Hot melt adhesive composition comprising a vulcanized styrene block copolymer

Abstract

The hot melt adhesive includes a dynamically vulcanized composition including a reaction product of a thermoplastic elastomer, a polyolefin polymer, an oil, a tackifier, and a silane compound. In various aspects disclosed herein, the thermoplastic elastomer includes a cross-linkable polymer composition including (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally an ethylene propylene diene terpolymer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and an EPDM. The hot melt adhesive can be extruded as a thin film and has hot water resistance making it particularly suitable for garment and textile seam applications.

Description

[0001] Priority requirements

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 596,083, filed November 3, 2023, Agent's File No. 1202322, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present invention generally relate to dynamically vulcanizable compositions and hot melt adhesives comprising said compositions. Background Technology

[0004] Hot melt adhesives are used as a solvent-free method for bonding solid or flexible substrates, such as textiles. These hot melt adhesives are typically prepared using film extrusion methods. To enable film extrusion, conventional hot melt adhesives use low molecular weight polymers. However, low molecular weight polymers may lack high-temperature properties, making them unsuitable for hot water washing. On the other hand, high molecular weight polymers exhibit improved high-temperature resistance but are not suitable for film extrusion.

[0005] Therefore, there is a need for alternative hot melt adhesives that are suitable for film extrusion while exhibiting good high-temperature performance, adhesion, and washability. Summary of the Invention

[0006] Based on the disclosure herein, without limiting the scope of the invention in any way, in a first aspect of the invention (unless otherwise stated, this aspect may be combined with any other aspects listed herein), the hot melt adhesive comprises a dynamically vulcanized composition comprising a reaction product of a crosslinkable thermoplastic elastomer composition, a polyolefin polymer, an oil, a tackifier, and a silane compound. In various aspects of the invention, the crosslinkable polymer composition comprises (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene trimer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and EPDM.

[0007] In the second aspect (unless otherwise stated, this aspect may be combined with any other aspects listed herein), the hot melt adhesive comprises partially unsaturated conjugated diene-vinyl aromatic copolymers selected from: partially hydrogenated styrene-butadiene rubber, partially hydrogenated styrene-butadiene block copolymers, partially hydrogenated styrene-isoprene block copolymers, partially hydrogenated styrene-butadiene-isoprene rubber, partially hydrogenated styrene-butadiene / isoprene block copolymers, partially hydrogenated styrene-butadiene-isoprene block copolymers, and combinations thereof.

[0008] In the third aspect, unless otherwise stated, hot melt adhesives include any other hot melt adhesives listed herein, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer is a block copolymer comprising blocks as defined by general formula (I):

[0009]

[0010] The w, x, y, and z units are randomly distributed in the block, each R1 is independently a hydrogen atom or a methyl group, and each R2 is independently a hydrogen atom or a methyl group, provided that at least one R2 in each unit is a hydrogen atom; and the total molar percentage of the y and z units is approximately 30-90% compared to the sum of the w, x, y, and z units in the block.

[0011] In the fourth aspect, unless otherwise stated, hot melt adhesives include any other hot melt adhesives listed herein, wherein the number average molecular weight of the partially unsaturated conjugated diene-vinyl aromatic copolymer is about 50,000-200,000 g / mol.

[0012] In the fifth aspect, unless otherwise stated, hot melt adhesives include any other hot melt adhesives listed herein, wherein the number-average molecular weight of the fully hydrogenated conjugated diene-vinyl aromatic copolymer is about 50,000-200,000 g / mol.

[0013] In the sixth aspect, unless otherwise stated, hot melt adhesive webbing includes any other hot melt adhesives listed herein.

[0014] In a seventh aspect, the hot-melt adhesive film comprises the hot-melt adhesive of any one of the first to fourth aspects. In some aspects, the thickness of the adhesive film is 20-300 µm. In some aspects, the adhesive film is part of a multilayer composite material comprising two or more films. According to some aspects, the adhesive film is part of a multilayer composite material comprising the film adhered to a fabric backing. In any aspect, the adhesive film is part of a multilayer composite material comprising the film adhered to a release liner. In some aspects, the width of the adhesive film is 5-40 cm.

[0015] In an eighth aspect, a seam includes a first portion of fabric, a second portion of fabric at least partially overlapping the first portion of fabric to form a seam portion, and a hot-melt adhesive layer in the seam portion that adheres the first portion of fabric to the second portion of fabric. Unless otherwise stated, said adhesive layer comprises an adhesive film or adhesive webbing comprising a hot-melt adhesive composition of any other aspect listed herein. According to some aspects, the seam portion includes a seam connecting the first portion of fabric to the second portion of fabric. According to other aspects, said seam portion is a seamless seam portion. In any aspect, both the first and second portion of fabric comprise nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, spandex, or combinations thereof. In any aspect disclosed herein, the adhesive layer is an adhesive film or adhesive webbing.

[0016] In a ninth aspect, a method of preparing a seam includes: providing a first portion of fabric, a second portion of fabric, and a hot melt adhesive layer; placing the hot melt adhesive layer between the first portion of fabric and the second portion of fabric to form a seam portion, wherein the second portion of fabric at least partially overlaps the first portion of fabric; and heating the seam portion such that the adhesive layer bonds the first portion of fabric to the second portion of fabric. In any aspect described herein, unless otherwise stated, the hot melt adhesive layer includes adhesive compositions from any other aspect described herein. Detailed Implementation

[0017] This document discloses hot melt adhesive compositions, and more specifically, hot melt adhesive compositions comprising dynamically vulcanized compositions containing reaction products of thermoplastic elastomers, polyolefin polymers, oils, tackifiers, and silane compounds. In various aspects of the invention, the thermoplastic elastomer comprises a crosslinkable polymer composition comprising (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene trimer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and EPDM. The hot melt adhesive compositions exhibit good high-temperature performance, adhesion, and washability, while also being suitable for film extrusion.

[0018] The terminology used herein is for descriptive purposes only and should not be construed as limiting the entire invention. Unless otherwise specified or the context of the reference clearly indicates otherwise, all references to a singular feature or limitation of the invention shall include the corresponding plural feature or limitation, and vice versa. Unless otherwise stated, the article and “at least one” may be used interchangeably. Furthermore, as applied in the specification and appended claims, unless the context clearly indicates otherwise, the article in the singular form includes its plural form.

[0019] When the terms “comprising” or “including” are used in the specification or claims, they are intended to be inclusive, similar to how the term “comprising” is interpreted as a transition word in the claims. Similarly, when the term “or” (e.g., A or B) is used, it is intended to mean “A or B or both”. The term “A or B only, and not both” will be used when the applicant intends to mean “only A or B, and not both”. Therefore, the application of the term “or” herein is inclusive rather than exclusive.

[0020] The hot melt adhesive of the present invention may include, be composed of or substantially composed of, the essential elements of the invention as described herein, and may also include any additional or optional elements as described herein, or these elements may be used in addition to the hot melt adhesive application.

[0021] Unless otherwise stated, all percentages, parts and ratios used herein are based on the “dry” basis weight of the total mixture, i.e., solvent-free.

[0022] All ranges and parameters disclosed herein, including but not limited to percentages, parts, and ratios, should be understood to include any and all subranges contained therein and every numerical value between the endpoints. For example, the range “1-10” should be understood to include any and all subranges (e.g., 1-6.1 or 2.3-9.4) that begin with a minimum value of 1 or greater and end with a maximum value of 10 or less, and every integer contained within that range (1, 2, 3, 4, 5, 6, 7, 8, 9, and 10). Ranges in this document may be expressed as “about” a particular value and / or to “about” another particular value. When such ranges are expressed, other embodiments include from one particular value and / or to another particular value. Similarly, when an approximate value is indicated by using the antecedent “about”, it should be understood that the particular value forms another embodiment. It should also be understood that the endpoints of each range are significant relative to each other and independently of each other.

[0023] Unless otherwise stated, the term "wt%" as used herein refers to the weight fraction of each component based on the total weight of the dynamic vulcanizing composition.

[0024] As described in this article, the term "number-average molecular weight" refers to the total weight of a polymer divided by the total number of molecules measured using gel permeation chromatography (GPC) and polystyrene standards.

[0025] As described in this article, the term “melt flow rate” refers to the ability of a material melt to flow under pressure, as measured by ASTM D1238 at a given temperature and weight.

[0026] As described in this article, the term “density” refers to the mass per unit volume of a material as measured at 23°C according to ASTM D792.

[0027] As described in this article, the term "specific gravity" refers to the ratio of the density of a material to the density of water, as measured by ASTM D792 at 23°C.

[0028] As described in this article, the term "Mounney viscosity" refers to the viscosity reached by a rotor after being rotated for a given time at a specified temperature, as determined by ASTM D1646.

[0029] As described in this article, the term "yield" refers to the point on the stress-strain curve that represents the limit of elastic behavior and the beginning of plastic behavior.

[0030] As described in this article, the term "yield tensile strength" refers to the maximum stress that a material can withstand when stretched before it begins to undergo permanent deformation, as measured by ASTM D638 at 23°C and a strain rate of 0.85 mm / s.

[0031] As described in this article, the term "yield tensile elongation" refers to the ratio between the increase in length at the yield point and the initial length, as measured by ASTM D638 at 23°C and a strain rate of 0.85 mm / s.

[0032] As described in this article, the term "tensile strength at break" refers to the maximum stress a material can withstand before fracture when stretched, as measured by ASTM D638 at 23°C and a strain rate of 0.85 mm / s.

[0033] As described in this article, the term "elongation at break" refers to the ratio of the increase in length after fracture to the initial length, as measured by ASTM D638 at 23°C and a strain rate of 0.85 mm / s.

[0034] As described in this article, the term "Shore A hardness" refers to the hardness of a material as measured according to ASTM D2240.

[0035] As described in this article, the term "Dynamic Mechanical Analysis (DMA) Storage Modulus" refers to the technique used to determine the storage modulus (MPa) as a function of temperature at a specific frequency.

