Method of producing the adhesive composition, the adhesive composition and the product containing the adhesive composition and / or based on the adhesive composition

Abstract

Method for producing an adhesive composition, adhesive composition and product containing an adhesive composition and / or based on an adhesive composition. The partially cross-linked elastomeric polymers according to the invention exhibit both elastomeric and thermoplastic properties. They can be further processed using conventional elastomer processing equipment and are suitable for use in preparations such as adhesives and sealants.

Description

[0001] Method of producing the adhesive composition, the adhesive composition and the product containing the adhesive composition and / or based on the adhesive composition

[0002] The subject of the invention is a method for producing an adhesive composition, the adhesive composition itself, and a product containing the adhesive composition and / or based on the adhesive composition. The invention is suitable for applications in construction, automotive engineering, household appliance industry, aviation, space industry, marine industry, mining, oil and gas extraction and transmission, in fire protection, anti-corrosion protection, waterproofing agents, sealants, adhesives, cables and electrical wires. Essentially, the invention is useful wherever it is advantageous to use a flexible material resistant to light mechanical stresses. In certain applications, such as sealing masses, pipe wrap tapes, or sealants, partial crosslinking of the rubber is desirable in order to eliminate cold flow and low mechanical strength.

[0003] In US Publication 5,817,413 A there is disclosed a pipe insulation whose adhesive layer contains, among other rubber materials, an effective amount of crosslinked halogenated butyl rubber. Crosslinking is carried out in a mixer containing the other adhesive ingredients. Only the halogenated butyl rubber is crosslinked, using a crosslinking agent specific to halogenated butyl rubber substituents. The preferred crosslinking agent for this purpose is zinc oxide. This is due to poor dispersion of the crosslinking agent and lack of control over the site of crosslinking. The production of the final product requires the addition of resin. After adding all the ingredients, including zinc oxide, the mixture must be heated in the mixer to at least 171 °C. A drawback of such selective crosslinking is thermal activation, which leads to the formation of hot spots in areas of the mixture with increased concentration of the crosslinking agent such as ZnO. Bromobutyl rubber in the presence of zinc oxide crosslinks very slowly and requires a high temperature (>160 °C), which leads to degradation of the rubber.

[0004] Publication EP 0 434 458 A2 (equivalent to US 5,102,958 A and US 5,200,469 A) discloses a partially crosslinked, unsaturated copolymer of isomonoolefin C4to C7and conjugated multiolefin C4to C14, containing essentially randomly distributed covalent crosslinks, an olefinic unsaturation ranging from about 0.05 to about 5.0 mole percent, a gel content ranging from about 10 weight percent to about 90 weight percent as measured in cyclohexane for 48 hours at 23 °C, wherein said crosslinks are formed after polymerization and halogenation of the corresponding uncrosslinked copolymer of isomonoolefin C4to C7and conjugated diene C4to C14, and wherein said crosslinked unsaturated copolymer is essentially free of chemically bound halogen. The essence of the process disclosed in this publication is an attempt to crosslink as many halogen sites as possible. The crosslinking agent is used here in stoichiometric excess relative to the chemically bound halogen of the initial uncrosslinked polymer and causes crosslinking only at the halogen sites, meaning that the halogen concentration controls the crosslink density of the crosslinked polymer product.

[0005] Publication GB 2,276,625 A discloses an elastomeric material containing submicroscopically intermingled regions of vulcanized and non- vulcanized or partially vulcanized portions within a single elastomer type. The material is manufactured by subjecting uncured elastomers to highly selective vulcanization under controlled conditions. Fully vulcanized and non-vulcanized or partially vulcanized elastomeric regions are produced in closely related positions, resulting in materials exhibiting properties of both the vulcanized and un cured states. Publication EP 0 517 067 discloses a window sealing tape comprising a polymer matrix with good resistance to cold flow. In the preferred embodiment, the polymer matrix is a semi-interpenetrating network. In an alternative preferred embodiment, the polymer matrix is cured rubber, preferably halogenated butyl or the like. To form a semi-interpenetrating network, butyl rubber and polyisobutylene are mixed together, entangling the chains of both polymers. Then a crosslinking agent is added, and the butyl rubber essentially crosslinks while the polyisobutylene portion of the mixture remains essentially unreacted. The process relies on conventional vulcanization but with a modified base polymer composition (part of the elastomer base does not vulcanize).

[0006] The drawbacks associated with the known partially vulcanized butyl rubber arise from the polymer production methods and the crosslinking mechanisms employed. For example, known partially crosslinked butyl rubber is produced by introducing a crosslinking agent such as a phenol-formaldehyde resin system or a sulfur-based system. The amount of crosslinking agent added is less than that required to achieve full crosslinking at all available sites. The result is a partially vulcanized elastomer in which only some of the available unsaturated bonds have been utilized in the vulcanization process. However, due to the relative abundance of unsaturated bonds and the process limitation by dispersion of crosslinking agents in the polymer, controlling vulcanization becomes extremely difficult. The end product is an elastomer with reduced unsaturation and inconsistent product quality resulting from inability to control the extent and location of crosslinking between the polymer chains.

[0007] Similar issues arise when the starting polymer before crosslinking is known halobutyl rubber. In this case, the halogen atoms present on the isoprene mers also participate in the crosslinking process, further complicating control. An alternative method of obtaining partially vulcanized butyl rubber involves introducing a crosslinking agent, such as divinylbenzene, into the reactor during copolymerization. However, controlling the degree and distribution of crosslinking along the copolymer chains remains a challenge, leading to variability in product properties.

[0008] There has been a need to develop new products with self-adhesive and / or sealing properties for broad industrial use, exhibiting favorable and uniform properties, achievable in an energy-efficient and easily controllable manner. The invention addresses this need.

[0009] It has been found that elastomeric materials with a controlled degree of crosslinking can be produced. These materials constitute useful products that can be applied wherever raw uncrosslinked elastomers were previously used, but without the disadvantages associated with the absence of crosslinking. Dynamically crosslinked elastomeric polymers according to the present invention can be further processed using conventional elastomer processing equipment and are suitable for use in formulations such as adhesives and sealants. Partially crosslinked elastomeric polymers according to the invention exhibit both elastomeric and thermoplastic properties.

[0010] The solution according to the invention combines the advantages of using uncrosslinked rubber and partially crosslinked rubber and eliminates the issue of reproducibility (e.g., dispersion of crosslinking agent and lack of control over the crosslinking site). The solution according to the invention also allows energy savings, as the process is single-stage and does not require an intermediate step of preparing partially crosslinked rubber prior to producing the final composition. The invention enables obtaining a composition in which one of the components is selectively crosslinked to a gel content greater than 50% as measured by extraction for 24 hours in boiling cyclohexane, hereinafter referred to as "fully crosslinked." In any case, the gel content of the crosslinked component will be greater than the gel content before crosslinking. With selective and full crosslinking of one component, process control is greatly simplified. An excess of crosslinking agent allows complete vulcanization of the component, avoiding problems associated with dispersion of crosslinking agents.

[0011] According to the invention, the crosslinking process can be conducted at low temperature and is activated by moisture.

[0012] The composition according to the invention has the advantageous characteristics of a high-molecular-weight elastomer but without processing drawbacks. A high-molecular-weight elastomer is typically difficult to homogenize with the other mixture components — an issue avoided by the method according to the invention. Importantly, the beneficial properties are obtained in a single process. The product also does not require a thickener, since the crosslinked elastomer itself acts as a thickening agent, enabling load transfer and retention of the article’s shape.

[0013] Compared to the prior art, the composition according to the invention exhibits increased resistance to static shear.

[0014] The essence of the invention is a method of producing an adhesive composition, particularly a self-adhesive and / or sealing composition, wherein two elastomers are mixed: elastomer A, where elastomer A is either a polymerized and halogenated unsaturated copolymer of C4to C7isomonoolefin and C4to Ci4conjugated multiolefin, containing essentially randomly distributed covalent bonds and olefinic unsaturation of about 0.05 to about 5.0 mole percent, or a polymerized and halogenated copolymer of C4to C7isomonoolefin and a vinylarene compound; and elastomer B, where elastomer B is either a polymerized unsaturated copolymer of C4to C7isomonoolefin and C4to C14conjugated multiolefin, containing essentially randomly distributed covalent bonds and olefinic unsaturation of about 0.05 to about 5.0 mole percent, or a polymerized C4to C7isomonoolefin polymer; the mixture is contacted with a crosslinking agent that removes chemically bound halogen from elastomer A, thereby essentially fully crosslinking only elastomer A; wherein: elastomer A and elastomer B are mutually miscible; the crosslinking agent is an organosilicon compound; the crosslinking process is activated and controlled by moisture; elastomer A constitutes 0.5-20% by weight of the composition; elastomer B constitutes 0.5-20% by weight of the composition; the crosslinking is carried out to a gel content in the composition of about 1 to about 50 weight percent, as determined by extraction in boiling cyclohexane for 24 hours at atmospheric pressure.

