Articles comprising thermoplastic elastomer compositions and related methods

Abstract

An article comprises a thermoplastic elastomer composition. The thermoplastic elastomer composition comprises a hydrogenated styrenic block copolymer, a plasticizer having a number average molecular weight of at least 2,000 grams per mole, and a wax having polar functional groups. For example, the article can be a filament or a gasket. Also described is a method for making the article, the method comprising direct co-extruding the thermoplastic elastomer composition and the pressure sensitive adhesive onto a substrate.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 605,353, filed December 1, 2023, the disclosure of which is incorporated herein by reference in its entirety. Background Technology

[0003] Rubber seals around openings can be used in industries such as automotive and construction, as described in WO 2018 / 161068 (Murree et al.), U.S. Patent Application Publication No. 2008 / 0182074 (Pasquale et al.), and FR2851193 published August 20, 2004. The seals may have multiple layers or additionally include various materials bonded together.

[0004] In unrelated disclosures, adhesives co-extruded with other materials are described in U.S. Patent Nos. 4,497,926 (Toy), 7,491,434 (Khandpur et al.), 9,486,982 (Emslander et al.), U.S. Patent Publication No. 2021 / 0324244 (Bieber et al.), and GB 1553881, published October 10, 1979.

[0005] In other unrelated disclosures, the adhesive provided as a core-sheath filament is described in U.S. Patent Application Publication Nos. 2023 / 0089703 (Kalish et al.), 2022 / 0290335 (Behling et al.), 2022 / 0290334 (Sahni et al.), 2022 / 0259465 (Kugel et al.), and 2022 / 0134652 (Napierala et al.) and International Patent Application Publication No. WO2021 / 130620 (Sahni et al.). Summary of the Invention

[0006] This disclosure provides a thermoplastic elastomer composition that can be easily extruded. Advantageously, the thermoplastic elastomer composition can be formed into filaments, which can then be extruded into another useful article, such as a gasket. More advantageously, the thermoplastic elastomer composition can be co-extruded with a pressure-sensitive adhesive composition.

[0007] In one aspect, this disclosure provides a thermoplastic elastomer composition. The thermoplastic elastomer composition comprises a hydrogenated styrene block copolymer, a plasticizer having a number-average molecular weight of at least 2,000 g / mol, and a wax having polar functional groups.

[0008] In another aspect, this disclosure provides articles comprising a thermoplastic elastomer composition. The thermoplastic elastomer composition comprises a hydrogenated styrene block copolymer, a plasticizer having a number-average molecular weight of at least 2,000 g / mol, and a wax having polar functional groups.

[0009] In some embodiments, the article is an extruded article. In some embodiments, the article is a filament. In some embodiments, the article is a gasket. In some embodiments, the article is a composite material article in direct contact between a thermoplastic elastomer composition and a pressure-sensitive adhesive. In some embodiments, the article is a co-extruded article of a thermoplastic elastomer composition and a pressure-sensitive adhesive.

[0010] In another aspect, this disclosure provides a method for preparing the aforementioned article. The method includes extruding a thermoplastic elastomer composition. The method may include co-extruding the thermoplastic elastomer composition with a pressure-sensitive adhesive composition.

[0011] In this application: Terms such as “a,” “an,” and “the / described” are not intended to refer to a single entity, but rather to encompass general categories, which may be illustrated with specific examples. The terms “a,” “an,” and “the / described” are used interchangeably with the term “at least one (kind).”

[0012] The phrase "including at least one of..." followed by a list means including any item in the list or any combination of two or more items in the list.

[0013] As used herein, the term "polystyrene" includes polymers and copolymers of substituted styrene monomers and / or unsubstituted styrene.

[0014] The term "elastomer" refers to a molecule having a structure that substantially comprises multiple repeating units, which are actually or conceptually derived from monomers with low relative molecular mass. The term "elastomer" also refers to a polymer that exhibits elastic properties.

[0015] Unless otherwise specified, all numerical ranges include the endpoints and the non-integer values ​​between them (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Attached Figure Description

[0016] Figure 1 A schematic exploded perspective view of a segment of a core-skin filament according to an embodiment of this disclosure.

[0017] Figure 2 It is used for allocation Figure 1 A side sectional view of an exemplary embodiment of the filament distribution head.

[0018] Figure 3 yes Figure 2 A side front view of the barrel component inside the dispensing head, with some inner surfaces shown in dashed lines.

[0019] Figure 4 yes Figure 2 A side front view of the screw component inside the distribution head.

[0020] Figure 5 yes Figure 4 A front sectional view of the screw component.

[0021] Figure 6 It is combined separately Figure 1 filaments and Figures 2 to 4 A perspective view of the distribution head system.

[0022] Figure 7 This is a side view of a system for co-extruded pressure-sensitive adhesives and thermoplastic elastomer compositions of the present disclosure, the system including an embodiment of a co-extruded dispensing head and comprising... Figure 6 Adhesive dispensing system.

[0023] Figure 8A This is a perspective view of one implementation of a co-extrusion dispensing head.

[0024] Figure 8B This is a front view of the co-extrusion dispensing head.

[0025] Figure 8C This is a side view of the co-extrusion dispensing head.

[0026] Figure 8D This is a top view of the co-extrusion dispensing head.

[0027] Figure 8E It is along Figure 8B The line aa in the middle is intercepted Figure 8C A side sectional view of the co-extrusion dispensing head.

[0028] Figure 8F It is a co-extrusion distribution head edge Figure 8B The perspective section view of line aa in the diagram.

[0029] Figure 9 It is possible to be Figures 8A to 8F A perspective view of D-shaped hollow co-extruded thermoplastic and adhesive products co-extruded by a co-extrusion distributor head.

[0030] Figure 10A This is a perspective view of another embodiment of the co-extrusion dispensing head.

[0031] Figure 10B This is a front view of the co-extrusion dispensing head.

[0032] Figure 10C This is a side view of the co-extrusion dispensing head.

[0033] Figure 10D This is a top view of the co-extrusion dispensing head.

[0034] Figure 10E It is along Figure 10B The line bb in the middle is cut off Figure 10A Side sectional view.

[0035] Figure 10F It is along Figure 10B The line bb in the middle is cut off Figure 10A A perspective sectional view.

[0036] Figure 11 This is a perspective view of the composite material article disclosed herein.

[0037] Figure 12 This is a perspective view of the flat strip co-extrusion distribution head.

[0038] Figure 13 This is a cross-sectional view of the flat strip co-extruded composite material product prepared in the examples.

[0039] Figure 14 This is a perspective view of an example of the shape of the product. Detailed Implementation

[0040] The thermoplastic elastomer compositions included in the articles of this disclosure comprise hydrogenated styrene block copolymers. The thermoplastic elastomer compositions may comprise a single block copolymer or a mixture of two or more block copolymers. In some embodiments, at least one block copolymer in the thermoplastic elastomer composition is a block copolymer comprising a hydrogenated intermediate block and two or more polystyrene end blocks. The intermediate block is typically a rubbery block (or a low-Tg block), and the polystyrene end blocks are sometimes referred to as glassy blocks or high-Tg blocks.

[0041] While this disclosure is not bound by theory, it is believed that at the operating temperature of the adhesive, the block copolymer microphases separate into ordered nanoscale domains, including rubbery and glassy block domains. Upon microphase separation, these copolymers form elastic, size-stable solids exhibiting significant shear strength. Unlike chemically crosslinked rubbers, block copolymers are capable of reversible melting and recuring; therefore, they are referred to as thermoplastic elastomers. Consequently, the thermoplastic elastomer compositions of this disclosure are not chemically crosslinked and advantageously do not require energy-intensive curing steps.

[0042] In some embodiments, the block copolymer is a linear block copolymer (SR) having the following general formula. m -S, where each S is an independent polystyrene block, each R is an independent rubbery block, and m is a value of at least 1. The variable m can be 1 to 10, 1 to 5, 1 to 3, or in some embodiments, less than, equal to, or greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, the linear block copolymer is a triblock copolymer, where m is 1 and can also be represented by the formula SRS.

[0043] In some embodiments, the block copolymer may be of the general formula (SR). n -Y star-shaped (also called radial or multi-armed) block copolymers, wherein each R and S is the same as defined above, n is an integer equal to at least 3, and Y is a residue of a multifunctional coupling agent used to form the star-shaped block copolymer. The variable n represents the number of arms in the star-shaped block copolymer and can be 3 to 10, 3 to 8, 3 to 6, or in some embodiments, less than, equal to, or greater than 3, 4, 5, 6, 7, 8, 9, or 10. For each arm, each S and each R can have a different length.

[0044] In block copolymers (including any of those described above), the polystyrene blocks may have the same or different molecular weights. In some embodiments, each polystyrene block independently has a weight-average molecular weight of 4,000 g / mol to 50,000 g / mol. Similarly, if more than one intermediate block (e.g., a rubbery block) is present, the intermediate blocks may have the same or different molecular weights. In some embodiments, each intermediate block independently has a weight-average molecular weight of 5,000 g / mol to 500,000 g / mol.

[0045] Generally speaking, each rubber-state block has a glass transition temperature (T0) lower than the ambient temperature. g For example, the glass transition temperature may be below 20°C, below 0°C, below -10°C, or below -20°C, below -40°C, below -60°C, or in some embodiments, below, equal to, or above -60°C, -55°C, -50°C, -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, or 20°C. The glass transition temperature can be determined using conventional methods known in the art, including differential scanning calorimetry or dynamic mechanical analysis.

[0046] In hydrogenated styrene block copolymers, each rubbery block is a hydrogenated derivative of a polymerized conjugated diene. The conjugated diene typically contains 4 to 12 carbon atoms. Examples of usable conjugated dienes include butadiene, isoprene, 2-ethylbutadiene, 1-phenylbutadiene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 3-ethyl-1,3-hexadiene, and combinations thereof. Each rubbery block can be a homopolymer or a copolymer. In some embodiments, the rubbery block comprises at least one of poly(ethylene / propylene), poly(ethylene / butene), or polyisobutylene.

[0047] The glass transition temperature of each polystyrene block is typically at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, or in some embodiments, at least 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or 100°C.

[0048] The styrene monomers used to prepare polystyrene blocks can be unsubstituted or substituted. Available styrene monomers have at least 8 carbon atoms, and in some embodiments contain at least 10 or at least 12 carbon atoms and up to 18, 16, or 14 carbon atoms. Examples of suitable styrene monomers include styrene, vinyltoluene (e.g., 2-vinyltoluene, 3-vinyltoluene, or 4-vinyltoluene), α-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, α-2-methylstyrene, 4-tert-butylstyrene, 4-isopropylstyrene, and combinations thereof. Each polystyrene block can be a homopolymer or a copolymer. In some embodiments, the polystyrene end blocks each comprise at least one of unsubstituted polystyrene, poly(vinyltoluene), poly(α-methylstyrene), poly(2,4-dimethylstyrene), poly(ethylstyrene), poly(2,4-diethylstyrene), poly(3,5-diethylstyrene), poly(4-tert-butylstyrene), or poly(4-isopropylstyrene). In some embodiments, the polystyrene blocks each comprise unsubstituted polystyrene. In some embodiments where one or more polystyrene end blocks comprise copolymers, at least 50 weight percent (wt%) (in some embodiments, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 98 wt%, or at least 99 wt%) of monomer units are derived from styrene.

[0049] The polystyrene blocks, including polystyrene end blocks, can comprise 5% to 50% by weight of the block copolymer. This amount of polystyrene in the block copolymer allows for a useful balance between cohesive strength and modulus. Based on the total weight of the block copolymer, the polystyrene block content can be 7% to 40% by weight, 9% to 40% by weight, 15% to 35% by weight, or in some embodiments, less than, equal to, or greater than 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 27% by weight, 30% by weight, 32% by weight, 35% by weight, 37% by weight, or 40% by weight.

[0050] In addition to polystyrene blocks and rubbery blocks, star-shaped block copolymers also contain residues of a multifunctional coupling agent Y. The coupling agent typically has multiple carbon-carbon double bonds, carbon-carbon triple bonds, or other groups that can react with the carbanions of the active polymers that can be used to form the star-shaped block copolymer. The multifunctional coupling agent can be aliphatic, aromatic, heterocyclic, or a combination thereof. Examples of suitable coupling agents include polyvinylacetylene, diacetylene, di(meth)acrylates (e.g., ethylene glycol dimethacrylate), divinylbenzene, divinylpyridine, and divinylthiophene. Other available coupling agents include multifunctional silyl halides (e.g., tetrafunctional silyl halides), polyepoxides, polyisocyanates, polyketides, polyanhydrides, polyolefins, and dicarboxylic acids.

[0051] The weight-average molecular weight of the hydrogenated styrene block copolymer typically does not exceed 1,200,000 g / mol. In some embodiments, the weight-average molecular weight does not exceed 1,000,000 g / mol, 900,000 g / mol, 800,000 g / mol, 600,000 g / mol, or 500,000 g / mol. In some embodiments, the weight-average molecular weight of the hydrogenated styrene block copolymer is at least 75,000 g / mol, at least 100,000 g / mol, at least 200,000 g / mol, at least 300,000 g / mol, or at least 400,000 g / mol. The weight-average molecular weight of the hydrogenated styrene block copolymer can be from 75,000 g / mol to 1,200,000 g / mol, 100,000 g / mol to 1,000,000 g / mol, 100,000 g / mol to 900,000 g / mol, or 100,000 g / mol to 500,000 g / mol.

[0052] In some embodiments, the thermoplastic elastomer composition comprises a hydrogenated styrene diblock copolymer. The hydrogenated styrene diblock copolymer typically has a single polystyrene block and a single rubbery block, and may be represented herein by the chemical structure SR, where S and R are as defined above in any of its embodiments.