[0036] As described herein, the term “fabric adhesive peel force” refers to a measure of adhesive bonding performance (average force per unit width of substrate (lbs / in)) and involves the tension applied to a flexible substrate bonded to another flexible substrate by an adhesive.

[0037] As described in this article, the term "polyolefin" refers to a polymer having a crystalline phase and an amorphous phase prepared from olefin monomers.

[0038] As described in this article, the term "polyolefin elastomer (POE)" refers to a polymer with low crystallinity (i.e., less than or equal to 25% crystallinity) prepared from olefin monomers.

[0039] As described herein, the term "silane-grafted" refers to a thermoplastic elastomer having silane side chains attached to the polymer backbone.

[0040] As described in this article, the term "polymer" refers to a polymer formed when two or more different monomers polymerize into chains.

[0041] As described herein, the term "block" refers to a polymer part comprising a number of constituent units that has a feature not present in at least one of the adjacent parts.

[0042] As discussed above, hot melt adhesives may possess excellent bonding and other properties, enabling their fabrication using film extrusion methods. However, they may lack the high-temperature resistance required for certain applications, such as those involving clothing and textile bonding. In these applications, the lack of high-temperature resistance can cause the adhesive to crack when clothing or textiles are washed in hot water.

[0043] The present invention relates to a hot melt adhesive composition comprising a dynamically vulcanizing composition, the dynamically vulcanizing composition comprising reaction products of a thermoplastic elastomer, a polyolefin polymer, an oil, a tackifier, and a silane compound. Dynamic vulcanization refers to the crosslinking of a thermoplastic material with an elastomer under dynamic conditions. The thermoplastic elastomer comprises a crosslinkable polymer composition comprising (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene trimer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and EPDM. The hot melt adhesive can be extruded as a film and exhibits good high-temperature resistance. Furthermore, the hot melt adhesive can be moisture-cured without the use of a catalyst, which can extend the shelf life of the hot melt adhesive.

[0044] The dynamically vulcanizable compositions disclosed herein exhibit advantageous temperature resistance (e.g., increased peel strength after immersion in water at 80°C for 24 hours) while also demonstrating good film extrusion properties at specific thicknesses (e.g., 1-3 mil). Vulcanization packages containing organic peroxides and silanes can crosslink the carbon-carbon bonds of thermoplastic elastomers and polyolefin polymers upon mixing, without requiring additional steps or materials such as moisture-curing catalysts.

[0045] Conventional methods for forming hot melt adhesives include film extrusion. While polymers such as styrene-ethylene-butene-styrene (SEBS) perform well in hot melt adhesives that are washed at room temperature and low temperatures, the low molecular weight of SEBS, which makes it suitable for film extrusion, also makes it unsuitable for high-temperature environments, such as washing at 80°C or higher. Using higher molecular weight SEBS can provide improved high-temperature resistance, but it is generally incompatible with film extrusion. The hot melt adhesive compositions of the present invention address these problems by providing a hot melt adhesive that is crosslinked to provide high-temperature performance while remaining processable by film extrusion. The thermoplastic elastomers of the present invention can be directly blended with silane crosslinking compositions during conventional conversion processes, thus eliminating the initial silane grafting step. The crosslinking of the thermoplastic elastomers is carried out in a one-step process, wherein a hot melt adhesive film is formed by extrusion. Furthermore, the hot melt adhesive compositions can be wet-cured without the use of a catalyst, which can extend the shelf life of the product.

[0046] thermoplastic elastomers

[0047] The thermoplastic elastomer of the hot melt adhesive composition comprises at least one crosslinkable polymer composition containing a vinyl aromatic monomer unit and a conjugated diene monomer unit. The conjugated diene monomer unit may be selected from 1,3-butadiene monomer units, 2,3-dimethyl-1,3-butadiene, isoprene monomer units, isoprene monomer units, and combinations thereof. The vinyl aromatic monomer unit may be selected from styrene monomer units, α-methylstyrene monomer units, p-methylstyrene monomer units, o-methylstyrene monomer units, p-butylstyrene monomer units, p-tert-butylstyrene monomer units, and combinations thereof.

[0048] In any exemplary aspect, the crosslinkable polymer composition may include a conjugated diene-vinyl aromatic copolymer selected from partially saturated or fully hydrogenated conjugated diene-vinyl aromatic copolymers. In any exemplary aspect, the conjugated diene-vinyl aromatic copolymer is selected from styrene-butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer (SIS), styrene-butadiene-isoprene rubber, styrene-butadiene / isoprene block copolymer, styrene-butadiene-isoprene block copolymer, nitrile-butadiene rubber, and combinations thereof, which may be partially unsaturated (i.e., partially hydrogenated) or fully hydrogenated.

[0049] According to any exemplary aspect, the conjugated diene-vinyl aromatic copolymer can be a block copolymer comprising blocks defined by general formula (I):

[0050] (I)

[0051] The w, x, y, and z units are randomly distributed in the block, each R1 is independently a hydrogen atom or a methyl group, and each R2 is independently a hydrogen atom or a methyl group, provided that at least one R2 in each unit is a hydrogen atom.

[0052] In a polymer block defined by general formula (I), the total molar percentage of y and z units can be about 30-90% relative to the sum of w, x, y, and z units in the block. The total molar percentage of y and z units can be about 50-70% relative to the sum of w, x, y, and z units in the block. The total molar percentage of y and z units can be greater than or equal to about 30%, greater than or equal to about 35%, greater than or equal to about 40%, greater than or equal to about 45%, or even greater than or equal to about 50% relative to the sum of w, x, y, and z units in the block. The total molar percentage of y and z units can be less than or equal to about 90%, less than or equal to 85%, less than or equal to 80%, less than or equal to 75%, or even less than or equal to about 70% relative to the sum of w, x, y, and z units in the block. Compared to the sum of w, x, y, and z units in a block, the total molar percentage of y and z units can be approximately 30-90%, approximately 30-85%, approximately 30-80%, approximately 30-75%, approximately 30-70%, approximately 35-90%, approximately 35-85%, approximately 35-80%, approximately 35-75%, approximately 35-70%, approximately 40-90%, approximately 40-85%, approximately 40-80%, approximately 40-75%, approximately 40-70%, approximately 45-90%, approximately 45-85%, approximately 45-80%, approximately 45-75%, approximately 45-70%, approximately 50-90%, approximately 50-85%, approximately 50-80%, approximately 50-75%, or approximately 50-70%, or any and all endpoints or subranges thereof.

[0053] In a polymer block defined by general formula (I), the ratio of y units to w units can be greater than the ratio of x units to z units. The ratio of y units to w units can also be less than the ratio of x units to z units.

[0054] In any or all respects described herein, a conjugated diene-vinyl aromatic copolymer can be a block copolymer comprising blocks defined by general formula (II):

[0055] (II)

[0056] Units a, b, c, and d are randomly distributed within the block.

[0057] In a polymer block defined by general formula (II), the total molar percentage of units c and d can be about 30-90% relative to the sum of units a, b, c, and d in the block. The total molar percentage of units c and d can be about 50-70% relative to the sum of units a, b, c, and d in the block. The total molar percentage of units c and d can be greater than or equal to about 30%, greater than or equal to about 35%, greater than or equal to about 40%, greater than or equal to about 45%, or even greater than or equal to about 50% relative to the sum of units a, b, c, and d in the block. The total molar percentage of units c and d can be less than or equal to about 90%, less than or equal to 85%, less than or equal to 80%, less than or equal to 75%, or even less than or equal to about 70% relative to the sum of units a, b, c, and d in the block. Compared to the sum of units a, b, c, and d in the block, the total molar percentage of units c and d can be approximately 30-90%, approximately 30-85%, approximately 30-80%, approximately 30-75%, approximately 30-70%, approximately 35-90%, approximately 35-85%, approximately 35-80%, approximately 35-75%, approximately 35-70%, approximately 40-90%, approximately 40-85%, approximately 40-80%, approximately 40-75%, approximately 40-70%, approximately 45-90%, approximately 45-85%, approximately 45-80%, approximately 45-75%, approximately 45-70%, approximately 50-90%, approximately 50-85%, approximately 50-80%, approximately 50-75%, or approximately 50-70%, or any and all endpoints and subranges thereof.

[0058] In a polymer block defined by general formula (II), the ratio of c units to a units can be greater than the ratio of d units to b units. The ratio of c units to a units can also be less than the ratio of d units to b units.

[0059] Depending on various aspects, conjugated diene-vinyl aromatic copolymers can be triblock copolymers comprising two polystyrene end blocks. The styrene content of the two polystyrene end blocks in a conjugated diene-vinyl aromatic copolymer can be about 10-50 wt%. The styrene content of the two polystyrene end blocks in a conjugated diene-vinyl aromatic copolymer can be greater than or equal to about 10 wt%, greater than or equal to about 15 wt%, greater than or equal to about 20 wt%, greater than or equal to about 25 wt%, or even greater than or equal to about 27 wt%. The styrene content of the two polystyrene end blocks in a conjugated diene-vinyl aromatic copolymer can be less than or equal to about 50 wt%, less than or equal to 45 wt%, less than or equal to 40 wt%, less than or equal to 35 wt%, or even less than or equal to about 33 wt%. The styrene content of the two polystyrene end blocks in the conjugated diene-vinyl aromatic copolymer can be approximately 10-50 wt%, approximately 10-45 wt%, approximately 10-40 wt%, approximately 10-35 wt%, approximately 10-33 wt%, approximately 15-50 wt%, approximately 15-45 wt%, approximately 15-40 wt%, approximately 15-35 wt%, approximately 15-33 wt%, approximately 20-50 wt%, approximately 20-45 wt%, approximately 20-40 wt%, approximately 20-35 wt%, approximately 20-33 wt%, approximately 25-50 wt%, approximately 25-45 wt%, approximately 25-40 wt%, approximately 25-35 wt%, approximately 25-33 wt%, or approximately 27-33 wt%. wt%, or any and all endpoints and subranges thereof.