[0015] Preferably, elastomer A is crosslinked to a content of less than about 0.1 % by weight of chemically bound halogen.

[0016] Preferably, elastomer A is a halogenated copolymer of isobutylene and isoprene, and elastomer B is a copolymer of isobutylene and isoprene.

[0017] Preferably, elastomer A is a halogenated copolymer of isobutylene, and elastomer B is polyisobutylene. crosslinking is performed under continuous mixing at about 80 °C to about 180 °C using equipment with periodic raw-material feed and a residence time of about 1 to about 70 minutes.

[0018] Preferably, the residence time is about 3 to about 10 minutes.

[0019] Preferably, additional components regulating gel morphology are added.

[0020] Preferably, a resin is added in an amount of about 1 to about 30% by weight.

[0021] Preferably, a plasticizer is added in an amount of about 1 to about 30% by weight.

[0022] Preferably, the plasticizer is polyisobutylene or polybutene with a molecular weight Mn < 15,000.

[0023] The invention also includes an adhesive composition, particularly a self-adhesive and / or sealing composition, having a gel content of about 1 to about 50 weight percent (boiling cyclohexane extraction for 24 hours at atmospheric pressure), comprising: a) 0.5-20% by weight of the composition of a substantially fully crosslinked unsaturated copolymer of C4to C7isomonoolefin and C4to Ci4conjugated multiolefin, containing essentially randomly distributed covalent bonds and olefinic unsaturation of about 0.05 to about 5.0 mole percent, or a substantially fully crosslinked copolymer of C4to C7isomonoolefin and a vinylarene compound, which is essentially free of chemically bound halogen after dynamic vulcanization by an organosilicon compound reacting with the halogen of the uncrosslinked polymerized halogenated copolymer of C4to C7isomonoolefin and C4to Ci4conjugated multiolefin, containing essentially randomly distributed covalent bonds and olefinic unsaturation of about 0.05 to about 5.0 mole percent, or the halogen of the uncrosslinked copolymer of C4to C7isomonoolefin and a vinylarene compound; and b) 0.5-20% by weight of the composition of an uncrosslinked, unsaturated copolymer of C4to C7isomonoolefin and C4to C14conjugated multiolefin, containing essentially randomly distributed covalent bonds and olefinic unsaturation of about 0.05 to about 5.0 mole percent, or a polymer of C4to C7isomonoolefin. Preferably, the composition includes, as the substantially fully crosslinked component, a halogen-free copolymer of isobutylene and isoprene, and as the uncrosslinked component, a copolymer of isobutylene and isoprene.

[0024] Preferably, the composition according to the invention, as the substantially fully crosslinked component, comprises a halogen-free copolymer of isobutylene and isoprene, and as the uncrosslinked component comprises polyisobutylene.

[0025] Preferably, in the composition according to the invention, the substantially halogen-free component contains less than about 0.1% by weight of chemically bound halogen.

[0026] Preferably, the composition according to the invention includes a plasticizer in an amount from about 1 % by weight to about 30% by weight.

[0027] Preferably, the composition according to the invention includes polyisobutylene or polybutene with a number-average molecular weight (Mn) < 15,000 as the plasticizer.

[0028] The scope of the invention also includes a product containing the composition and / or based on the composition according to the invention and / or containing the composition produced by the method according to the invention and / or based on the composition produced by the method according to the invention.

[0029] The product according to the invention is suitable, among others, for applications in construction, automotive engineering, household appliance industry, aviation, space industry, marine industry, mining, oil and gas extraction and transmission, fire protection, anti-corrosion protection, waterproofing agents, sealants, adhesives, cables, and electrical wires.

[0030] T rade names used in the description have the following meanings. Wherever the word “about” or similar is used, a deviation of up to 20% from the stated value is permissible.

[0031] Oppanol B and Oppanol N are trade names for BASF-produced polyisobutylenes with weight-average molecular weight (Mw) typically in the range of 53,000 to 3,050,000 and a glass transition temperature of - 64 °C. This polymer has a substantially saturated main chain and does not crosslink by conventional methods, including using organosilicon compounds. It is obtained by polymerization of isobutylene. CAS No. 9003-27-4.

[0032] Oppanol N100 is a high-molecular-weight polyisobutylene (Mw 1 ,550,000), commercially used to produce roofing membranes.

[0033] Oppanol B10 is a semi-fluid polymer, commercially used as a base for chewing gum production and secondary sealing in insulating glass manufacture. It can also be used as a plasticizer or binder in formulations used in anti-corrosion tapes for pipeline protection. Mw 53,000; Mn ~16,500.

[0034] Indopol H300 is a polybutene, a popular liquid plasticizerwith properties very similarto Oppanol B10, having Mn = 1 ,300; Mw ~2,150. This plasticizer is suitable for a wide range of applications such as lubricants, adhesives, rubber modification, sealants / rubbers / adhesives, stretch-wrap PE film, polymer modification, paints and coatings, personal hygiene and cosmetics, agriculture, and polybutene emulsions. Viscosity measured according to ASTM D445 at 100 °C in the range of 605-655 cSt. CAS No. 9003-29-6. Irganox 1010 is an antioxidant in powder form produced by BASF: tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxypentaerythritol]. CAS No. 6683-19-8.

[0035] Omyacarb 2t is a mineral filler — ground, stearate-treated calcium carbonate with a median particle size d50 of 2.6 pm. According to the invention, it can be used as a homogenization agent or as a filler (increases mixture viscosity). CAS No. 1317-65-3.

[0036] Bromobutyl is Exxon’s bromobutyl rubber (Exxon Bromobutyl 2222), a brominated copolymer of isobutylene-isoprene containing 1.03 mol% bromine, typically having a Mooney viscosity ML1+8 (125 °C) of 32 MU. CAS No. 68441 -14-5.

[0037] Exxon Butyl 268 is butyl rubber, an isobutylene-isoprene copolymer containing typically 1 .7 mol% unsaturation, with a Mooney viscosity ML1 +8 (125 °C) of 51 MU. CAS No. 9010-85-9.

[0038] Exxpro (Exxpro 3433) is Exxon’s brominated copolymer of isobutylene-p-methylstyrene, containing 0.75 mol% bromine, with a Mooney viscosity ML1+8 (125 °C) of 35 MU. CAS No. 134737-24-9.

[0039] Dynasylan AMEO is 3-aminopropyltriethoxysilane produced by Evonik - a crosslinking agent. CAS No. 919-30-2.

[0040] Dynasylan DAMO is N-2-aminoethyl-3-aminopropyltrimethoxysilane produced by Evonik - a crosslinking agent. CAS No. 1760-24-3.

[0041] Dynasylan MTMO is (3-mercaptopropyl)trimethoxysilane produced by Evonik - a crosslinking agent. CAS No. 4420-74-0.

[0042] DCP is dicumyl peroxide in powder form. CAS No. 80-43-3.

[0043] Wacker Finish WR 1100 produced by Wacker is polydimethylsiloxane terminated with reactive hydroxyl functional groups and aminoethyl-aminopropyl groups, with an amine number of 0.15 ml 1 N HCI / g and a viscosity of approx. 4000 mPa s at 25 °C. It can be used in the invention as a crosslinking agent. After reaction with bromobutyl rubber, it forms a hybrid copolymer. The amino group reacts with the halogen in halobutyl rubber, while the hydroxyl groups at the ends react to form a siloxane bond and release a molecule of water.

[0044] Escorez 1102 is an aliphatic C5 hydrocarbon resin produced by Exxon, with a softening point of 99.5 °C and a glass transition temperature of 51 °C. CAS No. 68478-07-9.

[0045] Zinc white is micronized zinc oxide (ZnO). CAS No. 1314-13-2.

[0046] Granulated recycled polyisobutylene mass supplied by TransLight sp. z o.o. sp.k. is a raw material recovered from recycling. It contains polyisobutylene, mineral filler (calcium carbonate or talc), may contain hydrocarbon resins or rosin esters, waxes, water or up to 20% water-soluble parts as determined by the extraction method described later (using water instead of cyclohexane). It has a density of about 1.15 g / cm3and a melt volume-flow rate (MVR) of about 140 ml / 10 min (2.16 kg / 80 °C) according to ISO 1133, in a yellowish, orange, or white color.

