Three-dimensional loop materials, methods for making them and uses thereof
Patent Information
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-05-05
- Publication Date
- 2026-03-11
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Figure PCTCN2023092146-FTAPPB-I100001 
Figure PCTCN2023092146-FTAPPB-I100002 
Figure PCTCN2023092146-FTAPPB-I100003
Abstract
Description
THREE-DIMENSIONAL LOOP MATERIALS, METHODS FOR MAKING THEM AND USES THEREOF
[0001] FIELD OF THE DISCLOSURE
[0002] The present disclosure relates to a three-dimensional loop (3D loop or 3DL) material made from polyethylene or ethylene / α-olefin elastomers, having desirable flame resistance properties for applications especially transportation industry, e.g., vehicle seat applications, methods of making the three-dimensional loop material, and use of the three-dimensional loop material, e.g., vehicle seats made by them.BACKGROUND
[0003] Three-dimensional loop (3D loop) materials or pads are fused polymer filaments to form the random network structures, e.g., which are made of polyethylene (PE) or polyolefin (POE) . They have been proved successful in mattress, pillow application and etc. Compared to polyurethane (PU) foams, 3D loop materials have good resilience, open structures for high breathability, good durability and easy clean performance. In addition, the thermoplastic feature of 3D loop materials makes them very friendly for recycling, which is a great contribution to reduce plastic waste compared to PU foams. Based on above advantageous performance, 3D loop materials have great potential for transportation industry, e.g., vehicle seat applications.
[0004] In transportation field, seats are used in a compacted space, and may be used for public purpose. The flame resistance requirement is more demanding than home use applications. For example, car seats should meet the standard of flammability of automotive interior materials. However, neat polyethylene or polyolefin 3D loop materials can hardly achieve such high flame resistance in view of both material and structure. As a result, incumbent polyethylene or polyolefin 3D loop materials are not able to apply in auto seat industry.
[0005] Flame retardant (FR) compounding is an effective strategy to improve flame resistance performance and it is preferable to utilize halogen-free flame retardant. However, the halogen-free flame retardant is required to ensure good flame resistance performance due to poor compatibility between halogen-free flame retardant and POE / PE matrix, such high loading will inevitably influence mechanical properties, e.g., rebound and durability performance, of the 3D loop materials.
[0006] Thus, there is unfulfilled need in the transportation industry especially vehicle seat applications for highly efficient flame-resistant polyethylene or polyolefin formulations for making 3D loop materials that provides good balance between flame resistance and mechanical properties.
[0007] SUMMARY OF THE DISCLOSURE
[0008] After persistent exploration, the inventors have surprisingly developed a three-dimensional loop material, which exhibits excellent horizontal burning speed of less than 100 mm / min and good flexural modulus of less than 100 MPa.
[0009] In an aspect, the present disclosure provides a three-dimensional loop material comprising loop fibers of polyethylene or ethylene / α-olefin elastomers coated with at least one flame retardant, wherein the loop fibers comprises from 0.5%to 40 %by weight of the flame retardant, based on total weight of the loop fibers.
[0010] In a further aspect, the present disclosure provides a method for making the three-dimensional loop material, comprising the steps of:
[0011] (i) providing loop fibers of polyethylene or ethylene / α-olefin elastomers; and
[0012] (ii) coating the loop fibers with at least one flame retardant and optional binder.
[0013] In a further aspect, the present disclosure provides a vehicle seat comprising the three-dimensional loop material.
[0014] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
[0015] DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 shows screw design of ZSK 18 to prepare for flame resistance POE compounds (from left to right) according to the embodiments of the present disclosure.
[0017] Figure 2 shows durability test on FR coated sample and sampling according to the embodiments of the present disclosure.
[0018] DETAILED DESCRIPTION OF THE DISCLOSURE
[0019] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Also, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.
[0020] I. Definitions
[0021] All percentages mentioned herein are by weight, and temperatures in ℃, unless stated to the contrary, implicit from the context, or customary in the art.
[0022] The term “and / or” means “and, or as an alternative” . All ranges include endpoints unless otherwise indicated.
[0023] The terms "comprising, " "including, " "having, " and their derivatives, as used herein, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically delineated or listed.
[0024] A "composition" or "formulation" is a mixture or blend of two or more components. In the context of a mix or blend of materials from which an article of manufacture is fabricated, the composition includes all the components of the mix, e.g., polymers, flame retardants, and any other additives or agents such as antioxidants, pigments, etc.
