Composite material made of randomly bonded polymer fibrous rings and polyurethane foam

Abstract

A composite material is provided comprising a polyurethane foam and a three-dimensional loop (3DL) preform comprising a plurality of randomly bonded rings of thermoplastic fibers wherein the 3DL preform is asymmetrically embedded in the polyurethane foam wherein the voids of the rings of fibers are partially or completely filled with the polyurethane foam, and wherein the composite material has an SAG factor of not less than 3.2, wherein the SAG factor is defined as a ratio of 65% Indentation Force Deflection (IFD) to 25% IFD. The invention also provides a preparation method and application thereof.

Description

Technical Field

[0001] This disclosure relates to composite materials, and specifically includes composite materials of three-dimensional cyclic (3DL) preforms and polyurethane foam. This composite material enables the provision of thin cushioning pads with desired comfort properties. Background Technology

[0002] Polyurethane foam is a widely used cushioning material in car seats. Its soft surface provides a pleasant feel and shock absorption, along with strong compressive strength to offer adequate support to the body. In car seat design, developing thinner cushioning pads to provide more space for drivers and passengers is a market trend. However, for such thinner cushioning designs with normal firmness, the support from conventional polyurethane foam is insufficient, and the user can feel the bottom when sitting in the seat; but when using high-firm foam, the surface softness is compromised, and the user may experience discomfort. Developing thin polyurethane foam cushioning pads that balance surface softness and effective support for the user is very challenging.

[0003] Therefore, there is still a need for materials that enable space-saving cushioning pads with desired comfort characteristics. Summary of the Invention

[0004] In one aspect, this disclosure provides a composite material comprising...

[0005] Polyurethane foam, and

[0006] A three-dimensional ring (3DL) preform comprising multiple randomly bonded thermoplastic fiber rings.

[0007] The 3DL preform is asymmetrically embedded in polyurethane foam, wherein the gaps in the fiber rings are partially or completely filled with polyurethane foam, and

[0008] The composite material has a SAG factor of not less than 3.2, where the SAG factor is defined as the ratio of 65% indentation force deflection (IFD) to 25% IFD.

[0009] In another aspect, this disclosure provides a method for preparing the composite material described herein, the method comprising:

[0010] A 3DL preform comprising multiple randomly bonded thermoplastic fiber rings is placed in a mold;

[0011] The reaction mixture is injected into a mold and foamed in situ, so that the 3DL preform is asymmetrically embedded in the polyurethane foam, wherein the gaps in the fiber rings are partially or completely filled with polyurethane foam.

[0012] To solidify the foam; and

[0013] Release the composite material from the mold.

[0014] In another aspect, this disclosure provides a product comprising the composite material described herein.

[0015] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and not intended to limit the invention as claimed. Attached Figure Description

[0016] Figure 1A and Figure 1B Each schematically illustrates an embodiment of the composite material according to the present disclosure.

[0017] Figure 2 The PU foam / 3DL composite material of the present invention is illustrated schematically. Detailed Implementation

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Furthermore, all publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference.

[0019] As disclosed herein, “and / or” means “and, or as an alternative”. Unless otherwise specified, all ranges include the endpoints.

[0020] Unless otherwise stated, all percentages mentioned herein are by weight and temperatures are in °C.

[0021] As used herein, the terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed using the term “comprising” may include any additional additives, adjuvants, or compounds, whether in polymeric or other forms. In contrast, the term “consistently comprising” excludes any other components, steps, or procedures from any subsequently listed scope, except those not essential for operability. The term “consisting of” excludes any components, steps, or procedures not specifically described or listed.

[0022] I. Composite Materials

[0023] In one aspect, a composite material is provided, the composite material comprising...

[0024] Polyurethane foam, and

[0025] A 3DL preform comprising a plurality of randomly bonded thermoplastic fiber rings.

[0026] 3DL preforms are asymmetrically embedded in polyurethane foam, wherein the gaps in the fiber rings are partially or completely filled with polyurethane foam.

[0027] As used herein, "asymmetric embedding" or "asymmetric positioning" means that the 3DL preform is not centrally embedded or positioned within the polyurethane foam, and the composite material has an asymmetric structure. Typically, the 3DL preform is embedded or positioned within the polyurethane foam such that it is further away from the intended stress surface of the composite material than from the opposite surface (i.e., the surface opposite the intended stress surface). In other words, the depth from the intended stress surface of the composite material to the preform is greater than the depth from the opposite surface to the preform. In some embodiments, the preform is closer to or more adjacent to the opposite surface of the composite material than from the intended stress surface. In some embodiments, the center of gravity of the composite material is not located at its geometric center.

[0028] As used in this article, the “intended stress surface” of a composite material refers to the surface of the composite material that is intended to withstand forces (such as pressure, such as pressure caused by body weight).

[0029] In some implementations, the force can be the force of sitting or leaning against the composite material.

[0030] In some implementations, the opposing surfaces may have a shape and / or area similar to the intended stress-bearing surface of the composite material.

[0031] In embodiments where the intended stress-bearing surface is the top, the 3DL preform is embedded or positioned in the lower portion of the composite material (in...). Figure 1A (illustrated in the middle) or bottom (in Figure 1B (Example shown in the text) and vice versa.

[0032] 3DL preforms can be in the form or shape designed to withstand forces such as sitting or leaning. In some embodiments, 3DL preforms can be in the form of layers that are partially or completely parallel to the intended stress-bearing surface and / or opposite surface of the composite material.