[0060] In any or all of the respects described herein, the number-average molecular weight of the conjugated diene-vinyl aromatic copolymer can be about 30,000-400,000 g / mol. For example, the number-average molecular weight of the conjugated diene-vinyl aromatic copolymer can be greater than or equal to 30,000 g / mol, greater than or equal to about 50,000 g / mol, greater than or equal to about 100,000 g / mol, or even greater than or equal to about 150,000 g / mol. The number-average molecular weight of the conjugated diene-vinyl aromatic copolymer can additionally or alternatively be less than or equal to about 400,000 g / mol, less than or equal to about 350,000 g / mol, less than or equal to 300,000 g / mol, or even less than or equal to about 250,000 g / mol. According to one or more aspects described herein, the number average molecular weight of the conjugated diene-vinyl aromatic copolymer can be about 30,000-400,000 g / mol, about 30,000-350,000 g / mol, about 30,000-300,000 g / mol, about 30,000-250,000 g / mol, about 50,000-400,000 g / mol, about 50,000-350,000 g / mol, about 50,000-300,000 g / mol, about 50,000-250,000 g / mol, about 50,000-200,000 g / mol, about 100,000-400,000 g / mol, about 100,000-350,000 g / mol. g / mol, about 100,000-300,000 g / mol, about 100,000-250,000 g / mol, about 150,000-400,000 g / mol, about 150,000-350,000 g / mol, about 150,000-300,000 g / mol, or even about 150,000-250,000 g / mol, or any and all endpoints and subranges thereof.

[0061] According to the present invention, when the thermoplastic elastomer has carbon-carbon double bond sites, the carbon-carbon double bonds can be partially hydrogenated. Without being limited by any theory, it is believed that the crosslinking of the partially hydrogenated conjugated diene-vinyl aromatic copolymer occurs at least partially at the unhydrogenated sites (i.e., carbon-carbon double bonds, such as those located on conjugated diene residues), and the number of reactive sites can be set by adjusting the degree of hydrogenation of the conjugated diene-vinyl aromatic copolymer. The amount of crosslinking can also be controlled by controlling the degree of hydrogenation. Reducing the degree of hydrogenation of the conjugated diene-vinyl aromatic copolymer can improve the crosslinking density and heat resistance of the resulting partially crosslinked polymer system. According to the present invention, based on the molar ratio of hydrogenated carbon-carbon double bonds to total carbon-carbon double bonds in the partially hydrogenated conjugated diene-vinyl aromatic copolymer, the degree of hydrogenation of the conjugated diene-vinyl aromatic copolymer can be greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 90%, or even greater than or equal to about 95%. In any exemplary aspect, based on the unsaturated groups of the conjugated diene monomer units in the partially hydrogenated conjugated diene-vinyl aromatic copolymer, the degree of hydrogenation of the conjugated diene-vinyl aromatic copolymer can be about 30-99%, or about 35-95%, or about 40-90%, or about 45-85%, or about 50-80%, or about 55-75%.

[0062] According to various aspects, conjugated diene-vinyl aromatic copolymers can be partially hydrogenated, possessing both hard and soft phases, with the following basic structure:

[0063] A―B,

[0064] A-B-A, or

[0065] A―B―A′,

[0066] Before hydrogenation, each A and A′ block is a hard phase composed of vinyl aromatic monomer units, and each B block is a soft phase containing conjugated diene monomer units. The "hard phase" refers to the block copolymer portion with a glass transition temperature of 90-120°C. The "soft phase" refers to the block copolymer portion with a glass transition temperature below -20°C.

[0067] In all respects, the amount of conjugated diene-vinyl aromatic copolymer contained in the hot melt adhesive composition is about 20-95 wt% based on the total weight of the hot melt adhesive composition. For example, the amount of conjugated diene-vinyl aromatic copolymer contained in the hot melt adhesive composition may be about 25-90 wt%, such as about 30-85 wt%, about 32-80 wt%, about 35-75 wt%, about 37-70 wt%, or about 40-65 wt%, including any and all endpoints and subranges therein, based on the total weight of the hot melt adhesive composition. In any respect disclosed herein, the amount of conjugated diene-vinyl aromatic copolymer contained in the hot melt adhesive composition may be about 20-60 wt% based on the total weight of the hot melt adhesive composition, such as including about 23-55 wt%, about 25-50 wt%, about 27-47 wt%, or about 30-45 wt%, including any and all endpoints and subranges therein, based on the total weight of the hot melt adhesive composition.

[0068] Examples of commercially available suitable conjugated diene-vinyl aromatic copolymers include those available from Kraton under the brand name KRATON. TM The obtained G1654 and G1650 (styrene-ethylene-butene-styrene (SEBS) triblock copolymers with molecular weights of approximately 200K and 100K, respectively) and p-SEBS (a partially hydrogenated SEBS with a molecular weight of approximately 100K, comprising approximately 30% styrene-terminated blocks and approximately 80% hydrogenation).

[0069] In any exemplary aspect, the crosslinkable polymer composition may further comprise at least one polymer containing at least one crosslinkable functional group. Exemplary polymers containing at least one crosslinkable functional group include ethylene-propylene-diene rubber (EPDM), pms-SEBS (styrene-ethylene-butene-styrene), thermosetting silicone rubber (HCR), ethylene-propylene rubber (EPR), butyl rubber, halogenated butyl rubber, hydrogenated rubber copolymers of p-alkylstyrene and at least one isomonoolefin having 4-7 carbon atoms, nitrile rubber and copolymers thereof, styrene-acrylate-acrylonitrile rubber (Sunigum®), hydrogenated nitrile rubber, acrylate rubber and copolymers thereof, ethylene-acrylate-glycidyl methacrylate elastomers, polyamide elastomers, polyester elastomers, natural rubber, and polyolefin copolymer elastomers having at least two repeating units derived from ethylene, propylene, butene, hexene, and octene. For example, the polymer containing at least one crosslinkable functional group may be an EPDM rubber having norbornene, hexadiene, or dicyclopentadiene monomer units.

[0070] Examples of commercially available suitable EPDM rubbers include extrusion grade NORDEL from Dow Chemical Company. TMIP 4725P.

[0071] In all respects, the content of a polymer containing at least one crosslinkable functional group in the hot melt adhesive composition is about 0-50 wt% based on the total weight of the hot melt adhesive composition. For example, the content of a polymer containing at least one crosslinkable functional group in the hot melt adhesive composition may be about 1-40 wt% based on the total weight of the hot melt adhesive composition, such as about 3-35 wt%, about 5-30 wt%, about 8-25 wt%, about 10-20 wt%, or about 7-22 wt%, including any and all endpoints and subranges therein.

[0072] In any exemplary aspect, when the crosslinkable polymer composition comprises a fully hydrogenated conjugated diene-vinyl aromatic copolymer, the crosslinkable polymer composition comprises at least one additional polymer having at least one crosslinkable functional group. In any exemplary aspect, when the crosslinkable polymer composition comprises a partially unsaturated conjugated diene-vinyl aromatic copolymer, the crosslinkable polymer composition may optionally comprise at least one additional polymer having at least one crosslinkable functional group.

[0073] vulcanized bags

[0074] The vulcanizing package of the dynamically vulcanizable composition contains a silane crosslinking agent and an organic peroxide. As described herein, the vulcanizing package facilitates peroxide vulcanization, resulting in carbon-carbon crosslinking of the thermoplastic elastomer upon blending, without the need for additional steps or materials. When thermoplastic elastomers are blended in hot melt adhesive compositions to form crosslinked polymer systems, the thermoplastic elastomers can be partially grafted with silane. The blends can be aged, allowing the crosslinked polymer system to form silane crosslinks from the silane grafting.

[0075] The silane crosslinking agent for the vulcanizing package can include various silanes. Examples of suitable silanes include those represented by the general formula: SiR x H 4-x , where x is 1-4, and each R is individually and independently a monovalent hydrocarbon group or a monovalent alkoxy group.

[0076] In all aspects, a monovalent hydrocarbon group can be a straight-chain, cyclic, or branched group. A monovalent hydrocarbon group can have 1-12 carbon atoms, 2-10 carbon atoms, or 3-8 carbon atoms. A monovalent hydrocarbon group can include one or more carbon-carbon double bonds. A monovalent hydrocarbon group can include one or more aromatic groups.

[0077] According to the present invention, the monovalent alkoxy group can be a monovalent hydrocarbon group attached to an oxygen atom. The monovalent hydrocarbon group of the monovalent alkoxy group can be a straight-chain, cyclic, or branched group. The monovalent hydrocarbon group of the monovalent alkoxy group can have 1-12 carbon atoms, 2-10 carbon atoms, or 3-8 carbon atoms. The monovalent hydrocarbon group of the monovalent alkoxy group can include one or more dicarbon-carbon bonds. The monovalent hydrocarbon group of the monovalent alkoxy group can include one or more aromatic groups.

[0078] In any exemplary aspect, the silane crosslinking agent may include vinyltrialkoxysilane. For example, the silane crosslinking agent may include vinyltrimethoxysilane, vinyltriethoxysilane, or combinations thereof.

[0079] The specific gravity of the silane crosslinking agent can be greater than or equal to about 0.90 or greater than or equal to about 0.95. The specific gravity of the silane can be less than or equal to about 1.05 or less than or equal to about 1. The specific gravity of the silane can be about 0.90-1.05, about 0.90-1.00, about 0.95-1.05, or about 0.95-1.00, including any and all endpoints and subranges therein.

[0080] In any aspect disclosed herein, the boiling point of the silane crosslinking agent may be greater than or equal to about 75°C or greater than or equal to about 100°C. The boiling point of the silane crosslinking agent may be less than or equal to about 150°C or less than or equal to about 125°C. For example, the boiling point of the silane crosslinking agent may be about 75°C-150°C, about 75°C-125°C, about 100°C-150°C, or about 100°C-125°C, including any and all endpoints and subranges therein.

