Coated three-dimensional loop materials, methods for making them and uses thereof
Coating 3D loop materials with polyurethane elastomer or acrylic polymer reduces noise and improves soft-touch feeling, making them suitable for high-end pillow applications.
Patent Information
- Application Number
- PCT/CN2024/089465
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-04-24
- Publication Date
- 2025-10-30
AI Technical Summary
Three-dimensional loop materials used in bedding applications suffer from noise generation due to fiber collisions and abrasion, limiting their entry into high-end pillow markets despite offering desirable properties like resilience, breathability, and durability.
A coating layer comprising polyurethane elastomer, styrene-butadiene rubber, or acrylic polymer is applied to the surface of 3D loop materials to buffer fiber collisions and absorb noise, enhancing the soft-touch feeling and reducing noise.
The coated 3D loop materials provide a noise-free experience with improved soft-touch sensation, addressing the noise issue and enhancing user satisfaction.
Smart Images

Figure PCTCN2024089465-FTAPPB-I100001 
Figure PCTCN2024089465-FTAPPB-I100002 
Figure PCTCN2024089465-FTAPPB-I100003
Abstract
Description
COATED 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 (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof, having desirable quiet property and hand-feeling for furniture applications especially bedding, methods of making the three-dimensional loop material, and an article comprising the three-dimensional loop material, e.g., pillows and mattresses.BACKGROUND
[0003] Three-dimensional loop (3D loop) materials 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.
[0004] For the bedding application, there remains a gap in the 3D Loop's entry into the high-end pillow market due to the cheap plastic feel and noise created when pressing the article. Regarding the origin of noise production, it is hypothesized that the noise may stem from the collision and abrasion of fibers during pressing. Some practices on the manufacturing side involve producing thinner fiber products to reduce the noise, but the improvement is limited.
[0005] Thus, there is unfulfilled need in the furniture industry especially bedding applications for noise-free 3D loop materials that provide excellent heat management, high breathability, good resilience and soft touch feeling.
[0006] SUMMARY OF THE DISCLOSURE
[0007] After persistent exploration, the inventors have solved the problem of noise creation by adding an extra coating layer to buffer fiber collisions and absorb noise through a soft filament surface. It is surprisingly found that the coating on the surface of the 3D Loop material also provides a soft-touch feeling. Thus, the article made by the coated 3D Loop material can provide greatly enhanced user experience.
[0008] In an aspect, the present disclosure provides a three-dimensional loop material comprising loop fibers made from polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof, wherein the three-dimensional loop material is coated with a coating layer comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof.
[0009] In a further aspect, the present disclosure provides a method for making the three-dimensional loop material, comprising the steps of:
[0010] (i) providing loop fibers made from polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof;
[0011] ii) 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, and
[0012] (ii) coating the three-dimensional loop material with a coating composition comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof.
[0013] In a further aspect, the present disclosure provides an article 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 the coated 3D loop material according to the embodiments of the present disclosure in the left and a neat 3D loop as a benchmark in the right.
[0017] Figure 2 shows the noise test method according to the Examples 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] An “polyethylene” or “PE” is an ethylene homopolymer.
[0029] The melt index (MI) is tested at 190 degrees Celsius (℃) , 2.16 kilograms (kg) in accordance with ASTM D-1238.
[0030] The term “Glass transition temperature” or “Tg” can be calculated by using a Fox equation (T.G. Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956) ) below. For example, for calculating the Tg of a copolymer of monomers M1 and M2,
[0031] where Tg (calc. ) is the glass transition temperature calculated for the copolymer, w (M1) is the weight fraction of monomer M1 in the copolymer, w (M2) is the weight fraction of monomer M2 in the copolymer, Tg (M1) is the glass transition temperature of the homopolymer of monomer M1, and Tg (M2) is the glass transition temperature of the homopolymer of monomer M2, all temperatures being in K. The glass transition temperatures of the homopolymers may be found, for example, in “Polymer Handbook” , edited by J. Brandrup and E. H. Immergut, Interscience Publishers.