[0047] Black pigment is a mixture of butyl rubber and N330 carbon black in a weight ratio of 100:70, prepared using a closed mixer and a two-roll mill. There are particular applications for butyl rubber in which the elastomer is advantageously maintained in a thermoplastic form. Butyl rubber (HR) and polyisobutylene (PIB) are promising materials for bonding low-surface-energy substrates due to their good adhesion to polyolefin-based materials. Moreover, the exceptional moisture and oxygen barrier properties of PIB suggest that PIB-based materials could potentially be used in seals for electronic assemblies or photovoltaic panels. However, characteristic features of uncured elastomers — such as cold flow under light loads, low cohesive strength, and low pre-vulcanization strength — present certain challenges. These applications include cases where butyl rubber and halobutyl rubber (XII R) serve as the polymeric material in formulations that are easy to process and suitable for sealing compounds, pipe wraps, sealants, cable fillers, etc. Formulations based on such uncured rubbers tend to exhibit flow during service. Therefore, it would be beneficial to employ partially cured butyl or halobutyl rubber in these formulations.

[0048] According to the invention, a thermoplastic semi-interpenetrating polymer network (SIPN) is obtained in which one component is crosslinked. This method involves dynamic vulcanization of rubber in a composition comprising two miscible elastomers. The vulcanization process is carried out selectively and results in crosslinking of only one elastomer in the composition. The invention focuses primarily on thermoplastic SIPNs. More specifically, the thermoplastic SIPN according to the present invention consists of a vulcanized elastomer and a thermoplastic elastomer. Vulcanization of the elastomer is advantageously carried out using an organosilicon compound in a moisture-rich environment.

[0049] Dynamic vulcanization is a process in which at least one elastomer is crosslinked in a composition containing the elastomer and at least one non-vulcanizing polymer, i.e., a thermoplastic polymer, while both polymers are subjected to mixing or mastication at elevated temperature; mixing or mastication continues until the desired vulcanization is achieved. More precisely, the uncrosslinked polymer, the uncrosslinked elastomer, the crosslinking system, and other ingredients such as filler, plasticizer, resin, stabilizer, and the like are fed into a mixer heated above the melting point of the thermoplastic components. Mixing equipment may include Banbury mixers, Brabender mixers, sigma-blade mixers, and certain compounding extruders such as single-screw, twin-screw, and counter-rotating extruders, as well as co-kneaders. Optional fillers, plasticizers, additives, and the like may be added at this stage or subsequently.

[0050] To obtain thermoplastic vulcanizates, it is important that mixing continues uninterrupted until vulcanization occurs. If mixing stops and significant crosslinking ensues, an unprocessable vulcanizate may result. Vulcanization progress can be monitored by measuring torque or energy consumption during mixing. The torque or mixing energy curve typically reaches a peak value, after which mixing may be continued to enhance processability. If necessary, additional ingredients such as a stabilizer package may be added after dynamic vulcanization. As mentioned previously, it is advantageous to introduce a stabilizer package into the thermoplastic vulcanizate after substantial consumption of the crosslinking agent.

[0051] After discharge from the mixer, the composition containing the vulcanized elastomer and the uncured thermoplastic elastomer may be processed by various techniques such as milling, sieving, extrusion, pelletizing, injection molding, or any other suitable method. Generally, it is desirable to allow fillers and part of the plasticizer to distribute within the elastomeric phase prior to crosslinking of the elastomeric phase(s). As noted above, the thermoplastic SIPN according to the present invention comprises a vulcanized elastomer and an uncured elastomer. Thermoplastic SIPNs are desirably homogeneous compositions in which the vulcanized elastomer appears as finely dispersed particles interpenetrating the uncured elastomeric matrix. It is important to understand that thermoplastic SIPNs, as defined herein, are not strictly limited to compositions containing a single phase. Indeed, compositions of this invention may exhibit other morphologies, including, without limitation, co-continuous morphologies.

[0052] It has been discovered that elastomeric materials with a controlled degree of crosslinking can be produced. These materials provide useful products that can be employed where raw, uncrosslinked elastomers were previously used, but without drawbacks associated with lack of crosslinking. Dynamically crosslinked elastomeric polymers according to the present invention may be further processed using conventional elastomer-processing equipment and are suitable for use in formulations such as adhesives and sealants. Partially crosslinked elastomeric polymers according to the invention exhibit both elastomeric and thermoplastic properties.

[0053] Various products can be prepared from compositions according to the invention.

[0054] Pressure-sensitive materials, common in both household and professional settings, typically comprise a pressure-sensitive adhesive layer and a carrier. Such a structure exhibits tack at application temperature and adheres to various substrates under light pressure, thereby forming a bond. Thus, adhesive tapes constitute complex surface-bonding systems. According to the Pressure Sensitive Tape Council (PSTC), pressure-sensitive adhesives (PSAs) exhibit the following properties: (1) aggressive and permanent tack, (2) adhesion under low finger pressure, (3) sufficient adhesion to the adhered substrate, and (4) adequate cohesive strength for clean removal from the substrate. Polymers specially formulated and developed to exhibit the necessary viscoelastic properties have been identified as effective PSA base materials. These properties yield the desired balance of tack, peel adhesion, and shear resistance. PSAs are characterized by innate adhesiveness at room temperature (e.g., 20 °C). It should be noted that PSAs do not include compositions based solely on their viscoelastic nature and adhesive properties.

[0055] The aforementioned properties are typically evaluated using tests designed to measure adhesion (peel strength) and cohesion (shear strength) in accordance with "Adhesion and Adhesives Technology: An Introduction, 2nd Ed., Hanser Gardner Publication, Cincinnati, OH, 2002." The collective measurements from these tests provide a profile of properties commonly used to characterize PSAs.

[0056] With the increasing popularity of pressure-sensitive tape applications, quality requirements have become more stringent. For example, shear resistance, initially designed for light-load applications at room temperature, has risen significantly in many uses in terms of both operating temperature and load. High-performance pressure-sensitive tapes capable of bearing loads at elevated temperatures for 10,000 minutes have emerged. Increased shear resistance is typically achieved by crosslinking the PSA; however, care must be taken to maintain high levels of tack and adhesion to preserve the aforementioned balance of properties.

[0057] Numerous pressure-sensitive materials are now available based on polymers such as natural rubber or synthetic rubbers, block copolymers, and acrylic ester-based polymer compositions. The goal of all PSAs is to achieve a balance between adhesion and cohesion, often accomplished by fine-tuning physical attributes of the elastomer, such as glass transition temperature (Tg) and storage and loss moduli. For instance, if the Tg or storage modulus of the elastomer exceeds the Dahlquist criterion for tackiness (storage modulus 3 x 10A5 Pa at room temperature and 1 Hz), the material will not exhibit tack and thus will fail as a PSA. In such cases, low-molecular-weight, high-Tg resins or low-molecular-weight, low-Tg polymers (plasticizers) are often used to adjust Tg and modulus into the optimal PSA range. EP 2 646 482 B1 discloses PSA compositions comprising an isobutylene polymer grafted with pendant silicon groups via unsaturated-bond grafting.

[0058] Pressure-sensitive materials containing or based on the composition according to the invention provide the desired balance of tack, peel adhesion, and shear resistance and meet the Dahlquist criteria (tack modulus < 3 x i oA5 Pa at 1 Hz and application temperature, typically room temperature), ensuring material tackiness.

[0059] PSAs according to the invention are easy to use and environmentally friendly due to their low volatile organic compound (VOC) content, such as solvents.

[0060] PSAs of the invention can be applied to various flexible and rigid substrates using standard coating methods to produce self-adhesive sheet materials. Flexible substrates include, but are not limited to, plastic films such as polypropylene, polyethylene, polyvinyl chloride, polyester (PET), polycarbonate, polymethyl methacrylate (PMMA), cellulose acetate, triacetate, and ethyl cellulose, as well as foam backings. Rigid substrates include, but are not limited to, metals, metallized polymer films, tin-oxide-coated glass or polyester, PMMA sheet, polycarbonate sheet, glass, and ceramic tile. Coated sheet materials may take any form traditionally associated with adhesive constructions, such as labels, tapes, signs, shields, marking indicators, display elements, and touch panels.

[0061] For single-coated tape, the side of the backing opposite the adhesive-coated side is typically coated with a release material such as silicone, polyethylene, polycarbonate, or polyacrylate. For double-coated tapes, a second adhesive layer — either a conventional acrylic PSA or the PSA of the invention (in the same or a different formulation) — is applied to the opposite side of the backing and carried on a release liner.