[0053] The polystyrene block content in the diblock copolymer can be 10% to 50% by weight, 10% to 40% by weight, 15% to 50% by weight, 15% to 40% by weight, 20% to 50% by weight, 20% to 40% by weight, or in some embodiments, less than, equal to, or greater than 10% by weight, 12% by weight, 15% by weight, 17% by weight, 20% by weight, 22% by weight, 25% by weight, 27% by weight, 30% by weight, 32% by weight, 35% by weight, 37% by weight, or 40% by weight. The weight-average molecular weight of the diblock copolymer can be 75,000 g / mol to 250,000 g / mol, 100,000 g / mol to 250,000 g / mol, 125,000 g / mol to 250,000 g / mol, or 125,000 g / mol to 200,000 g / mol.

[0054] In some embodiments, the hydrogenated styrene block copolymer includes at least one of a polystyrene-containing diblock copolymer, a polystyrene-containing triblock copolymer, or a polystyrene-containing star-shaped block copolymer, wherein the polystyrene-containing diblock copolymer, polystyrene-containing triblock copolymer, and polystyrene-containing star-shaped block copolymer each independently comprises at least one of poly(ethylene / propylene), poly(ethylene / butene), or polyisobutylene, and in some embodiments, a poly(ethylene / butene) block. In some embodiments, the hydrogenated styrene block copolymer comprises a styrene-ethylene / butene-styrene block copolymer.

[0055] Hydrogenated styrene block copolymers may be present in the thermoplastic elastomer composition in any suitable amount. In some embodiments, the hydrogenated styrene block copolymers are present in amounts of 10% to 40% by weight, 20% to 40% by weight, 10% to 30% by weight, or 20% to 30% by weight, based on the total weight of the thermoplastic elastomer composition.

[0056] Suitable materials, used alone or in combination, for use as hydrogenated styrene block copolymers may be commercially available, for example, under the trade name KRATON (e.g., KRATON G1633 and G1654) from Kraton Performance Polymers (Houston, TX, USA), under the trade name SEPTON (e.g., SEPTON8004) from Kuraray (Tokyo, Japan), under the trade name TUFTEC (e.g., TUFTEC 1051) from Asahi Kasei Corporation (Tokyo, Japan), and under the trade names VECTOR and TAIPOL from TSRC Corporation (New Orleans, LA, USA).

[0057] The thermoplastic elastomer compositions of this disclosure, as included in the articles thereof, comprise a plasticizer having a number-average molecular weight of at least 2,000 g / mol. Combinations of two or more plasticizers may also be used. In some embodiments, the plasticizer comprises a hydrocarbon plasticizer. Any plasticizer commonly known to those skilled in the art (in some embodiments, a hydrocarbon plasticizer) may be used in the context of this disclosure. In some embodiments, the number-average molecular weight M of the plasticizer is... n Not greater than 10,000 g / mol, not greater than 8,000 g / mol, not greater than 6,000 g / mol, or not greater than 5,000 g / mol. The number-average molecular weight of the plasticizer can be determined by any method known to those skilled in the art, such as gel permeation chromatography (GPC) or by light scattering techniques. Unless otherwise stated, the number-average molecular weight of the plasticizer is measured using the methods described in the examples below. When the thermoplastic elastomer compositions of this disclosure are co-extruded with a pressure-sensitive adhesive (PSA), molecular weights within these ranges will, for example, limit the migration of the plasticizer into the PSA. Migration of the plasticizer into the PSA can lower the glass transition temperature (T0). g This causes the elastic network to swell and can separate to the bond line, each of which can adversely affect the adhesive properties of the PSA, especially after thermal aging.

[0058] In some embodiments, the plasticizers that can be used to practice this disclosure are polymeric hydrocarbon plasticizers (e.g., polybutene or polyisobutylene), liquid hydrocarbon plasticizers (e.g., REGALREZ 1018 hydrocarbon resin from Synthomer, London, England), or hydrocarbon mineral oils. Examples of useful hydrocarbon mineral oils include naphthalene oil, paraffin oil, aromatic oil, and castor oil. Other examples of useful plasticizers include phthalates, adipates, and liquid aliphatic resins that can be purchased under the trade name “NEVTAC LT” from Neville Chemical Company, Pittsburgh, PA, which can be used with, for example, a rubber phase having a temperature of about -40°C or higher. g It is used together with hydrogenated styrene block copolymers.

[0059] In some embodiments, the plasticizer is present in the thermoplastic elastomer composition in an amount not exceeding 45 wt%, not exceeding 42.5 wt%, not exceeding 40 wt%, or not exceeding 35 wt%, based on the total weight of the thermoplastic elastomer composition. In some embodiments, the plasticizer is present in the thermoplastic elastomer composition in an amount from 10 wt% to 45 wt%, from 15 wt% to 42.5 wt%, from 20 wt% to 40 wt%, from 15 wt% to 40 wt%, or from 20 wt% to 35 wt%, based on the total weight of the thermoplastic elastomer composition.

[0060] The thermoplastic elastomer compositions of this disclosure included in the articles comprise waxes having polar functional groups. In some embodiments, the polar functional groups include at least one of a hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, an amino group, or a carboxamide group. In some embodiments, the melting point of the wax is in the range of 35°C to 65°C. The wax can be used, for example, to reduce the surface tack of the article. The polar functional groups can be used, for example, to cause the wax to precipitate onto the surface. The wax can be derived from, for example, fatty acids having at least 16, 18, or 20 carbon atoms. Examples of available waxes include ethylene bis-stearamide, erucamide, oleamide, and methyl 12-hydroxystearate. Examples of commercially available waxes having polar functional groups include waxes purchased under the trade names “PROAID” and “AKROWAX” from Akrochem Corporation, Akron, OH, Ohio. In some embodiments, the wax is present in an amount of at least 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% and / or no more than 10 wt%, 9 wt%, 8 wt%, 7 wt%, or 6 wt% based on the total weight of the thermoplastic elastomer composition. In some embodiments, the wax is present in an amount of 1 wt% to 10 wt%, 2 wt% to 8 wt%, 3 wt% to 7 wt%, or 4 wt% to 6 wt% based on the total weight of the thermoplastic elastomer composition. Combinations of two or more waxes are available.

[0061] In some embodiments, the thermoplastic elastomer compositions of this disclosure included in the articles of manufacture further comprise a polyolefin thermoplastic elastomer. This polyolefin thermoplastic elastomer may be a mixture of an olefin thermoplastic material and an elastomer (e.g., a non-crosslinked or crosslinked elastomer), or an olefin copolymer having at least one hard segment and a soft segment (in some embodiments, a block copolymer). Compositions comprising a thermoplastic polyolefin matrix and having an elastomer within the matrix are sometimes referred to as thermoplastic vulcanizates (TPVs). Examples include a polypropylene matrix having ethylene propylene diene monomer (EPDM) rubber within the matrix. Examples of dienes in EPDM include dicyclopentadiene, alkyldicyclopentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-heptadiene, 2-methyl-1,5-hexadiene, cyclooctadiene, 1,4-octadiene, 1,7-octadiene, 5-ethylidene-2-norbornene, 5-n-propylidene-2-norbornene, and 5-butylidene-2-norbornene. In some embodiments, the polyolefin thermoplastic elastomer is an olefin copolymer, and in some embodiments, a block copolymer. The hard segments of such copolymers may include polyethylene segments and polypropylene segments. The soft segments of such copolymers may include C4-C4 segments. 18 C5-C 12Or C6-C8 poly(1-olefin) segments. Examples of useful soft segments include those prepared from 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 1-octadecene. Polyolefin block copolymers are typically prepared via metallocene catalysis. Available polyolefin block copolymers include those available under the trade names “INFUSE” and “ENGAGE” from Dow Chemical (Midland, Michigan). Available thermoplastic vulcanizates include those available under the trade name “SANTOPRENE” from Celenase Corporation (Irving, Texas). Combinations of two or more polyolefin thermoplastic elastomers can be used in thermoplastic elastomer compositions.

[0062] In some embodiments, the thermoplastic elastomer composition comprises no more than 40 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, or no more than 10 wt% and / or at least 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% of polyolefin thermoplastic elastomer based on the total weight of the thermoplastic elastomer composition. In some embodiments, the thermoplastic elastomer composition comprises 0 wt% to 40 wt%, 1 wt% to 40 wt%, 2 wt% to 30 wt%, 5 wt% to 30 wt%, 0 wt% to 15 wt%, or 5 wt% to 15 wt% of polyolefin thermoplastic elastomer, wherein the weight percentages are based on the total weight of the thermoplastic elastomer composition.

[0063] In some embodiments, the thermoplastic elastomer composition further comprises a polyphenylene ether resin, which may also be referred to as a polyphenylene oxide resin. Combinations of two or more polyphenylene ether resins may be used in the thermoplastic elastomer composition. In some embodiments, the polyphenylene ether resin contains a repeating unit –[C6H5-O-]-. In some of these embodiments, hydrogen may be replaced by a halogen, an alkyl group, a haloalkyl group having at least two carbon atoms between the halogen atom and the phenyl nucleus, an alkoxy group, or a haloalkoxy group having at least two carbon atoms between the halogen atom and the phenyl nucleus. In some embodiments, the polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene ether). In some embodiments, the polyphenylene ether is poly(p-phenylene ether). In some embodiments, the number average molecular weight (M) of the polyphenylene ether resin is... nThe concentrations are 300 g / mol to 25,000 g / mol, 300 g / mol to 10,000 g / mol, 1,000 g / mol to 8,000 g / mol, or in some embodiments, less than, equal to, or greater than 1,000 g / mol, 1,200 g / mol, 1,500 g / mol, 1,700 g / mol, 2,000 g / mol, 2,500 g / mol, 3,000 g / mol, etc. The molecular weights are 0 g / mol, 3,500 g / mol, 4,000 g / mol, 4,500 g / mol, 5,000 g / mol, 5,500 g / mol, 6,000 g / mol, 6,500 g / mol, 7,000 g / mol, 7,500 g / mol, or 8,000 g / mol, 10,000 g / mol, 25,000 g / mol, or 50,000 g / mol. The number-average molecular weight is determined using gel permeation chromatography according to methods known to those skilled in the art. In some embodiments, the polyphenylene ether resin is present in the thermoplastic elastomer composition in amounts from 0% to 15% by weight, 1% to 10% by weight, 2% to 8% by weight, or 3% to 7% by weight, based on the total weight of the thermoplastic elastomer composition.

[0064] Polyphenylene ether resins can be prepared by any known method. Suitable preparation methods are described in U.S. Patent Nos. 3,306,874 (Hay); 3,306,875 (Hay); 3,257,357 (Stamatoff); and 3,257,358 (Stamatoff). Examples of suitable polyphenylene ether resins are commercially available under the trade names “NORYL SA90” and “NORYL SA120” from SABIC, Houston, TX, and under the trade name “STARAIR” from China Bluestar International Chemical Co., Ltd., Beijing, China.

[0065] Many additives may also be used in the thermoplastic elastomer compositions of this disclosure contained in the articles of this disclosure. Examples of such additives include antioxidants such as hindered phenols, amines, sulfur and phosphorus hydroperoxide decomposers, and butylated hydroxytoluene (BHT); fillers such as talc, zinc oxide, titanium dioxide, alumina, clay (e.g., kaolin), diatomaceous earth, wollastonite, glass, and silica (e.g., fumed silica) and calcium carbonate; pigments such as carbon black; activated carbon; thermally conductive particles; flame retardants; and foaming agents or hollow spheres. Fillers may have various sizes and shapes (e.g., fibers and nanoparticles of various materials). If desired, the thermoplastic elastomer compositions may also contain at least one of dyes, ultraviolet light absorbers, hindered amine light stabilizers, and heat stabilizers (e.g., sodium benzoate).

[0066] Magnetic fillers can be particularly important for applications related to gaskets in refrigerators and freezers. Various ferrite powders, such as magnesium ferrite, barium ferrite, and strontium ferrite, can be added to thermoplastic elastomer compositions. These fillers can be included to impart surface magnetic strength to the gasket, thereby maintaining the seal. The particles may have anisotropic shapes to orient themselves to a magnetic field during dispensing. An external magnetic field may be required after dispensing to align the particles, especially isotropic particles.

[0067] Foam is a porous material consisting of a network or chambers of gas segmented by a solid matrix. In some embodiments, the thermoplastic elastomer compositions and / or articles of this disclosure are foams. In some embodiments, the thermoplastic elastomer compositions and / or articles of this disclosure are not foams and / or do not contain a blowing agent or hollow spheres. In some embodiments, the thermoplastic elastomer compositions comprise hollow ceramic microspheres (e.g., glass bubbles), expandable polymer microspheres (e.g., expandable microspheres filled with pentane), gas cavities, or mixtures thereof. The term "ceramic" refers to glass, crystalline ceramics, glass ceramics, and combinations thereof. For example, physical or chemical blowing agents can be used to introduce gas cavities into the thermoplastic elastomer composition. Examples of suitable physical blowing agents include carbon dioxide, nitrogen, SF6, nitrous oxide, inert gases (e.g., argon, helium, or xenon), air (e.g., a nitrogen and oxygen blend), and combinations thereof. Examples of suitable chemical blowing agents include diazo compounds, sulfonyl hydrazides, tetrazolium, nitroso compounds, acylsulfonyl hydrazides, hydrazones, thiatriazoles, azides, sulfonyl azides, oxalates, thiatriazine dioxide, or any combination thereof. More specific examples of suitable chemical blowing agents include blends of sodium bicarbonate and citric acid, dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, 4,4'-oxybis(benzenesulfonyl hydrazide), azodicarbonamide (1,1'-azodicarbonamide), p-toluenesulfonylaminourea, 5-phenyltetrazole, 5-phenyltetrazole analogs, diisopropylhydrazine carboxylate, 5-phenyl-3,6-dihydro-1,3,4-oxadiazine-2-one, and sodium borohydride.