[0032] “Aqueous” system herein means that particles dispersed in an aqueous medium, for example, the aqueous system can be an emulsion. By “aqueous medium” herein is meant water and from 0 to 30%, by weight based on the weight of the medium, of water-miscible compound (s) such as, for example, alcohols, glycols, glycol ethers, glycol esters, or mixtures thereof.
[0033] Solids content of an aqueous system was measured as follows: weigh 10-20 grams of a sample into a dish and record the sample weight number as m1, then put it into a 150℃ oven for 30 minutes for drying, then take it out to weigh and record the sample weight as m2, solids content is calculated as m2 / m1 by percentage.
[0034] “Acrylic” in the present disclosure includes (meth) acrylic acid, alkyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile and their modified forms such as hydroxyalkyl (meth) acrylate. Throughout this document, the word fragment “ (meth) acryl” refers to both “methacryl” and “acryl” . For example, (meth) acrylic acid refers to both methacrylic acid and acrylic acid, and methyl (meth) acrylate refers to both methyl methacrylate and methyl acrylate. Specific examples of acrylic polymer include acrylic homopolymers, styrene acrylic copolymers, or mixtures thereof.
[0035] II. Three-dimensional loop material
[0036] 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.
[0037] The vast majority of the fibers comprised in the three-dimensional loop material are made from polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof in 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 polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof in the present disclosure.
[0038] 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.
[0039] 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 1.2 mm.
[0040] In some embodiments, the coated 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 120 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, 100, 110 and 120 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 120 kg / m3, from about 40 kg / m3 to about 100 kg / m3, from about 40 kg / m3 to about 80 kg / m3, or from about 50 kg / m3 to about 70 kg / m3.
[0041] In some embodiments, the three-dimensional loop material is a nonwoven material.
[0042] Ethylene / α-olefin multi-block interpolymer
[0043] The term “ethylene / α-olefin multi-block interpolymer” , also called “ethylene / α-olefin multi-block copolymer” or “olefin block copolymer (OBC) ” as used herein, refers to an interpolymer that includes ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more (preferably three or more) polymerized monomer units, the blocks or segments differing in chemical or physical properties. Specifically, this term refers to a polymer comprising two or more (preferably three or more) chemically distinct regions or segments (referred to as “blocks” ) joined in a linear manner, that is, a polymer comprising chemically differentiated units which are joined (covalently bonded) end-to-end with respect to polymerized functionality, rather than in pendent or grafted fashion. The blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the type of crystallinity (e.g., polyethylene versus polypropylene) , the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic) , region-regularity or region-irregularity, the amount of branching, including long chain branching or hyper-branching, the homogeneity, and / or any other chemical or physical property. The block copolymers are characterized by unique distributions of both polymer polydispersity (PDI or Mw / Mn) and block length distribution, e.g., based on the effect of the use of a shuttling agent (s) in combination with catalyst systems. Non-limiting examples of the olefin block copolymers of the present disclosure, as well as the processes for preparing the same, are disclosed in U.S. Patent Nos. 7,858,706 B2, 8,198,374 B2, 8,318,864 B2, 8,609,779 B2, 8,710,143 B2, 8,785,551 B2, 9,243,090 B2, and US20230058913 which are all incorporated herein by reference in their entirety.
[0044] Ethylene / α-olefin multi-block interpolymers are characterized by multiple blocks or segments of two or more polymerized monomer units, differing in chemical or physical properties.