[0062] SIPNs consist of a vulcanized elastomer and a thermoplastic elastomer, with the vulcanized component produced using an organosilicon compound in a moisture-rich environment. Dynamic vulcanization of at least one curable rubber in a composition containing that rubber and at least one thermoplastic rubber yields the SIPN, in which one polymer network is crosslinked (the elastomer) while the other remains unreacted. SIPNs may also exhibit co-continuous morphologies, but are distinguished from IPNs in that the uncrosslinked linear or branched polymer can be separated from the network without breaking chemical bonds.

[0063] SIPNs may optionally include fillers, oils, plasticizers, antioxidants, and other additives commonly used in rubber or PSA formulations. In a preferred embodiment, the SIPN includes a thermal stabilizer, and the crosslinked rubber can be any rubber or combination thereof crosslinkable by an organosilicon compound.

[0064] Useful rubbers include those with some degree of unsaturation in their backbone, such as elastomeric copolymers, butyl rubber, natural rubber, styrene-butadiene copolymers, butadiene rubber, acrylonitrile rubbers, halogenated isobutylene-isoprene copolymers, styrene-butadiene-vinylpyridine rubber, urethane rubber, polyisoprene rubber, epichlorohydrin terpolymers, and polychloroprene. Preferred rubbers include elastomeric copolymers, para-methylstyrene-brominated isobutylene terpolymers, and butyl rubber.

[0065] According to the specification defined herein, the C4to C7isomonoolefins include, but are not limited to: isobutylene (2-methylpropene), 2-methyl-1 -butene, 3-methyl-1 -butene, 2-methyl-2-butene, 2-methyl-1 -pentene, 3-methyl-1 -pentene, 4-methyl-1 -pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,

[0066] 4-methyl-2-pentene, 2-methyl-1 -hexene, 3-methyl-1 -hexene, 4-methyl-1 -hexene, 5-methyl-1 -hexene, 2-methyl-2-hexene, 3-methyl-2-hexene, 4-methyl-2-hexene, and 3-methyl-3-hexene.

[0067] According to the specification defined herein, C4to C14multiolefins include but are not limited to: butadiene, isoprene, piperylene, cyclopentadiene, hexadiene, cyclohexadiene, dicyclopentadiene, myrcene, terpinolene, and limonene.

[0068] According to the specification defined herein, „Vinylarene compounds” include but are not limited to: styrene, para-methylstyrene, chlorostyrene, alpha-methylstyrene, and divinylbenzene.

[0069] According to the specification defined herein, the term "elastomeric copolymer" refers to rubber copolymers polymerized from ethylene, isobutylene, n-butylene, and at least one a-olefin monomer and at least one diene monomer, a-olefins may include, among others, propylene, 1 -butene, 1 -hexene, 4-methyl-1 -pentene, 1 -octene, 1 -decene, or combinations thereof. Preferred a-olefins are propylene, isobutylene, 1 -hexene, 1 -octene, or combinations thereof. Diene monomers may include, without limitation, isoprene, butadiene,

[0070] 5-ethylidene-2-norbornene, 1 ,4-hexadiene, 5-methyleno-2-norbornene, 1 ,6-octadiene, 5-methyl-1 ,4-hexadiene, 3, 7-dimethyl-1 ,6-octadiene, 1 ,3-cyclopentadiene, 1 ,4-cyclohexadiene, dicyclopentadiene, 5-vinyl-2-norbornene, and the like, or combinations thereof. Preferred diene monomers are 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and isoprene.

[0071] When the copolymer is prepared from ethylene, isobutylene, an a-olefin, and diene monomers, the copolymer may be referred to as a terpolymer or even a tetrapolymer in cases where multiple a-olefins or dienes are employed. Preferred elastomeric copolymers include terpolymers of ethylene, propylene, isobutylene, para-methylstyrene, and 5-ethylidene-2-norbornene.

[0072] According to the specification defined herein, the term "butyl rubber" refers to amorphous elastomeric copolymers of isobutylene and isoprene or amorphous terpolymers of isobutylene, isoprene, styrene, and a divinyl aromatic monomer. These copolymers and terpolymers should contain from about 0.5 to about 10 percent by weight, or more preferably from about 1 to about 4 percent by weight, isoprene. The term "butyl rubber" also encompasses copolymers and terpolymers that are halogenated from about 0.1 to about 10 percent by weight, and preferably from about 0.5 to about 3.0 percent by weight, of chlorine or bromine. This halogenated copolymer is commonly referred to as halogenated butyl rubber. Any butyl rubber is useful for achieving the present invention, but a halogenated butyl rubber containing from about 0.6 to about 3.0 percent unsaturation is preferred, with a particularly preferred butyl rubber having a polydispersity of about 2.5 or less.

[0073] Butyl rubbers are commercially prepared by low-temperature polymerization in the presence of a Friedel- Crafts catalyst, as disclosed in U.S. Pat. Nos. 2,356,128 and 2,944,576. Butyl rubber is available commercially from numerous sources, as disclosed in the Rubber World Blue Book. For example, butyl rubber is marketed under the trade name X_Butyl™ (Arlanxeo) or Exxon Butyl™ (Exxon Chemical Co.), and the styrene-isobutylene-styrene block copolymer is marketed under the trade name Sibstar™ (Kaneka).

[0074] In some embodiments, the copolymers are primarily homopolymers of isobutylene, such as polyisobutylene resins. These may be modified to introduce an unsaturated group at the end of the main chain and are commercially available under the trade names Oppanol™ (BASF AG), Efrolen™ (EZSK), Glissopal™ (BASF AG), or Indopol™ (Ineos). Copolymers also include those consisting predominantly of isobutylene with n-butene or butadiene, which may also be modified to introduce an unsaturated group. In certain embodiments, combinations of copolymers are employed. For example, a first polyisobutylene may comprise an isobutylene homopolymer while a second comprises butyl rubber, or vice versa, a first polyisobutylene may comprise butyl rubber and a second may comprise an initially random isobutylene copolymer subsequently modified.

[0075] The isobutylene copolymer may include a random copolymer of isobutylene and paramethylstyrene-modified units. This random copolymer, containing from about 1 to about 20 wt% of the paramethylstyrene-modified units, possesses a network structure. Commercial examples of this random copolymer include Exxon Chemical Co.’s EXXPRO series, particularly grades 3745 and 3433. The network structure may be formed by the technique disclosed herein.

[0076] Paramethylstyrene monomer units can contribute to the copolymer’s heat resistance and strength due to the inherent cohesive force and hardness of paramethylstyrene. To take advantage of this effect, it is beneficial for the copolymer to contain paramethylstyrene in amounts greater than zero, preferably about 1 to 20 parts by weight based on the total amount of the copolymer. When the paramethylstyrene content is less than 1 part by weight, cohesive strength may be insufficient, making it difficult to achieve adequate adhesive strength for practical applications. Conversely, when the para methylstyrene content exceeds 20 parts by weight, the flexibility of the copolymer decreases significantly, and a key adhesive property, tack, diminishes, making it unsuitable for classification as a pressure-sensitive material.

[0077] Preferably, plasticizers and oils, or combinations thereof, are employed in compositions according to the present invention. The type of oil selected will typically be consistent with those commonly used with the specific elastomer(s) present in the composition. Oils may include, without limitation, aromatic, naphthenic, and paraffinic oils. Preferred synthetic oils are polyolefin a-olefins. Oils may also include organic esters, alkyl ethers, or combinations thereof.

[0078] Generally, about 5 to about 400 parts by weight of plasticizer-oil per 100 parts by weight of rubber are added. Preferably, about 30 to about 300 parts by weight, and more preferably about 80 to about 250 parts by weight, of plasticizer-oil per 100 parts by weight of rubber are added. The amount of oil added depends on the desired properties, with the upper limit determined by the compatibility of the specific oil and the composition ingredients; this limit is exceeded when excessive oil migration occurs.

[0079] In U.S. Patent No. 5,397,832, it has been disclosed that the addition of certain low- to medium-molecular-weight organic esters and alkyl ether esters to compositions covered by the invention significantly lowers the Tg of the rubber components and of the overall composition and improves low-temperature properties, in particular flexibility and strength. It is important that the plasticizer be compatible or miscible with both rubber components of the composition; that is, it should blend with the other ingredients to form a single phase.

[0080] Plasticizers may be incorporated into a pressure-sensitive material formulation to facilitate wetting and / or control viscosity. Suitable plasticizers known in this field include hydrocarbon oils, liquid or soft resins (including liquid hydrocarbon resins), liquid polyterpenes, liquid poly(isobutylenes) such as Glissopal™, waxes, and oil mixtures.