[0081] In any aspect disclosed herein, the number-average molecular weight of the silane crosslinking agent may be greater than or equal to about 50 g / mol, greater than or equal to about 100 g / mol, greater than or equal to 150 g / mol, or greater than or equal to about 200 g / mol. The number-average molecular weight of the silane crosslinking agent may be less than or equal to about 500 g / mol, less than or equal to 400 g / mol, or less than or equal to about 300 g / mol. The number average molecular weight of the silane crosslinking agent can be approximately 50-500 g / mol, approximately 50-400 g / mol, approximately 50-300 g / mol, approximately 100-500 g / mol, approximately 100-400 g / mol, approximately 100-300 g / mol, approximately 150-500 g / mol, approximately 150-400 g / mol, approximately 150-300 g / mol, approximately 200-500 g / mol, approximately 200-400 g / mol, or approximately 200-300 g / mol, including any and all endpoints and subranges therein.

[0082] Examples of commercially available suitable silane crosslinking agents include SILQUEST from Momentive. TM A-171 grade vinyltrimethoxysilane under the brand.

[0083] As mentioned above, the vulcanizing package also contains an organic peroxide. The organic peroxide of the vulcanizing package can include a variety of peroxides and is not particularly limited. Examples of suitable peroxides include peroxides represented by the general formula ROOR, where each R is a single and independent monovalent hydrocarbon group.

[0084] According to the present invention, the monovalent hydrocarbon group of the organic peroxide can be a straight-chain, cyclic, or branched group. The monovalent hydrocarbon group of the organic peroxide can have 1-16 carbon atoms, 3-12 carbon atoms, or 5-10 carbon atoms. The monovalent hydrocarbon group of the organic peroxide can include one or more carbon-carbon double bonds. The monovalent hydrocarbon group of the organic peroxide can include one or more aromatic groups. According to the present invention, the organic peroxide can include peroxyketal peroxide, di-tert-alkyl peroxide, or combinations thereof. For example, the organic peroxide can include diisopropylbenzene peroxide (a di-tert-alkyl peroxide).

[0085] According to the present invention, the density of the organic peroxide can be greater than or equal to about 1.00 g / cm³. 3 or greater than or equal to approximately 1.05 g / cm³ 3 The density of organic peroxides can be less than or equal to about 1.20 g / cm³. 3 or less than or equal to approximately 1.15 g / cm³ 3 The density of organic peroxides can be approximately 1.00-1.20 g / cm³. 3 Approximately 1.00-1.15 g / cm³ 3 Approximately 1.05-1.20 g / cm³ 3 Or approximately 1.05-1.15 g / cm³ 3 This includes any and all endpoints and subranges within it.

[0086] Examples of commercially available suitable organic peroxides include BC-FF grade diisopropylbenzene peroxide from AkzoNobel's PERKADOX® brand.

[0087] According to the present invention, the dry weight ratio of the silane crosslinking agent to the organic peroxide in the vulcanizing package can be 3:1 or greater, 4:1 or greater, or 5:1 or greater. The dry weight ratio of the silane crosslinking agent to the organic peroxide in the vulcanizing package can be 20:1 or less, 15:1 or less, or 10:1 or less. The dry weight ratio of the silane crosslinking agent to the organic peroxide in the vulcanizing package can be 3:1 to 20:1, 3:1 to 15:1, 3:1 to 10:1, 4:1 to 20:1, 4:1 to 15:1, 4:1 to 10:1, 5:1 to 20:1, 5:1 to 15:1, 5:1 to 10:1, including any and all endpoints and sub-ranges therein. The dry weight of the silane crosslinking agent and the organic peroxide in the vulcanizing package can be 0.5-10% of the mass of the thermoplastic elastomer in the hot melt adhesive, including 1-8%, 2-7%, and 3-6%.

[0088] In any aspect disclosed herein, the vulcanizing package may be in the form of a dry silane masterbatch comprising a carrier material loaded with a silane crosslinking agent and an organic peroxide. The carrier material may include porous particles, fillers (such as silica, talc, calcium carbonate, microspheres, etc.), or combinations thereof. The porous particles may include highly porosimetric particles, such as plastics selected from polypropylene, ethylene vinyl acetate, polyethylene, and mixtures thereof. The carrier material may be loaded by immersing it in a solution containing the silane crosslinking agent, the organic peroxide, and other components (if present, such as additives) and then drying the carrier material to remove the solvent from the solution. Based on the dry weight ratio of silane / peroxide to carrier, the silane / peroxide loading of the carrier material may be 20% or more, 30% or more, or 40% or more. Based on the dry weight ratio of silane / peroxide to carrier, the silane / peroxide loading of the carrier material may be 80% or less, 70% or less, or 60% or less. Based on the dry weight ratio of silane / peroxide to carrier, the silane / peroxide loading of the carrier material can be 20-80%, 20-70%, 20-60%, 30-80%, 30-70%, 30-60%, 40-80%, 40-70%, 40-60%, including any and all endpoints and sub-ranges within this range. The dry silane masterbatch can be dry-blended with thermoplastic elastomers and fed into extrusion or injection molding processes to crosslink the thermoplastic elastomers.

[0089] Vulcanizates can exist in the form of solutions, dispersions, or emulsions containing silane crosslinking agents and organic peroxides. When forming dry silanes, vulcanizates can be mixed with porous particles to form a dry silane masterbatch, which can then be fed into an extrusion or injection molding process to crosslink thermoplastic elastomers. Alternatively, or in addition to dry silanes, vulcanizates can be directly injected into molten thermoplastic elastomers during extrusion or injection molding.

[0090] The hot melt adhesive may contain about 0.5-5 wt% silane. In any exemplary aspect, the amount of silane in the hot melt adhesive composition may be greater than or equal to about 0.5 wt%, for example including at least 0.75 wt%, at least 0.9 wt%, at least 1 wt%, at least 1.25 wt%, at least 1.5 wt%, at least 1.75 wt%, or at least 2 wt%, including all endpoints and subranges therein. In any exemplary aspect, the amount of silane in the hot melt adhesive composition may be less than or equal to about 5 wt%, for example including less than or equal to about 4.75 wt%, less than or equal to 4.5 wt%, less than or equal to 4.2 wt%, less than or equal to 4 wt%, less than or equal to 3.7 wt%, less than or equal to 3.5 wt%, less than or equal to 3.2 wt%, or less than or equal to about 3 wt%, including all endpoints and subranges therein. The amount of silane in the hot melt adhesive composition may be 0.5-5 wt%, for example including 0.5-about 4 wt%, about 0.5-3 wt%, about 1-5 wt%, about 1-4 wt%, or about 1-3 wt%, including any endpoints and subranges therein.

[0091] While not wishing to be bound by theory, it is believed that increasing the amount of organic peroxide in a dynamically vulcanizable composition can improve the crosslinking density and heat resistance of the resulting crosslinked polymer composition. In any aspect disclosed herein, the hot melt adhesive composition may contain about 0.05-1 wt% of organic peroxide. The amount of organic peroxide in the hot melt adhesive composition may be greater than or equal to about 0.05 wt%, greater than or equal to about 0.1 wt%, or even greater than or equal to about 0.2 wt%. The amount of organic peroxide in the hot melt adhesive composition may be less than or equal to about 1 wt%, less than or equal to 0.8 wt%, less than or equal to 0.6 wt%, or even less than or equal to about 0.4 wt%. The amount of organic peroxide in the hot melt adhesive composition may be about 0.05-1 wt%, about 0.05-0.8 wt%, about 0.05-0.6 wt%, about 0.05-0.4 wt%, about 0.1-1 wt%, about 0.1-0.8 wt%, about 0.1-0.6 wt%, about 0.1-0.4 wt%, about 0.2-1 wt%, about 0.2-0.8 wt%, about 0.2-0.6 wt%, or about 0.2-0.4 wt%, including all endpoints and subranges therein.

[0092] Olefin polymers

[0093] The hot melt adhesive composition also includes an olefin polymer to adjust hardness and mechanical properties and improve flow properties. The olefin polymer may include polyolefins, polyolefin elastomers, or combinations thereof. Suitable examples of polyolefins include polypropylene, polyethylene, or combinations thereof. The polyolefin may be high-density polyethylene (e.g., greater than or equal to 0.940 g / cm³). 3 It is one of the following: ) or crystalline polypropylene with a crystallinity percentage of at least about 60%.

[0094] According to the present invention, the olefin polymer may include polypropylene. Polypropylene may include polypropylene homopolymers (i.e., composed of propylene monomers) or polypropylene copolymers, the latter having more than 50 wt% propylene monomers and one or more additional comonomers such as C2 and C4-C. 12 Olefins. Polyethylene may include polyethylene homopolymers (i.e., composed of ethylene monomers) or polyethylene copolymers, the latter having more than 50 wt% ethylene monomers and additional comonomers such as C3-C. 12 Olefins.

[0095] The melt flow rate of polypropylene (230°C / 2.16 kg) can be greater than or equal to about 0.1 g / 10 min, greater than or equal to about 0.5 g / 10 min, greater than or equal to about 1 g / 10 min, or even greater than or equal to about 3 g / 10 min. The melt flow rate of polypropylene (230°C / 2.16 kg) can be less than or equal to about 10 g / 10 min, or even less than or equal to about 5 g / 10 min. The melt flow rate of polypropylene (230°C / 2.16 kg) can be about 0.1-10 g / 10 min, about 0.1-5 g / 10 min, about 0.5-10 g / 10 min, about 0.5-5 g / 10 min, about 1-10 g / 10 min, about 1-5 g / 10 min, about 3-10 g / 10 min, or about 3-5 g / 10 min, or any and all subranges formed by any of these endpoints.

