average of three measurements. Between curing and testing, the samples were stored at room temperature (23°C) for at least 16 hours. [Examples]

[0152] The following embodiments further illustrate the present invention, but should not be construed as limiting its scope.

[0153] 1. Preparation of curable compositions and their cured counterparts 1.1 Examples E1a-E1c, E2a-E2c, and E3a-E3c (all of the present invention), and C1-C4, and C4a-C4c (all of comparative examples) Curable rubber compositions E1a-E1c, E2a-E2c, and E3a-E3c (all of the present invention) and C1-C4 and C4a-C4c (all comparative examples) were prepared in two steps, and the types and amounts of each component contained therein are shown in Table 1 and Table 2 below. Each curable composition was obtained by using bromobutyl rubber (X_Butyl® BB 2030), stearic acid, magnesium oxide, zinc oxide, sulfur (Struktol® SU 95) as a curing agent, and 2,2'-dibenzothiazolyl disulfide (MBTS-80 GE).

[0154] For the preparation of E1a-E1c and C1, an STSA surface area of ​​approximately 11 m² is required. 2 A lignin-based packing material 1 (UPM BioMotion® X10) at a concentration of / g was used. For the preparation of E2a-E2c and C2, an STSA surface area of ​​approximately 23m² was used. 2 A lignin-based packing material 2 (UPM BioMotion® X20) at a concentration of / g was used. For the preparation of E3a-E3c and C3, an STSA surface area of ​​approximately 40m² was used. 2A lignin-based packing agent 3 (UPM BioMotion® X40) was used at a concentration of / g. Carbon black packing agent (CB, classified under ASTM code N-660) was used for the preparation of E4a-E4c and C4.

[0155] Each of the Examples E1a-E1c, E2a-E2c, and E3a-E3c of the present invention, as well as Comparative Examples C4a-C4c, further contained one or both of resin 1 and resin 2. As resin 1, unsaturated aromatic C9 / C 10 A commercially available product, Novares® YT C 90, a polymerization product from hydrocarbons (indene-coumarone resin), was used. As resin 2, a commercially available product, Impera® R1508, an aliphatic hydrocarbon resin, was used. Each of the comparative examples C1 to C4 did not contain either resin 1 or resin 2, but instead contained commercially available mineral oil as a processing oil.

[0156] [Table 1]

[0157] [Table 2]

[0158] 1.2 Each of the compositions shown in Table 1 and Table 2 was prepared using a HAAKE Rheomix® 3000 S equipped with a Banbury rotor set to 40°C and 50 rpm, with a two-step mixing cycle and a 70% fill density, following the procedures and conditions outlined in Tables 3 and 4 below for the first and second steps. Before and after the second step, the mixture was homogenized in an open mill, placed on a cooling stand, and cooled to room temperature. The composition obtained after the second step was then heated at 170°C. 90 It was allowed to cure for a period of +2 minutes.

[0159] [Table 3]

[0160] [Table 4]

[0161] 2. Investigation of the physical properties and curing characteristics of the cured composition. 2.1 Curing properties of Examples E1a-E1c, E2a-E2c, and E3a-E3c (all of the present invention), and C1-C4 and C4a-C4c (all of comparative examples) The curing properties for the compositions of Examples E1a-E1c, E2a-E2c, and E3a-E3c (all of the present invention) and C1-C4 and C4a-C4c (all of comparative examples) were investigated according to the methods described in the "Methods" section. The results are summarized in Tables 5 and 6.

[0162] [Table 5]

[0163] [Table 6]

[0164] As is clear from Tables 5 and 6, in Examples E1a to E1c, using a lignin-based filler in combination with at least one of resins 1 and 2 instead of the processing oil in Comparative Example C1 resulted in optimized t, for example, >10 minutes and <20 minutes. 90 Shorter time, etc. 90 In contrast to time, the t observed in hardened C1 90 The duration is much longer, significantly exceeding 20 minutes. Similar effects are observed in Examples E2a-E2c vs. C2, and Examples E3a-E3c vs. C3.

[0165] In comparative examples C4a to C4c, when the carbon black filler is used in combination with at least one of resins 1 and 2 instead of the processing oil in comparative example C4, t 90 As shown by comparing C4a and C4, which have similar time intervals, the same effect is not necessarily observed. Furthermore, the effect is far less pronounced when carbon black is used as the filler compared to the aforementioned examples of the present invention in which a lignin-based filler was used instead of carbon black (C4b and C4c vs. C4). Moreover, the t interval is significantly less than 10 minutes, as observed in C4b and C4c. 90 The timing is not well optimized because these examples tend to over-cur in industrial methods.