[0081] Conventional pressure-sensitive materials exhibit suboptimal adhesion to certain substrates, including some automotive coatings and low-surface-energy surfaces. To enhance adhesive performance — i.e., to achieve more aggressive adhesion to these surfaces — it is common practice to increase the tackiness of the base polymer. Various tackifiers are used, including phenol-modified terpenes, hydrocarbon resins such as polyvinylcyclohexane and poly(t-butylstyrene), and rosin esters such as glycerol rosin esters and pentaerythritol rosin esters.

[0082] These tackifiers include phenol-modified terpenes and rosin esters such as glycerol rosin and pentaerythritol rosin esters, available commercially under trade names Nuroz™, Nutac™ (Newport Industries), Permalyn™, Staybelite™, and Foral™ (Eastman). Additionally, hydrocarbon resin binders, typically derived from C5 and C9 monomers as byproducts of petroleum cracking, are available under trade names Piccotac™, Eastotac™, Regalrez™, Regalite™ (Eastman), Arkon™ (Arakawa), Norsolene™, Wintack™ (Cray Valley), Nevtac™, LX™ (Neville Chemical Co.), Hikotack™, Hikorez™ (Kolon Chemical), Novares™ (Rutgers N.V.), Quintone™ (Zeon), Escorez™ (ExxonMobil Chemical), Nures™, and H-Rez™ (Newport Industries).

[0083] For the purposes of the invention, various crosslinking agents may be employed.

[0084] A nucleophilic organosilicon compound contains at least two reactive functional groups. The first reactive functional group “HX1-” is capable of displacing a halogen atom from the halogenated isobutylene copolymer. For example, reactive functional groups such as amino, hydroxyl, or mercapto may displace complementary halide leaving groups (chloro-, bromo-, iodo-) present in the isobutylene copolymer.

[0085] Some aminosilanes useful in the practice of this disclosure are described in U.S. Patent No. 4,378,250

[0086] (Treadway et al.) and include:

[0087] Aminoethyltriethoxysilane, P-aminoethyltrimethoxysilane, P-aminoethyltriethoxysilane P-aminoethyltributoxysilane, a-aminoethyltrimethoxysilane, a-aminoethyltriethoxysilane Y-aminopropyltri methoxysilane, y-aminopropyltriethoxysilane, y-aminopropyltributoxysilane P-aminopropyltri methoxysilane, P-aminopropyltriethoxysilane, p-aminopropyltributoxysilane a aminopropyltrimethoxysilane, a-aminopropyltriethoxysilane, a-aminopropyltributoxysilane.

[0088] The halogen functional group in these materials allows the introduction of pendant alkoxysilane groups via a nucleophilic alkoxysilane of the formula:

[0089] H-Xi-R2-[Si(OR3)x(R3)3-x]q, where X1is -O-, -S-, -NR4-, where R4is H or C1-C4 alkyl; R2is a polyvalent saturated or unsaturated alkylene or arylene, R3 is an alkyl or aryl group, x is from 1 to 3, preferably 3, and q is 1 or 2.

[0090] The reaction scheme comprises a displacement reaction with a “nucleophilic alkoxysilane compound,” an organic compound having at least one nucleophilic functional group and at least one alkoxysilane group. where:

[0091] R7denotes H or CH3;

[0092] X1is -S-, -NR4-, where R4is H or C1 -C4 alkyl, R1is a polyvalent alkylene or arylene;

[0093] R2is a polyvalent saturated or unsaturated alkylene or arylene;

[0094] R3is an alkyl or aryl group; x is from 1 to 3, preferably 3; q is 1 or 2;

[0095] X2is a leaving group, such as a halide, preferably bromide.

[0096] In the presence of moisture, the alkoxysilane groups hydrolyze to silanol groups, which crosslink the polymer by forming siloxane bonds with adjacent alkoxysilane groups. As hydrolysis and crosslinking proceed, the adhesive’s mechanical strength increases with the degree of crosslinking. The crosslinking and formation of siloxane bonds are illustrated in Scheme V, where R6represents an isobutylene polymer radical of at least 20 repeating units. No additional crosslinking agents, such as di- or polyvalent alcohols or amines, are required to form ionic crosslinks. It should be understood that siloxane bonds are dynamic in the presence of moisture, continuously cleaving and reforming. where

[0097] R2is a polyvalent saturated or unsaturated alkylene or arylene;

[0098] R3is alkyl or aryl group, x is 1 to 3, preferably 3.

[0099] Faster crosslinking is achieved in the presence of a silanol condensation catalyst. Suitable catalysts include organic metal compounds such as tin carboxylates and titanium esters or chelates, e.g., tetrabutyl titanate and bis(acetoacetato)diisopropoxy titanium; organic bases such as ethylamine, hexylamine, and piperidine; and acids such as mineral acids and fatty acids. Preferred catalysts are organic tin compounds, for example dibutyltin dioctoate, dibutyltin dioctoate, and dibutyltin dioctoate. A skilled practitioner will readily determine a sufficient or efficacious amount of crosslinker to employ without undue experimentation. The amount of crosslinking agent should be sufficient to achieve at least partial vulcanization of the elastomeric polymer. Generally, the amount of organosilicon crosslinker ranges from about 1 to about 20 parts by weight, more preferably from about 2 to about 10 parts by weight, and most preferably from about 4 to about 8 parts by weight of the organosilicon compound per 100 parts by weight of rubber (PHR).

[0100] After sufficient mixing in the molten state to form a homogenous composition, the crosslinking agents are typically added. A curative may also be introduced as a solution in a liquid carrier, such as a rubber processing oil compatible with the other ingredients. Rubber crosslinking can occur within minutes or less, depending on mixing temperature, shear rate, and activators in the organosilicon curatives. Suitable vulcanization temperatures range from about 110 °C to about 220 °C, more preferably from about 120 °C to about 160 °C. Heating and mixing at vulcanization temperature are generally sufficient to complete the vulcanization reaction in minutes or less; higher temperatures may be employed if shorter cure times are desired. For organosilicon curatives, vulcanization is controlled by moisture in the composition and mixing environment. Water or humid air can be introduced into the mixing equipment to accelerate crosslinking. In the absence of a silanol condensation catalyst, hydrolysis proceeds slowly at low relative humidity (below 50%). An alternative technique involves mixing the PIB polymer with one to ten parts by weight, preferably one to two parts by weight, of a hydrated salt, and then mixing at elevated temperature to effect moisture curing. Suitable hydrated salts include CuSO45H2O, MgSO47H2O, BaSO42H2O, BaCI22H2O, and CaSO4-2H2O.

[0101] The compositions described above are coated onto substrates using conventional coating techniques modified as appropriate for each substrate. For example, these compositions may be applied to various rigid substrates by roller coating, slot flow coating, dip coating, spin coating, spray coating, knife coating, and die coating. These methods allow placement of the compositions at varying thicknesses, enabling broader application. Coating thickness may range from 0.2 to 2 mm (dry thickness), preferably about 0.5 to 1 mm.

[0102] Examples of Embodiments of the Invention

[0103] “PHR” denotes parts by weight per one hundred parts by weight of the solid polymer, i.e., the mass of all (co)polymers of polyisobutylene, but not the mass of the liquid polyisobutylene.

[0104] Dynamic Vulcanization - this term refers to a part of the method of manufacture. It is essential that the composition be prepared by this method. If the composition is prepared by anothertechnique — for example, in the conventional manner used for rubber — then the resulting composition will not be thermoplastic and will not be useful. The process parameters depend on the equipment and raw materials used. A person skilled in the art should have no difficulty selecting appropriate process parameters. It is not possible to enumerate process parameters for every piece of equipment available on the market. The situation is analogous to, for example, selecting the appropriate injection temperatures.

[0105] Gel Content is the result of a measurement. It is the weight of the insoluble portion of the composition remaining on the filter after extraction with a solvent. The gel content reflects the crosslinking of the polymer, since uncrosslinked polymer is dissolved and washed away by the solvent. Crosslinked polymer forms a gel, swells in the solvent but does not dissolve. Determination of the gel content is an easy way to verify whether the polymer has vulcanized. During vulcanization, the gel content increases. It is not critical what exactly the gel comprises; what matters is that its content after vulcanization is greater than before vulcanization. According to the invention, the gel may, for example, be crosslinked bromobutyl rubber (depending on the embodiment of the invention, the gel fraction may also contain filler and other ingredients), whereas what is washed out is uncrosslinked polymer together with plasticizers and other ingredients not chemically bound to the crosslinked fraction. The gel may also entrap mechanically filler particles that are insoluble in the chosen solvent. In such a case, the content of the organic fraction can be determined indirectly by measuring the ash content in the gel.