[0096] According to the present invention, the density of the polyolefin can be greater than or equal to about 0.80 g / cm³. 3 or even greater than or equal to approximately 0.85 g / cm³ 3 The density of polyolefins can be less than or equal to approximately 1.10 g / cm³. 3 Or even less than or equal to about 1.00 g / cm³ 3 The density of polyolefins can be approximately 0.80-1.10 g / cm³. 3 Approximately 0.80-1.00 g / cm³ 3Approximately 0.85-1.10 g / cm³ 3 Or approximately 0.85-1.00 g / cm³ 3 or any and all subranges formed by any of these endpoints.

[0097] According to the present invention, the melting point of polyolefins can be greater than or equal to about 100°C, greater than or equal to about 110°C, or even greater than or equal to about 120°C.

[0098] According to the present invention, the yield tensile strength of the polyolefin can be greater than or equal to about 25 MPa, or even greater than or equal to about 30 MPa. The yield tensile strength of the polyolefin can be less than or equal to about 45 MPa, or even less than or equal to about 40 MPa. The yield tensile strength of the polyolefin can be about 25-45 MPa, about 25-40 MPa, about 30-45 MPa, or about 30-40 MPa, including any and all endpoints and subranges therein.

[0099] According to the present invention, the yield tensile elongation of the polyolefin can be greater than or equal to about 3%, or even greater than or equal to about 5%. The yield tensile elongation of the polyolefin can be less than or equal to about 20%, or even less than or equal to about 15%. The yield tensile elongation of the polyolefin can be about 3-20%, about 3-15%, about 5-20%, or about 5-15%, including any and all endpoints and subranges therein.

[0100] Examples of commercially available suitable polyolefins include polypropylene homopolymer grade 1102KR from Formosa Plastics' FORMOLENE® brand.

[0101] According to the present invention, polyolefin elastomers may include polypropylene elastomers. Examples of commercially available suitable polyolefin elastomers include polypropylene elastomer grades 6201 and 6202 from Exxon's VISTAMAXX™ brand.

[0102] According to the present invention, polyolefin elastomers may include olefin block copolymers, ethylene... -Olefin copolymers or combinations thereof. Olefin block copolymers may include ethylene. -Olefin repeating unit. Ethylene -The repeating unit of the olefin is ethylene followed by C3-C4. 12 Products of olefin polymerization. For example, ethylene. -Olefin repeating units may include ethylene-octene copolymers, ethylene-hexene copolymers, ethylene-butene copolymers, or combinations thereof.

[0103] According to the present invention, the melt flow rate (190°C / 2.16 kg) of the olefin block copolymer can be greater than or equal to about 1 g / 10 min, or even greater than or equal to about 5 g / 10 min. The melt flow rate (190°C / 2.16 kg) of the olefin block copolymer can be less than or equal to about 25 g / 10 min, or even less than or equal to about 20 g / 10 min. The melt flow rate (190°C / 2.16 kg) of the olefin block copolymer can be about 1-25 g / 10 min, about 1-20 g / 10 min, about 5-25 g / 10 min, or about 5-20 g / 10 min, or any and all subranges formed by any of these endpoints.

[0104] According to the present invention, the density of the olefin block copolymer can be greater than or equal to about 0.80 g / cm³. 3 or even greater than or equal to approximately 0.85 g / cm³ 3 The density of olefin block copolymers can be less than or equal to about 0.95 g / cm³. 3 or even less than or equal to approximately 0.90 g / cm³ 3 The density of olefin block copolymers can be approximately 0.80-0.95 g / cm³. 3 Approximately 0.80-0.90 g / cm³ 3 Approximately 0.85-0.95 g / cm³ 3 Or approximately 0.85-0.90 g / cm³ 3 This includes any and all endpoints and subranges within it.

[0105] According to the present invention, the Shore A hardness of the olefin block copolymer can be greater than or equal to about 50 or even greater than or equal to about 60. The Shore A hardness of the olefin block copolymer can be less than or equal to about 85 or even less than or equal to about 75. The Shore A hardness of the olefin block copolymer can be about 50-85, about 50-75, about 60-85, or about 60-75, including any and all endpoints and subranges therein.

[0106] Examples of commercially available suitable olefin block copolymers include 9500 and 9817 from Dow Chemical Company’s INFUSE™ brand.

[0107] ethylene -Olefin copolymers are ethylene and C3-C 12 Products of olefin polymerization. For example, ethylene. olefin copolymers may include ethylene-octene copolymers, ethylene-hexene copolymers, ethylene-butene copolymers, or combinations thereof.

[0108] According to the present invention, ethylene- The melt flow rate (190℃ / 2.16 kg) of the olefin copolymer can be greater than or equal to 0.1 g / 10 min or even greater than or equal to 0.25 g / 10 min. Ethylene- The melt flow rate (190℃ / 2.16 kg) of olefin copolymers can be less than or equal to 3 g / 10 min or even less than or equal to 1 g / 10 min. Ethylene- The melt flow rate (190°C / 2.16 kg) of the olefin copolymer can be 0.1-3 g / 10 min, 0.1-1 g / 10 min, 0.25-3 g / 10 min, or even 0.25-1 g / 10 min, including any and all endpoints and subranges therein.

[0109] According to the present invention, ethylene- The density of olefin copolymers can be greater than or equal to 0.80 g / cm³. 3 Or even greater than or equal to 0.85 g / cm³ 3 Ethylene- The density of olefin copolymers can be less than or equal to 0.95 g / cm³. 3 Or even less than or equal to 0.90 g / cm³ 3 Ethylene- The density of olefin copolymers can be 0.80-0.95 g / cm³. 3 0.80-0.90 g / cm³ 3 0.85-0.95 g / cm³ 3 Or even 0.85-0.90 g / cm³ 3 This includes any and all endpoints and subranges within it.

[0110] According to the present invention, ethylene- The Mooney viscosity (ML 1+4, 121℃) of olefin copolymers can be greater than or equal to 20, greater than or equal to 30, or even greater than or equal to 40. Ethylene- The Mooney viscosity (ML 1+4, 121℃) of olefin copolymers can be less than or equal to 70, less than or equal to 60, or even less than or equal to 50. Ethylene- The Mooney viscosity (ML 1+4, 121°C) of the olefin copolymer can be 20-70, 20-60, 20-50, 30-70, 30-60, 30-50, 40-70, 40-60, or 40-50, or any and all subranges formed by any of these endpoints.

[0111] According to the present invention, ethylene- The Shore A hardness of olefin copolymers can be greater than or equal to 40 or even greater than or equal to 45. Ethylene- The Shore A hardness of olefin copolymers can be less than or equal to 60 or even less than or equal to 65. Ethylene- The Shore A hardness of the olefin copolymer can be 40-60, 40-55, 45-60, or 45-55, or any and all subranges formed by any of these endpoints.

[0112] Commercially available suitable ethylene Examples of olefin copolymers include XLT 8677 from the ENGAGE™ brand of Dow Chemical Company.

[0113] According to the present invention, the hot melt adhesive composition may contain about 2-50 wt% of an olefin polymer, about 4-40 wt% of an olefin polymer, or about 6-30 wt% of an olefin polymer. The amount of olefin polymer in the hot melt adhesive composition may be greater than or equal to about 2 wt%, greater than or equal to about 4 wt%, or even greater than or equal to about 6 wt%. The amount of olefin polymer in the hot melt adhesive composition may be less than or equal to about 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, less than or equal to 17 wt%, less than or equal to 15 wt%, less than or equal to 13 wt%, or even less than or equal to about 10 wt%. The amount of olefin polymer in the hot melt adhesive composition may be about 2-50 wt%, about 2-40 wt%, about 2-30 wt%, about 2-20 wt%, about 2-17 wt%, about 2-15 wt%, about 2-13 wt%, about 2-10 wt%, about 4-50 wt%, about 4-40 wt%, about 4-30 wt%, about 4-20 wt%, about 4-17 wt%, about 4-15 wt%, about 4-13 wt%, about 4-10 wt%, about 6-50 wt%, about 6-40 wt%, about 6-30 wt%, about 6-20 wt%, about 6-17 wt%, about 6-15 wt%, about 6-13 wt%, or about 6-10 wt%, or any and all subranges formed by any of these endpoints.

[0114] plasticizer

[0115] According to the present invention, the hot melt adhesive composition further comprises a plasticizer. The plasticizer can help improve the flowability of the hot melt adhesive composition. According to the present invention, the plasticizer may include a non-polar plasticizer (such as mineral oil). In any exemplary aspect, the hot melt adhesive composition comprises an oil.

[0116] According to the present invention, the amount of plasticizer in the hot melt adhesive composition can be greater than or equal to about 0 wt%, greater than or equal to about 10 wt%, greater than or equal to about 20 wt%, greater than or equal to about 25 wt%, greater than or equal to about 30 wt%, or greater than or equal to about 35 wt%. The amount of plasticizer in the hot melt adhesive composition can be less than or equal to about 60 wt%, less than or equal to 55 wt%, less than or equal to 50 wt%, less than or equal to 45 wt%, less than or equal to 40 wt%, or less than or equal to about 35 wt%. The amount of plasticizer in the hot melt adhesive composition can be about 0-60 wt%, including about 10-55 wt%, about 20-50 wt%, about 25-45 wt%, about 30-40 wt%, and any and all subranges formed by any of these endpoints.

[0117] Examples of commercially available suitable plasticizers include PSO 380 from Petro-Canada's PURETOL™ brand.

[0118] Tackifier

[0119] According to the present invention, the hot melt adhesive composition further comprises a tackifier for adhesive applications (such as hot melt adhesives).

[0120] According to the present invention, the tackifier may include a hydrocarbon resin. Exemplary hydrocarbon resins may include aliphatic resins (such as C5 resins), aromatic resins (such as C9 resins), dicyclopentadiene resins, and resins comprising two or more combinations of aliphatic monomers, aromatic monomers, and dicyclopentadiene. The hydrocarbon resin may be hydrogenated. According to the present invention, the number average molecular weight of the hydrocarbon resin may be less than or equal to about 2,000 g / mol, less than or equal to 1,500 g / mol, less than or equal to 1,200 g / mol, less than or equal to 1,100 g / mol, less than or equal to 1,000 g / mol, or less than or equal to about 900 g / mol.