[0166] 2.2 Air permeability and other physical properties of Examples E1a-E1c, E2a-E2c and E3a-E3c (all of the present invention) and C1-C4 and C4a-C4c (all of comparative examples) The air permeability and several physical properties of the cured compositions of Examples E1a-E1c, E2a-E2c, and E3a-E3c (all of the present invention) and C1-C4 and C4a-C4c (all of comparative examples) were investigated according to the methods described in the "Methods" section. The results are summarized in Tables 7 and 8.

[0167] [Table 7]

[0168] [Table 8]

[0169] As is clear from Tables 7 and 8, in Examples E1a to E1c, using a lignin-based filler in combination with at least one of resins 1 and 2 instead of the processing oil in Comparative Example C1 results in an improvement (increase) in elongation at break. The same effect is observed in Examples E2a to E2c vs. C2, and further in Examples E3a to E3c vs. C3. In Comparative Examples C4a to C4c, using a carbon black filler in combination with at least one of resins 1 and 2 instead of the processing oil in Comparative Example C4 results in a similar effect. However, using carbon black instead of a lignin-based filler increases density, which is disadvantageous.

[0170] Furthermore, as is evident from Tables 7 and 8, using at least one of resins 1 and 2 instead of machining oil resulted in improved (decreased) air permeability in all examples. However, only the combination of lignin-based filler and at least one of resins 1 and 2 yielded particularly low air permeability.

Claims

1. As different constituent components, At least one type of halobutyl rubber that can be cured by at least one type of curing agent, At least one curing agent suitable for curing at least one type of halobutyl rubber, Different from carbon black, 200m 2 At least one lignin-based filler F1 having an STSA surface area up to / g, and i) aromatic resins excluding phenolic resins, ii) aliphatic resins, and iii) at least one resin R1 selected from mixtures thereof A curable rubber composition comprising the above, wherein the total amount of phr of at least one resin R1 present in the composition exceeds the total amount of phr of any of the paraffin oil, naphthenic oil, and aromatic oil, each optionally present in the composition.

2. The composition according to claim 1, characterized in that the total amount of phr of at least one resin R1 present in the composition is at least 1.05 times, preferably at least 1.15 times, more preferably at least 1.25 times, even more preferably at least 1.50 times, still more preferably at least 2.00 times, still more preferably at least 2.50 times, and most preferably at least 5.00 times, greater than the total amount of phr of paraffin oil, naphthenic oil, and aromatic oil, each optionally present in the composition.

3. The composition according to claim 1 or 2, characterized in that it does not contain any paraffin oil, naphthenic oil, or aromatic oil, or substantially does not contain any paraffin oil, naphthenic oil, or aromatic oil, where the term "substantially does not contain" in this context means that none of the paraffin oil, naphthenic oil, or aromatic oil are intentionally added to the composition, preferably it does not contain any kind of mineral oil and aromatic oil, or substantially does not contain any kind of mineral oil and aromatic oil, where the term "substantially does not contain" in this context means that none of the kind of mineral oil and aromatic oil are intentionally added to the composition.

4. The composition according to one or more of claims 1 to 3, characterized in that the total amount of any one of paraffin oil, naphthenic oil, and aromatic oil is ≤6 phr, preferably ≤5 phr, more preferably ≤4 phr, even more preferably ≤3 phr, still more preferably ≤2 phr, and most preferably ≤1 phr.

5. The composition according to one or more of claims 1 to 4, characterized in that the total amount of at least one resin R1 is in the range of 0.1 to 30.0 phr, preferably 0.5 to 27.5 phr, more preferably 1.0 to 25.0 phr, even more preferably 2.0 to 22.5 phr, still more preferably 3.0 to 20.0 phr, and most preferably 5.0 to 17.5 phr.

6. At least one resin R1 is made from unsaturated aliphatic and / or aromatic hydrocarbons, more preferably unsaturated C 5 Or C 8 ~C 30 Aliphatic and / or C 5 Or C 8 ~C 30 The composition according to one or more of claims 1 to 5, characterized in that it is an oligomer or polymer resin obtainable from aromatic hydrocarbons, preferably an oligomerized or polymerized product.

7. A composition according to one or more of claims 1 to 6, characterized in that at least one curing agent is at least one of sulfur, amine, phenol resin, hydroquinone, metal oxide, and peroxide, and / or at least one curing agent is present in the composition in an amount ranging from 0.05 to 30 phr, preferably 0.2 to 20 phr, more preferably 0.5 to 12 phr, even more preferably 0.9 to 8.0 phr, and most preferably 1.0 or 1.5 to 7.5 or 7.0 phr.

8. At least one filler F1 has a STSA surface area in the range of 2.5 to 200 m 2 / g, preferably 5.0 to <200 m 2 / g, more preferably 7.5 to 175 m 2 / g, even more preferably 10.0 to 150 m 2 / g, and is characterized by this, the curable rubber composition according to one or more of claims 1 to 7.