[0025] A "polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term "polymer" thus embraces the term homopolymer, usually employed to refer to polymers prepared from only one type of monomer, and the term interpolymer.
[0026] An "interpolymer" is a polymer prepared by the polymerization of two or more different types of monomers. This generic term includes copolymers, usually employed to refer to polymers prepared from two different types of monomers, and polymers prepared from more than two different types of monomers, e.g., terpolymers, tetrapolymers, etc.
[0027] An "alpha-olefin" or "α-olefin" generally is a C3-20 linear, branched or cyclic hydrocarbon molecule comprising an ethylenic unsaturation between the first and second carbon atoms.
[0028] A "polyolefin" or "POE" is a polymer that contains more than 50 mole percent polymerized olefin monomer (based on total amount of polymerizable monomers) , and optionally, may contain one or more comonomer (s) . Non-limiting examples of olefin-based polymer include ethylene-based polymer and propylene-based polymer.
[0029] An "ethylene / alpha-olefin interpolymer" is an interpolymer that comprises a majority amount (i.e., over 50 mole percent) polymerized ethylene monomer (based on the total amount of polymerizable monomers) and one or more alpha-olefin comonomers.
[0030] The term "flame retardant" is used herein to indicate a flame retardant which can be any halogen-containing compound or mixture of compounds which imparts flame resistance to the compositions or material of the present disclosure.
[0031] II. Three-dimensional loop material
[0032] The present disclosure provides a three-dimensional loop material which comprises fibers of random looped structures. In some embodiments, the random looped fibers are bonded with one another, wherein the loops are randomly formed by allowing continuous fibers to bend to come in contact with one another in a molten state and be heat-bonded at a plurality of contact points.
[0033] The vast majority of the fibers comprised in the three-dimensional loop material are made from the polyethylene or ethylene / α-olefin of the present disclosure, which are also referred to herein as "polymer fibers" . In some embodiments, based on the total weight of the fibers comprised in the three-dimensional loop material, more than 90%, more than 95%, more than 98%, more than 99%, more than 99.5%or more than 99.9%of the fibers are made from the polyethylene or ethylene / α-olefin of the present disclosure.
[0034] In some embodiments, based on the total weight of the fibers comprised in the three-dimensional loop material, less than 10%, less than 5%, less than 2%, less than 1%, less than 0.5%or less than 0.1%of the fibers are made from other materials, for example, aramid fibers, polyester fibers, cellulose fibers (e.g., regenerated cellulose fibers) . In some embodiments, based on the total weight of the fibers comprised in the three-dimensional loop material, less than 10%, less than 5%, less than 2%, less than 1%, less than 0.5%or less than 0.1%of the fibers are made from a propylene-based polymer. In some embodiments, the propylene-based polymer does not include PBE.
[0035] In some embodiments, the fibers comprised in the three-dimensional loop material have a diameter that is no less than about 0.3 mm. In some embodiments, the fibers comprised in the three-dimensional loop material have a diameter that is no more than about 2.0 mm. In some embodiments, the fibers comprised in the three-dimensional loop material have a diameter that is within the range formed by taking any two of the numerical values in the following list as the endpoints: 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 1.9, and 2.0 mm. In some embodiments, the fibers comprised in the three-dimensional loop material have a diameter that is within the range from about 0.3 mm to about 2.0 mm, from about 0.5 mm to about 2.0 mm, from about 0.3 mm to about 1.8 mm, or from about 0.5 mm to about 1.8 mm.
[0036] In some embodiments, the three-dimensional loop material has a density that is no less than about 30 kg / m3. In some embodiments, the three-dimensional loop material has a density that is no more than about 100 kg / m3. In some embodiments, the three-dimensional loop material has a density that is within the range formed by taking any two of the numerical values in the following list as the endpoints: 30, 40, 50, 60, 70, 80, 90 and 100 kg / m3. In some embodiments, the three-dimensional loop material has a density that is within the range from about 30 kg / m3 to about 100 kg / m3, from about 50 kg / m3 to about 100 kg / m3, from about 30 kg / m3 to about 80 kg / m3, or from about 50 kg / m3 to about 100 kg / m3.
[0037] In some embodiments, the three-dimensional loop material is a nonwoven material.
[0038] In some embodiments, the loop fibers comprises: from 0.5%to 40%by weight, from 0.5%to 30%by weight, from 0.5%to 20%by weight, from 0.5%to 10%by weight or from 0.5%to 5%by weight of the flame retardant, based on total weight of the loop fibers.