[0121] According to the present invention, based on the total weight of the hot melt adhesive composition, the hot melt adhesive composition may contain about 15-50 wt% of a tackifier, or about 17-40 wt% of a tackifier, or about 20-30 wt% of a tackifier. Based on the total weight of the hot melt adhesive composition, the amount of tackifier in the hot melt adhesive composition may be greater than or equal to about 15 wt%, greater than or equal to about 17 wt%, or even greater than or equal to about 20 wt%. Based on the total weight of the hot melt adhesive composition, the amount of tackifier in the hot melt adhesive composition may be less than or equal to about 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 27 wt%, or even less than or equal to about 25 wt%. In any aspect disclosed herein, the amount of tackifier in the hot melt adhesive composition may be about 15-50 wt%, about 15-40 wt%, about 15-30 wt%, about 15-27 wt%, about 15-25 wt%, about 17-50 wt%, about 17-40 wt%, about 17-30 wt%, about 17-27 wt%, about 17-25 wt%, about 20-50 wt%, about 20-40 wt%, about 20-30 wt%, about 20-27 wt%, or even about 20-25 wt%, or any and all endpoints and subranges thereof.

[0122] Examples of commercially available suitable tackifiers include brand name R1140 from Eastman Chemicals' PLASTOLYN™ brand and ESCOREZ from Exxon Mobil Corporation. TM 5340 (softening point is 140℃).

[0123] Co-crosslinked polymers

[0124] According to the present invention, the hot melt adhesive composition may further include a co-crosslinked polymer, which can be crosslinked with a thermoplastic elastomer through a vulcanization package.

[0125] According to the present invention, the co-crosslinked polymer may include ethylene-vinyl acetate. Based on the total weight of ethylene-vinyl acetate, the vinyl acetate content of the ethylene-vinyl acetate is greater than or equal to about 10 wt%, greater than or equal to about 25 wt%, greater than or equal to about 40 wt%, or even greater than or equal to 55 wt%. The vinyl acetate content of the ethylene-vinyl acetate may be less than or equal to about 80 wt%, less than or equal to 70 wt%, or even less than or equal to about 60 wt%. The vinyl acetate content of the ethylene-vinyl acetate may be about 10-80 wt%, about 10-70 wt%, about 10-60 wt%, about 25-80 wt%, about 25-70 wt%, about 25-60 wt%, about 40-80 wt%, about 40-70 wt%, about 40-60 wt%, about 55-80 wt%, about 55-70 wt%, or about 55-60 wt%, or any and all endpoints and subranges thereof.

[0126] According to the present invention, the hot melt adhesive composition may contain about 25-45 wt% of a co-crosslinked polymer, or about 27-43 wt% of a co-crosslinked polymer, or about 30-40 wt% of a co-crosslinked polymer. The amount of co-crosslinked polymer in the hot melt adhesive composition may be greater than or equal to about 25 wt%, greater than or equal to about 27 wt%, or even greater than or equal to about 30 wt%. The amount of co-crosslinked polymer in the hot melt adhesive composition may be less than or equal to about 45 wt%, less than or equal to 43 wt%, or even less than or equal to about 40 wt%. The amount of co-crosslinked polymer in the hot melt adhesive composition may be about 25-45 wt%, about 25-43 wt%, about 25-40 wt%, about 27-45 wt%, about 27-43 wt%, about 27-40 wt%, about 30-45 wt%, about 30-43 wt%, or about 30-40 wt%, or any and all endpoints and subranges thereof.

[0127] Examples of commercially available suitable co-vulcanizing polymers include grade 265 from the ELVAX™ brand of Dow Chemical Company.

[0128] additive

[0129] According to the present invention, the hot melt adhesive composition may further comprise one or more additives. The additives may include: adhesion promoters; bactericides; antifogging agents; antistatic agents; foaming agents; adhesives and bonding polymers; dispersants; flame retardants and smoke suppressants; mineral fillers; initiators; lubricants; mica; pigments, colorants and dyes; processing aids; release agents; silanes, titanates and zirconates; anti-slip and anti-blocking agents; stearates; ultraviolet absorbers; viscosity modifiers; waxes; or combinations thereof.

[0130] Crosslinking of thermoplastic elastomers

[0131] According to the present invention, hot melt adhesive compositions comprising thermoplastic elastomers, vulcanizing agents (such as silanes), oils, tackifiers, olefin polymers, and any optional components can be blended to form dynamic vulcanized compositions with favorable crosslinking density and heat resistance.

[0132] In any exemplary aspect, the hot melt adhesive composition may include 90-99.9 parts of thermoplastic elastomer and 0.1-10 parts of vulcanizing package, for example, 94-99.5 parts of thermoplastic elastomer and 0.5-5 parts of vulcanizing package. In any exemplary aspect, based on the dry weight of the vulcanizing package relative to the weight of the thermoplastic elastomer in the hot melt adhesive composition, the hot melt adhesive composition may include 0.1-10% of the vulcanizing package, for example, 0.2-6%, 0.3-4%, 0.5-3%, and 1.0-2%, including all endpoints and subranges therein.

[0133] Hot melt adhesive compositions can be prepared by batch or continuous methods. Blending (also known as compounding) apparatus is well known to those skilled in the art and typically includes: feeding facilities, particularly at least one hopper for powdered materials and / or at least one injection pump for liquid materials; high-shear blending apparatus, such as a co-rotating or counter-rotating twin-screw extruder, typically including a feed screw placed in a heated cylinder (or tube); an output head that imparts shape to the extrudate; and facilities for cooling the extrudate by air or circulating water. The extrudate is typically in the form of rods that exit the equipment continuously and can be cut or formed into granules. However, other forms can also be obtained by fitting a die of the desired shape onto the output die.

[0134] For example, a hot melt adhesive composition (i.e., thermoplastic elastomer, polyolefin polymer, oil, tackifier, vulcanizing agent, and any additives) can be fed into an extruder (e.g., a 27 mm Leistriz Twin Extruder (L / D 52)) and blended. Blending (e.g., in the extruder barrel) can be performed at temperatures of 240-450°C. The process is carried out at approximately 115-232°C. According to the present invention, blending leads to carbon-carbon crosslinking, and silane moieties are grafted onto thermoplastic elastomers and polyolefin polymers.

[0135] As described herein, a vulcanizing package containing both an organic peroxide and a silane enables the carbon-carbon bonds of a thermoplastic elastomer to crosslink without the need for additional steps or materials (e.g., a moisture-curing catalyst). Therefore, in some aspects, a blending step involving a thermoplastic elastomer, an organic peroxide, and a silane can be performed without a catalyst. Furthermore, a blending step involving a thermoplastic elastomer, an organic peroxide, and a silane can be performed in the absence of moisture (e.g., water). Therefore, silanes can also be grafted onto the thermoplastic elastomer in an extruder. However, due to the absence of moisture, no silane crosslinking occurs in the extruder, or only a very small degree (to any extent that crosslinking occurs completely). Upon exiting the extruder, the thermoplastic elastomer contains little or no silane-silane crosslinking. The extrudate can be applied to a substrate as a hot melt adhesive. In some aspects, the hot melt adhesive is immersed in hot water to cure it, such that the crosslinked polymer system contains silane-silane crosslinks.

[0136] performance

[0137] In all aspects described herein, the elongation at break of the hot melt adhesive, measured according to ASTM D412, is greater than or equal to about 500% after extrusion and before hot water immersion. For example, the elongation at break of the hot melt adhesive may be greater than or equal to about 500%, greater than or equal to about 525%, greater than or equal to about 550%, greater than or equal to about 575%, greater than or equal to about 600%, greater than or equal to about 625%, or greater than or equal to about 650%. In all aspects of the invention, the elongation at break of the hot melt adhesive is about 500-800%, about 550-775%, about 575-750%, about 600-725%, or any and all endpoints and subranges thereof.

[0138] According to the present invention, prior to hot water immersion, the Shore A hardness of the hot melt adhesive, measured according to ASTM D2240, can be greater than or equal to about 20, including, for example, greater than or equal to about 25, greater than or equal to about 30, greater than or equal to about 35, or greater than or equal to about 40. The Shore A hardness of the hot melt adhesive can be less than about 95, including, for example, less than or equal to 90, less than or equal to 85, less than or equal to 80, less than or equal to 75, less than about 70, less than about 65, less than about 60, less than about 55, or even less than or equal to about 50. The Shore A hardness of the hot melt adhesive... Hardness A can range from approximately 20-95, 20-90, 20-85, 20-80, 20-75, 20-65, 20-60, 20-55, 20-50, 25-95, 25-90, 25-85, 25-80, 25-75, 25-65, 25-60, 25-55, 25-50, 30-95, 30-90, 30-85, 30-80, 30-75, and approximately 3... 0-65, approximately 30-60, approximately 30-55, approximately 30-50, approximately 35-95, approximately 35-90, approximately 35-85, approximately 35-80, approximately 35-75, approximately 35-65, approximately 35-60, approximately 35-55, approximately 35-50, approximately 40-95, approximately 40-90, approximately 40-85, approximately 40-80, approximately 40-75, approximately 40-65, approximately 40-60, approximately 40-55, or even approximately 40-50, including all endpoints and subranges in between.