[0033] As used herein, “partially filled” means that at least 50% of the voids in the fiber rings of a 3DL preform are filled, for example, with polyurethane foam. In some embodiments, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98%, or 100% of the voids in the fiber rings are filled.

[0034] In some embodiments, the thickness of the polyurethane foam is greater than that of the 3DL preform. In some embodiments, the thickness of the polyurethane foam is 1.5 to 2.5 times the thickness of the 3DL preform, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5 times the thickness of the 3DL preform. To provide a soft feel, the composite material includes a pure polyurethane foam portion extending from the intended stress-bearing surface of the composite material to a depth of at least 10% (e.g., at least 10%, at least 15%, at least 20%, or at least 25%) of the total thickness of the composite material. The total thickness of the composite material is typically the distance between the intended stress-bearing surface of the composite material and the opposing surface.

[0035] In some embodiments, the 3DL preform is partially or completely embedded in polyurethane foam. As used herein, "partially embedded" means that at least 70% of the volume of the 3DL preform is embedded in the polyurethane foam. In some embodiments, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98%, or 100% of the volume of the 3DL preform is embedded in the polyurethane foam. In some embodiments, the 3DL preform is completely embedded in the composite material.

[0036] Composite materials can be designed to have a desired shape (e.g., an ergonomic chair or cushion shape). In some embodiments, the composite material can be designed to be encased in layers of leather, fabric, or polymer (e.g., a cushioning cover) to hold it in place. In some embodiments, the composite material may also include one or more engagement elements that extend beyond the composite material to secure it in place.

[0037] It has been found that thinner cushioning or seat padding materials can be obtained by providing an asymmetric composite material (where the upper or top portion is polyurethane foam for shock absorption and a good feel, and the lower or bottom portion is reinforced with 3DL for strong compression resistance and weight support). This saves more space without compromising the desired cushioning comfort characteristics.

[0038] The SAG factor (defined as the ratio of 65% indentation force deflection to 25% indentation force deflection (IFD 65% vs. IFD 25%)) is used in the foam industry as an indicator of cushioning quality. IFD values ​​can be measured according to the standard ASTM D3574-2017.

[0039] Typically, the SAG value of polyurethane foam ranges from 2.0 to 3.0. A high SAG value indicates resistance to "bottoming out," and foam products with an SAG factor greater than 2.8 are considered high support factor foams and are not easily achieved. The composite material according to this disclosure achieves an SAG factor of ≥3.2, which indicates good support and comfort for the user. In some embodiments, the SAG factor of the composite material may be not less than 3.2, for example, not less than 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0.

[0040] In some implementations, the compressive residual strain of the composite material, as measured according to ASTM D3574-2017 (D), is ≤20%, for example, ≤15%, ≤12%, or ≤10%.

[0041] In some implementations, the post-fatigue thickness variation of the composite material, as measured according to ASTM D 3574-2017 (I3), is ≤5%, for example, ≤2.5%, ≤1.5%, or ≤1%.

[0042] In some implementations, the post-fatigue stiffness change of the composite material, as measured according to ASTM D 3574-2017 (I3), is ≤25%, for example, ≤20%, ≤18%, or ≤16%.

[0043] In some implementations, the composite material has a resilience of ≥40%, for example, ≥42%, ≥43%, or ≥45%, as measured according to ASTM D3574-2017.

[0044] In some implementations, the composite material has a hysteresis loss of ≤40%, for example, ≤38%, ≤37%, or ≤35%, as measured according to ASTM D3574-2017.

[0045] II. Polyurethane Foam

[0046] The foam contained in the composite material according to this disclosure is made of polyurethane.

[0047] Polyurethane foam is the reaction product of a reaction mixture comprising (i) a polyol component comprising one or more polyols selected from the group consisting of polyester polyols, polyether polyols, and combinations thereof, and (ii) an isocyanate component comprising one or more isocyanate compounds.

[0048] The polyol component and the isocyanate component are separated from each other before use. Typically, the polyol component and the isocyanate component are prepared, stored, transported, and supplied separately, and are combined shortly or immediately before application, for example, to a mold used to produce a composite material. It is anticipated that a curing reaction will begin when the two components come into contact, wherein the polyol groups react with the isocyanate groups to form urethane linkages. The reactive polyurethane dispersion formed by bringing the two components into contact can be referred to as a “reaction mixture” or “curable mixture.”

[0049] The NCO / OH molar ratio of the isocyanate component to the polyol component in the polyurethane foam composition can range from 0.5:1 to 1.2:1. As used herein, the term "NCO / OH molar ratio" refers to the ratio of the number of isocyanate groups to the number of hydroxyl groups in the reaction mixture; or more specifically, the ratio between the number of isocyanate groups in the isocyanate component and the number of hydroxyl groups in the polyol component of the reaction mixture. In some embodiments, the NCO / OH molar ratio of the isocyanate component to the polyol component can be within the range obtainable by combining any two of the following endpoints: 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1. In some specific embodiments, the NCO / OH molar ratio of the isocyanate component to the polyol component can be in the range of 0.5:1 to 1.2:1, 0.6:1 to 1.1:1, 0.7:1 to 1:1, 0.8:1 to 1.2:1, 0.9:1 to 1.1:1, 0.9:1 to 1:1, or 1:1 to 1:1.1.