[0039] In some embodiments, the loop fibers of polyethylene or ethylene / α-olefin elastomers have a melting index (MI) in a range of from 2 to 20 g / 10min, from 4 to 15 g / 10min, or from 6 to 10 g / 10min.
[0040] In some embodiments, the horizontal burning speed of the three-dimensional loop material is less than 100 mm / min, less than 80 mm / min, less than 60 mm / min, less than 40 mm / min, or less than 20 mm / min.
[0041] In some embodiments, flexural modulus of the polymers (e.g., polymer fibers or fibers of polyethylene or ethylene / α-olefin elastomers) comprised in the three-dimensional loop material is less than 100 MPa, less than 70 MPa, or less than 30 MPa, as measured in accordance with ASTM D790.
[0042] III. Polyethylene or ethylene / α-olefin elastomers
[0043] The three-dimensional loop material comprises (a) at least one polyethylene or ethylene / α-olefin, (b) at least one flame retardant, and (c) optional binder.
[0044] In some embodiments, the at least one flame retardant as well as the optional binder are coated on the loop fiber s of the at least one polyethylene or ethylene / α-olefin, instead of being mixed or blended together (i.e., a blending / filling process) .
[0045] In some embodiments, the polyethylene or ethylene / α-olefin have a melting index (MI) in a range of from 2 to 20 g / 10min @190C, 2.16 kg, for example, from 5 to 20, from 8 to 15 or from 10 to 15 g / 10min @190C, 2.16 kg, as measured in accordance with ASTM D1238.
[0046] In some embodiments, the polyethylene or ethylene / α-olefin elastomers have a melting peak temperature (Tm) of lower than 121 ℃.
[0047] In some embodiments, the polyethylene or ethylene / α-olefin can further comprise one or more additives such as antioxidants, pigments, processing aids and the like.
[0048] IV. Ethylene / alpha-olefin copolymer
[0049] In some embodiments, the ethylene / alpha-olefin copolymer is a random ethylene / alpha-olefin interpolymer or a block ethylene / alpha-olefin interpolymer.
[0050] The ethylene / alpha-olefin copolymer comprises ethylene as a major monomer. In some embodiments, the ethylene / alpha-olefin copolymer comprises at least 60%, for example, at least 65%, at least 70%, at least 75%or at least 80%by weight of the copolymer of ethylene as the major monomer. In some embodiments, the amount of ethylene comprised in the ethylene / alpha-olefin copolymer is within the range formed by taking any two of the numerical values in the following list as the endpoints: 60%, 65%, 70%, 75%, 80%, 85%and 90%, by weight of the copolymer. In some embodiments, the ethylene / alpha-olefin copolymer comprises from 60%to 90%, from 65%to 90%, from 70%to 90%or from 75%to 90%by weight of the copolymer of ethylene.
[0051] The ethylene / alpha-olefin copolymer comprises at least one alpha-olefin as a comonomer. Typically, the at least one alpha-olefin comprised in the ethylene / alpha-olefin copolymer of the present disclosure has four or more carbon atoms. In some embodiments, the ethylene / alpha-olefin copolymer comprises one or more C4-10 alpha-olefins as comonomers. In some exemplary embodiments, the C4-10 alpha-olefin can be selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and combinations thereof. In some embodiments, the C4-10 alpha-olefin comprises 1-octene. In some exemplary embodiments, the ethylene / alpha-olefin copolymer can be selected from the group consisting of ethylene / 1-hexene copolymer, ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene / 1-nonene copolymer, ethylene / 1-decene copolymer, and combinations thereof. In some embodiments, the ethylene / alpha-olefin copolymer comprises ethylene / 1-octene copolymer.
[0052] In some embodiments, the ethylene / alpha-olefin copolymer comprises at most 40%, for example, at most 35%, at most 30%, at most 25%, at most 20%, at most 15%or at most 10%by weight of the copolymer of a C4-10 alpha-olefin as comonomer. In some embodiments, the amount of the C4-10 alpha-olefin comprised in the ethylene / alpha-olefin copolymer is within the range formed by taking any two of the numerical values in the following list as the endpoints: 40%, 35%, 30%, 25%, 20%, 15%, and 10%, by weight of the copolymer. In some embodiments, the ethylene / alpha-olefin copolymer comprises from 40%to 10%, from 35%to 10%, from 30%to 10%or from 25%to 10%by weight of the copolymer of a C4-10 alpha-olefin.