[0106] The copolymer comprises commercial butyl rubber. The isomonoolefins, once polymerized, are theoretically fully saturated — apart from two terminal unsaturations, which are negligible — so any overall unsaturation of 0.05-5 % can only originate from the multiolefin component. Isobutylene-isoprene copolymers contain approximately 2 mol % isoprene units (and thus unsaturated bonds) and 98 mol % isobutylene units (which are saturated).

[0107] The network according to the invention is formed following prior polymerization and halogenation steps. Accordingly, elastomer A has been both polymerized and halogenated, whereas elastomer B has been polymerized only. A rubber manufacturer polymerizes butyl rubber (HR); this commercial rubber is then halogenated by the manufacturer to yield halobutyl rubber. In the method of the invention, halobutyl rubber may be employed. During the crosslinking process, the halogen atoms depart from the polymer chain. After crosslinking, the polymer should be essentially free of halogen atoms in its backbone.

[0108] As used herein, the term “polymer” may refer to a homopolymer, a copolymer, or any mixture thereof.

[0109] All tapes were conditioned at 23 °C and 50 % relative humidity before testing for 180° peel adhesion and static shear strength. The term “PHR” (parts per hundred resin) refers to parts by weight per hundred parts by weight of the solid polymer (i.e., the mass of all polyisobutylene copolymers), excluding the mass of liquid polyisobutylene.

[0110] Peel adhesion force was measured at 180° using a tensile testing machine at a peel rate of 300 mm / min, in accordance with the procedure described in FINAT FTM 1. Test panels were prepared by wiping with a cloth moistened with extraction solvent, then with acetone, applying firm hand pressure to wipe each panel 8-10 times. This cleaning procedure was repeated twice more using fresh solvent-wetted cloths, and the panels were allowed to dry. Samples were pressed to a thickness of 1 mm using a hydraulic press and then laminated onto 40 pm PET film as the backing substrate. From these laminates, strips measuring 2.5 cm * 20 cm were cut and rolled onto the cleaned panels with a 2.0 kg rubber roller, making two passes. Two specimens were tested for each example, and the averaged values are reported in N / 25 mm.

[0111] Static shear strength was evaluated using a non-standard procedure described herein. The procedure is similar to the FINAT FTM 8 method. Test conditions were 70 °C with a 135 g load. Tape test specimens measuring 50 mm x 25 mm and 1 mm thick were adhered to stainless steel (SS) panels measuring 53 mm x 25 mm using the panel cleaning and adhesive application method described for the peel adhesion test. An L-shaped metal panel was attached to the specimens. A 135 g weight was affixed to the L-shaped panel, and the panel was adhered to a vertical steel surface placed in an environmental chamber set at 70 °C. The displacement of the panel from its initial position was recorded after 7 days. If displacement exceeded 50 mm or the panel detached from the fixture, the result was recorded as failure.

[0112] Penetration was measured using a cone penetrometer in accordance with ISO 2137, following a method developed based on that standard. Samples were pressed to a thickness of approximately 24 mm and conditioned for 24 h at 21 °C. The penetration depth was then measured with a 150 g cone after a 5 s penetration time. The result represents the average of five measurements.

[0113] Ash content (wt %) was determined using a muffle furnace. A sample of the composition weighing approximately 1.5 g was dried in an oven at 70 °C for 24 h and weighed to 0.1 mg accuracy (sample weight). It was then placed in a 10 ml ceramic crucible of known weight (crucible weight). The sample and crucible were heated in a muffle furnace at 400 °C for 2 h. After cooling, the crucible and residue were weighed (post-combustion weight). When the sample is contained within packaging, the packaging weight must be subtracted from the sample weight, and the post-combustion packaging weight must be subtracted from the combined post-combustion weight.

[0114] Ash content is expressed as:

[0115] Insolubles content (wt %) was determined using a method developed based on ASTM D2716-16, Method A. A sample of the composition weighing approximately 1.5 g was tightly wrapped in a filter bag. The filter-bagged sample for quantitative analysis was placed in a stainless steel mesh basket. The sample, filter bag, and basket were weighed to 0.1 mg accuracy, and, accounting for the weight of the filter bag and basket as tare, the initial sample mass was determined (sample weight). The basket with the sample was immersed in cyclohexane (>100 mL), in an amount sufficient to fully cover the sample. The vessel was heated to the boiling point of the solvent under reflux. After 24 hours, the basket and sample were removed from the vessel, drained, and dried at 70 °C for at least 2 hours until constant weight was achieved (residue after extraction weight).

[0116] Organic content in the gel was determined by measuring the ash content of the sample remaining after the insolubles content determination. The sample used for the ash content measurement is the post-extraction residue containing the insoluble fractions.

[0117] % organic content in gel = 100% — % ash content

[0118] The content of the organic fraction of the gel in the entire formulation was determined as follows:

[0119] % organic gel content in formulation = % insolubles content . % organic content in gel

[0120] If the ash content in the sample is less than 1 %, then the percentage of the organic fraction of the gel in the composition may be assumed to be equal to the percentage of insolubles. The gel content in the gel-forming portion (gellable fraction) of the formulation was determined as follows:

[0121] Mooney viscosity was measured according to ASTM D1646-04.

[0122] Example 1 and Comparative Example 1

[0123] Method of preparing the adhesive compositions:

[0124] The base of the composition (denoted in the table as “base”) was obtained as follows. A 5 L sigma-blade mixer (Almara) was heated to 145 °C. The impeller speed was set to 37.5 rpm. Unless otherwise specified, each subsequent mixing step was initiated once the previously added material was fully incorporated into the blend and no unmixed particles remained; this does not imply full homogenization at that stage.

[0125] In the mixer chamber, 300 g bromobutyl rubber, 700 g Oppanol® B100, and 6 g lrganox® 1010 were placed.

[0126] After 6 min, 200 g Oppanol® B10 was added.

[0127] After 12 min, 142 g Oppanol® B10 was added.

[0128] After 13 min, 200 g Omyacarb® 2T was added.

[0129] After 5 min, 300 g Omyacarb® 2T was added.

[0130] After 7 min, 120 g Oppanol® B10 was added.

[0131] After 3 min, 180 g Oppanol® B10 was added.

[0132] After 6 min, 226 g Oppanol® B10 was added.

[0133] After 8 min, 168 g Oppanol® B10 was added.

[0134] After 5 min, 235 g Oppanol® B10 was added.

[0135] After 7 min, 220 g Oppanol® B10 was added.

[0136] After 7 min, 125 g Oppanol® B10 was added.

[0137] After 2 min, 160 g Oppanol® B10 was added.

[0138] After 7 min, 237 g Oppanol® B10 was added.

[0139] After 10 min, half of the base composition (1 760 g) was discharged from the mixer.

[0140] The resulting composition contained no unmixed polymer particles and was visually homogeneous when formed into a film.

[0141] In the mixer chamber, the remaining base composition was built up to the formulation described in Example 1 as follows. All parameters remained unchanged from the method of obtaining the base composition. 1.5 g of Dynasylan AMEO and 150 g of Omyacarb 2T were added.

[0142] After 10 min, 2.5 g of Dynasylan AMEO and 150 g of Omyacarb 2T were added.

[0143] After 6 min, 100 g of Indopol H300, 300 g of Omyacarb 2T, and 3 g of Dynasylan AMEO were added. Approximately 10 min after the addition of the crosslinking agent, a change in the surface of the composition was observed. The surface was visually matte and felt nap-like. Samples taken from the mixer were more flexible compared to samples before the addition of the crosslinking agent.

[0144] After 5 min, 66 g of Indopol H300 and 300 g of Omyacarb 2T were added.

[0145] After 5 min, 92 g of Indopol H300 and 400 g of Omyacarb 2T were added.

[0146] After 2 min, 3 g of Dynasylan AMEO and 50 Base g of Omyacarb 2T were added.

[0147] After 5 min, 5 g of Dynasylan AMEO and 50 g of Omyacarb 2T were added.

[0148] After 5 min, 250 g of Escorez 1102 were added. El 1ampex

[0149] After 5 min, 100 g of Indopol H300 and 100 g of Omyacarb 2T were added.

[0150] After 10 min, the composition was discharged from the mixer.

[0151] Citomparaev

[0152] Comparative Example 1 was prepared in an analogous manner to Ell eampexxample 1 , with the exception that the crosslinking agent charging step was omitted.

[0153] El 2ampex

[0154] Table 1

[0155] The quantities indicated are expressed in parts by weight per 100 parts of rubber (per hundred rubber - PHR). The formulations in the examples have been recalculated according to t El 3hampexe size of the mixer.