[0050] In some implementations, the polyurethane foam has a density of 15 kg / m³. 3 Up to 150kg / m 3 The density.

[0051] (i) Polyol components

[0052] The polyol component may contain one or more polyols selected from the group consisting of polyester polyols, polyether polyols, and any combination thereof.

[0053] As used herein, the term "polyol" refers to a compound having two or more hydroxyl groups. When a polyol has exactly two hydroxyl groups, it is a "diol"; when it has exactly three hydroxyl groups, it is a "triol"; when it has exactly four hydroxyl groups, it is a "tetraol"; when it has exactly five hydroxyl groups, it is a "pentanol," and so on.

[0054] One or more polyols in the polyol component may have an average hydroxyl group functionality of 2 to 8. In some embodiments, one or more polyols have an average hydroxyl group functionality of 2 to 8, 2 to 7, 2 to 6, or 3 to 6.

[0055] One or more polyols in the polyol component may have an average number of hydroxyl groups ranging from 19 mg KOH / g to 1000 mg KOH / g, for example, from 19 mg KOH / g to 800 mg KOH / g, from 19 mg KOH / g to 500 mg KOH / g, or from 19 mg KOH / g to 200 mg KOH / g.

[0056] One or more polyols in the polyol component may have a molecular weight not exceeding 14,000 g / mol, 12,000 g / mol or 10,000 g / mol.

[0057] In some embodiments, the polyol component may have a viscosity of 200 cSt to 38,000 cSt at 25°C, such as 200 cSt to 35,000 cSt or 250 cSt to 35,000 cSt, as measured according to ASTM D2196.

[0058] In some implementations, the polyol component may comprise one or more polyether polyols.

[0059] Compounds containing two or more ether bonds in the same linear atomic chain are referred to herein as "polyethers". Compounds that are polyethers and polyols are referred to as "polyether polyols".

[0060] In some embodiments, polyether polyols can be obtained by addition polymerization of an epoxide with a polyol starting compound. Examples of such polyols include, but are not limited to, glycerol, sorbitol, sucrose, glucose, fructose, lactose, or other sugars. In some embodiments, the starting compound is sorbitol or sucrose. These polyols, as well as mixtures of these alcohols with water, glycerol, propylene glycol, ethylene glycol, or diethylene glycol, can be used as starting compounds. In some embodiments, the polyether polyol may comprise a styrene-acrylonitrile (SAN)-based copolymer polyether polyol, which is a grafted polyol.

[0061] Examples of suitable polyether polyols that can be used include, but are not limited to, VORANOL. ™ 446. VORANOL ™ 520, VORANOL ™ 550, VORANOL ™ RN 482, VORANOL ™ CP 6001, VORANOL ™ CP 4711, VORALUX™ HL 400, SPECFLEX ™ NC 702 polyols, all of which are available from The Dow Chemical Company.

[0062] In some implementations, the polyol component may comprise one or more polyester polyols.

[0063] Compounds containing two or more ester bonds in the same linear atomic chain are referred to herein as "polyesters". Compounds that are both polyesters and polyols are referred to herein as "polyester polyols".

[0064] In some embodiments, the polyester polyol may include, but is not limited to, diols and optional polyols (e.g., triols, tetraols) and dicarboxylic acids and optional polycarboxylic acids (e.g., tricarboxylic acids, tetracarboxylic acids) or hydroxycarboxylic acids or lactones. The polyester polyol may also be derived from the corresponding polycarboxylic anhydride or the corresponding lower alcohol polycarboxylic ester, rather than a free polycarboxylic acid.

[0065] Suitable diols may include, but are not limited to, ethylene glycol, butanediol, diethylene glycol, triethylene glycol, pentanediol, hexanediol, polyalkylene glycols such as polyethylene glycol, and 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and neopentanediol. If a polyester polyol functionality greater than 2 is desired, polyols having a functionality of 3 or greater may optionally be included in the polyol composition (e.g., trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene, or triethyl isocyanurate).

[0066] Suitable dicarboxylic acids may include, but are not limited to, aliphatic acids, aromatic acids, and combinations thereof. Examples of suitable aromatic acids may include, but are not limited to, phthalic acid, isophthalic acid, terephthalic acid, and tetrahydrophthalic acid. Examples of suitable aliphatic acids may include, but are not limited to, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, octanoic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2,2-dimethylsuccinic acid, and trimellitic acid. As used herein, the term "acid" also includes any acid anhydride of the acid. Additionally, monocarboxylic acids, such as benzoic acid and hexanecarboxylic acid, should be minimized or excluded from the disclosed compositions as much as possible. Saturated aliphatic and / or aromatic acids are also applicable to this disclosure, such as adipic acid or isophthalic acid.

[0067] (ii) Isocyanate components

[0068] The isocyanate component may contain one or more isocyanate compounds that react with one or more polyols in the polyol component.

[0069] In some embodiments, the isocyanate compound may be one or more selected from isocyanate monomers, isocyanate prepolymers, modified isocyanates, and combinations thereof.

[0070] As used herein, "isocyanate monomer" is any compound containing two or more isocyanate groups. "Aromatic isocyanate" is an isocyanate containing one or more aromatic rings. "Aliphatic isocyanate" does not contain an aromatic ring. In some embodiments, the isocyanate compound comprises an aromatic isocyanate.