[0068] Examples of suitable hollow ceramic microspheres include glass bulbs sold as “3M GLASS BUBBLES” by 3M Company, Saint Paul, Minnesota, in grades K1, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S38XHS, S42HS, S42XHS, S60, S60HS, iM30K, iM16K, XLD3000, XLD6000, and G-65, as well as any of the HGS series of “3M GLASS BUBBLES”; and those sold under the trade name “Q-CEL HOLLOW”. Glass bulbs (e.g., grades 30, 6014, 6019, 6028, 6036, 6042, 6048, 5019, 5023, and 5028) sold by Potters Industries, Carlstadt, NJ; and hollow glass pellets sold by Silbrico Corp., Hodgkins, IL under the trade name “SIL-CELL” (e.g., grades SIL 35 / 34, SIL-32, SIL-42, and SIL-43) by Silbrico Corp., Hodgkins, IL. Examples of suitable expandable microspheres include those that may be purchased under the trade name “MATSUMOTO MICROSPHERE F-2800D” from Matsumoto Yushi Seiyaku Co., Ltd., Osaka, Japan; those that may be purchased under the trade name “DUALITE U010-185D” from Chase Corporation, Westwood, MA; those that may be purchased under the names “F30D”, “F80SD”, and “F100D” from Pierce Stevens (Buffalo, NY); and those that may be purchased under the trade names “EXPANCEL 551”, “EXPANCEL 461”, “EXPANCEL 091”, and “EXPANCEL 930” from AkzoNobel (Sundsvall, Sweden). Each of these microspheres is characterized by a polymer shell.

[0069] In some embodiments, the thermoplastic elastomer composition comprises thermally conductive particles. The thermally conductive particles may be of a single type (i.e., the composition) or may include multiple (i.e., more than one) different types of thermally conductive particles. Furthermore, the thermally conductive particles may have a single distribution of particle size (i.e., a unimodal size distribution). Alternatively, the thermally conductive particles may have a multimodal size distribution. For example, the thermally conductive particles may have a bimodal or trimodal size distribution. A multimodal size distribution may be generated by a mixture of different types of thermally conductive particles with different sizes, a mixture of the same type of thermally conductive particles with different sizes, or both.

[0070] Examples of available thermally conductive particles include those made of or containing the following materials: diamond, polycrystalline diamond, silicon carbide, silicon nitride, aluminum oxide, boron nitride (hexagonal or cubic), boron carbide, silica (silicon dioxide), graphite, amorphous carbon, aluminum nitride, aluminum hydroxide (e.g., aluminum hydroxide (ATH)), aluminum, aluminum silicate, zinc oxide, zirconium oxide, tin oxide, copper oxide, chromium oxide, titanium oxide, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium carbonate, barium titanate, carbon nanotubes, carbon black, carbon fiber, clay, nickel, tungsten, copper, silver, gold, nickel, platinum, and any combination of these materials.

[0071] In some embodiments, the thermoplastic elastomer compositions of this disclosure included in the articles of manufacture of this disclosure further comprise flame retardants. Examples of flame-retardant particles include phosphorus-containing compounds, nitrogen-containing polymers, boron-containing compounds, antimony oxide, magnesia / hydrothermalon blends, wollastonite, glass frits (e.g., as disclosed in U.S. Patent No. 4,879,066 (Crompton)), and mixtures thereof. As used herein, the term "phosphorus-containing flame retardant" means that the flame retardant contains at least one phosphorus atom. As used herein, the term "nitrogen-containing polymer" means that the polymer contains at least one nitrogen atom. Other refractory compounds that may be used in thermoplastic elastomer compositions include endothermic particles (aluminum hydroxide (i.e., aluminum trihydrate, Al(OH)3) and magnesium hydroxide (i.e., Mg(OH)2)) and intumescent compounds (e.g., intumescent graphite).

[0072] When present, any of the above-mentioned additives may be included in the thermoplastic elastomer composition in any suitable amount, for example, up to 30% by weight, up to 25% by weight, or up to 20% by weight, based on the total weight of the thermoplastic elastomer composition. In some embodiments, fillers, thermally conductive particles, or hollow spheres may be present in an amount of at least 1% by weight or at least 3% by weight, or in an amount ranging from 2% to 30% by weight, 2% to 20% by weight, or 2% to 15% by weight, based on the total weight of the thermoplastic elastomer composition. Antioxidants and pigments may be present in the thermoplastic elastomer composition in an amount of at least 0.1% by weight or at least 0.5% by weight, or in an amount ranging from 0.1% to 5% by weight, 0.5% to 4% by weight, or 0.5% to 3% by weight, based on the total weight of the thermoplastic elastomer composition.

[0073] In some embodiments, the thermoplastic elastomer composition of this disclosure included in the articles of manufacture has a Shore A hardness of not more than 60, as measured using a hardness tester according to the method described in the following examples. In some embodiments, the thermoplastic elastomer composition has a Shore A hardness of not more than 55, 50, 45, 40, or 35 and / or at least 20, 25, or 30. Shore A hardnesses within these ranges generally allow the thermoplastic elastomer composition to be used well as a seal. Such hardness can be achieved in the thermoplastic elastomer composition even in the absence of gas cavities, for example when the composition is not a foam.

[0074] In some embodiments, the thermoplastic elastomer composition included in the articles of this disclosure has a complex melt viscosity, measured on a rheometer at a temperature of 1 radians / second at a shear rate of 1 radian / second at a temperature of 175°C, as described in the examples below, ranging from 4,000 Pascal-second (Pa-s), and in some embodiments from 4,000 Pa-s to 25,000 Pa-s or up to 20,000 Pa-s. Melt viscosities within these ranges allow the thermoplastic elastomer composition to retain its shape once it leaves the extrusion die, and also conform to and reshape corners and curves. Furthermore, melt viscosities within these ranges allow for good throughput and are suitable for a variety of dies.

[0075] In some embodiments, the thermoplastic elastomer compositions and / or articles of this disclosure are substantially free of volatile organic solvents. Volatile organic solvents are typically those with boiling points up to 150°C at atmospheric pressure. Commonly used organic solvents include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, and cyclohexane), hydrocarbon solvents (e.g., benzene, toluene, xylene, and d-limonene); acyclic and cyclic ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, pentanone, hexanone, cyclopentanone, and cyclohexanone); ethers (e.g., diethyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, and tetrahydrofuran), esters (e.g., ethyl acetate and butyl acetate), sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone), halogenated solvents (e.g., methyl chloroform, 1,1,2-trichloro-1,2,2-trifluoroethane, trichloroethylene, and trifluorotoluene), and alcohol solvents (e.g., methanol, ethanol, or propanol (such as isopropanol)). Thermoplastic elastomer compositions and / or articles may be substantially free of any of these solvents. "Substantially free of volatile organic solvents" means that volatile organic solvents may be present in an amount of up to 2.5% by weight (in some embodiments, up to 2% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight, or 0.00% by weight) based on the total weight of the adhesive (e.g., from previous synthesis steps or in commercially available components).

[0076] In some embodiments, the articles of this disclosure further comprise a PSA. In some embodiments, the thermoplastic elastomer composition has a surface in direct contact with the PSA. The articles of this disclosure may have more than one layer of thermoplastic elastomer and / or more than one layer of PSA. However, the article may have only one layer of thermoplastic elastomer composition in direct contact with a single layer of PSA. In some embodiments, the thermoplastic elastomer composition is co-extruded with the PSA. PSA is generally known to have the following desirable properties: (1) strong and durable adhesion, (2) adhesion with pressure not exceeding finger pressure, (3) sufficient ability to remain on the adherend, and generally (4) sufficient cohesive strength for clean removal from the adherend. Materials found to be well-suited for use as PSA are polymers designed and formulated to exhibit the desired viscoelasticity, thereby achieving a desired balance of adhesive strength, peel adhesion, and shear retention. The Dahlquist standard is commonly used to describe such properties of PSA. The PSA's Dahlquist standard states that when an oscillating strain of 1 Hz is applied in the linear viscoelastic region of the PSA at 25°C, the shear storage modulus G' should not exceed 0.3 MPa.

[0077] PSA can be made from a variety of different chemicals, including styrene block copolymers, (meth)acrylic acid, (meth)acrylic acid block copolymers, natural rubber, styrene-butadiene rubber, butyl rubber, polyisobutylene, ethylene-vinyl acetate, amorphous poly(α-olefin), siloxane, polyvinyl ether, polyisoprene, polybutadiene, butadiene-acrylonitrile rubber, polychloroprene, polyurethane, polyvinylpyrrolidone, or combinations thereof.

[0078] In some embodiments, the PSA comprises a styrene block copolymer. The PSA composition may comprise a single block copolymer or a mixture of two or more block copolymers. The styrene block copolymer may have any of the characteristics described above in conjunction with the thermoplastic elastomer composition in any of its embodiments. Additionally, each rubbery block in the block copolymer may be a polymer of a conjugated diene, a hydrogenated derivative of a polymerized conjugated diene, or a combination thereof. Conjugated dienes typically contain 4 to 12 carbon atoms. Examples of usable conjugated dienes include butadiene, isoprene, 2-ethylbutadiene, 1-phenylbutadiene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 3-ethyl-1,3-hexadiene, and combinations thereof. Each rubbery block may be a homopolymer or a copolymer. In some embodiments, the rubbery block comprises at least one of poly(butadiene), poly(isoprene), poly(2-ethylbutadiene), poly(1-phenylbutadiene), poly(1,3-pentadiene), poly(1,3-hexadiene), poly(2,3-dimethyl-1,3-butadiene), poly(3-ethyl-1,3-hexadiene), poly(ethylene / propylene), poly(ethylene / butene), or poly(isoprene / butadiene). In some embodiments, the rubbery block comprises at least one of polybutadiene, polyisoprene, poly(isoprene / butadiene), poly(ethylene / butene), poly(ethylene / propylene), or polyisobutylene. In some embodiments, the rubbery block comprises poly(ethylene / butene).

[0079] In some embodiments of PSA, the block copolymer includes at least one of a polystyrene-containing diblock copolymer, a polystyrene-containing triblock copolymer, or a polystyrene-containing star-shaped block copolymer, wherein each of the polystyrene-containing diblock copolymer, polystyrene-containing triblock copolymer, and polystyrene-containing star-shaped block copolymer independently comprises a block of at least one of polyisoprene, polybutadiene, poly(ethylene / propylene), poly(ethylene / butene), or polyisobutylene. In some embodiments, the block copolymer includes at least one of a polystyrene-containing diblock copolymer, a polystyrene-containing triblock copolymer, or a polystyrene-containing star-shaped block copolymer, wherein each of the polystyrene-containing diblock copolymer, polystyrene-containing triblock copolymer, and polystyrene-containing star-shaped block copolymer independently comprises a block of at least one of polyisoprene or polybutadiene. In some embodiments, the block copolymer includes at least one of a styrene-isoprene-styrene triblock copolymer or a styrene-butadiene-styrene triblock copolymer.

[0080] Suitable materials, used alone or in combination as block copolymers, are available, for example, under the trade name KRATON (e.g., KRATOND1161P, D1118, D1119, and A1535) from Kraton Performance Polymers, Inc. (Houston, Texas, USA); under the trade name SOLPRENE (e.g., SOLPRENE S-1205) from Dynasol (Houston, Texas, USA); under the trade name QUINTAC from Zeon Chemicals (Louisville, KY, USA); and under the trade names VECTOR and TAIPOL from TSRC Corporation (New Orleans, Louisiana, USA).

[0081] In some embodiments of the articles of manufacture disclosed herein, the PSA may comprise a tackifying resin. When the PSA is based on a styrene block copolymer, it typically comprises a tackifying resin. Tackifiers are different from plasticizers, as will be understood by those skilled in the art. Generally, the difference between tackifiers and plasticizers is that adding a tackifier increases the TT of the rubber phase of the adhesive. g Adding plasticizers will reduce the T of the rubber phase of the adhesive. g .

[0082] In some embodiments, the tackifying resin comprises at least one of the following: polyterpenes (e.g., those based on α-pinene, β-pinene, or limonene), terpene phenolic tackifiers, aromatic modified terpene resins, rosin acids, rosin esters, aliphatic hydrocarbon resins (e.g., those based on cis- or trans-pentadiene, isoprene, 2-methyl-but-2-ene, cyclopentadiene, dicyclopentadiene, or combinations thereof), aromatic resins (e.g., those based on styrene, α-methylstyrene, methylindene, indene, coumarone, or combinations thereof), or mixtures of aliphatic-aromatic hydrocarbon resins. The aromatic hydrocarbon resin may be a C9 type petroleum resin obtained by copolymerizing the C9 fraction produced from the thermal decomposition of naphtha, and the aliphatic hydrocarbon resin may be a C5 type petroleum resin obtained by copolymerizing the C5 fraction produced from the thermal decomposition of naphtha. The mixed aliphatic / aromatic resins can be C5 / C9 type petroleum resins obtained by polymerizing a combination of C5 and C9 fractions produced from the thermal decomposition of naphtha. Any of these tackifying resins can be hydrogenated (e.g., partially or completely). The term rosin, as used herein, includes: refined or unrefined natural rosin (refined rosin will typically contain about 90% by weight of rosin acid and about 10% by weight of inert matter), such as pine resin from logs, natural gum rosin, and tall oil rosin; refined or unrefined modified rosin, such as disproportionated rosin, hydrogenated rosin, and polymerized rosin; and pure or substantially pure acids comprising rosin, alone or in mixtures. In some embodiments, the rosin includes rosin acid C... 19 H 29 COOH, in some embodiments, at least one of abietic acid, neoabietic acid, longleaf abietic acid, L-piperidine, piratic acid, or isopiratic acid. In some embodiments, the rosin includes dehydrogenated or hydrogenated abietic acids, such as dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid. The tackifying resin may also contain metal abirate (sometimes referred to in the art as metal resin salts). The metal abirate can be a metal salt (e.g., zinc, calcium, or magnesium) of any of the rosins described above.

[0083] In some embodiments, a tackifying resin compatible with the rubbery blocks of the thermoplastic elastomer block copolymer is selected. The compatibility of the tackifying resin with the rubbery blocks can be determined by measuring the effect of the tackifying resin on the glass transition temperature of the rubbery blocks. If the tackifying resin is compatible, it will typically increase the glass transition temperature of the rubbery blocks, as measured by differential scanning calorimetry or dynamic mechanical analysis. In some embodiments, the tackifying resin is a hydrocarbon tackifier, an aromatic-modified aliphatic tackifier, or a terpene tackifier.