[0053] Examples of the ethylene / alpha-olefin copolymers suitable for use in the present disclosure include those marketed by The Dow Chemical Company under the trade name ENGAGETM.
[0054] V. Flame retardant
[0055] At least one flame retardant is coated on the loop fibers to make them capable of extinguishing flames or at least slowing the spread of fire in the material and find suitable use in transportation industry.
[0056] In some embodiments, the at least one flame retardant is selected from halogen-containing flame retardants or halogen-free flame retardants. In some embodiments, the flame retardant comprises halogen-free flame retardant. In some embodiments, the at least one flame retardant is selected from phosphates, phosphonates and a combination thereof.
[0057] In some specific embodiments, the at least one flame retardant is selected from cyclic phosphonates, triaryl phosphates, cresyl diphenyl phosphate, tricresyl phosphate, trixylyl phosphate, triethyl phosphate, isodecyl diphenyl phosphate, oligomeric phosphate-phosphonate, cyclic organophosphates and phosphonates, and nitrogen-containing polyol phosphate.
[0058] Optionally, other known flame retardants such as metal hydroxides can be additionally coated on the loop fibers.
[0059] In some embodiments, a flame retardant synergist can also be used to enhance the effectiveness of flame retardants. The flame retardant synergist includes inorganic and organic flame retardant synergists. Examples of inorganic flame retardant synergists include, but are not limited to, metal oxides, e.g. iron oxide, tin oxide, zinc oxide, aluminum oxide, alumina, antimony oxide and antimony oxide, bismuth oxide, molybdenum trioxide, and tungsten trioxide, boron compounds such as zinc borate, zinc stannate, zinc hydroxystannate, ferrocene and mixtures thereof. Examples of organic flame retardant synergists include, but are not limited to organic peroxides, such as dicumyl peroxide and polycumyl peroxide. Non-limiting examples of flame retardant synergist include antimony oxide (CAS#1309-64-4) .
[0060] In some embodiments, a flame retardant synergist can be coated on the loop fibers in amount from 0.3%to 3%, from 0.5%to 2.5%, from 0.5%to 2%, from 0.5%to 1.5%, or from 0.7 to 1.2%by weight.
[0061] In some embodiments, the halogen-free flame retardants and the flame retardant synergists are used at a weight ratio of from 0.25: 1 to 15: 1, for example, at a weight ratio in the range formed by taking any two of the numerical values in the following list as the endpoints: 0.5: 1, 0.8: 1, 1: 1, 1.5: 1, 1.8: 1, 2: 1, 2.5: 1, 3: 1, 3.5: 1, 4: 1, 4.5: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, 12: 1, 13: 1, 14: 1 and 15: 1. In some embodiments, the halogen-free flame retardants and the flame retardant synergists are used at a weight ratio of from 0.25: 1 to 10: 1, from 0.5: 1 to 5: 1, from 1: 1 to 5: 1, from 2: 1 to 4: 1, or around 3: 1.
[0062] In some embodiments, the total loading amount of the flame retardant and the flame retardant synergist in the three-dimensional loop material is no more than 5%by weight of the material, for example, no more than 4.5%, 4%, 3.5%, or 3%by weight of the material.
[0063] In some embodiments, the loop fibers of polyethylene or ethylene / cresyl diphenyl phosphate, comprises from 0.3%to 3%by weight of an intumescent flame retardant, based on the weight of the loop fibers, and the intumescent flame retardant is selected from the group consisting of , ammonium polyphosphate, polymeric piperazine pyrophosphate, melamine phosphates, intumescent blends.
[0064] In the present disclosure, exemplary flame retardants include those commercially available from ZhongKang Guochuang Advanced Technology Research Institute of Dyeing and Finishing Co, under the trade name FR-8201, R-8051, FR-8038 and FR-8031, those commercially available from Hangzhou Electrochemical Group Co. Ltd, under the trade name Antiblaze CU, or those commercially available from Archroma (formerly Clariant) , under the trade name Pekoflam PES, Aflammit PE Conc and PCO 900, which contain cyclic phosphonates:
[0065] Alternatively, exemplary flame retardants include those commercially available from ADEKA, under the trade name FP-2500S, which contains piperazine pyrophosphate (PPAP) etc.
[0066] Exemplary flame retardants available from Hangzhou Jiersi, under the trade name JIL-PNA220-A, which contains ammonium polyphosphate (APP) etc.