[0071] The isocyanate monomers suitable for use in this disclosure may be selected from the group consisting of aromatic isocyanates, aliphatic isocyanates, carbodiimide-modified isocyanates, and combinations thereof. Examples of aromatic isocyanates suitable for use in accordance with this disclosure may include, but are not limited to, isomers of methylene diphenyl diisocyanate (“MDI”), such as 4,4-MDI, 2,4-MDI, and 2,2'-MDI, or modified MDI, such as carbodiimide-modified MDI, urethane-modified MDI, or urea-formaldehyde-modified MDI; isomers of toluene diisocyanate (“TDI”), such as 2,4-TDI and 2,6-TDI; isomers of naphthalene diisocyanate (“NDI”), such as 1,5-NDI; and combinations thereof. Examples of aliphatic isocyanates suitable for use according to this disclosure may include, but are not limited to, isomers of hexamethylene diisocyanate (“HDI”), isomers of isoflavone diisocyanate (“IPDI”), isomers of xylene diisocyanate (“XDI”), isomers of methylene-bis-(4-cyclohexyl isocyanate) (“HMDI”), and combinations thereof. In some embodiments, the isocyanate monomer comprises diisocyanate monomers selected from the group consisting of isoflavone diisocyanate (IPDI), methylene-bis-(4-cyclohexyl isocyanate) (HMDI), hexamethylene diisocyanate (HDI), methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), and combinations thereof.

[0072] In some embodiments, the isocyanate component of the reaction mixture can be prepared using any organic polyisocyanate, modified polyisocyanate, isocyanate-based prepolymer, and mixtures thereof. These may include aliphatic and cycloaliphatic isocyanates, but aromatic and especially polyfunctional aromatic isocyanates such as 2,4- and 2,6-toluene diisocyanate and mixtures of the corresponding isomers; 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI) and mixtures of the corresponding isomers; and mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate (PMDI). In some embodiments, a mixture of PMDI and toluene diisocyanate is included. In some embodiments, the polyisocyanate used to prepare the prepolymer formulation of the present invention is MDI or PMDI or a crude mixture of any of these.

[0073] In some embodiments, the isocyanate component may have a viscosity of 50 mPa·s to 20,000 mPa·s, 50 mPa·s to 18,000 mPa·s, or 100 mPa·s to 18,000 mPa·s at 25°C, as measured according to ASTM D2196.

[0074] (iii) Other components

[0075] In some embodiments, the reaction mixture further comprises one or more catalysts, including amine compounds (e.g., tertiary amine compounds), organometallic compounds, and any combination thereof. Exemplary tertiary amine compounds may include, but are not limited to, triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, N,N',N'-dimethylaminopropylhexahydrotriazine, 2-hydroxy-N,N,N-trimethylpropyl-1-ammonium formate, pentamethyldiethylenetriamine, tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine, N,N-dimethyl-N',N'-dimethylisopropylpropanediamine, N,N-diethyl-3-diethylaminopropylamine, and dimethylbenzylamine. Exemplary organometallic catalysts may include, but are not limited to, organomercury, organolead, organoiron, and organotin catalysts. Suitable tin catalysts may include, but are not limited to, stannous chloride, tin salts of carboxylic acids such as dibutyltin dilaurate, and other organometallic compounds such as those disclosed in U.S. Patent 2,846,408. Catalysts for the trimerization of polyisocyanates to produce polyisocyanurates, such as alkali metal alkoxides, may also be optionally employed herein. Such catalysts are used in amounts that measurably increase the polyurethane formation rate. One or more catalysts may be contained in either or both of the polyol component and the isocyanate component. A typical amount is 0.001 to 3 parts by weight of catalyst per 100 parts by weight of polyol component. In some embodiments, the reaction mixture comprises an amine catalyst, a tin catalyst, or a mixture thereof. The catalyst may be present in the polyol component. The catalyst may be present in an amount from 0.25% to 5% by weight of the polyol component.

[0076] In some embodiments, the reaction mixture further comprises one or more blowing agents. The blowing agent used in the reaction mixture may include at least one physical blowing agent selected from hydrocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, fluorocarbons, dialkyl ethers, or fluorinated dialkyl ethers, or any combination thereof. These types of blowing agents may include, but are not limited to, propane, isopentane, n-pentane, n-butane, isobutane, isobutene, cyclopentane, dimethyl ether, 1,1-dichloro-1-fluoroethane (HCFC-141b), dichlorofluoromethane (HCFC-22), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1-difluoroethane (HFC-152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3-pentafluoropropane (HFC-245fa), hydrofluoroolefins (HCFO), hydrofluoroolefins (HFO) (such as LBA), and any combination thereof. The reaction mixture may also contain chemical blowing agents, such as water, carboxylic acids, formic acid, and any combination thereof. One or more blowing agents may be contained in either or both of the polyol component and the isocyanate component. In some embodiments, one or more blowing agents are contained in the polyol component. Typically, the blowing agent accounts for 1 to 20 parts by weight per 100 parts by weight of the polyol component. The blowing agent may be present in the polyol component. The blowing agent may be present in an amount of 1% to 5% by weight of the polyol component.