[0084] Suitable tackifying resins are available commercially under the trade name “ARKON” from Arakawa Chemical Industries Co., Ltd. (Osaka, Japan); “ESCOREZ” from ExxonMobil Chemical Company (Spring, Texas); “REGALITE”, “REGALREZ” and “PICCOTAC” from Eastman Chemical (Kingsport, TN); “WINGTACK” from Cray Valley (Exton, PA); and other companies listed in the examples below.

[0085] In some embodiments, the PSA comprises a tackifying resin that is highly compatible with the styrene-terminated blocks of the block copolymer. Such aromatic resins include coumarone-indene resin, polyalphamethylstyrene, polystyrene resin, vinyltoluene-alpha-methylstyrene copolymer, polyindene resin, and polyphenylene ether resins such as unsubstituted polyphenylene ether resins and substituted polyphenylene ether resins (e.g., poly(2,6-dimethyl-1,4-phenyl) ether).

[0086] In some embodiments, the PSA comprises at least about 30% by weight and at most about 60% by weight of a tackifying resin based on the total weight of the PSA. In some embodiments, the tackifying resin is present in the range of 32% to 50% by weight, 34% to 48% by weight, 30% to 40% by weight, 35% to 50% by weight, or 35% to 55% by weight based on the total weight of the PSA.

[0087] Various additives may also be used in the PSA of the articles of this disclosure. Examples, if desired, include antioxidants, inorganic fillers, plasticizers, pigments, dyes, UV absorbers, hindered amine light stabilizers, and heat stabilizers (e.g., sodium benzoate) as described above in any of its embodiments. When present, antioxidants are typically present in the PSA at an amount of 0.1 to 5 parts by weight per 100 parts by weight of the block copolymer; UV absorbers are typically present in the PSA at an amount of 0.1 to 3 parts by weight per 100 parts by weight of the block copolymer; inorganic fillers may be present in the PSA at an amount of up to 50 parts by weight per 100 parts by weight of the block copolymer; and plasticizers may be present in the composition at an amount of 1% to 30%, 20%, 15%, or 10% by weight of the total PSA weight.

[0088] In some embodiments, the articles of this disclosure comprising the thermoplastic elastomer compositions described above in any of its embodiments are filaments. The PSA as described above may also be provided in the form of filaments. In some embodiments, the filaments have a relatively narrow diameter, and in some embodiments, the average diameter is 1 mm or greater, 2 mm or greater, 3 mm or greater, 4 mm or greater, or 5 mm or greater, and 20 mm or less, 18 mm or less, 15 mm or less, 12 mm or less, or any combination of these diameters. In some embodiments, the filaments may have an average diameter of 1 mm to 20 mm, 5 mm to 15 mm, 8 mm to 12 mm, or 10 mm.

[0089] In some embodiments, the filament has a length-to-diameter ratio of 50:1 or greater, 100:1 or greater, or 250:1 or greater. Filaments having a length of at least about 20 feet (6 meters) can be used in the methods according to this disclosure. Depending on the application using the filament, a relatively consistent diameter along its length may be desirable. In some embodiments, the filament includes a maximum diameter variation of 20% over a length of 50 centimeters (cm), or a maximum diameter variation of 15% over a length of 50 centimeters. In some embodiments, the filament has a cylindrical shape, i.e., the filament is in the shape or form of a cylinder.

[0090] In some embodiments of the articles of manufacture disclosed herein, the articles comprise core-sheath filaments. The core comprises the thermoplastic elastomer composition described above in any of its embodiments, and the sheath comprises a composition different from the core, which in some embodiments is a polyolefin. In some embodiments, the sheath exhibits a melt flow index (MFI) of less than 15 g / 10 min. Typically, the sheath is non-sticky. Reference Figure 1 A schematic exploded perspective view of a segment of a core-sheath filament 100 is provided, the core-sheath filament comprising a core 102 and a sheath 104 enclosing the outer surface 106 of the core 102. In some embodiments, the article of this disclosure is a filament wound on a spool, for example for storage.

[0091] The PSA used in practicing this disclosure can also be provided as a core-sheath filament, wherein the core comprises the PSA described above in any of its embodiments, and the sheath comprises a generally non-adhesive composition. Core-sheath filaments comprising a PSA core can also be wound on a spool.

[0092] Filaments according to this disclosure and / or some embodiments of the methods applicable to practicing this disclosure are typically prepared using techniques known in the art for preparing filaments. Filaments can be prepared by extrusion through a die (such as a coaxial die) to form a core-skin structure. The optional additives described above can be added to a thermoplastic elastomer composition in an extruder equipped with a side-filler (e.g., a twin-screw extruder), which allows the inclusion of additives. Similarly, optional additives can be added to a skin composition in an extruder. The core can be extruded through a central layer of a coaxial die having a suitable diameter, while the skin can be extruded through an outer layer of the coaxial die. Typically, the central layer is circular or elliptical in shape, and the outer layer is concentrically shaped about the central layer. A suitable die is a filament spinning die as described in U.S. Patent No. 7,773,834 (Ouderkirk et al.). Optionally, the strand can be cooled using a water bath during extrusion. A belt traction machine can be used to lengthen the filament. The speed of the belt traction machine can be adjusted to achieve the desired filament diameter.

[0093] The core typically comprises 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 97% or less, 94% or less, 90% or less, 85% or less, 80% or less, 70% or less, or 65% or less, or any combination of these weight percentages. In some embodiments, the core comprises 50% to 97% of the core-sheath filament, 60% to 90% of the core-sheath filament, 70% to 90% of the core-sheath filament, 50% to 70% of the core-sheath filament, or 80% to 97% of the core-sheath filament.

[0094] Without being bound by theory, it is believed that the overall final material properties of core-sheath filaments with a thermoplastic elastomer composition as the core will exhibit viscoelasticity; that is, stress relaxation over time.

[0095] The skin can provide structural integrity to the core-skin filament and limit the core's contact with itself or other surfaces. The presence of the skin generally does not adversely affect the final material properties, either because it is thin enough to contribute a relatively small amount of material to the core material or because it is formed from a material that is a component of the core thermoplastic elastomer composition. The skin can advantageously be thick enough to support the filament shape factor and allow the core-skin filament to be delivered to the deposition site. In some embodiments, the desired property of the skin material is its ability to retain energy under static load, thus exhibiting minimal stress dissipation over time. Low MFI and high tensile strength help prevent the core-skin filament from breaking under high inertial forces, such as when the core-skin begins to unwind.

[0096] In some embodiments of the thermoplastic elastomer composition or PSA filament, the sheath comprises a polyolefin (e.g., a polyethylene homopolymer, a polyvinyl copolymer, a polypropylene homopolymer, or a polypropylene copolymer). In some embodiments, the sheath material exhibits an MFI of less than 15 g / 10 min. This low melt flow index indicates that the sheath material has sufficient strength to allow the core-sheath filament to withstand the physical manipulation required for handling. For example, the core-sheath filament may need to be unwound from a spool, introduced into the equipment, and advanced into a nozzle for melting, all without causing the core-sheath filament to break. In some embodiments, the leather material exhibits an MFI of 14 g / 10 min or less, 13 g / 10 min or less, 11 g / 10 min or less, 10 g / 10 min or less, 8 g / 10 min or less, 7 g / 10 min or less, 6 g / 10 min or less, 5 g / 10 min or less, 4 g / 10 min or less, 3 g / 10 min or less, 2 g / 10 min or less, or 1 g / 10 min or less. In some embodiments, the leather material is non-adhesive. If the material passes a “self-adhesion test,” it is considered non-adhesive, in which the force required to peel the material from itself is equal to or less than a predetermined maximum threshold amount without causing the material to crack. The self-adhesion test is described in U.S. Patent Application Publication No. 2022-0259465 (Kugel et al.). Using a non-adhesive leather is advantageous for handling filaments.

[0097] In some embodiments, the skin material exhibits a combination of at least two of the following: low MFI (e.g., less than 15 g / 10 min), moderate elongation at break (e.g., 100% or higher as determined by ASTM D638-14 using test sample type IV), low tensile stress at break (e.g., 10 MPa or more as determined by ASTM D638-14 using test sample type IV), or moderate Shore D hardness (e.g., 30-70 as determined by ASTM D2240-15).

[0098] In some embodiments, the skin comprises at least one of a styrene block copolymer, a polyolefin, ethylene vinyl acetate, a polyurethane, or a styrene-butadiene copolymer. In some embodiments, the skin comprises any of these materials as a main component (e.g., the skin may also comprise one or more additives). Examples of suitable styrene block copolymers and styrene-butadiene copolymers are described in detail above with respect to the core. Suitable polyolefins are not particularly limited. Examples of suitable polyolefin resins include polypropylene (e.g., polypropylene homopolymers, polypropylene copolymers, and / or blends containing polypropylene), polyethylene (e.g., polyethylene homopolymers, polyethylene copolymers, high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE)), and combinations thereof. For example, suitable commercially available LDPE resins include “PETROTHENE NA217000” available from LyondellBasell (Rotterdam, Netherlands) and “MARLEX 1122” available from ChevronPhillips (Woodlands, TX).

[0099] As used herein, the term "polyurethane" applies to polymers made from the reaction products of compounds containing at least two isocyanate groups (-N=C=O), referred to herein as "isocyanates," with compounds containing at least two groups containing active hydrogen. Examples of groups containing active hydrogen include primary alcohols, secondary alcohols, phenols, and water. Other groups containing active hydrogen include primary and secondary amines, which react with isocyanates to form urea bonds, thereby preparing polyureas. A variety of isocyanate-terminated materials and suitable co-reactants are well known, and many are commercially available (see, for example, Gunter Oertel, "Polyurethane Handbook", Hanser Publishers, Munich (1985)). Suitable commercially available thermoplastic polyurethanes for the sheath of core-skin filaments include those purchased from Lubrizol Corporation (Wickliffe, OH) under the trade names “ESTANE 58213” and “ESTANE ALR 87A”.

[0100] Suitable ethylene vinyl acetate (EVA) polymers (i.e., copolymers of ethylene and vinyl acetate) for use in leather include resins available under the trade name “ELVAX” from DuPont (Wilmington, DE). Typical vinyl acetate contents range from 9% to 40% by weight and melt flow index as low as 0.03 g / min (according to ASTM D1238). Suitable EVAs also include high vinyl acetate ethylene copolymers available under the trade name “ULTRATHENE” from LyondellBasell (Houston, TX). Typical vinyl acetate contents range from 12% to 18% by weight. Suitable EVAs also include EVA copolymers available under the trade name “ATEVA” from Celanese Corporation (Dallas, TX). Typical vinyl acetate contents range from 2% to 26% by weight.

[0101] In some embodiments, the skin comprises one or more polymers from the aforementioned thermoplastic elastomer compositions. For example, the skin may comprise styrene block copolymers, polyolefin thermoplastic elastomers, or combinations thereof. The skin may also contain additives of the thermoplastic elastomer compositions described above in any of its embodiments. If the polymer used for the skin is not a polymer in the thermoplastic elastomer composition, the polymer may be included in a low weight percentage of the total core-skin filaments to minimize interference with the properties of the thermoplastic elastomer composition. Similarly, when PSA is provided as a core-skin filament for use in the methods of this disclosure, the skin may comprise one or more polymers from the aforementioned PSA compositions. If the polymer used for the skin is not a polymer in the PSA composition, the polymer may be included in a low weight percentage of the total core-skin filaments to minimize interference with the adhesive properties of the PSA.

[0102] In some embodiments, the sheath comprises 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12% or more, 13% or less, 20% or less, 18% or less, 16% or less, 14% or less, 12% or less, 10% or less, or 8% or less, or any combination of these amounts. In some embodiments, the sheath may be present in amounts from 3% to 20% of the core-sheath filaments, from 4% to 20% of the core-sheath filaments, from 4% to 14% of the core-sheath filaments, from 4% to 10% of the core-sheath filaments, or from 3% to 7% of the core-sheath filaments.

[0103] Other examples of PSA that can be used in articles of this disclosure and as an adhesive provided as a core-sheath filament are described in U.S. Patent Application Publication Nos. 2023 / 0089703 (Kalish et al.), 2022 / 0290335 (Behling et al.), 2022 / 0290334 (Sahni et al.), 2022 / 0259465 (Kugel et al.), and 2022 / 0134652 (Napierala et al.) and International Patent Application Publication No. WO 2021 / 130620 (Sahni et al.).

[0104] Once the core-sheath filaments are melted and mixed, the advantages provided by preparing or using at least one of the thermoplastic elastomer compositions or PSAs as core-sheath filaments include one or more of the following: low volatile organic compound (VOC) properties, avoidance of die-cutting, design flexibility, ability to achieve complex non-planar bonding patterns, printing on thin and / or fine substrates, and printing on irregular and / or complex morphological features.

[0105] In some embodiments, the articles of this disclosure comprising the thermoplastic elastomer compositions described above in any of its embodiments are gaskets. Gaskets can be used in automotive, construction, and industrial applications, such as for filling and sealing gaps in irregularly shaped openings commonly found in appliances and / or automotive parts. Gaskets can be used in the automotive industry, for example as sunroof seals, drip tray seals, radiator seals, trunk seals, clamp protection seals, clamping protection seals, rear window seals, or headlight seals. Gaskets can also be used as gaskets for, for example, refrigerator doors, ovens, washing machines, dryers, dishwashers, or freezers.

[0106] This disclosure provides a method for preparing articles of this disclosure. The method includes extruding a thermoplastic elastomer composition. In some embodiments, the method includes co-extruding the thermoplastic elastomer composition and a pressure-sensitive adhesive; in some embodiments, it includes direct co-extrusion onto a substrate.