[0067] VI. Binder
[0068] In the present disclosure, the loop fibers are coated with a mixture of at least one flame retardant and a binder, and a weight ratio of the halogen-free flame retardant to the binder is 1: (0.05-5) , 1: (0.05-4) , 1: (0.05-3) , 1: (0.05-2) , 1: (0.05-1) , 1: (0.05-0.5) or 1: (0.05-0.1) . Various binders may be employed to stabilize the three-dimensional loop material. The term “binder” herein refers to a material within the 3D loop material (other than the loop fibers) that secures the loop fibers. In some embodiments, the binder is an adhesive. The binder preferably fully penetrates and permeates the interstices between individual loop fibers in the entanglements of the 3D loop material. When employing a liquid binder, the binder is preferably selected to have a sufficiently low viscosity and surface tension to enable it to flow into the untightened (or tightening) entanglements. In the embodiments in which the entanglements are subsequently tightened (such as the loop material) , this selected distribution of the fluid binder helps to secure associated knots with minimal stiffening of the overall product and without requiring substantial amounts of binder.
[0069] In any event, the amount and penetration of the binder should be selected to avoid substantial interference with the desired hook-engaging function of the loop fibers while adequately stabilizing the loop materials and securing the loops against being pulled from their associated entanglements. For use in applications in which the loop materials may come in direct contact with sensitive skin, such as in vehicle seat, the amount and type of binder should also be selected to be biocompatible to avoid skin irritation. Formaldehyde-free binders, for instance, are preferred. As irritation can be aggravated by stiffness, preferably only enough binder to perform the above functions is applied. In some applications, for instance those in which the loop material is directly adhered to a supporting fabric and which does not require substantial fastener strength, the loop product may be provided without a binder.
[0070] In some embodiments, the binder can comprise, but not limited to: olefin (co) polymer, (meth) acrylic (co) polymer, acrylate-based emulsion copolymer and polyurethane resin. A suitable binder used in the present disclosure can be an aqueous dispersion comprising at least one olefin (co) polymer and at least one olefin- (meth) acrylic copolymer. The olefin (co) polymer can be a homopolymer of a C2-C16 alkene, a copolymer of two or more C2-C16 alkenes, or a copolymer of at least one C2-C16 alkenes with at least one vinyl comonomer other than olefin. The olefin (co) polymer may have a melt flow rate (MFR) in the range of from 0.1 to 50 g / 10 minutes, measured in accordance with ASTM D-1238 (at 190° C / 2.16 Kg) . The content of the olefin (co) polymer can be 10-50 wt%, based on the total weight of the dispersion. The olefin-(meth) acrylic copolymer can be a copolymer of at least one C2-C16 alkene with at least one (meth) acrylic monomer. The (meth) acrylic monomer may comprise methacrylic acid, acrylic acid, methacrylamide, acrylamide, methacrylonitrile, acrylonitrile, (C1-C12) alkyl methacrylate (e.g. methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, etc. ) , (C1-C12) alkyl acrylate (e.g. methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, etc. ) , and any combinations thereof. The olefin- (meth) acrylic copolymer may have a melt flow rate (MFR) in the range of from 0.1 to 50 g / 10 minutes, measured in accordance with ASTM D-1238 (at 190° C / 2.16 Kg) , The content of the olefin- (meth) acrylic copolymer can be 2-30 wt%, based on the total weight of the dispersion.
[0071] A suitable binder used in the present disclosure can be acrylate-based emulsion copolymer. The acrylate-based emulsion copolymer comprises a Tg ranging from -40 ° C to 15 ° C. The acrylate-based emulsion copolymer pH ranges from 6.0 to 8.5; Solid content from 25%to 50%. The copolymer in acrylate-based emulsion copolymer can comprise copolymerizable acrylate monomers with Tg range from -20 ° C to -80 ° C, wherein the acrylate monomers include, but are not limited to 2-ethyl hexyl acrylate, butyl acrylate, ethyl acrylate, and combination thereof. The copolymer in acrylate-based emulsion copolymer can comprise a copolymerizable monomers with Tg range from 20 ° C to 200 ° C, wherein the monomers include, but are not limited to methyl methacrylate, styrene, vinyl acetate, acrylic acid, methacrylic acid, and combinations thereof.