[0077] In some embodiments, the reaction mixture further comprises one or more foam-stabilizing surfactants. Foam-stabilizing surfactants help stabilize bubbles formed during the foaming process until the polymer cures. A variety of silicone surfactants commonly used in the manufacture of polyurethane foams can be used to manufacture the composites disclosed herein. Surfactants that are self-dispersible or water-soluble are preferred. An example of such a silicone surfactant is one that can be marketed under the trade name Tegostab. ™ Niax ™ and Dabco ™ Commercially available. Other useful surfactants include block copolymers of ethylene oxide with propylene oxide and / or butane oxide, wherein one or more poly(ethylene oxide) blocks comprise 35% to 75% of the total weight of the block copolymer. Such block copolymers may have one or more hydroxyl groups. The surfactant may be present in the polyol component. The amount of surfactant may be from 0.25% to 5% by weight of the polyol component.

[0078] Optionally, the reaction mixture further comprises one or more chain extenders and / or crosslinking agents. Examples of such agents include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene oxide, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, cyclohexanediol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, and sucrose, as well as alkoxylates, diethanolamine, monoethanolamine, triethanolamine, mono(isopropanol)amine, di(isopropanol)amine, or tri(isopropanol)amine, glycerol, trimethylolpropane, and combinations thereof. Such agents may be present in the polyol component, for example, in an amount from 0.25% by weight to 5% by weight.

[0079] Optionally, the reaction mixture may also contain one or more additives, such as antioxidants, preservatives, pigments, colorants, and flame retardant additives.

[0080] III. Three-dimensional ring (3DL) preform

[0081] The composite material according to this disclosure includes a 3DL preform comprising a plurality of randomly bonded thermoplastic fiber rings.

[0082] In some implementations, the fiber rings are randomly formed by bending continuous fibers to contact each other in a molten state and thermally bonding them at multiple contact points.

[0083] The majority (greater than 50%) of the fibers contained in the 3DL preform are made of polyolefin, preferably polyolefin elastomer.

[0084] In some embodiments, the polyolefin elastomer may be selected from the group consisting of ethylene-propylene copolymers (such as ethylene propylene rubber (EPM) and ethylene propylene diene rubber (EPDM)), ethylene / α-olefin copolymers (such as ethylene / α-olefin random copolymers (POE) and ethylene / α-olefin block copolymers (OBC)), and combinations thereof.

[0085] In some embodiments, the polyolefin elastomer has a content of 0.88 g / cm³. 3 Up to 0.92 g / cm 3 The density.

[0086] "α-olefin" typically contains an olefinically unsaturated carbon atom between the first and second carbon atoms. 3-20 Straight-chain, branched-chain, or cyclic hydrocarbon molecules.

[0087] "Polyolefin" or "PO" is a polymer containing more than 50 mol% of a polymerizable olefin monomer (based on the total amount of polymerizable monomer) and optionally one or more comonomers. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.

[0088] "Ethylene / α-olefin interpolymer" is an interpolymer containing a major amount (i.e., more than 50 mol%) of polymerizable ethylene monomer (based on the total amount of polymerizable monomers) and one or more α-olefin comonomers.

[0089] In some embodiments, the 3DL preform comprises at least one ethylene / α-olefin copolymer. In some embodiments, the ethylene / α-olefin copolymer is a random ethylene / α-olefin interpolymer or a block ethylene / α-olefin interpolymer.

[0090] The ethylene / α-olefin copolymer contains ethylene as the main monomer. In some embodiments, the ethylene / α-olefin copolymer contains at least 60%, for example at least 65%, at least 70%, at least 75%, or at least 80% ethylene by weight of the copolymer as the main monomer. In some embodiments, the amount of ethylene contained in the ethylene / α-olefin copolymer is within a range formed by taking any two values ​​from the following list as endpoints: 60%, 65%, 70%, 75%, 80%, 85%, and 90% by weight of the copolymer. In some embodiments, the ethylene / α-olefin copolymer contains 60% to 90%, 65% to 90%, 70% to 90%, or 75% to 90% ethylene by weight of the copolymer.

[0091] The ethylene / α-olefin copolymer contains at least one α-olefin as a comonomer. Typically, the at least one α-olefin contained in the ethylene / α-olefin copolymer of this disclosure has four or more carbon atoms. In some embodiments, the ethylene / α-olefin copolymer contains one or more C atoms. 4-10 α-olefins are used as comonomers. In some exemplary embodiments, C 4-10 The α-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, C 4-10 α-olefins include 1-octene. In some exemplary embodiments, the ethylene / α-olefin copolymer may be selected from the group consisting of ethylene / 1-hexene copolymers, ethylene / 1-heptene copolymers, ethylene / 1-octene copolymers, ethylene / 1-nonene copolymers, ethylene / 1-decene copolymers, and combinations thereof. In some embodiments, the ethylene / α-olefin copolymer includes an ethylene / 1-octene copolymer.

[0092] In some embodiments, the ethylene / α-olefin copolymer contains up to 40%, for example up to 35%, 30%, 25%, 20%, 15%, or 10% C by weight of the copolymer. 4-10 α-olefins are used as comonomers. In some embodiments, the C1 contained in the ethylene / α-olefin copolymer... 4-10 The amount of α-olefin is within a range formed by taking any two values ​​from the following list as endpoints: 40%, 35%, 30%, 25%, 20%, 15%, and 10% by weight of the copolymer. In some embodiments, the ethylene / α-olefin copolymer contains 40% to 10%, 35% to 10%, 30% to 10%, or 25% to 10% C by weight of the copolymer. 4-10 α-olefins.