[0107] For the purposes of this disclosure, co-extrusion means the simultaneous melting and processing of multiple melt flows, and the combination of such melt flows, for example, from a single extrusion die into a single integrated structure. Thermoplastic elastomer compositions and PSA can be co-extruded using any suitable type of co-extrusion die. In some embodiments, multilayer melt flows may be formed by multilayer feed heads, such as the multilayer feed head shown in U.S. Patent No. 4,839,131 (Cloeren) or other specialized feed heads or dies, such as those manufactured by Cloeren Co., Orange, TX. The feed heads and dies used are typically heated to promote polymer flow and layer adhesion, with the die temperature depending on the polymer used. Co-extrusion technology is available in numerous polymer processing references, including Progelhof, RC and Throne, JL, “Polymer Engineering Principles,” Hanser / Gardner Publications, Inc., Cincinnati, Ohio, 1993.

[0108] Compatible chemicals in the co-extruded layer can lead to interfacial diffusion. Such interlayer diffusion has not been observed in the laminated layer. In embodiments of the co-extruded thermoplastic elastomer composition and PSA, the polymer compositions used for each can be selected to have similar properties, such as chemical structure and melt viscosity. Compatibility between the thermoplastic elastomer composition and PSA can improve interlayer adhesion during co-extrusion.

[0109] The advantages gained from co-extruding thermoplastic elastomer compositions and PSAs include excellent sealing and bonding strength properties, as well as process simplification and automation. Conventional gaskets consist of high-hardness rubber or mechanical attachments and a lower-hardness material for the seal. This complexity is avoided by the co-extruded thermoplastic elastomer compositions and PSAs disclosed herein, which exhibit strong interlaminar adhesion, as illustrated in the following examples. Therefore, the high-hardness portion of the seal can be omitted without issue, thereby simplifying the process and seal construction.

[0110] In some embodiments of the method disclosed herein, the method includes forming a core-sheath filament as described above. The method also includes melting the core-sheath filament and blending the sheath with the core to form a molten composition. This molten composition may be formed before reaching the nozzle, for example, by mixing in the nozzle, or by forming during dispensing through the nozzle, or a combination thereof. The sheath composition may be uniformly blended throughout the core composition.

[0111] A suitable method for utilizing core-sheath filaments as described above employs a continuous, non-pumped filament feed distribution unit. In such a distribution unit, the distribution throughput is adjusted by a linear feed rate of the core-sheath filaments allowed to enter the distribution head. In some embodiments, the unheated filaments are mechanically pushed into the heating zone, which provides sufficient force to expel the filaments from the nozzle. A variation of this method incorporates a conveyor screw within the heating zone, which is used to pull the filaments from the spool and also to create pressure to distribute the material through the nozzle. The conveyor screw allows for increased throughput and provides opportunities to mix and / or blend components at desired levels.

[0112] Compared to traditional thermomelt deposition methods, filament feed distribution methods offer several advantages. First, filament feed distribution methods typically allow for faster changeovers to different materials. Furthermore, these methods avoid the semi-batch mode used with melt tanks, minimizing the chance of material thermal degradation and associated defects in the deposited material. Filament feed distribution methods can utilize materials with higher melt viscosities, providing thermoplastic beads that can be deposited with greater geometric accuracy and stability without separate curing or crosslinking steps. Additionally, the higher permissible melt viscosity allows for the use of higher molecular weight raw materials within the binder.

[0113] Deposition systems with various extruder types are commercially available, including single-screw extruders, twin-screw extruders, hot-end extruders (e.g., for filament feeding systems), and direct-drive hot-end extruders (e.g., for elastomer filament feeding systems). The deposition systems may also have different motion types for material deposition, including the use of XYZ tables, gantry cranes, and robotic arms.

[0114] Typically, gasket seals are manufactured in one location with non-customized lengths and shapes, and then manually applied in a manufacturing assembly plant. The method disclosed herein provides a gasket and adhesive that are directly produced and bonded to a substrate in a single step in a manufacturing workshop. Directly co-extruded the pressure-sensitive adhesive and thermoplastic elastomer onto the substrate allows for a more desirable adhesive bond between the thermoplastic elastomer and the adhesive. Another potential advantage of directly co-extruded the pressure-sensitive adhesive and thermoplastic elastomer onto the substrate is that the thermoplastic article can be naturally shaped into irregular shapes (e.g., corners or sharp edges), which would otherwise not be desirable to manufacture independently. Furthermore, customized lengths and shapes of such gasket seals can be produced, particularly gasket seals that include desired radii or curves in continuous lengths of gaskets directly adhered to a workpiece or substrate. The method of co-extruded the pressure-sensitive adhesive and thermoplastic elastomer onto the substrate can include a variety of features designed to improve manufacturing efficiency and gasket effectiveness in unique applications.

[0115] In some implementation schemes, the use of Figures 2 to 14The apparatus shown co-extrudes thermoplastic elastomer compositions and pressure-sensitive adhesives. Figure 2 It shows a device for receiving, melting, mixing and dispensing. Figure 1 A dispensing head 150 is configured for core-sheath filament 100. The dispensing head 150 includes a barrel 152 and a rotatable screw 154 received therein. A gearbox 156 and a motor 158 are operatively coupled to the screw 154, and a possibly motorized alignment wheel 160 is attached to one side of the barrel 152 through which the filament is guided into the dispensing head 150. Further details regarding each of these components are as follows.

[0116] The barrel 152 has a configuration for use in a single-screw extruder. The barrel 152 has a cylindrical inner surface 170 and engages the screw 154 in a circumferential relationship. The inner surface 170 terminates in an outlet 172 at the distal end of the barrel 152. The outlet 172 is generally circular, but may also be rectangular or have any other suitable shape. The barrel 152 includes one or more embedded heating elements (not visible) for heating the inner surface 170 and melting the filament during dispensing operations. Optionally, the inner surface 170 of the barrel 152 may be grooved or otherwise textured to increase friction between the barrel 152 and the extruded material.

[0117] Refer again Figure 2 Inlet 174 extends through the top side of the barrel for receiving filaments. As further shown, inlet 174 includes a front sidewall 176 that defines a skewed roller gap where the front sidewall 176 converges with the outer surface of the screw 154. Advantageously, the skewed roller gap prevents the filaments from breaking as they are drawn into the barrel 152. The skewed roller gap is part of a robust feeding mechanism that allows the filaments to be continuously fed into the barrel 152 without operator intervention.

[0118] The drive mechanism for the dispenser head 150 is provided by a gearbox 156 and a motor 158. In some embodiments, the dispenser head 150 includes controls that allow adjustment of the speed and / or torque of the rotatable screw 154. In some embodiments, the motor 158 is a servo motor. Servo motors are advantageous because they can provide high torque over a wide range of rotational speeds.

[0119] As shown in the figure, inlet 174 typically has an inverted funnel shape, wherein the cross-sectional area of ​​inlet 174 increases with increasing proximity to screw 154. Inlet 174 has one or more sidewalls, such as front sidewall 176 as shown in the figure. Front sidewall 176 may be planar or curved. When viewed in the transverse direction, at least a portion of front sidewall 176 extends at an acute angle relative to the longitudinal axis of screw 154. The acute angle favorable for feeding the filament adhesive may be 10 to 70 degrees, 18 to 43 degrees, 23 to 33 degrees, or in some embodiments, less than, equal to, or greater than 10 degrees, 13 degrees, 15 degrees, 17 degrees, 20 degrees, 22 degrees, 25 degrees, 27 degrees, 30 degrees, 32 degrees, 35 degrees, 37 degrees, 40 degrees, 42 degrees, 45 degrees, 47 degrees, 50 degrees, 53 degrees, 55 degrees, 57 degrees, 60 degrees, 65 degrees, or 70 degrees.

[0120] Figure 3 A top view of the barrel 152 is shown, revealing further details regarding the shape of the inlet 174. The inlet 174 includes an outer inlet 175 and a concealed surface extending from the outer inlet 175, shown in dashed lines. Figure 3 As can be seen, the front sidewall 176 is not planar, but has a complex composite curvature. The curved surface of the inlet 174, including the front sidewall 176, collectively defines a recess in the inner surface 170 of the barrel 152 to accommodate the filament as it is fed. Generally, the inlet 174 may extend along 10% to 40%, 15% to 35%, 20% to 30% of the nominal screw length, or in some embodiments, less than, equal to, or greater than 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, or 40%.

[0121] Thus, the recess external to the inlet 174 can extend relative to the screw 154 in both the axial and circumferential directions. By providing space for the filament to move within the barrel 152, the recess reduces the likelihood that the threads of the rotatable screw 154 will cut the filament during operation of the dispensing head 150. This is inconvenient because filament breakage will interrupt the dispensing process and require the operator to manually reinsert the filament into the dispensing head 150 before restarting the process.

[0122] Figure 4 and Figure 5 The features of the screw 154 are shown in more detail. The screw 154 includes a shank 180 at one end for coupling to a drive mechanism. The shank 180 is connected to a shaft 182 having a diameter that gradually increases along its length. A helical thread 184 extends around the shaft 182 for conveying molten material in a forward direction as the screw 154 rotates within the barrel 152.

[0123] At the location adjacent to where the filament 100 is fed into the distribution head 150, a notch 188 is provided in the helical thread 184 to provide a gripping lug 186, as well as... Figure 5 As shown in the cross-sectional view, the gripping lug 186 provides an additional edge that helps to grip the continuous filament and actively feed it through the inlet 174 and into the barrel 152. This is significantly superior to feeding mechanisms that require pushing the filament into the feed zone, which can cause buckling and kinking of the filament. The gripping lug 186 may extend through 1% to 30%, 3% to 25%, 5% to 20% of the nominal screw length, or in some embodiments, less than, equal to, or greater than 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 25%, 27%, or 30%.

[0124] Located at the opposite ends of the screw 154 is a mixing segment 190. The mixing segment 190 includes multiple mixing elements, here cylindrical posts 192. However, the mixing segment 190 can... Figure 4 Other configurations not shown are represented. Other screw features that can be used as mixing elements include a grooved cylinder (as found in Maddock mixers), a densely threaded screw segment with a cross-cut (as found in Saxton mixers), or any of a variety of known column patterns, including those used in pineapple mixers. Optionally, a column or pin may be provided on the inner sidewall of the barrel 152 and facilitate the mixing process; if so, a cross-cut may be present in the threads of the screw 154 to avoid interference. Orifices may also be present for dispersing or distributing the composition within the barrel, and these orifices may also serve as mixing elements.

[0125] The length of the mixing segment 190 is not particularly limited and can depend on various factors, including the extruded composition and the filament feed rate. The mixing segment 190 can be 5% to 30%, 7% to 25%, 8% to 20% of the nominal screw length, or in some embodiments, less than, equal to, or greater than 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 25%, 27%, 30%, or 35%.

[0126] To effectively melt, mix, and distribute filaments within a relatively compact housing, the nominal screw length to screw diameter ratio may be 8:1 to 20:1, 9:1 to 17:1, 10:1 to 14:1, or in some embodiments, less than, equal to, or greater than 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, or 20:1.

[0127] The provided dispensing head 150 can exhibit significant throughput. In some embodiments, the dispensing head is capable of dispensing the composition at a throughput of at least 3 kg / hour, at least 4 kg / hour, at least 5 kg / hour, at least 6 kg / hour, at least 7 kg / hour, or at least 8 kg / hour.

[0128] Figure 6 A schematic diagram of a dispensing system 228 is shown, which includes a dispensing head 250 equipped with a mounting base for attachment to the end of a movable arm 230. The dispensing head 250 may have features similar to those of the dispensing head 150 described previously. The movable arm 230 is attached to a stage 232 and may have any number of joints to allow the dispensing head 250 to translate and rotate in up to six degrees of freedom. The movable arm 230 allows the dispensing head 250 to dispense the extruded composition precisely and reproducibly and over a wide range of positions relative to the stage 232.

[0129] The distribution system 228 further includes filaments 100 for continuous feeding into the distribution head 250, such as Figure 6 As shown. The filament 100 can be continuously unwound from the reel 236 as shown. It should be understood that the position of the reel 236 relative to other components of the distribution system 228 is not critical and can be installed in a convenient location. The reel 236 can be fixed to the table 232 or a structure on the table.

[0130] In various embodiments, the portion of the spool 236 that contacts the filament 100 may have structural features that facilitate the transport of the filament 100. For example, this portion of the spool 236 may include a spiked area, an adhesive surface, or any other feature that facilitates the unwinding of the filament 100. Although Figure 6 The filament 100 may be guided along a channel or conduit extending between the spool 236 and the dispensing head 250, but this channel or conduit may include a low-friction (e.g., fluoropolymer) surface to facilitate travel and prevent the filament 100 from twisting therein.

[0131] Figure 6The dispensing head 250 is shown dispensing the composition 238 in a hot-melt form onto the bonding surface of the substrate 240. The substrate 240 is not limited and can be, for example, an industrial part to be adhesively attached to an assembly. Alternatively, the substrate 240 can be mounted on a stage 232, thereby providing a spatial reference point for positioning the dispensing head 250. This can be particularly useful in automated processes using a controller to control the position and orientation of the dispensing head 250.

[0132] Figure 7 A front view of a co-extrusion dispensing system 500 for directly applying the pressure-sensitive adhesive (PSA) and thermoplastic elastomer (TPE) of this disclosure to a substrate is depicted, the co-extrusion dispensing system combining the addition of filament adhesive 100 and thermoplastic elastomer 314. Filament adhesive 100 is fed into an adhesive barrel 152, where it is converted into molten adhesive and ultimately applied through a co-extrusion dispensing head 150. The molten adhesive travels through an adhesive transfer tube 302 from an adhesive dispensing head 250 to a co-extrusion dispensing head 150. The co-extrusion dispensing head 150 is controlled by a movable arm 230. Thermoplastic elastomer 314 is fed into a thermoplastic elastomer dispensing head 312 and enters a co-extrusion dispensing head 304. The co-extrusion dispensing head 150 may contain various ports to aid processing, such as a heating cylinder 316, an air inlet 308, or a thermocouple channel 310. The co-extrusion dispensing head 150 may contain more or fewer additional ports, depending on the configuration of the head 150 and the desired gasket shape. Pressure-sensitive adhesive and thermoplastic elastomer are co-extruded from the dispensing head 150 onto the substrate 240. The co-extrusion dispensing head 150 includes a forming dispensing surface 292 for producing a gasket of the desired shape made of molten TPE and molten adhesive, as further described below. Air introduced into the system 500 is... Figure 8A The material is discharged through outlet 319. The co-extrusion dispensing head 150 may be movable relative to the substrate 240 (e.g., the head moves while the substrate remains stationary), or the substrate 240 may be movable relative to the dispensing head 150.