[0139] According to the present invention, the tensile strength at break of the hot melt adhesive, measured according to ASTM D412 before hot water immersion, can be greater than or equal to about 1.5 MPa, greater than or equal to about 2.0 MPa, greater than or equal to about 2.5 MPa, or even greater than or equal to about 3.0 MPa. The tensile strength at break of the hot melt adhesive can be less than or equal to about 8.0 MPa, for example including less than or equal to 7.5 MPa, less than or equal to 7.0 MPa, less than or equal to 6.5 MPa, or even less than or equal to about 6.0 MPa. The tensile strength at break of the hot melt adhesive can be approximately 1.5-8.0 MPa, approximately 1.5-7.5 MPa, approximately 1.5-7.0 MPa, approximately 1.5-6.5 MPa, approximately 1.5-6.0 MPa, approximately 2.0-8.0 MPa, approximately 2.0-7.5 MPa, approximately 2.0-7.0 MPa, approximately 2.0-6.5 MPa, approximately 2.0-6.0 MPa, approximately 2.5-8.0 MPa, approximately 2.5-7.5 MPa, approximately 2.5-7.0 MPa, approximately 2.5-6.5 MPa, approximately 2.5-6.0 MPa, approximately 3.0-8.0 MPa, approximately 3.0-7.5 MPa, approximately 3.0-7.0 MPa, approximately 3.0-6.5 MPa, or even approximately 3.0-6.0 MPa, including all endpoints and subranges therein.

[0140] According to the present invention, before hot water immersion, the dynamic mechanical analysis (DMA) storage modulus of the hot melt adhesive at 30°C and 10 Hz can be greater than or equal to about 9 MPa, greater than or equal to about 10 MPa, greater than or equal to about 11 MPa, greater than or equal to about 12 MPa, or greater than or equal to about 13 MPa. For example, the dynamic mechanical analysis (DMA) storage modulus of hot melt adhesives at 30°C and 10 Hz can be approximately 9–17 MPa, approximately 9–16 MPa, approximately 9–15 MPa, approximately 9–14 MPa, approximately 10–17 MPa, approximately 10–16 MPa, approximately 10–15 MPa, approximately 10–14 MPa, approximately 11–17 MPa, approximately 11–16 MPa, approximately 11–15 MPa, approximately 11–14 MPa, approximately 12–17 MPa, approximately 12–16 MPa, approximately 12–15 MPa, or approximately 12–14 MPa, including all endpoints and subranges therein.

[0141] According to the present invention, the dynamic mechanical analysis (DMA) storage modulus of the hot melt adhesive at 80°C and 10 Hz before hot water immersion can be greater than or equal to about 4 MPa, greater than or equal to about 4.5 MPa, greater than or equal to about 5 MPa, greater than or equal to about 5.5 MPa, or greater than or equal to about 6 MPa. For example, the dynamic mechanical analysis (DMA) storage modulus of the hot melt adhesive at 80°C and 10 Hz can be about 4-10 MPa, about 4-9 MPa, about 4-8 MPa, about 4.5-10 MPa, about 4.5-9 MPa, about 4.5-8 MPa, about 5-10 MPa, about 5-9 MPa, about 5-8 MPa, about 5.5-10 MPa, about 5.5-9 MPa, or about 5.5-8 MPa, including all endpoints and sub-ranges therein.

[0142] According to the present invention, after immersion in hot water (80°C for 24 hours), the dynamic mechanical analysis (DMA) storage modulus of the crosslinked hot melt adhesive at 30°C and 10 Hz can be greater than or equal to about 10 MPa, greater than or equal to about 11 MPa, greater than or equal to about 12 MPa, or greater than or equal to about 13 MPa. For example, the DMA storage modulus of the crosslinked hot melt adhesive at 30°C and 10 Hz can be about 10-20 MPa, about 10-19 MPa, about 10-18 MPa, about 10-17 MPa, about 11-20 MPa, about 11-19 MPa, about 11-18 MPa, about 11-17 MPa, about 12-20 MPa, about 12-19 MPa, or about 12-18 MPa, including all endpoints and subranges therein.

[0143] According to the present invention, after immersion in hot water (80°C for 24 hours), the dynamic mechanical analysis (DMA) storage modulus of the crosslinked hot melt adhesive at 80°C and 10 Hz can be greater than or equal to about 6 MPa, greater than or equal to about 6.5 MPa, greater than or equal to about 7 MPa, greater than or equal to about 7.5 MPa, or greater than or equal to about 8 MPa. For example, the DMA storage modulus of the crosslinked hot melt adhesive at 80°C and 10 Hz can be about 6-12 MPa, about 6-11.5 MPa, about 6-11 MPa, about 6.5-12 MPa, about 6.5-11.5 MPa, about 6.5-11 MPa, about 7-12 MPa, about 7-11.5 MPa, about 7-11 MPa, about 7.5-12 MPa, about 7.5-11.5 MPa, or about 7.5-11 MPa, including all endpoints and sub-ranges therein.

[0144] In all aspects of the invention, prior to hot water immersion, the fabric adhesive peel strength of the hot melt adhesive is about 4-7 lb / in, about 4.5-7 lb / in, about 5-7 lb / in, about 4-6.5 lb / in, about 4.5-6.5 lb / in, about 5-6.5 lb / in, about 4-6 lb / in, about 4.5-6 lb / in, about 5-6 lb / in, about 4-5.5 lb / in, about 4.5-5.5 lb / in, or about 5-5.5 lb / in, including all endpoints and sub-ranges therein.

[0145] In all aspects of the invention, after immersion in hot water (80°C for 24 hours), the crosslinked hot melt adhesive exhibits a fabric adhesive peel strength of approximately 4-7 lb / in, approximately 4.5-7 lb / in, approximately 5-7 lb / in, approximately 4-6.5 lb / in, approximately 4.5-6.5 lb / in, approximately 5-6.5 lb / in, approximately 4-6 lb / in, approximately 4.5-6 lb / in, approximately 5-6 lb / in, approximately 4-5.5 lb / in, or approximately 4.5-5.5 lb / in, including all endpoints and sub-ranges therein.

[0146] In all respects described herein, the crosslinked hot melt adhesive maintains a peel strength greater than approximately 75% of the peel strength measured before immersion in hot water. For example, after immersion in hot water (80°C for 24 hours), the crosslinked hot melt adhesive maintains a peel strength greater than approximately 75%, greater than approximately 80%, greater than approximately 85%, or greater than approximately 90% of the peel strength measured before immersion in hot water.

[0147] Crosslinking methods for thermoplastic elastomers

[0148] According to the present invention, a method for forming a crosslinked thermoplastic elastomer includes blending one or more of a thermoplastic elastomer, a polyolefin polymer, an oil, a tackifier, and a vulcanizing package to form a thermoplastic polymer blend. As described above, the vulcanizing package may be a dry silane masterbatch, and the thermoplastic elastomer, the polyolefin polymer, and the dry silane masterbatch may be dry-blended. The method further includes melting the thermoplastic elastomer and the polyolefin polymer to form a crosslinkable thermoplastic polymer melt, and extruding the crosslinkable thermoplastic polymer melt to form a hot melt adhesive. The method includes a one-step conversion process in which the thermoplastic elastomer in the polymer particles undergoes crosslinking, and there is no separate silane grafting process.

[0149] As described above, instead of dry silane masterbatch, the vulcanizing package may include a solution of silane crosslinking agent and organic peroxide. Therefore, instead of dry polymer blends (such as thermoplastic elastomers and polyolefin polymers) and dry silane masterbatch, and subsequently melting the thermoplastic polymer blend, the method may include blending one or more polymers with a solution and melting the blend to form a crosslinkable thermoplastic polymer melt, which is then extruded to form a hot melt adhesive composition.

[0150] In any of the aspects described herein, the hot melt adhesive composition may be prepared as a hot melt adhesive film or any other form generally known and used for hot melt adhesive applications, including but not limited to sheets, multilayer laminates, coatings, tapes, strips, foams, adhesive tapes, fabrics, filaments, ribbons, fibers, multi-fibers or fiber webs.

[0151] In any of the exemplary aspects described herein, crosslinked hot melt adhesive compositions can be wet-cured by immersion in hot water to further increase storage modulus and significantly improve hot water resistance. In any aspect disclosed herein, the hot melt adhesive can be laminated together between substrates, and heat and pressure can be applied to form a laminate. The laminate is then immersed in hot water (e.g., water at a temperature greater than or equal to about 80°C) in direct contact to cure the hot melt adhesive. Thus, in any of the aspects described herein, direct contact with water, such as contact with hot water during a washing cycle, effectively cures the hot melt adhesive without the use of a catalyst.

[0152] application

[0153] As described above, the hot melt adhesive composition can be prepared in any form, such as an adhesive film or adhesive tape. When the hot melt adhesive composition is prepared as an adhesive film, the film thickness is about 15-300 μm, about 18-100 μm, or about 20-55 μm. The film width can be about 5-40 cm.

[0154] In any respect, a hot-melt adhesive composition (e.g., an adhesive film, adhesive webbing, etc.) may be incorporated into a multilayer composite material. A multilayer composite material may include two or more films or layers. According to the aspects described herein, a multilayer composite material may include an adhesive film adhered to a fabric backing (such as a substrate). In one or more aspects described herein, a multilayer composite material may include an adhesive film adhered to a release liner.

[0155] In any aspect disclosed herein, the hot melt adhesive composition can be used in textile or apparel applications. In these applications, the substrate to which the hot melt adhesive composition adheres can include a variety of fabrics and textiles, including but not limited to nylon, polyester, acrylic, polyurethane, olefins, neoprene, acetate, spandex, and combinations thereof. According to the various aspects provided herein, the hot melt adhesive composition is used to form an adhesive layer in a seam. The adhesive layer can be, for example, an adhesive film or adhesive webbing. The seam can include a first portion of fabric, a second portion of fabric, and the adhesive layer. The first and second portions of fabric can be of the same type (e.g., nylon, polyester, acrylic, polyurethane, olefins, neoprene, acetate, spandex, and combinations thereof) or of different types. The second portion of fabric at least partially overlaps the first portion of fabric to form the seam portion. The adhesive layer is located in the seam portion and adheres the first portion of fabric to the second portion of fabric.