[0093] Examples of polyolefins that can be used for 3DL preforms may include those marketed under the trade name ELITE. ™ ENGAGE ™ VERSIFY ™ and INFUSE ™ Those purchased from The Dow Chemical Company.

[0094] In some implementations, based on the total weight of the fibers contained in the 3DL preform, more than 50%, more than 50%, more than 55%, more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, more than 95%, or 100% of the fibers are made of polyolefin elastomer.

[0095] In some implementations, based on the total weight of the fibers contained in the 3DL preform, 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 of other materials, such as aramid fibers, polyester fibers, or cellulose fibers (e.g., regenerated cellulose fibers).

[0096] In some embodiments, the diameter of the fibers included in the 3DL preform is not less than about 0.3 mm. In some embodiments, the diameter of the fibers included in the 3DL preform is not greater than about 2.0 mm. In some embodiments, the diameter of the fibers included in the 3DL preform is within a range formed by taking any two values ​​from the following list as endpoints: 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.8 mm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, 1.9 mm, and 2.0 mm. In some embodiments, the diameter of the fibers included in the 3DL preform is in the range of about 0.3 mm to about 2.0 mm, about 0.5 mm to about 2.0 mm, about 0.3 mm to about 1.5 mm, or about 0.5 mm to about 1.2 mm.

[0097] In some implementations, the density of the 3DL preform is not less than about 20 kg / m³. 3 In some implementations, the density of the 3DL preform is no greater than approximately 100 kg / m³. 3 In some implementations, the density of the 3DL preform is within a range formed by taking any two values ​​from the following list as endpoints: 20 kg / m³ 3 30kg / m 3 40kg / m 3 50kg / m 3 60kg / m 3 70kg / m 3 80kg / m 3 90kg / m 3 and 100kg / m 3 In some implementations, the density of the 3DL preform is approximately 20 kg / m³. 3 Approximately 100 kg / m 3 Approximately 20kg / m 3 Approximately 80 kg / m 3 Approximately 20kg / m 3 Approximately 70 kg / m 3 or approximately 30 kg / m 3 Approximately 60 kg / m 3 Within the range.

[0098] In some embodiments, the melt index (MI) of the polyolefin (e.g., polyolefin elastomer) contained in the 3DL preform is in the range of 1 g / 10 min to 35 g / 10 min at 190°C and 2.16 kg, for example, 1 g / 10 min to 30 g / 10 min at 190°C and 2.16 kg, or 1 g / 10 min to 20 g / 10 min, as measured according to ASTM D1238.

[0099] In some implementations, the 3DL preform is made of a nonwoven material.

[0100] In some implementations, the 3DL preform may also contain one or more additives or agents such as antioxidants, pigments, flame retardants, etc.

[0101] VI. The Development of Composite Materials

[0102] This disclosure also provides a method for producing the composite material described herein. In an exemplary embodiment, the method includes...

[0103] A 3DL preform comprising multiple randomly bonded thermoplastic fiber rings is placed in a mold;

[0104] The reaction mixture is injected into a mold and foamed in situ, so that the 3DL preform is asymmetrically embedded in the polyurethane foam, wherein the gaps in the fiber rings are partially or completely filled with polyurethane foam.

[0105] To solidify the foam; and

[0106] Release the composite material from the mold.

[0107] V. Applications and Uses

[0108] The present invention also provides the use of composite materials as cushioning pad materials or seat padding materials.

[0109] Composite materials are suitable for a wide variety of applications. Examples include, but are not limited to, applications of composite materials in conjunction with: chairs, stools, household furniture, beds, sofas, mattresses, pillows, automobiles, motorcycles, trains, airplanes, small boats, ships, ocean-going vessels, aircraft, spacecraft, tractors, bicycles, unicycles, tricycles, recreational vehicles, ATVs, jet skis, stadium seating, spacecraft, hovercraft, ski lifts, roller coasters, gliders, sleds, toboggans, lounge chairs, wheelchairs, beds, yoga mats, pet carrier linings, gardening knee pads, or any other type of bicycle, vehicle, seat, or furniture. In some embodiments, composite materials are used for seats in automobiles, motorcycles, trains, airplanes, small boats, ocean-going vessels, aircraft, spacecraft, etc. In some embodiments, composite materials are used for chairs, stools, household furniture, beds, sofas, mattresses, etc.

[0110] In some implementations, the composite material can be covered with an outer coating.

[0111] This disclosure also provides a product comprising a composite material as disclosed herein.

[0112] In some implementations, the product may be a cushioning pad, such as a vehicle cushioning pad. In some implementations, the product may be a seat from a car, motorcycle, train, airplane, small boat, sea vessel, aircraft, spacecraft, etc. In some implementations, the product may be a chair, stool, household furniture, bed, sofa, mattress, etc.

[0113] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and not intended to limit the invention as claimed.

[0114] Example

[0115] Some embodiments of the invention will now be described in the following examples, wherein all parts and percentages are by weight unless otherwise stated.

[0116] The three-dimensional randomly bonded fiber ring cushioning pads were prepared at Zhangjiagang City Dida Machinery Co., Ltd. using raw materials supplied by Dow. Information on the raw materials used in the examples is listed in Table 1.