[0133] In some implementations, the thermoplastic elastomer 314 can be... Figure 2 The similar dispensing head 250 shown feeds into the co-extrusion dispensing head 150.

[0134] Depending on the desired product, multiple inlet ports for PSA and thermoplastic elastomers may be useful. The selected configuration can depend on the orientation and design characteristics of the final product. Similarly, the co-extrusion dispensing head 150 may include multiple heaters, air inlets, and temperature probes to increase the ability to process different types of PSA and thermoplastic elastomers that require different process conditions.

[0135] Figures 8A to 8F Explained for production Figure 9One embodiment of the co-extrusion dispensing head 150 for a molded thermoplastic article 400 (such as a gasket with PSA) is described in the figure. Figure 8E and Figure 8F It is along Figure 8B The image shows a cross-sectional view of the co-extrusion dispensing head 150, taken from line aa. The co-extrusion dispensing head 150 is configured to receive molten thermoplastic elastomer fed into the system 500 from the top of the head 150 via a thermoplastic elastomer inlet 330. The co-extrusion dispensing head 150 is also configured to receive molten pressure-sensitive adhesive fed into the system 500 from the side of the co-extrusion head 150 via an adhesive inlet 352. The pressure-sensitive adhesive and thermoplastic elastomer exit the dispensing surface 292a through a forming dispensing surface 322a that imparts its shape to the extruded thermoplastic article 400. In the illustrated embodiment, the forming dispensing surface 322 includes a lower extrusion lip 320 and an upper extrusion lip 324 to form a shape resembling the letter D and to... Figure 9 The hollow D-shaped article 400 is extruded onto the substrate 240. Air introduced into the system 500 is discharged from the air outlet 319. The lower dispensing lip 320 shapes the pressure-sensitive adhesive portion, while the upper dispensing lip 324 shapes the top of the thermoplastic elastomer portion. The two portions together form a composite article 400, which may be a gasket with PSA applied to... Figure 9 The substrate 240 is in the middle. The co-extrusion dispensing head 150 may contain an air inlet 308, a thermocouple channel 310, or a heating cylinder 316. The co-extrusion dispensing surface 326 may be perpendicular to the bottom edge 290a of the co-extrusion dispensing head 150, and the angle α shall not exceed 90 degrees.

[0136] Figure 8C A side view of the co-extrusion dispenser 150 is shown, with the thermocouple channel 310 and air inlet 308 shown in detail. In some other embodiments, the co-extrusion dispenser 150 may contain more or fewer ports.

[0137] Figure 8D This is a top view of the co-extrusion dispenser 150, in which thermoplastic elastomer is fed into the system 500. The thermoplastic elastomer inlet 330 contains a TPE channel 340 that keeps the TPE separate from the pressure-sensitive adhesive, which is fed through the co-extrusion dispenser 150 via another inlet.

[0138] Figure 8E and Figure 8FA cross-sectional view of the co-extrusion dispenser 150 is depicted, facilitating discussion of material flow through the co-extrusion dispenser 150. A thermoplastic elastomer inlet 330 is isolated from the incoming pressure-sensitive adhesive inlet 352 via a dedicated TPE channel 340, which in one embodiment has a length of at least 240 mm. The adhesive inlet 352 is similarly in fluid communication with the isolated adhesive channel 354. In another embodiment, the adhesive channel 354 has a length of at least 240 mm. The pressure-sensitive adhesive channel 354 and the TPE channel 340 are separated by a fluid barrier 356. In some embodiments, the fluid barrier 356 has a length of at least 240 mm. The length, width, and angle of the fluid barrier 356 may vary between designs based on the desired configuration of the co-extrusion dispenser 150. The pressure-sensitive adhesive and TPE are merged in a third channel (co-extrusion channel 358), where the PSA and TPE may be in fluid communication for at least 4 mm in length. In some embodiments, the co-extrusion channel 358 can maintain fluid communication between PSA and TPE of less than, equal to, or greater than 10 mm, 15 mm, and 17 mm. One advantage provided by the co-extrusion channel 358 is the strong adhesion between the PSA and TPE in the final gasket. An extruded article is formed when the co-extrusion channel 358 feeds the PSA and TPE through the forming distribution surface 322, the lower distribution lip 320, and the upper distribution lip 324. Air introduced into the co-extrusion distribution head 150 is discharged from the air outlet 319. In some embodiments, the forming distribution surface 322 may include various shapes or configurations of different sizes to form a desired article configuration.

[0139] In some embodiments of the co-extrusion dispenser 150, the co-extrusion channel 358 is configured to provide a desired amount of time for the PSA and TPE to contact the co-extrusion dispenser 150 prior to extrusion. The contact time between the PSA and TPE may be proportional to the extrusion dispensing rate, which may be at least 20 mm / s and no more than 60 mm / s. In some embodiments, at a dispensing rate of 20 mm / s and co-extrusion channel lengths of 4 mm, 10 mm, 15 mm, and 17 mm, the PSA and TPE are in fluid communication for 0.2 seconds, 0.5 seconds, 0.8 seconds, and 0.9 seconds, respectively. In some embodiments, at a dispensing rate of 60 mm / s and co-extrusion channel lengths of 4 mm, 10 mm, 15 mm, and 17 mm, the PSA and TPE are in fluid communication for 0.1 seconds, 0.2 seconds, 0.3 seconds, and 0.3 seconds, respectively.

[0140] Figure 9This diagram shows a perspective view of the two materials after a pressure-sensitive adhesive and a thermoplastic elastomer forming a TPE article 400 (in this case, a gasket with PSA) are co-extruded together onto a substrate 240. When the materials are co-extruded onto the substrate 240, the outer surface 403 and the inner surface 402, including a flat surface 410, are formed by the configuration shape of the forming surface 322a. A pressure-sensitive adhesive layer 404 is bonded to the flat outer surface opposite the flat inner surface 410 of the TPE article 400 and adheres to the substrate 240. The TPE article 400 can exhibit various curves and lengths depending on the desired application or gasket.

[0141] Figures 10A to 10F Explained for production Figure 11 Another embodiment of the co-extrusion dispensing head 300 of another molded thermoplastic article 400 (such as a gasket) described herein. Figure 10E and Figure 10F It is along Figure 10B The image shows a cross-sectional view of the co-extrusion dispensing head 300, taken from line bb.

[0142] The co-extrusion dispensing head 300 is configured to receive molten thermoplastic elastomer fed into the system 500 from the top of the co-extrusion dispensing head 300 through a thermoplastic elastomer inlet 330. The co-extrusion dispensing head 300 is also configured to receive molten pressure-sensitive adhesive fed into the system 500 from the side of the co-extrusion head 300 through an adhesive inlet 352. The pressure-sensitive adhesive and thermoplastic elastomer exit the dispensing surface 326 via a forming dispensing surface 322b that shapes the extruded article. A lower dispensing lip 320 shapes the pressure-sensitive adhesive layer, while an upper dispensing lip 324 shapes the top portion of the thermoplastic elastomer article. Additionally, a middle dispensing lip 325 forms the middle portion of the thermoplastic elastomer article. In the illustrated embodiment, the forming dispensing surface 322 includes a lower extrusion lip 320 and an upper extrusion lip 324 to form an intersecting circle shape and... Figure 11 The hollow article 400 is extruded onto the substrate 240. The lower dispensing lip 320 forms the pressure-sensitive adhesive portion, while the upper dispensing lip portions 325 and 324 form the intersecting circular portions of the thermoplastic elastomer. Together, they form the TPE article 400, which can be a gasket with PSA applied to... Figure 11 The substrate 240 is located within the co-extrusion dispenser 300. The co-extrusion dispenser 300 may include a thermocouple channel 310, an air inlet 308, or a heating element 316. The co-extrusion dispenser surface 326 may be at an angle β of 90 degrees relative to the bottom edge 290b of the co-extrusion dispenser 300. Air introduced into the system is discharged from the air outlet 319.

[0143] Figure 10CA side view of the co-extrusion dispenser 300 is shown, with the thermocouple channel 310 and air inlet 308 shown in detail. In some other embodiments, the co-extrusion dispenser 300 may contain more or fewer ports, for example, to accommodate additional material flow.

[0144] Figure 10D This is a top view of the co-extrusion dispenser 300, in which thermoplastic elastomer is fed into the system. The thermoplastic elastomer inlet 330 contains a TPE channel 340 that keeps the TPE separate from the pressure-sensitive adhesive, which is fed through the co-extrusion dispenser 300 via another inlet. Figure 10E and Figure 10F A cross-sectional view of the co-extrusion distributor 300 is depicted. The material flow rate, channel length, forming distribution surface, distribution lip, distribution rate, and fluid communication time through the co-extrusion distributor 150 are described above. Figure 8E and Figure 8F As stated above.

[0145] Figure 11 This diagram shows a perspective view of the two materials after the molten pressure-sensitive adhesive and the thermoplastic elastomer forming the alternative article 400 (in this case, a gasket with PSA) are co-extruded together onto the substrate 240. When the materials are co-extruded onto the substrate 240, the outer surfaces 403a, 403b, inner surfaces 402a, 402b, and flat surface 410 are formed by the configuration shape of the forming surface 322a. The pressure-sensitive adhesive layer 404 is bonded to the flat outer surface opposite the flat inner surface 410 of the TPE article 400 and adhered to the substrate 240. The thermoplastic article 400 can exhibit various curves and lengths depending on the desired application or gasket.

[0146] Figure 12 A perspective view of another embodiment of a co-extrusion distributor 380 is shown, which is commonly referred to as a "flat strip" co-extrusion distributor. The co-extrusion distributor 304 includes a dispensing surface 322a and a first outlet 323, the first outlet including a surface 292c having a semi-circular portion 426a, wherein a flat strip profile is co-extruded to form... Figure 13 Thermoplastic product 400 as described in the text.

[0147] Figure 13 A cross-sectional view of a flat strip article 400 is shown. TPE 430 and PSA 432 are co-extruded onto a substrate 240. In some embodiments, TPE 430 has a strip 426 to increase the ability to form a seal.

[0148] Figure 14Various gasket shapes envisioned to be formed by the co-extrusion head outlet are shown. Shallow D-shaped hollow profile is depicted at 450. Deep D-shaped hollow profile is depicted at 452. Stacked intersecting circular shapes are depicted at 454. Profile shapes are depicted at 456. Hollow L-shaped profiles are depicted at 458. Hollow shapes with top strips are depicted at 460. Flat strip shapes are depicted at 462.

[0149] Further details regarding suitable methods of using the thermoplastic elastomer compositions of the present invention are disclosed in patent application number PCT / IB2024 / 061804 entitled “Coextrusion Dispensing Head for Pressure Sensitive Adhesives and Thermoplastic Elastomers and Methods of Using the Same”, which has the same priority date as this application and is jointly owned by the same assignee as this application, and is incorporated herein by reference.

[0150] As described above, the methods disclosed herein may include directly co-extruded a thermoplastic elastomer composition and a pressure-sensitive adhesive onto a substrate. The substrate may contain any desired material. In some embodiments, the surface of the substrate comprises at least one of a metal (e.g., stainless steel or aluminum), a ceramic (e.g., glass), a polymer (e.g., plastic, rubber, thermoplastic elastomer, or thermosetting material), or a composite material. The composite material may be made of any two or more constituent materials with different physical or chemical properties. When components are combined to manufacture a composite material, materials with properties different from those of the individual components are typically obtained. Some examples of useful composite materials include fiber-reinforced polymers (e.g., carbon fiber-reinforced epoxy resins and glass-reinforced plastics); metal matrix compositions; and ceramic matrix composites. The surface of the substrate onto which the adhesive article is applied may include polymers such as polyolefins (polypropylene, polyethylene, high-density polyethylene, polypropylene blends), polyamide 6 (PA6), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), PC / ABS blends, polyvinyl chloride (PVC), polyamide (PA), polyurethane (PUR), thermoplastic elastomers (TPE), polyoxymethylene (POM), polystyrene (PS), acrylates (e.g., poly(meth)methyl acrylate (PMMA)), and combinations thereof. The surface of the substrate may also include a metallic coating on such polymers.

[0151] Before depositing the co-extruded thermoplastic elastomer composition and PSA onto the surface of the substrate, the substrate may be treated with one or more primers. The primer can be applied as a solvent-based liquid by any suitable method, including, for example, brushing, spraying, dipping, etc. In some embodiments, the substrate surface may be treated with one or more organic solvents (e.g., methyl ethyl ketone, aqueous isopropanol solution, acetone) prior to applying the primer.

[0152] In some embodiments, the article of this disclosure includes a release liner. In some embodiments, the thermoplastic elastomer composition has a surface in direct contact with the PSA, and the article of this disclosure further includes a release liner on the surface of the pressure-sensitive adhesive opposite to the thermoplastic elastomer composition. Various release liners can be used. In some embodiments, the release liner includes at least one of polyester film, polyethylene film, polypropylene film, polymer film coated with polyolefin, paper coated with polyolefin, polymer film coated with acrylic resin, and kraft paper coated with polymer. The polyolefin-coated film or paper may be a polyethylene-coated film or paper. In some embodiments, the release liner is coated on at least one main surface of a main surface having a release coating. In some embodiments, both main surfaces of the release liner are coated with a release coating. In this case, the release coating on each of the main surfaces of the release liner may be the same or different. Examples of materials that can be used as the release coating for the liner disclosed herein include acrylic resins, silicone, siloxanes, fluoropolymers, and polyurethanes. In some embodiments, the release coating is a silicone coating. In some embodiments, the thermoplastic elastomer composition and PSA can be co-extruded onto a release liner. An article comprising the thermoplastic elastomer composition and PSA can be removed from the liner and applied to another substrate, including any of those described above.