[0072] A suitable binder used in the present disclosure can be an aqueous dispersion of polyurethane resin. The binder can comprise one or more one or more conventional additives such as surfactant, emulsifier, filler, film-forming agent, colorant, pigment, thickener, anti-migration aid, curing agent, coalescent, biocide, plasticizer, wax, anti-aging agent or anti- oxidant. Besides, in addition to the above stated components, the binder may comprise balance amount of water, such as having a water content of about 30 wt%to 75 wt%.
[0073] In the present disclosure, exemplary binders include those commercially available from The Dow Chemical Company, under the trade name PRIMAL ST-954, PRIMALTM TR-3349, PRIMALTM ECO-1291, Hypol 8501, Lucidene 606APEF, PRIMAL NPC64A and PUB.
[0074] VII. Production of three-dimensional loop material
[0075] The present disclosure also provides a method for producing the three-dimensional loop material disclosed herein, comprising the steps of:
[0076] (i) providing loop fibers of polyethylene or ethylene / α-olefin elastomers; and
[0077] (ii) coating the loop fibers with at least one flame retardant and optional binder.
[0078] The term “coating” used herein comprises making the loop fibers or 3D loop materials exposure to the flame retardant and optional binder, including but not limited to: spray coating, soaking, dip coating and so on. In some embodiments, the loop fibers can be coated before and / or after forming a 3D loop material. Different from the blending or filling process used in prior arts, the coating process of the present disclosure can reduce loading of flame retardant to at most 10 wt%of the loop fibers, while maintaining desired flame resistance, e.g., a horizontal burning speed of less than 100 mm / min. In the blending or filling process used in prior arts, it generally requires at least 40 wt%loading of flame retardant.
[0079] In further embodiments of the present disclosure, the method further comprises the steps of:
[0080] (a) melting a polyethylene or ethylene / α-olefin copolymer as well as optional additives to form a molten composition; and
[0081] (b) discharging the molten composition to a downward direction from a nozzle with a plurality of orifices to obtain continuous loop fibers in a molten state;
[0082] (c) cooling the loop fibers.
[0083] In further embodiments of the present disclosure, the method further comprises the steps of:
[0084] (d) allowing loop fibers coated with at least one flame retardant and optional binder to come into contact with one another and to be heat-bonded whereby to form the three-dimensional loop material in a random loop structure.
[0085] In an alternative embodiment of the present disclosure, the method further comprises allowing loop fibers to come into contact with one another and to be heat-bonded whereby to form the three-dimensional loop material in a random loop structure before above step (ii) .
[0086] In some embodiments, the melting is carried out at a temperature ranged from 170 ℃ to 220 ℃, for example, from 170 ℃ to 210 ℃, from 180 ℃ to 210 ℃, or from 180 ℃ to 200 ℃.
[0087] In some embodiments, the cooling is carried out at a temperature ranged from 25 ℃ to 40 ℃, for example, from 30 ℃ to 40 ℃, or from 30 ℃ to 35 ℃.
[0088] In some embodiments, the steps (c) and (d) can be carried out simultaneously, for example, in a cold bath comprising the at least one flame retardant and optional binder.
[0089] In some embodiments, the method further comprises a step of drying the formed three-dimensional loop material before use or storage.
[0090] VIII. Use of three-dimensional loop material
[0091] The present disclosure also provides use of the three-dimensional loop material as a cushioning material.
[0092] The three-dimensional loop material can be adapted for a variety of uses. Examples include, but are not limited to, use of the three-dimensional loop material with chairs, stools, home furniture, beds, sofas, mattress, pillows, automobiles, motorcycles, trains, airplanes, boats, ships, seacraft, aircraft, spacecraft, tractors, bicycles, unicycles, tricycles, recreational vehicles, dune buggies, jet skis, stadium seats, spacecraft, hovercraft, ski lifts, roller coaster, glider, luge, bobsled, recliners, gurneys, beds, yoga mats, pet crate liners, gardening knee mats, or any other kind of cycle, vehicle, seat, or furniture. In some embodiments, the three-dimensional loop material is used in the seats of automobiles, motorcycles, trains, airplanes, boats, seacraft, aircraft, spacecraft and so on. In some embodiments, the three-dimensional loop material is used in chairs, stools, home furniture, beds, sofas, mattress, pillows and so on.
[0093] When the three-dimensional loop material provided herein is used as a cushioning material, the specific polymers to be used, fineness, fiber diameter and bulk density should be selected depending on the purpose of use and where it is to be used.
[0094] In some embodiments, the three-dimensional loop material provided herein can be used upon forming the structure into a suitable shape with the use of a mold etc. to the degree the three-dimensional loop material is not impaired, and covering the same with an outerwrap or overwrap.