[0156] Ingredients

[0157] El 4ampex

[0158] [PHR] [PHR] [PHR] [PHR] [PHR] [PHR]

[0159] Oppanol B10 200 200 200 - - -

[0160] Granulated recycled polyisobutylene - - - 150 - - mass

[0161] Oppanol B100 70 70 70 - - 80

[0162] Exxon butyl 268 - - - 60 60 -

[0163] Exxpro - - - - 30 20

[0164] Bromobutyl 30 30 30 30 - -

[0165] Black pigment 17 17 17

[0166] Omyacarb 2t 50 350 350 400 450 125

[0167] Indopol H300 - 72 72 175 175 125

[0168] Escorez 1102 - 50 50 - 60 -

[0169] Wacker Finish WR 1300 - - - - 30 -

[0170] Dynasylan AMEO - 3 - 3 - -

[0171] Dynasylan DAMO - - - - - 2

[0172] Irganox 1010 0,6 0,6 0,6 1 - 1 Formulation properties

[0173] Penetration [1 / 10 mm] 54 58 37 62 35

[0174] Density [g / cm3] 1 ,30 1 ,30 1 ,42 1 ,44 1 ,24

[0175] Peel 180° [N / 24mm] 85 89 15 63 30 300 mm / min

[0176] Peel 180° [N / 25mm] 11 10 mm / min

[0177] MVR (5 / 140) 39 31

[0178] MVR (13 / 140) 18

[0179] Static shear [mm] 13 mm destruct 15 mm 10 mm ion

[0180] Ash content [%] 44,6 % 45,0 % 52,6% 55,6 % 41 ,78 %

[0181] Insolubles content [%] 34,95 % 14,76% 41 ,71 % 40,38% 55,21 %

[0182] Organic content in gel [%] 8,29% 0,83% 10,52% 9,49% 6,06%

[0183] Organic gel content in formulation [%] 2,90% 0,12% 4,39% 3,83% 3,35%

[0184] Gel content in gellable fraction [%] 74,88% 3,17% 122,32 52,58% 61 ,89% %

[0185] Thermoplastic yes yes yes yes yes yes

[0186] Example 2

[0187] The equipment used was the same as in Example 1 , with the temperature set to 155 °C. The weight of the composition was calculated to 4180 g.

[0188] The mixer was charged with the entire amounts of Exxon butyl rubber, bromobutyl rubber, black pigment, and Irganox 1010.

[0189] After 15 min, % of the total amount of Indopol H300 and % of the total amount of Omyacarb 2T were added.

[0190] After 15 min, another % of the total amount of Indopol H300 and % of the total amount of Omyacarb 2T were added.

[0191] After 10 min, 1 / 8 of the total amount of Indopol H300 and % of the total amount of Omyacarb 2T were added.

[0192] After 10 min, another 1 / 8 of the total amount of Indopol H300 and % of the total amount of Omyacarb 2T were added.

[0193] After 5 min, the entire amount of Dynasylan AMEO was added.

[0194] After 15 min, the remaining Indopol H300 was added, and the recycled blend was gradually dosed for homogenization.

[0195] Example 3

[0196] The equipment used was the same as in Example 1 , with the temperature set to 100 °C. The weight of the composition was calculated to 4115 g. The mixer was charged with the entire amounts of Exxon butyl rubber, Exxpro, black pigment, and Irganox 1010.

[0197] After4 min, 1 / 8 of the total amount of Indopol H300 and % of the total amount of Omyacarb 2T were added.

[0198] After 5 min, 1 / 5 of the total amount of Indopol H300 and 1 / 5 of the total amount of Omyacarb 2T were added.

[0199] After 6 min, 1 / 3 of the total amount of Indopol H300 and 1 / 5 of the total amount of Omyacarb 2T were added.

[0200] After 10 min, 1 / 5 of the total amount of Indopol H300 and 1 / 8 of the total amount of Omyacarb 2T were added.

[0201] After 7 min, 1 / 3 of the total amount of Wacker WR 1300 and a small amount of Omyacarb 2T were added to ensure proper homogenization. The temperature was raised to 125 °C.

[0202] After 7 min, 1 / 3 of the total amount of Wacker WR 1300 and a small amount of Omyacarb 2T were added to ensure proper homogenization. The temperature was raised to 135 °C.

[0203] After 7 min, 1 / 3 of the total amount of Wacker WR 1300 and a small amount of Omyacarb 2T were added to ensure proper homogenization. The temperature was raised to 150 °C.

[0204] After 15 min, the remaining raw materials were gradually dosed, ensuring homogenization.

[0205] Example 4

[0206] The equipment used was the same as in Example 1 , with the temperature set to 160 °C. The weight of the composition was calculated to 2590 g.

[0207] The mixer was charged with the entire amounts of Exxpro, Oppanol N100, pigment, and Irganox 1010.

[0208] Every 7 min, 1 / 10 of the total amount of Indopol H300 and Omyacarb 2T were added to the mixer, with homogenization of the previously added portions.

[0209] Then, % of the total amount of Dynasylan DAMO was added every 3 min.

[0210] Mixing continued for 10 min after the last portion of DAMO was added.

[0211] An expert in the field will be able to produce a homogeneous mixture using an analogous mixing apparatus by selecting process parameters within the specified ranges. The order of raw-material addition (Oppanol, bromobutyl, Escorez, Irganox 1010, Indopol, Omyacarb 2T) is essentially arbitrary; an expert will adjust the quantities and timing of each feed to achieve a homogeneous blend. It is advantageous to introduce the crosslinking agent only after obtaining a homogeneous mixture of elastomer A and elastomer B. After addition of the crosslinking agent (in this case, a silane), mixing must continue continuously without interruption for a duration sufficient to effect complete crosslinking of elastomer A or complete consumption of the crosslinker. In the case of crosslinking with an organosilicon compound, moisture exposure is required. Moisture may be supplied from ambient air (optimal conditions are approximately 50 % relative humidity) or from residual moisture in the fillers or polymers. The progress of crosslinking can be monitored by measuring the drive torque of the mixer (torque or power consumption over time). Typically, maximum torque is reached when elastomer A is fully crosslinked or the crosslinker is fully depleted. It is advantageous to continue mixing until the torque or power consumption stabilizes. This does not preclude alternative process controls, such as visual inspection of the batch. Visual monitoring of crosslinking in an open sigma mixer (or similar apparatus) involves observing the appearance of the composition's surface. Low-viscosity material is generally plastic with a smooth, glossy surface. Upon addition of the crosslinker and initiation of crosslinking, the surface becomes matte and exhibits a nap-like texture, which persists until the crosslinking process is com Citomparaevplete. l 2 eampex

[0212] Comparative examples

[0213] Citomparaev Table 2 l 3 eampex

[0214] Ingredients

[0215] Citomparaev l 4 eampex

[0216] Citomparaev

[0217] Exxpro 50 l 5 eampex 12,5 6,25

[0218] Exxon butyl 268 100 100 100 50 87,5 93,75

[0219] Bromobutyl Citomparaev 100

[0220] Omyacarb 2t l 6 eampex 20

[0221] Dynasylan AMEO 5 2,5 0,625 0,3125

[0222] Wacker Finish WR 1300 Citomparaev 10

[0223] DCP 2 l 7 eampex

[0224] Dynasylan MTMO 2,5

[0225] Formulation properties Citomparaev

[0226] Ash content [%] 0,09% 0,69% 18,l 87 eampex5%

[0227] Insolubles content [%] 2,07% 16,23% 16,46%

[0228] Organic content in gel [%] - - 42,82%

[0229] Organic gel content in - - 7,05% formulation [%]

[0230] Gel content in gellable - 16,55% 8,33% fraction [%]

[0231] Thermoplastic yes no yes no no no no Table 3

[0232] Ingredients

[0233] Exxpro 100 50

[0234] Citomparaev

[0235] Exxon butyl 268 l 9 eampex 50 50 100

[0236] Bromobutyl 100 50 100

[0237] Zinc white ZnO 10 10 10 10 10

[0238] Dynasylan AMEO Citomparaev 5

[0239] Formulation properties l 10 eampex

[0240] Ash content [%] 1 ,5%

[0241] Insolubles content [%] 33,94% 65,22%

[0242] Citomparaev

[0243] Organic content in gel [%] 74,66% l 11 eampex 97,7%

[0244] Organic gel content in 25,34% 63,72% formulation [%]

[0245] Gel content in gellable 25,34% 60,68% fraction [%] Citomparaev

[0246] Thermoplastic no no yes yesl 12 eampex yes no

[0247] Mooney viscosity 93 100 63 62 62 -

[0248] ML1 +4 (125°C) [MU]

[0249] Citomparaev

[0250] Comparative Examples 2-13 were prepared as follows: l 13 eampex

[0251] The total amount of polymer in the formulation was set to 1 kg, and the quantities of the remaining

[0252] Citomparaev ingredients were calculated proportionally. The mixer temperature was set to 145 °C. All of the pl 14 eampexolymers (Exxpro, Exxon butyl, bromobutyl, depending on the example) were charged into the mixer. After 20 min of homogenization, the remaining formulation ingredients were added, and mixing continued for 40 min.