[0153] In some embodiments, articles comprising a thermoplastic elastomer composition and a PSA can be easily removed from a substrate by pulling the material away at a low angle. This removability is possible despite the high bond strength achieved between the article and the substrate because the tensile action transmits a very large force at the peel front. The stretchable peelability of the article from its substrate allows for end-of-life disassembly and recycling, which is advantageous.

[0154] Some implementation schemes disclosed herein

[0155] In a first embodiment, this disclosure provides a thermoplastic elastomer composition comprising a hydrogenated styrene block copolymer, a plasticizer having a number-average molecular weight of at least 2,000 g / mol, and a wax having polar functional groups. In a second embodiment, this disclosure provides a thermoplastic elastomer composition according to the first embodiment, wherein the polar functional group comprises at least one of a hydroxyl group, a carboxylic acid group, a carboxylic ester group, an amino group, or a carboxamide group. In a third embodiment, this disclosure provides a thermoplastic elastomer composition according to the first or second embodiment, wherein the wax has a melting point in the range of 35°C to 65°C. In a fourth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to third embodiments, wherein the wax is present in an amount of 1% to 10% by weight based on the total weight of the thermoplastic elastomer composition. In a fifth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to fourth embodiments, wherein the thermoplastic elastomer composition comprises 10% to 40% by weight of the hydrogenated styrene block copolymer based on the total weight of the thermoplastic elastomer composition. In a sixth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to fifth embodiments, wherein the hydrogenated styrene block copolymer is a styrene-ethylene / butene-styrene block copolymer. In a seventh embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to sixth embodiments, wherein the plasticizer is present in an amount of 10% to 45% by weight based on the total weight of the thermoplastic elastomer composition. In an eighth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to seventh embodiments, wherein the plasticizer is a hydrocarbon plasticizer. In a ninth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to eighth embodiments, wherein the plasticizer is a polybutene polymer.

[0156] In a tenth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to ninth embodiments, the thermoplastic elastomer composition further comprising a polyolefin thermoplastic elastomer. In an eleventh embodiment, this disclosure provides a thermoplastic elastomer composition according to the tenth embodiment, wherein the polyolefin thermoplastic elastomer is a polyolefin block copolymer. In a twelfth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the tenth or eleventh embodiments, wherein the polyolefin thermoplastic elastomer is present in the composition in an amount not exceeding 40% by weight, based on the total weight of the composition. In a thirteenth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to twelfth embodiments, the thermoplastic elastomer composition further comprising a polyphenylene ether resin. In a fourteenth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to thirteenth embodiments, the thermoplastic elastomer composition further comprising at least one of a filler, activated carbon, a flame retardant, or thermally conductive particles. In a fifteenth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to fourteenth embodiments, the thermoplastic elastomer composition further comprising at least one of hollow ceramic microspheres, expandable polymer microspheres, entrained gas, or a chemical foaming agent. In a sixteenth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to fifteenth embodiments, the thermoplastic elastomer composition having a Shore A hardness not exceeding 60. In a seventeenth embodiment, this disclosure provides a thermoplastic elastomer composition according to any one of the first to sixteenth embodiments, wherein the thermoplastic elastomer composition has a complex melt viscosity in the range of 4,000 Pascal-second to 30,000 Pascal-second, measured on a rheometer at a temperature of 175°C and a shear rate of 1 radians / second.

[0157] In an eighteenth embodiment, this disclosure provides an article comprising a thermoplastic elastomer composition according to any one of the first to seventeenth embodiments. In a nineteenth embodiment, this disclosure provides an article according to the eighteenth embodiment, wherein the article is an extruded article. In a twentieth embodiment, this disclosure provides an article according to either the eighteenth or nineteenth embodiment, wherein the article is a filament. In a twenty-first embodiment, this disclosure provides an article according to the twentieth embodiment, wherein the filament has a diameter in the range of 5 mm to 20 mm. In a twenty-second embodiment, this disclosure provides an article according to either the twentieth or twenty-first embodiment, wherein the filament has a core and a sheath, wherein the core comprises the thermoplastic elastomer composition, and wherein the sheath comprises a composition different from the core. In a twenty-third embodiment, the article of this disclosure is an adhesive according to the twenty-second embodiment, wherein the sheath comprises a polyolefin. In a twenty-fourth embodiment, this disclosure provides an article according to any one of the nineteenth to twenty-third embodiments, wherein the filament is wound on a spool.

[0158] In a twenty-fifth embodiment, this disclosure provides an article of the eighteenth or nineteenth embodiment, wherein the article is a gasket. In a twenty-sixth embodiment, this disclosure provides an article of the eighteenth, nineteenth, or twenty-fifth embodiment, wherein the thermoplastic elastomer composition has a surface in direct contact with the pressure-sensitive adhesive. In a twenty-seventh embodiment, this disclosure provides an article of the twenty-sixth embodiment, wherein the thermoplastic elastomer composition is co-extruded with the pressure-sensitive adhesive. In a twenty-eighth embodiment, this disclosure provides an article of the twenty-sixth or twenty-seventh embodiment, wherein the pressure-sensitive adhesive comprises a styrene block copolymer. In a twenty-ninth embodiment, this disclosure provides an article of the twenty-eighth embodiment, wherein the styrene block copolymer comprises at least one of a polystyrene triblock copolymer or a polystyrene star-shaped block copolymer, wherein the polystyrene triblock copolymer and the polystyrene star-shaped block copolymer independently comprise blocks of at least one of polyisoprene, polybutadiene, ethylene / butene, or ethylene / propylene, and wherein the pressure-sensitive adhesive further comprises a tackifier. In a thirtieth embodiment, this disclosure provides an article according to the twenty-eighth or twenty-ninth embodiment, wherein the styrene block copolymer of the pressure-sensitive adhesive is hydrogenated, i.e., it comprises ethylene / butene or ethylene / propylene blocks. In a thirty-first embodiment, this disclosure provides an article according to any one of the twenty-fifth to thirty-thirtieth embodiments, wherein the article is a gasket, and wherein the pressure-sensitive adhesive adheres the gasket to a frame surrounding an opening and / or to an appliance. In a thirty-second embodiment, this disclosure provides an article according to any one of the twenty-sixth to thirty-thirtieth embodiments, wherein the article further includes a release liner on the surface of the pressure-sensitive adhesive opposite the thermoplastic elastomer composition.

[0159] In a thirty-third embodiment, this disclosure provides a method for preparing an article according to any one of embodiments twenty-five to thirty-two, the method comprising extruding the thermoplastic elastomer composition onto a substrate. In a thirty-fourth embodiment, this disclosure provides a method for preparing an article according to any one of embodiments twenty-six to thirty-two, the method comprising directly co-extruding the thermoplastic elastomer composition and the pressure-sensitive adhesive onto a substrate. In a thirty-fifth embodiment, this disclosure provides a method according to an embodiment thirty-four, wherein the substrate includes an opening, and wherein the co-extrusion comprises directly co-extruding the thermoplastic elastomer composition and the pressure-sensitive adhesive onto the substrate to surround the opening. In a thirty-sixth embodiment, this disclosure provides a method according to an embodiment thirty-four, wherein the substrate is a release liner. In a thirty-seventh embodiment, this disclosure provides a method according to any one of embodiments thirty-four to thirty-six, the method further comprising providing the pressure-sensitive adhesive in the form of a filament and melting the filament. In a thirty-eighth embodiment, this disclosure provides a method according to any one of embodiments thirty-three to thirty-seven, the method further comprising providing the thermoplastic elastomer composition in the form of a filament and melting the filament.

[0160] The following examples further illustrate embodiments of the compositions and methods disclosed herein, but the specific materials and amounts mentioned in these examples, as well as other conditions and details, should not be construed as undue limitation of the invention.

[0161] Example

[0162] Unless otherwise stated, all parts, percentages, ratios, etc., in the examples and the remainder of this specification are by weight. The following abbreviations are used in this section: rpm = revolutions per minute, g = gram, mg = milligram, mol = mole, cm = cm, mm = millimeter, in. = inch, ft = foot, ℃ = degree Celsius, ℉ = degree Fahrenheit, phr = parts per hundred, wt% = weight percentage, lb = pound, mL = milliliter, sec = second, oz = ounce, hr = hour, and min. = minute.

[0163]

[0164] Thermoplastic elastomer compositions of Examples 1 to 9 and Illustrative Examples 1 to 3

[0165] Examples 1 to 9 (Ex.1-9) and illustrative Examples 1 to 3 (IE1-3) were prepared using the compositions shown in Table 2 below (hereinafter). All amounts shown are provided in parts by weight (parts by weight). Additionally, each of Ex.1-9 and IE1-3 comprises 1 pbw of antioxidant, 2 pbw of pigment, and 4 pbw of LDPE. The total pbw of each of Ex.1-9 and IE1-3 is 100.

[0166]

[0167] Samples of Examples 1 to 9 and Illustrative Examples 1 to 3 were prepared using a ZE30R co-rotating twin-screw extruder (obtained from KraussMaffei Berstorff, Hanover, Germany) and subjected to 200 rpm of pressure via a gear pump (a Nordson Xaloy 042709 gear pump rotating at 20 rpm) and exiting from an aluminum slit die with a 2 mm × 75 mm outlet orifice. The extruder and pump temperatures were set to 180°C. The samples were then subjected to the following tests: friction test, Shore A hardness test, stress relaxation test, compression set test, and melt viscosity test.

[0168] The samples from Examples 1 to 9 and Illustrative Examples 1 to 3 were also compounded using a ZE30R co-rotating twin-screw extruder from KraussMaffei Berstoff and subjected to mixing at 250 rpm for 3 minutes. A Nordson Xaloy 042709 gear pump was used at 30 rpm to pump the molten binder out through a 9.5 mm inner diameter brass threaded connector. The filaments fell 150 mm into a stainless steel bath filled with water at ambient temperature. The filaments were manually pulled through the water bath, dried, and reserved for further testing. The extruder and gear pump were set to 160°C, except for the inlet area, which was set to 150°C. Similarly, the thermoplastic elastomer compositions in filament form were then co-extruded with PSA separately according to the method described below, and the co-extruded samples were subjected to dispensability and removability tests.

[0169] Test methods : Friction test Friction tests were conducted according to ASTM D1894, except that no sample ran a minimum distance of 130 mm due to stick-slip or uneven slippage. However, all samples ran a minimum of 50 mm or more, clearly distinguishing the examples. Tests were performed on an MTS Standard 45 electromechanical load frame equipped with a 10 N force sensor. Anodized aluminum panels were used as the contact material. Sample sizes were 64 mm × 64 mm, and four samples were measured for each example. Sample thicknesses ranged from 1.04 mm to 1.17 mm. Average values ​​are reported in Table 3. A value of <3 for the coefficient of kinetic friction is considered acceptable.

[0170] Shore hardness A test

[0171] The sample was prepared according to ASTM D2240-15 Type A. The sample was prepared by pressing it to a nominal thickness of 6 mm using metal shims positioned between multiple peeling pads 1 within a heated metal press set to 140°C. Actual sample thickness was between 5.5 mm and 7.6 mm.

[0172] Stress relaxation test

[0173] 2-inch samples with a width of 6.2 mm were cut directly from the extruded sample. The thickness of the samples was measured and recorded in Table 3 below. All samples were tested using an RSA-G2 solids analyzer (TA Instruments, New Castle, DE) equipped with a tension clamping device capable of testing samples with rectangular dimensions, and TRIOS software (TA Instruments) was used to program the experiments and collect data. At the start of each test, the tension clamps were set to a distance of 25 mm. The test sample was then loaded into the tension clamping device and tightened until it was gripped tightly by hand. The width and thickness of the sample were recorded under the "Geometry" tab in the TRIOS software. The action of clamping the sample creates some slack in the gauge length region, resulting in a small compressive force on the sample; therefore, a small tension of 0.03 N was applied to remove the slack. To ensure correct stress calculation, the initial gauge length was recorded to account for the removal of slack. The gauge lengths are recorded in Table 3 below. The test began with equilibration at 25°C for 1 minute, followed by an application of 5% strain and holding at 25°C for 10 minutes. The final gauge length (length after strain application) is 5% higher than the initial gauge length. Five points per second were collected using TRIOS software. The stress relaxation as a function of force response from t=1s to t=600s was calculated using the following equation and recorded in Table 3: SR=(F(1s)-F(600s)) / F(1s).

[0174] Compression permanent deformation test

[0175] The sample was tested using Type 2 specimens according to ASTM D389-18 Type B (Compression Permanence under Constant Deflection in Air), where the compression spacer was modified to be only 4.0 mm thick instead of the prohibited 4.5 mm. The specimens were prepared to an initial thickness of 5.5 mm to 8.2 mm using a multilayer extruded film pressed together in a heated metal press at 140°C. Alternatively, the specimens were prepared to a nominal thickness of 6 mm by pressing them with metal shims positioned between multiple release liner 1s in a heated metal press set to 140°C, and then punched out using a 15 mm diameter die punch (instead of the 13 mm diameter specified by ASTM).

[0176] Melt viscosity test

[0177] Viscosities were measured using a TA Instruments DHR-3 rheometer with a 25 mm disposable parallel plate (TA Instruments, Newcastle, Delaware). Melt viscosities were measured at temperatures ranging from 125°C to 200°C, with shear rates from 100 rad / sec to 0.1 rad / sec, three points were taken at every decibel and with a strain of 5%, and data were acquired at 25°C temperature intervals. The complex viscosity at 1 rad / sec at 175°C was selected as representative of the distribution conditions and is reported in Table 3 below.