[0095] The present disclosure further provides a vehicle seat comprising the three-dimensional loop material disclosed herein.
[0096] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.EXAMPLES
[0097] Some embodiments of the invention will now be described in the following Examples, wherein all parts and percentages are by weight unless otherwise specified.
[0098] A. Materials / Ingredients
[0099] Table 1: Raw materials
[0100] B. Flame Retardant Coating Process
[0101] As shown in Table 2, the FR aqueous solutions were directly using the commercial FR products from Guochuang. The FR / binder solutions were obtained by simply mixing the commercial FR product and the binder solutions. FR Coating of 3DL article was both achieved via spray or soaking the obtained FR / binder solutions. The coated article was then moved to 85 ℃ oven and dried for 22 h.
[0102] FR Loading of the coating was obtained via the equation below:
[0103] Where Mafter coating refers to the mass of the 3DL article after coating with the FR / binder solutions; and Mbefore coating refers to the mass of the 3DL article before coating with the FR / binder solutions.
[0104] The sample size of 3DL article for horizontal burning test was 50 mm X 100 mm X 10 mm.
[0105] Table 2: 3DL materials coated with flame retardant (FR) aqueous solution 1&2: FR fillers were blended with binder and used as coating material3:Using common blending / filling process in the prior arts
[0106] C. Property tests
[0107] The FR coated 3DL samples were subjected to durability test (80,000 times of constant displacement repeated compression on MTS 810) , the loading loss was then recorded and FR performance was tested. Due to the up surface and bottom surface might experience different abrasion during durability test, up surface and bottom surface (thickness 10 mm) were cut off separately from the sample for burning test. The result was summarized in Table 5. FR / binder formulation can effectively stabilize the coating during the test. Loading loss of coating with FR only is more severe than FR / binder formulation. High loading loss will hurt the FR performance during burning test as can be seen in Table 5.
[0108] Table 5: FR horizontal burning result after durability test
[0109] The coating layer was stabilize during aging test (90 ℃, 200 h) , as summarized in Table 6. The FR performance can maintain during burning test after aging.
[0110] Table 6: FR horizontal burning result after aging test
[0111] The coating layer did not influence the physical performance including heat resistance (70 ℃ residual strain) and durability (both thickness loss and hardness loss) as can be seen in Table 7 and Table 8.
[0112] Table 7: 70 ℃ compression residual strain data after coating *std<5%
[0113] Table 8: Durability test result *std<5%
[0114] D. Measurement information
[0115] 1.Melt index
[0116] Melt index was tested in Tinius Olsen MP600 in accordance with ASTM D1238. To meet the fiber extrusion requirement, melt index of polymer range 2 -20 g / 10min.
[0117] 2. Flexural modulus
[0118] Flexural modulus of the polymer was measured in Instron 5566 in accordance with ASTM D790. The secant at 2%was used as the test result for flexural modulus. The flexural modulus directly influences the 3D loop fiber bending resistance, which is a key factor to influence the 3D loop cushion hardness. And usually with more fillers in the polymer formulation, the higher flexural modulus compounds will get. To control this hardness impact on POE 3D loop, flexural modulus target of the polymer compound was set at 64± 5 MPa, so the acceptable flexural modulus was defined to be < 70 MPa.
[0119] 3. Hardness
[0120] Hardness were measured in accordance with ASTM D2240, Shore D method was used on these samples. The more fillers used, the higher hardness of the polymer compound will get, our target for material hardness was 40 ± 3 D.
[0121] 4. Compression Residual Strain
[0122] The compression set of the plastic plate was measured according to ASTM D3574-2017. The specimens were 3D loop plates 20 cm by 20 cm square shape, with uniform thickness around 5 cm. After compressed for 50%compression using a compression fixture with 22 hours at 70 ℃, the compression was removed, and 3D loop samples were allowed to recover for 30 min at room temperature. The final specimen thickness was measured, and the compression set was calculated using the following equation.
[0123] Compression residual strain (%) = [ (To -Tf) / To ] × 100
[0124] Where To is the original sample thickness, and Tf is the final sample thickness.
[0125] 5. Aging condition
[0126] The sample was placed in oven set up @90 ℃, and lasted for 200 h.
[0127] 6. Compounding:
[0128] All polymer formulations were compounded by Twin Screw Extruder ZSK18 with an 18 mm diameter and L / D 40 screw. The profile temperature was set between 70-140 ℃, with 500 RPM and 10 kg / hour output during the compounding. The screw design was shown in Figure 1.