9. A curable rubber composition according to one or more of claims 1 to 8, characterized in that at least one filler F1 is present in the curable rubber composition in an amount ranging from 0.25 to 150 phr, preferably 0.75 to 125 phr, more preferably 1.00 to 100 phr, even more preferably 1.50 to 85 phr, and still more preferably 1.75 to 70 phr.

10. A curable rubber composition according to one or more of claims 1 to 9, characterized in that at least one filler F1 has a d99 value of <25 μm, preferably <20 μm, more preferably <18 μm, even more preferably <15 μm, even more preferably <10 μm, and / or a mass-average molecular weight in the range of 1000 to 4000 Da, preferably 1300 to 3700 Da, more preferably 1700 to 3200 Da, even more preferably 2500 to 3000 Da, even more preferably 2600 to 2900 Da, and most preferably 2650 to 2850 Da, when determined in each case based on the soluble fraction of filler F1,

11. A curable rubber composition according to one or more of claims 1 to 10, characterized in that at least one filler F1 has a carbon content in the range of >60% to <90% by mass, preferably >60% to <85% by mass, and more preferably >60% to ≤80% by mass.

12. A curable rubber composition according to one or more of claims 1 to 11, further comprising zinc oxide.

13. The curable rubber composition according to one or more of claims 1 to 12, characterized in that the curable composition further comprises at least one filler F2 and / or F3 which are different from each other and different from at least one filler F1, wherein at least one filler F2 is carbon black and at least one filler F3 is an inorganic filler, preferably a silicate.

14. Part A) is at least a portion of the rubber composition described in one or more of claims 1 to 13, however part A) is at least a portion of the rubber composition that does not contain at least one curing agent suitable for curing at least one type of halobutyl rubber. Optionally, as part B), the remaining portion of the rubber composition described in one or more claims 1 to 13 that is not present in part A), but part B) does not contain at least one curing agent suitable for curing at least one type of halobutyl rubber, and Part C) at least one curing agent suitable for curing at least one type of halobutyl rubber. A kit of parts that includes these parts in a spatially separated form.

15. A curable rubber composition obtainable by curing a curable rubber composition obtained by curing one or more of the curable rubber compositions described in claims 1 to 13, or by curing a curable rubber composition obtainable by mixing A), optionally B), and C) of the kit of parts described in claim 14.

16. The cured rubber composition is 3.50・10 -17 m 2 Less than / (Pa·s), preferably 3.25·10 -17 m 2 Less than / (Pa·s), more preferably 3.00·10 -17 m 2 Less than / (Pa·s), more preferably 2.75·10 -17 m 2 Less than / (Pa·s), more preferably 2.50·10 -17 m 2 Less than / (Pa·s), more preferably 2.30-10 -17 m 2 The cured rubber composition according to claim 15, characterized by having an air permeability in the range of less than / (Pa・s).

17. Use of a curable rubber composition according to one or more of claims 1 to 13, a kit of parts according to claim 14, or a curable rubber composition according to claim 15 or 16 for manufacturing articles, parts and / or components, which are preferably suitable for use in the automotive and / or aerospace and / or engineering industries and / or the pharmaceutical and / or consumer goods industries, and more preferably suitable for rubber items requiring gas impermeability, particularly hoses, personal protective equipment, protective clothing, pharmaceutical closures, vacuum seals and membranes, tank linings, conveyor belts, consumer products, particularly ball bladders, and tires, particularly suitable when used as an inner liner for a tire or at least as part of an inner liner for a tire, and even more preferably suitable for the manufacture of pneumatic tires.

18. In each case, articles, parts and / or components that are available from one or more of the curable rubber compositions described in claims 1 to 13, the kit of parts described in claim 13, or the curable rubber compositions described in claims 15 to 16, and are suitable for use in the automotive and / or aerospace and / or engineering industry and / or pharmaceutical industry and / or consumer goods industry, preferably for use in rubber items requiring gas impermeability, particularly hoses, personal protective equipment, protective clothing, pharmaceutical closures, vacuum seals and membranes, tank linings, conveyor belts, consumer products, particularly ball bladders, and tires, especially when used as an inner liner for a tire or as at least part of an inner liner for a tire, and more preferably for use in pneumatic tires.

19. A method for preparing an article, part and / or component according to claim 18, wherein the method comprises at least one step, wherein a curable rubber composition according to one or more of claims 1 to 13 is formed into an article, part and / or component, preferably before curing, by injection molding, compression molding, transfer molding, extrusion, co-extrusion, extrusion coating, lamination, calendering, or a combination thereof, for example, at least one of extrusion or co-extrusion and calendering.

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