[0178] Co-extrusion of thermoplastic elastomer composition and PSA

[0179] A three-piece co-extrusion die head was hand-machined using a Jet JMD18 vertical end mill. The body of the die head was milled from a 75mm × 50mm × 50mm aluminum block of 6061. Four countersunk holes were drilled to accommodate 35mm long M6 bolts for attachment to the end of the dispenser barrel. The die head was attached to be centered below the spindle of the thermoplastic elastomer (TPE) composition dispenser screw. A 10mm through hole was drilled at the center along the spindle shaft. The bottom of the block was cut at an angle to reduce the height of the die head back to 38mm. Four M5 threaded holes were formed at the bottom of the die head for attaching the base plate. An internal cavity with a lip was machined so that the inner plate could be placed on a 1mm × 25mm × 25mm recessed lip. With the inner plate in place, the cavity was cut to further create a 23mm × 23mm × 10mm deep recess for TPE flow. The internal cavity slopes downwards to an outlet lip with a 2mm × 20mm cross-section, featuring three additional hemispherical protrusions, each with a diameter of 3.1mm. A 1 / 4” NPT fitting centered on the left side of the die accommodates a 9.5mm outer diameter copper tube with PSA flow. A vertical 6mm orifice guides the PSA flow from the side of the body to the bottom. Holes are formed to accommodate and attach two heaters (McMaster #4877K126) and a thermocouple (McMaster #3860K203). The three-piece die (body, inner plate, and bottom plate) guides the TPE and PSA flow, ensuring they contact within the die for 22mm before exiting.

[0180] The inner plate is used to redirect the flow, allowing them to flow parallel to each other before contacting each other. The inner plate is made of a 1mm × 25mm × 25mm steel sheet. The front of the inner plate narrows to 20mm wide to fit the slit at the die lip.

[0181] The base plate is machined from a 6.3mm × 75mm × 53mm aluminum block of 6061. A slit is cut to allow PSA to flow from the bottom of the body to the lower lip of the die head. The slit is 43mm × 10mm × 3mm deep. The lower lip of the die head has a cross-section of 1mm × 20mm.

[0182] The redirection block was manufactured from a 41mm × 63.5mm × 32mm high steel block using a CNC vertical end mill. Four countersunk holes were drilled to accommodate 35mm long M6 bolts for attachment to the end of the dispenser barrel. A 10mm diameter hole was drilled down the center of the top face to align with the PSA screw shaft. Vertical holes redirected the PSA from the right side of the block. A 9 / 16”-18 threaded hole accommodated 37-degree JIS fittings for attachment to a 9.5mm outer diameter copper tube. Compression fittings were used at both ends of the copper tube, which was approximately 200mm long, to accommodate separation between the PSA and the thermoplastic elastomer composition dispenser. Silicone-coated fiberglass fabric (McMaster 7569K17) was cut and wrapped around the copper tube for insulation. Holes were drilled to accommodate and attach two heaters (McMaster # 4877K126) and a thermocouple (McMaster #3860K203).

[0183] Attach a 300mm × 300mm × 6.3mm aluminum plate to the end of the UR-10 robotic arm. Secure the base to the plate with tape for dispensing. The movement speed is 50 mm / min. The PSA dispenser operates at 50 RPM for the feed motor and 500 RPM for the screw motor. The thermoplastic elastomer composition dispenser operates at 150 RPM for the feed motor and 1500 RPM for the screw motor. The PSA filaments are on a spool mounted on a free-rotating shaft. Manually feed the thermoplastic elastomer composition filaments into the dispenser.

[0184] Two identical miniaturized single-screw distributors are used, one for the thermoplastic elastomer composition and the other for PSA. Each extruder screw is rotated using a 1kW 240V servo motor attached to a 10:1 planetary gearbox. Graphite-filled bronze thrust bearing washers are used to minimize the forces transmitted to the motor and gearbox. Both distributors are attached to a fixed metal frame 1100mm above the floor.

[0185] The barrel is manufactured from a 382mm × 95mm × 50mm block of 4140 steel using a CNC vertical end mill. A 30mm diameter hole is drilled downwards along the main central axis of the barrel to accommodate the extrusion screw. The outer surface of the barrel is machined to a 55mm × 41mm cross-section, leaving a 20mm thick flange at the end of the barrel closest to the engine / gearbox. The flange is bolted to a semi-circular bearing mounting plate containing graphite-filled bronze thrust washers. The bearing mounting plate is bolted to a backing plate to secure the barrel's position. A 6.3mm diameter circular channel is cut along the length of the barrel to receive the heater (McMaster #4877K173). The heater mounting plate is fabricated from two 310mm × 55mm × 7mm aluminum 6061 plates using a CNC vertical end mill. The channel is machined to match the shape of the heater and arranged in a clamshell pattern to firmly press the heater onto the barrel. The barrel inlet plate is made of 6061 aluminum sheet, measuring 55mm × 7mm × 51mm. It includes a U-shaped inlet with a downward angle to provide a slanted roll gap, improving the gripping of the filament between the screw and the barrel. The U-shaped orifice is 17mm wide and extends downward 28mm from the upper surface of the barrel flange. An opening larger than the U-shaped orifice in the inlet plate is machined into the barrel.

[0186] The barrel is fabricated from 4140 steel bar, 416mm long x 29.8mm in diameter, using a 4-axis CNC vertical end mill. The motor mounting shaft is machined to a diameter of 17mm x a length of 36mm, with a slit cut to accommodate the shaft key. The main screw thread has a 20mm pitch and is 4mm thick. The thread height at the inlet is 7.8mm. The thread height decreases to 0mm along the length of the screw. At the end of the screw opposite the motor shaft, a hollow cylinder is cut inwards 215mm. The hollow core begins with a diameter of 15mm and gradually decreases to 6.5mm. A 2mm diameter passage hole is cut from the thread tip to the hollow core. A small semi-circular notch with a diameter of 1.5mm is cut in the thread tip exposed at the inlet to act as a gripping lug. The screw shaft and gearbox shaft are connected to a steel split-shaft coupling, which is connected to a ceramic pin. Each half of the split-shaft coupling is connected to the shaft and has holes to receive the ceramic pins to connect the two halves. Ceramic pins help prevent heat from flowing into the gearbox.

[0187] A backplate is used to facilitate the connection of the engine / gearbox to the barrel. It also provides a mounting surface for the feed mechanism and a way to attach the distributor to a bracket mounted on a metal frame. The backplate is fabricated from a 19mm × 177mm × 105mm machinable ceramic sheet (McMaster #8489K123) using a CNC vertical end mill. Holes are drilled to accommodate the gearbox, barrel, and mounting bracket. The mounting bracket is a steel right-angle bracket, with each side of the right angle measuring 125mm × 105mm, and the steel is 9.5mm thick. Holes are drilled in the mounting bracket so that it can be used to attach the backplate to the mounting rail.

[0188] An attached feeding mechanism is used to directly feed the filament into the barrel inlet opening. The feeding mechanism is oriented such that the filament is perpendicular to the barrel. The main feature of the feeding mechanism is a spiked wheel consisting of spiked cylindrical wheels on a shaft. The diameter of the spiked wheel is 25.4 mm from the tip of the spike. Each spike is 5 mm high and forms an equilateral triangle. The spiked wheel is 12.7 mm wide and consists of 5 rows of spikes. The shaft is 46 mm long and 8 mm in diameter. The shaft is connected to a NEMA 17 stepper motor via a 4:1 gear set, such that the spiked wheel RPM is 1 / 4 that of the stepper motor. A free-rotating bearing (12.7 mm wide, 22 mm in diameter) is mounted on a hinge shaft including a torsion spring, and the bearing presses the filament against the spiked wheel for strong gripping. The entire assembly is housed in a housing that guides the filament into the spiked wheel and then into the barrel inlet.

[0189] When TPE and PSA are co-extruded, it is impossible to manually separate PSA from TPE to produce tabs, which indicates that there is good adhesion between TPE and PSA.

[0190] Distribution quality test

[0191] Obtain an anodized aluminum substrate (102mm × 152mm × 1.6mm) and attach PTFE tape (3M 5490 PTFE extruded film tape) along the longest edge, covering a 25mm × 152mm segment. Co-extrude two sample strips onto each panel, equidistant and aligned parallel to the 102mm long edge. Co-extrude a 125mm long segment of thermoplastic elastomer composition (TPE) / PSA, with 77mm directly bonded to the anodized aluminum substrate, a 25mm sample applied to the PTFE tape, and the remaining 25mm segment suspended on the substrate. Set the PSA dispenser to 193°C and the TPE dispenser to 205°C. Visually inspect both sample strips. If no visible delamination is observed and the die geometry variability of the co-extruded product does not exceed 10%, the filament is considered acceptable. Based on the qualitative assessment of the extruded thermoplastic elastomer, assign excellent / average / unacceptable values ​​to match those with... Figure 13The mold profiles for the three large ridges shown.

[0192] Removability test

[0193] Sample strips for the dispensing quality test are used for the removability test. The sample strip segments bonded to the PTFE tape and the hanging segments are used as tabs for manually gripping the co-extruded strip. The strip is manually gripped near the initial peel front and not re-gripped during the test. The strip is pulled perpendicularly (i.e., at 90 degrees) to the substrate at approximately 25 mm / s. The strip is pulled until the peel front has moved at least 40 mm (i.e., 40 mm of the strip has detached from the substrate). A pass value is obtained if both sample strips completely detach from the substrate without leaving any residue and no signs of delamination (i.e., wrinkling, bubbling, or deformation associated with delamination) are observed between the PSA and thermoplastic elastomer compositions.

[0194] Friction tests, Shore A hardness tests, stress relaxation tests, compression set tests, and melt viscosity tests were performed on each of Examples 1 to 9 and Illustrative Examples 1 to 3 prepared as described in the test methods. Similarly, thermoplastic elastomer compositions in filament form were produced and then co-extruded with PSA according to the methods described above, and the co-extruded samples were subjected to dispensability and removability tests. The results are shown in Table 3 below.

[0195]

[0196] Gel permeation chromatography

[0197] The molecular weight of the polymers mentioned in this disclosure can be measured using gel permeation chromatography (“GPC”) with polystyrene calibration standards. GPC is an established method in which polymers are separated according to molecular size, with the largest molecules eluting first. The elution graph is calibrated using a commercially available polystyrene molecular weight standard (EASICAL, Agilent Technologies, Santa Clara, CA). The molecular weight of the polymer measured using a GPC thus calibrated is the styrene isomeric molecular weight. The molecular weights reported herein will be polystyrene isomeric molecular weights derived from a GPC system using tetrahydrofuran (1.0 mL / min) as the mobile phase and an Agilent 1260 HPLC system (Agilent Technologies, Santa Clara, CA) comprising two columns in tandem, PLgel MIXED-B and MIXED-C, and a refractive index detector.

[0198] “dw / dlogMw” is the weight fraction of a sample with the corresponding molecular weight (logM) of a styrene equivalent. For a given sample formulation, the dw / dlogMW value at a specific molecular weight (MW) can be tracked as a quantitative, but indirect, method for assessing the relative amount of material at that molecular weight.

[0199] The molecular weight at the peak dw / dlogMW represents the molecular weight present in the material at its highest weight fraction (peak MW). M p The number-average molecular weight (NMR) for plasticizer 1 is 6134 g / mol and for plasticizer 2 is 385 g / mol. M n The concentration of M for plasticizer 2 is 3272 g / mol. n It is 319 g / mol.

[0200] Various modifications and alterations may be made to this disclosure by those skilled in the art without departing from its scope and spirit, and it should be understood that the invention should not be unduly limited to the exemplary embodiments set forth herein.

Claims

1. An article comprising a thermoplastic elastomer composition, said thermoplastic elastomer composition comprising: Hydrogenated styrene block copolymer; Plasticizer, said plasticizer having a number-average molecular weight of at least 2,000 g / mol; and The wax has polar functional groups.

2. The article of claim 1, wherein the polar functional group comprises at least one of a hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, an amino group, or a carboxamide group.

3. The article according to claim 1 or 2, wherein the melting point of the wax is in the range of 35°C to 65°C.

4. The article of any one of claims 1 to 3, wherein, based on the total weight of the thermoplastic elastomer composition, the thermoplastic elastomer composition comprises 10% to 40% by weight of the hydrogenated styrene block copolymer, 10% to 45% by weight of the plasticizer, and 1% to 10% by weight of the wax.

5. The article of any one of claims 1 to 4, wherein the thermoplastic elastomer composition further comprises a polyolefin thermoplastic elastomer in an amount not exceeding 40% by weight based on the total weight of the composition.

6. The article according to claim 5, wherein the polyolefin thermoplastic elastomer is a polyolefin block copolymer.

7. The article according to any one of claims 1 to 6, wherein the hydrogenated styrene block copolymer is a styrene-ethylene / butene-styrene block copolymer.

8. The article according to any one of claims 1 to 7, wherein the plasticizer is a hydrocarbon plasticizer.

9. The article according to any one of claims 1 to 8, wherein the thermoplastic elastomer composition further comprises at least one of polyphenylene ether resin, filler, activated carbon, flame retardant, thermally conductive particles, magnetic filler, hollow ceramic microspheres, expandable polymer microspheres, entrained gas or chemical foaming agent.

10. The article according to any one of claims 1 to 9, wherein the article has a Shore hardness A of not more than 60.

11. The article according to any one of claims 1 to 10, wherein the article is a filament with a diameter in the range of 5 mm to 20 mm.

12. The article of claim 11, wherein the filament has a core and a sheath, wherein the core comprises the thermoplastic elastomer composition, and wherein the sheath comprises a polyolefin.

13. The article of claim 1 to 10, wherein the article of claim 1 to 10 is a gasket.

14. The article of any one of claims 1 to 10 or 13, wherein the thermoplastic elastomer composition has a surface in direct contact with the pressure-sensitive adhesive.

15. A method for preparing an article according to claim 14, the method comprising directly co-extruding the thermoplastic elastomer composition and the pressure-sensitive adhesive onto a substrate.

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