[0117]

[0118] The material formulations for the 3DL cushioning pads used in this invention are listed in Table 2, with blended resin densities ranging from 0.885 g / cc to 0.916 g / cc. Generally, higher polyolefin density indicates higher polymer crystallinity, resulting in a stiffer material but reduced resilience. ™ 9530 is an olefin block copolymer (OBC), and compared with POE (olefin random copolymer), OBC exhibits higher heat resistance and good elasticity.

[0119]

[0120] The chemicals used to prepare PU foam are listed in Table 3.

[0121]

[0122] 3D ring manufacturing :

[0123] Polymer resin granules (dry-blended if using more than one resin) are fed into a single-screw extruder and then extruded as melt through a T-die with 80×5 nozzles. The fiber diameter is approximately 0.8 mm, and the extruder and die temperature are set to 200°C (235°C for sample 3DL-2). The fiber melt is dropped into cold water (25°C), where the fibers curl and bond together, and are then cooled to form 3D ring samples. The 3DL cushioning pad samples are controlled to a thickness of 30 mm, and each formulation is used for three densities (30 / 40 / 50 kg / m³). 3 The samples were prepared for different support effects in PU foam. The samples were stabilized at room temperature for 24 hours and then cut into 400×400×30mm pieces for further use.

[0124] Preparation of PU foam / 3DL composite material :

[0125] The isocyanate reactive compound (polyol, water, catalyst, silicone surfactant, etc.) and isocyanate were weighed into a 1-liter cup and mixed using a high-speed mixer. The mixture was then placed in a mold (400mm × 400mm × 50mm) at a temperature ranging from 50°C to 70°C. After pouring the reaction mixture onto the bottom of the mold itself (CE1) or onto the surface of a 3DL preform if 3DL preforms are used (IE), the mold was closed. Demolding time varied depending on the selected catalyst and catalyst concentration; however, all inventive examples (IE) and comparative examples (CE) demolded 300 seconds after pouring.

[0126]

[0127] Four commercially available cushioning materials were used as comparative examples, as shown in Table 4. They are all uniform single-layer structures made of PU foam or 3DL (not a composite material). In embodiments of the invention, 3DL made of different materials and densities is embedded at the bottom of the PU foam, such as... Figure 2 As shown. Sample information is listed in Table 5.

[0128]

[0129]

[0130]

[0131] Test characteristics and results

[0132] Table 6. Mechanical properties of the cushioning pad samples used in this invention

[0133]

[0134]

[0135]

[0136] The characteristics of the cushioning pad samples are shown in Table 6. For CE1 (PU foam), the SAG factor is only 2.6, far below the target (≥3.2). Samples CE2-CE4 failed the compressive residual strain (heat resistance) and durability tests (post-fatigue thickness change or firmness change).

[0137] All samples from this invention exhibited a SAG factor ≥ 3.2, demonstrating excellent compressive residual strain and durability properties. The composite material samples showed a resilience of >40% and a hysteresis loss of <40%, indicating good comfort characteristics of the cushioning pad.

[0138] The sample's 25% IFD ranged from 550N to 650N, and did not increase significantly when using a higher-density 3DL in the composite. This is likely due to the asymmetric structure of the composite foam. While the bottom layer of the composite was strengthened by using high-density 3DL, the top layer remained pure PU foam, and therefore the surface strength was not significantly affected, but the overall strength of the composite was greatly improved. This is why this composite can reduce the total thickness of the seat cushion without significant changes on soft surfaces while maintaining sufficient strength to support body weight.

[0139] This composite cushioning pad with an extremely high SAG factor can be used in thinner seat designs to save space while maintaining comfort features for passengers.

[0140] Measured values

[0141] Density of composite materials

[0142] Determine the mass and dimensions of the sample, and calculate its volume (in kilograms per cubic meter):

[0143] Density = M / V

[0144] Where: M = sample mass, kg; V = sample volume, m³ 3 .

[0145] Elasticity (resilience) of composite materials

[0146] The elasticity test shall be performed according to standard ASTM D3574-2017. The ball rebound tester shall consist of a vertical, transparent plastic (such as acrylic) tube with an inner diameter of 40±4 mm. A steel ball with a diameter of 16.0±0.2 mm and a weight of 16.3±0.2 g shall be released into the tube by a magnet or other device. The drop height shall be 500 mm. Place the specimen at the center of the tube base and adjust the tube height so that zero rebound is 16.0±0.2 mm above the surface of the foam specimen. Mount the steel ball on the release mechanism and drop it, recording the maximum rebound height (top of the ball). If the ball impacts the tube during drop or rebound, the obtained value is invalid. This condition is usually due to the tube not being vertical or irregularities on the specimen surface. To minimize parallax error, the circle in the area where the rebound percentage is read on the tube must be represented as a line. Perform two more drops on the same specimen at the same location, record the maximum rebound height, and calculate the average of the three rebound values.

[0147] Hysteresis Loss Test

[0148] Hysteresis loss is defined as the difference between the loading energy and the unloading energy, expressed as a percentage of the loading energy. It is tested according to ASTM D3574-2017. This measures the loss of a flexible foam's ability to return to its original support properties after compression. The indenter foot is brought into contact with the specimen at a rate of 50 ± 5 mm / min while a contact force of 4.5 ± 0.5 N is applied to determine the initial thickness of the specimen. The specimen is immediately indented to 75% of its initial thickness at a rate of 50 ± 5 mm / min. The compression force is immediately removed at 50 ± 5 mm / min until the indenter has fully returned to its original position. Hysteresis loss is calculated as defined below.