[0253] Comparative Example 2 demonstrates that the mixing process alone does not produce a beneficial change in properties. After completion of mixing, the blend was thermoplastic - by using a hydraulic press at 80 °C, a visually flat 1 mm-thick molding was obtained. The insolubles content is equivalent to the gel content in this example.

[0254] Comparative Example 3 shows that it is possible to increase the gel content by using butyl rubber and an organosilicon crosslinking agent. In this case, the peroxide used is a source of radicals that cause rubber degradation. Simultaneously, the radicals allow attachment of an S-H group from the silane to the butyl rubber chain. In this example, two competing processes occur - peroxide-induced rubber degradation and crosslinking. The resulting composition is not thermoplastic - the moldings are visually unattractive, the surface resembles orange peel, is nap-like and heterogeneous. Additionally, the blend emits an unpleasant mercaptan odor. Comparative Example 4 shows no significant reaction between butyl rubber and the crosslinking agent used. The blend is thermoplastic, with properties similar to those of Comparative Example 2.

[0255] Comparative Examples 5 and 6 show the reaction between halogenated rubber and the crosslinking agent. The resulting blend was granulated in the mixer, resembled a powder, was brittle, and exhibited no tackiness. It was impossible to form a molding from it. Comparative Example 7 shows a blend that, despite crosslinking of the halogenated rubber, remains thermoplastic to a degree similar to Comparative Example 3. A molding can be formed from the composition, but it exhibits the same defects as in Comparative Example 3.

[0256] Comparative Example 8 shows a partially crosslinked blend made from halogenated rubber. It behaves similarly to Comparative Example 3.

[0257] The data presented in Comparative Examples 9-14 indicate a distinct crosslinking behavior depending on the crosslinking system used, which distinguishes the invention from the prior art. Zinc oxide acts as a selective crosslinking agent for bromobutyl rubber. This effect manifests as an increased Mooney viscosity in compositions containing bromobutyl rubber and zinc oxide (Comparative Examples 9, 10) compared to control compositions without bromobutyl rubber (Comparative Examples 1 1-14). Simultaneously, zinc oxide was shown to be ineffective for crosslinking the halogenated Exxpro elastomer (Comparative Examples 1 1-14), where no increase in Mooney viscosity was observed and the material remained thermoplastic. Effective crosslinking of the Exxpro elastomer was achieved using organosilicon compounds (Comparative Examples 5-7). Moreover, comparison of results obtained under identical processing conditions shows that using an organosilicon compound to crosslink bromobutyl rubber results in significantly higher gel content than when using zinc oxide (comparison of the effect demonstrated in Comparative Example 9 with the results for the organosilicon system).

Claims

AMENDED CLAIMS received by the International Bureau on 12 September 2025 (12.09.2025)1. A method of producing an adhesive composition, particularly a self-adhesive and / or sealing composition, comprising the mixing, in the presence of moisture, of: a) elastomer A, which is a polymerized and halogenated unsaturated copolymer of C4 to C7 isomonoolefin and conjugated multiolefin of C4 to C14, containing essentially randomly distributed covalent bonds and olefinic unsaturation in the range of about 0.05 to about 5.0 mol%, or ii. a polymerized and halogenated copolymer of C4 to C7 isomonoolefin and a vinylarene compound; b) elastomer B, which is a polymerized unsaturated copolymer of C4 to C7 isomonoolefin and conjugated multiolefin of C4 to C14, containing essentially randomly distributed covalent bonds and olefinic unsaturation in the range of about 0.05 to about 5.0 mol%, or ii. a polymerized C4 to C7 isomonoolefin polymer; c) organosilicon compound being crosslinking agent that removes chemically bound halogen from elastomer A; and d) filler(s), plasticizer(s), resin(s) and / or stabilizer(s); to effect substantially complete crosslinking of only elastomer A during mixing; wherein elastomer A and elastomer B are mutually miscible, elastomer A constitutes 0.5 to 20 wt% of the composition, elastomer B constitutes 7 to 25 wt% of the composition, the resulting composition exhibits both elastomeric and thermoplastic properties, the crosslinking process is a dynamic vulcanization, which is activated and controlled by moisture, and performed in one stage during the mixing process, and the crosslinking is conducted to a gel content in the composition in the range of about 1 wt% to about 50 wt% as determined by extraction with boiling cyclohexane for 24 hours at atmospheric pressure.

2. Method according to claim 1 , characterized in that the crosslinking agent is introduced after obtaining a homogeneous mixture of elastomer A and elastomer B and mixing continue without interruption for a duration sufficient to effect substantially complete crosslinking of elastomer A.

3. Method according to claim 1 , characterized in that the moisture is derived from ambient air, and / or from residual moisture in the fillers and / or polymers A and B, and / or introduced in the form of water into the mixer.

4. Method according to claim 1 , characterized in that elastomer A is crosslinked to a content of less than about 0.1 % by weight of chemically bound halogen.

5. Method according to claim 1 , characterized in that elastomer A is a halogenated copolymer of isobutylene and isoprene, and elastomer B is a copolymer of isobutylene and isoprene.

6. Method according to claim 1 , characterized in that elastomer A is a halogenated copolymer of isobutylene, and elastomer B is polyisobutylene.

7. Method according to claim 1 , characterized in that the crosslinking is carried out under continuous mixing conditions at a temperature of from about 80°C to about 180°C using an apparatus in which the raw materials are fed periodically, and the residence time of the raw materials in the apparatus is from about 1 to about 70 minutes.

8. Method according to claim 7, characterized in that the residence time of the raw materials in the apparatus is from about 3 to about 10 minutes.

9. Method according to claim 1 , characterized in that additional ingredients regulating the morphology of the gel are added to the mixture.

10. Method according to claim 1 , characterized in that a plasticizer is added to the mixture in an amount from about 1 % by weight to about 30% by weight of the composition.11 . Method according to claim 1 , characterized in that the plasticizer is polyisobutylene or polybutene having a molecular weight Mn < 15,000.

12. Adhesive composition, in particular self-adhesive and / or sealing, having a gel content in the range from about 1% to about 50% by weight as determined by extraction with boiling cyclohexane for 24 hours at atmospheric pressure, exhibiting both elastomeric and thermoplastic properties, and constituting semi-interpenetrating polymer network of: a) 0.5 to 20 wt% of substantially complete crosslinked elastomer A, which is a polymerized unsaturated copolymer of C4 to C7 isomonoolefin and conjugated multiolefin of C4 to C14, containing essentially randomly distributed covalent bonds and olefinic unsaturation in the range of about 0.05 to about 5.0 mol%, or ii. a polymerized copolymer of C4 to C7 isomonoolefin and a vinylarene compound; b) 7 - 25% by weight of an uncrosslinked od elastomer B, which is a polymerized unsaturated copolymer of C4 to C7 isomonoolefin and conjugated multiolefin of C4 to C14, containing essentially randomly distributed covalent bonds and olefinic unsaturation in the range of about 0.05 to about 5.0 mol%, or ii. a polymerized C4 to C7 isomonoolefin polymer; and c) filler(s), plasticizer(s), resin(s) and / or stabilizer(s).

13. Composition according to claim 12, characterized in that the essentially fully crosslinked component comprises a halogen-free copolymer of isobutylene and isoprene, and the uncrosslinked component comprises a copolymer of isobutylene and isoprene.

14. Composition according to claim 12, characterized in that the essentially fully crosslinked component comprises a halogen-free copolymer of isobutylene and isoprene, and the uncrosslinked component comprises polyisobutylene.

15. Composition according to claim 12, characterized in that the essentially halogen-free component contains less than about 0.1 % by weight of chemically bound halogen.

16. Composition according to claim 12, characterized in that it contains a plasticizer in an amount from about 1 % by weight to about 30% by weight.

17. Composition according to claim 16, characterized in that the plasticizer comprises polyisobutylene or polybutene having a number-average molecular weight (Mn) of less than 15,000.

18. A product comprising the composition of claims 12-17 and / or based on the composition of claims 12-17 and / or comprising the composition produced by the method of claims 1-11 and / or based on the composition produced by the method of claims 1-11 .

19. Use of the product according to claim 18 in construction, automotive, household appliances, aviation, space industry, marine industry, mining, oil and gas extraction and transmission, fire protection, anticorrosion protection, waterproofing, sealants, adhesives, cables and electrical wires.

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