[0156] As described herein, a seam is prepared by providing a first part fabric, a second part fabric, and an adhesive layer. As mentioned above, the first and second part fabrics can be of the same type (e.g., nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, spandex, and combinations thereof) or different types of fabrics. An adhesive layer is positioned between the first and second part fabrics to form a seam portion, wherein the second part fabric at least partially overlaps the first part fabric. The seam portion may be seamless (e.g., not containing seams connecting the first and second part fabrics) or may include seams connecting the first and second part fabrics. The seam portion is then heated, thereby bonding the first and second part fabrics together with the adhesive layer.

[0157] Example

[0158] Table 1 below describes the sources of the components that form Comparative Examples C1-C2 and Examples E1-E5.

[0159] Table 1:

[0160]

[0161] Tables 2-3 below describe the formulations used to form Comparative Examples C1-C2 and Examples E1-E5, as well as some characteristics of Comparative Examples C1-C2 and Examples E1-E5.

[0162] To prepare samples for comparative examples C1-C2 and examples E1-E5, the components of the formulations listed in Tables 2-3 were added to a 27 MM Leistriz twin-screw extruder (L / D / 52) and mixed at a barrel temperature of 194°C and a speed of 400 rpm. The mixture was extruded using a 6-inch (approximately 15.2 cm) wide die at 194°C at a speed of approximately 6.30-7.6 g / s.

[0163] A laminated film is prepared by placing a membrane between two layers of fabric. The fabric is a nylon / spandex fabric. Lamination is performed by heating each layer to a temperature of 160°C for 30 seconds.

[0164] Temperature resistance was recorded using Dynamic Mechanical Analysis (DMA) storage modulus, measured using a Q800 DMA where samples were heated from 30°C to 100°C at a rate of 3°C / min with an oscillation frequency of 10 Hz. For samples immersed in water, the laminate was dried at room temperature for 24 hours after immersion, followed by a peel test. Peel force was measured using Instron at a peel angle of 180°. Shore A hardness, modulus at 100%, tensile strength at break, and elongation at break were measured prior to immersion in water.

[0165] Table 2

[0166]

[0167] Failed at 55℃

[0168] Table 3

[0169]

[0170] As shown in Table 2, Comparative Examples C1 and C2 used standard, fully hydrogenated SEBS with either low molecular weight (Comparative Example C1) or high molecular weight (Comparative Example C2). The comparative examples were not crosslinked as described herein. Comparative Example C1 exhibited good film extrusion properties at thicknesses of 1–2 mil, but the DMA storage modulus could only be measured up to 55°C, after which the film lost rigidity and could not be further evaluated. Additionally, Comparative Example C1 lost over 40% of its peel strength after immersion in water. Comparative Example C2 comprised fully hydrogenated SEBS with a higher molecular weight than the SEBS in Comparative Example C1. Due to the increased molecular weight, Comparative Example C2 could not be extruded into a film. The DMA storage modulus (7 MPa) of Comparative Example C2 at 80°C was comparable to that of Comparative Example C1 at 30°C (7 MPa), indicating that the higher molecular weight SEBS had better temperature resistance than the lower molecular weight hydrogenated SEBS.

[0171] As shown in Table 3, the crosslinked polymer systems (Examples E1-E4) formed from the dynamically vulcanizable compositions formed good films while exhibiting improved hot water resistance. These dynamically vulcanizable compositions comprise a thermoplastic elastomer in the form of partially hydrogenated SEBS (p-SEBS), a polyolefin polymer (FORMOLENE® 1102K or INFUSE), and... TM D9500), Oil (PURETOL) TM PSO 380), tackifier (ESCOREZ) TM 5340), silane (SILQUEST) TM Example E3 is similar in formulation to Examples E1 and E2, but also contains EPDM rubber. Example E4 contains EPDM rubber and an olefin block copolymer (INFUSE). TM D9500) replaced the polypropylene (FORMOLENE® 1102K) used in Examples E1-E3. Examples E1 and E3 exhibited higher DMA storage modulus at 80°C than Comparative Example C2 at 80°C, and this increase further after immersion in hot water. Furthermore, Examples E1-E4 maintained greater than 90% of their peel strength after hot water immersion. Example E3 showed no loss of peel strength after hot water immersion. Examples E3 and E4 demonstrate that various polyolefin polymers can be added without negatively impacting processability or hot water resistance. Additionally, Examples E3 and E4 show that the addition of EPDM can further improve hot water resistance without negatively impacting processability.

[0172] Example E5 in Table 3 illustrates that the crosslinked polymer system formed from the dynamically vulcanizable composition can form a good film while exhibiting improved hot water resistance. The dynamically vulcanizable composition contains fully hydrogenated SEBS (KRATON). TM Thermoplastic elastomers in the form of G1650, EPDM rubber, polyolefin polymers (FORMOLENE® 1102K), and oils (PURETOL) TM PSO 380), tackifier (ESCOREZ) TM 5340), silane (SILQUEST) TM A-171) and organic peroxide (PERKADOX® BC-FF). Specifically, Example E5 contains the same SEBS polymer (KRATON) as Comparative Example C1. TMWhile G1650 was used, the addition and crosslinking of EPDM provided an improved DMA modulus at 80°C. Although the DMA modulus of Example E5 at 80°C was initially lower than that of Comparative Example C2 at 80°C, after immersion in hot water, the DMA modulus of Example E5 at 80°C was greater than that of Comparative Example C2. Furthermore, after immersion in hot water for 24 hours, Example E5 retained a peel strength greater than 90%.

[0173] Therefore, Examples E1-E5 demonstrate that moisture curing results in a higher DMA modulus at 80°C than Comparative Example C2 (containing high molecular weight SEBS), while also enabling the compositions of Examples E1-E5 to be extruded into films. Examples E1-E5 also each exhibit a significant improvement in hot water resistance.

[0174] It is obvious that various adjustments and changes can be made without departing from the scope of the invention as defined in the appended claims. More specifically, while some aspects of the invention are identified herein as preferred or particularly advantageous, it is contemplated that the invention is not limited to these aspects.

Claims

1. A hot melt adhesive composition comprising: Dynamic vulcanization compositions comprising reaction products of the following substances: Crosslinkable thermoplastic elastomers, including: Partially unsaturated conjugated diene-vinyl aromatic copolymers and optionally ethylene-propylene diene trimers; or fully hydrogenated conjugated diene-vinyl aromatic copolymers and ethylene-propylene diene trimers; Polyolefin polymers; Oil; Tackifiers; and Silane compounds.

2. The hot melt adhesive composition of any of the preceding claims, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer is selected from partially hydrogenated styrene-butadiene rubber, partially hydrogenated styrene-butadiene block copolymer, partially hydrogenated styrene-isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene rubber, partially hydrogenated styrene-butadiene / isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene block copolymer, and combinations thereof.

3. The hot melt adhesive composition of any of the preceding claims, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer is a block copolymer comprising blocks defined by general formula (I): The w, x, y, and z units are randomly distributed in the block, each R1 is independently a hydrogen atom or a methyl group, and each R2 is independently a hydrogen atom or a methyl group, provided that at least one R2 in each unit is a hydrogen atom; and the total molar percentage of the y and z units is approximately 30-90% compared to the sum of the w, x, y, and z units in the block.

4. The hot melt adhesive composition of any of the preceding claims, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer has a number average molecular weight of about 50,000-200,000 g / mol.

5. The hot melt adhesive composition of any of the preceding claims, wherein the fully hydrogenated conjugated diene-vinyl aromatic copolymer has a number average molecular weight of about 50,000-200,000 g / mol.

6. A hot melt adhesive webbing comprising an adhesive composition of any one of the preceding claims.

7. A hot melt adhesive film comprising the adhesive composition of any one of claims 1-6.

8. The hot melt adhesive film of claim 7, wherein the thickness of the adhesive film is 20-300 µm.

9. The hot melt adhesive film of claim 8, wherein the adhesive film is part of a multilayer composite material comprising two or more films.

10. The hot melt adhesive film of any one of claims 7-9, wherein the adhesive film is part of a multilayer composite material comprising the film adhered to a fabric backing.

11. The hot melt adhesive film of any one of claims 7-9, wherein the adhesive film is part of a multilayer composite material comprising the film adhered to a release liner.

12. The hot melt adhesive film of any one of claims 7-9, wherein the width of the adhesive film is 5-40 cm.

13. A seam comprising: First part: fabric; The second part of the fabric overlaps at least partially with the first part of the fabric to form the seam portion; and A hot-melt adhesive layer in the seam portion, which adheres a first portion of fabric to a second portion of fabric, wherein the adhesive layer comprises an adhesive film or adhesive webbing containing a hot-melt adhesive composition of any one of claims 1-5.

14. The seam of claim 13, wherein the seam portion includes a stitch that connects the first portion of the fabric to the second portion of the fabric.

15. The seam of claim 13 or 14, wherein the seam portion is a seamless seam portion.

16. The seam of any one of claims 13-15, wherein both the first and second part of the fabric comprises nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, spandex, or combinations thereof.

17. The joint of any one of claims 13-16, wherein the adhesive layer is an adhesive film.

18. The seam of any one of claims 13-16, wherein the adhesive layer is an adhesive webbing.

19. A method for preparing a seam, comprising: Provides a first part of fabric, a second part of fabric, and a hot melt adhesive layer; A hot melt adhesive layer is placed between the first part of the fabric and the second part of the fabric to form a seam portion, wherein the second part of the fabric at least partially overlaps with the first part of the fabric; and The seam is heated, thereby bonding the first part of the fabric to the second part of the fabric using the adhesive layer. The hot melt adhesive layer comprises an adhesive composition containing a dynamic vulcanizing composition, wherein the dynamic vulcanizing composition comprises reaction products of the following substances: Thermoplastic elastomer comprising a crosslinkable polymer composition comprising: a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally an ethylene propylene diene trimer; or a fully hydrogenated conjugated diene-vinyl aromatic copolymer and an ethylene propylene diene trimer; Polyolefin polymers; Oil; Tackifiers; and Silane compounds.

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