[0149] Hysteresis loss = (Loaded energy - Unloaded energy) / Loaded energy × 100%

[0150] Wherein: Energy is defined as the area under the force / deflection curve. Loading energy is the energy required to indent or compress the flexible specimen to a preset deflection (compression cycle). Unloading energy is the energy recovered when the indentation or compression plate retracts from the preset deflection and is completely unloaded (decompression cycle).

[0151] Indentation force deflection (IFD) and SAG factor

[0152] Indentation Force Deflection (IFD) testing measures the firmness of foam cushioning pads according to the standard ASTM D3574-2017. A high IFD result indicates increased stiffness. A low IFD result indicates a soft foam product. The Indentation Force Deflection procedure measures the force required to indent a 20cm diameter steel plate into the foam sample to a specified percentage of the initial height of the test sample (typically 5cm). Common IFD values ​​are generated at 25% and 65% of the initial height. One of the measurement results of the IFD test is called the Comfort Support Factor (SAG factor), which is the ratio of 65% IFD to 25% IFD in the Indentation Force Deflection measurement. The support factor is an important indicator of the point of impact of the foam cushioning pad. A low support factor indicates a higher likelihood of impact to the bottom.

[0153] Compressive residual strain

[0154] The compressive residual strain reflects the heat resistance of the cushioning pad product. Specimens were cut into 20cm × 20cm square shapes with a uniform thickness of approximately 5cm. After being compressed to 50% at 70°C for 22 hours using a compression clamp, the compression was removed, and the 3D ring samples were allowed to recover at room temperature for 30 minutes. The final specimen thickness was measured, and the compressive permanent deformation was calculated using the following equation.

[0155] Compressive residual strain (%) = [(T o - T f ) / T o ] × 100

[0156] Where T o It is the initial sample thickness, T f This is the final sample thickness.

[0157] Durability (fatigue) test conditions

[0158] Durability of the 3D ring samples was measured in MTS 810 according to ASTM D 3574-2017, with indentation force deflection (IFD) used to characterize the stiffness of the cushioning material. The impact load was set at 750 N ± 20 N (simulating adult weight), and the pusher was a 20 cm disc with rounded edges (similar to the hip contact area), with 80,000 impact cycles used to simulate 7 years of daily use. The sample was placed on the test platform with the PU foam side in contact with the pusher. After fatigue, the sample was placed under stress-free conditions for 10 ± 0.5 minutes, and the final stiffness and thickness were characterized, with thickness variation and IFD variation calculated.

Claims

1. A composite material, the composite material comprising Polyurethane foam, and Three-dimensional ring (3DL) preforms, the 3DL preforms comprising a plurality of randomly bonded thermoplastic fiber rings, The 3DL preform is asymmetrically embedded in the polyurethane foam, wherein the gaps in the fiber rings are partially or completely filled with the polyurethane foam, and The composite material has a SAG factor of not less than 3.2, wherein the SAG factor is defined as the ratio of 65% indentation force deflection (IFD) to 25% IFD.

2. The composite material according to claim 1, wherein the thickness of the polyurethane foam is greater than that of the 3DL preform.

3. The composite material according to claim 1, wherein more than 50% of the fiber rings included in the 3DL preform are made of polyolefin, preferably a polyolefin elastomer.

4. The composite material according to claim 3, wherein the melt index (MI) of the polyolefin is from 1 g / 10 min to 35 g / 10 min at 190°C and 2.16 kg.

5. The composite material of claim 3, wherein the polyolefin has a density of 0.88 g / cm 3 to 0.92 g / cm 3 .

6. The composite material according to claim 1, wherein the polyurethane foam is a reaction product of the reaction mixture, the reaction mixture comprising (i) a polyol component comprising one or more polyols selected from the group consisting of polyester polyols, polyether polyols and combinations thereof, and (ii) an isocyanate component comprising one or more isocyanate compounds.

7. The composite material according to claim 6, wherein the reaction mixture further comprises one or more components selected from the group consisting of: catalysts, foaming agents, foam-stabilizing surfactants, chain extenders and / or crosslinking agents, and combinations thereof.

8. The composite material of claim 1, wherein the polyurethane foam has a density of 15 kg / m 3 to 150 kg / m 3 .

9. The composite material according to claim 1, wherein the compressive residual strain of the composite material, as measured according to ASTM D 3574-2017 (D), is ≤20%.

10. The composite material according to claim 1, wherein the post-fatigue thickness variation of the composite material, as measured according to ASTM D 3574-2017(I3), is ≤5%.

11. The composite material according to claim 1, wherein the post-fatigue stiffness change of the composite material, as measured according to ASTM D 3574-2017(I3), is ≤25%.

12. The composite material of claim 1, wherein the composite material comprises a pure polyurethane foam portion extending from the intended stress surface of the composite material to a depth of at least 10% of the total thickness of the composite material.

13. A method for preparing the composite material according to claim 1, the method comprising: A 3DL preform comprising multiple randomly bonded thermoplastic fiber rings is placed in a mold; The reaction mixture is injected into the mold and foamed in situ, such that the 3DL preform is asymmetrically embedded in the polyurethane foam, wherein the gaps in the fiber rings are partially or completely filled with the polyurethane foam. The foam solidifies; as well as Release the composite material from the mold.

14. A product comprising the composite material according to claim 1.

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