[0129] 7. Durability test condition:
[0130] Figure 2 shows durability test on FR coated sample and sampling. Durability of 3D loop samples were measured in MTS 810 following with JIS K 6400-4 6.2 B, Indentation Load Deflection (ILD) is used to character the hardness of cushion materials. The impact load was set at 750 ± 20 N (mimic an adult’s weight) and push head was a 20 cm round disk with round edge (similar to hip contact area) , and 80,000 impact cycles to mimic 7 years daily use. The sample was then placed under unstressed condition for 10 ± 0.5 minutes, then character the final hardness and thickness.
[0131] 8. Horizontal burning test
[0132] The flame resistance tests were conducted in Shanghai Dow Center lab. The 3D loop article horizontal burning rate test was conducted on ATLAS horizontal burning machine, the 3D loop samples were cut into pieces with size 356 × 50 × 30 mm and the product original surface towards the flame, the burning rate was calculated from the below formula, and each sample used 5 specimens for calculation, the maximum burning rate from five specimens was taken to the test result.
[0133] Where, s = burning rate, in mm / min; i = burnt distance, in mm; T = time taken to burn L, in seconds.
[0134] To achieve the premium flame resistance, target for horizontal burning speed of 3D loop was set < 20 mm / min.
[0135] Variations and modifications from the described embodiments exist. Finally, any number disclosed herein should be construed to mean approximate, regardless of whether the word "about" or "approximately" is used in describing the number. The appended claims intend to cover all those modifications and variations as falling within the scope of the invention.
Claims
1.A three-dimensional loop material comprising loop fibers of polyethylene or ethylene / α-olefin elastomers coated with at least one flame retardant, wherein the loop fibers comprises from 0.5%to 40%by weight of the flame retardant, based on total weight of the loop fibers.2.The three-dimensional loop material according to claim 1, wherein the flame retardant comprises a halogen-free flame retardant.3.The three-dimensional loop material according to claim 1 or 2, wherein the loop fibers are coated with a mixture of the at least one flame retardant and at least one binder, and a weight ratio of the flame retardant to the binder is 1: (0.05-5) .4.The three-dimensional loop material according to claim 1, wherein the at least one halogen-free flame retardant comprises phosphates, phosphonates and a combination thereof.5.The three-dimensional loop material according to claim 2, wherein the at least one halogen-free flame retardant is selected from the group consisting of cyclic phosphonates, triaryl phosphates, cresyl diphenyl phosphate, tricresyl phosphate, trixylyl phosphate, triethyl phosphate, isodecyl diphenyl phosphate, oligomeric phosphate-phosphonate, cyclic organophosphates and phosphonates, nitrogen-containing polyol phosphate and any combinations thereof.6.The three-dimensional loop material according to claim 1, wherein the ethylene / alpha-olefin copolymer comprises from 60%to 90%by weight of the copolymer of ethylene.7.The three-dimensional loop material according to claim 1, wherein the ethylene / alpha-olefin copolymer comprises from 10%to 40%by weight of the copolymer of a C4-10 alpha-olefin.8.The three-dimensional loop material according to claim 5, wherein the C4-10 alpha-olefin comprises 1-octene.9.The three-dimensional loop material according to claim 1, wherein the loop fibers of polyethylene or ethylene / α-olefin elastomers have a melting index (MI) in a range of from 2 to 20 g / 10min.10.The three-dimensional loop material according to claim 1, wherein the horizontal burning speed of the three-dimensional loop material is less than 100 mm / min.11.The three-dimensional loop material according to claim 1, wherein the flexural modulus of the loop fibers of polyethylene or ethylene / α-olefin elastomers is less than 100 MPa.12.The three-dimensional loop material according to claim 1, wherein the loop fibers of polyethylene or ethylene / α-olefin elastomers further comprises from 0.3%to 10%by weight of an intumescent flame retardant, based on the weight of the loop fibers, and the intumescent flame retardant is selected from the group consisting of ammonium polyphosphate, polymeric piperazine pyrophosphate, melamine phosphates and intumescent blends.13.A method for making the three-dimensional loop material according to claim 1, comprising the steps of:(i) providing loop fibers of polyethylene or ethylene / α-olefin elastomers; and(ii) coating the loop fibers with at least one flame retardant and optional binder.14.A vehicle seat comprising the three-dimensional loop material according to claim 1.