[0045] In some embodiments, the multi-block copolymers can be represented by the following formula: (AB) n, where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher. Here, “A” represents a hard block or segment, and “B” represents a soft block or segment. Preferably the A segments and the B segments are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, the A segments and the B segments are randomly distributed along the polymer chain. In other words, for example, the block copolymers usually do not have a structure as follows: AAA-AA-BBB-BB. In still other embodiments, the block copolymers do not usually have a third type of block or segment, which comprises different comonomer (s) . In yet other embodiments, each of block A and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
[0046] The olefin block copolymers, in general, are produced via a chain shuttling process, such as, for example, described in U.S. Patent 7,858,706, which is herein incorporated by reference. Some chain shuttling agents and related information are listed in Col. 16, line 39, through Col. 19, line 44. Some catalysts are described in Col. 19, line 45, through Col. 46, line 19, and some co-catalysts in Col. 46, line 20, through Col. 51 line 28. Some process features are described in Col 51, line 29, through Col. 54, line 56. See also the following: U.S. Patent 7,608,668; U.S. Patent 7,893,166; and U.S. Patent 7,947,793 as well as US Patent Publication 2010 / 0197880. See also U.S. Patent 9,243,173.
[0047] Preferably, ethylene comprises the majority mole fraction of the whole ethylene / α-olefin multi-block copolymer, i. e., ethylene comprises at least 40 wt%of the whole ethylene / α-olefin multi-block copolymer. More preferably, ethylene comprises at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt%, with the substantial remainder of the whole ethylene / α-olefin multi-block interpolymer comprising the C4–C8 α-olefin comonomer, preferably, the C4-C8 α- olefin comonomer may be selected from butene, pentene, hexene, heptane, and octene, preferably 1-butene, 1-hexene, and 1-octene. In an embodiment, the ethylene / α-olefin multi-block interpolymer contains from 40 wt%, 50 wt%, or 60 wt%, or 65 wt%to 80 wt%, or 85 wt%, or 90 wt%of ethylene. For many ethylene / octene multi-block interpolymers, the composition comprises an ethylene content greater than 80 wt%of the whole ethylene / octene multi-block interpolymer and an octene content of from 10 wt%to 15 wt%, or from 15 wt%to 20 wt%of the whole ethylene / octene multi-block interpolymer.
[0048] The ethylene / α-olefin multi-block copolymer includes various amounts of “hard” segments and “soft” segments. “Hard” segments are blocks of polymerized units in which ethylene is present in an amount greater than 90 wt%, or 95 wt%, or greater than 95 wt%, or greater than 98 wt%, based on the weight of the polymer, up to 100 wt%. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 10 wt%, or 5 wt%, or less than 5 wt%, or less than 2 wt%, based on the weight of the polymer, and can be as low as zero. In some embodiments, the hard segments include all, or substantially all, units derived from ethylene. “Soft” segments are blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than 5 wt%, or greater than 8 wt%, or greater than 10 wt%, or greater than 15 wt%, based on the weight of the polymer. In an embodiment, the comonomer content in the soft segments is greater than 20 wt%, or greater than 25 wt%, or greater than 30 wt%, or greater than 35 wt%, or greater than 40 wt%, or greater than 45 wt%, or greater than 50 wt%, or greater than 60 wt%and can be up to 100 wt%.
[0049] The soft segments can be present in an ethylene / α-olefin multi-block interpolymer from 1 wt%, or 5 wt%, or 10 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%to 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 99 wt%of the total weight of the ethylene / α-olefin multi-block interpolymer. Conversely, the hard segments can be present in similar ranges. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed in, for example, USP 7,608,668, the disclosure of which is incorporated by reference herein in its entirety. In particular, hard and soft segment weight percentages and comonomer content may be determined as described in column 57 to column 63 of USP 7,608,668.
[0050] In an embodiment, the ethylene / α-olefin multi-block copolymer is produced in a continuous process and possesses a polydispersity index (Mw / Mn) from 1.7 to 3.5, or from 1.8 to 3, or from 1.8 to 2.5, or from 1.8 to 2.2. When produced in a batch or semi-batch process, the ethylene / α-olefin multi-block copolymer possesses Mw / Mn from 1.0 to 3.5, or from 1.3 to 3, or from 1.4 to 2.5, or from 1.4 to 2.
[0051] Nonlimiting examples of suitable ethylene / α-olefin multi-block copolymer are disclosed in U.S. Patent No. 7,608,668, the entire content of which is incorporated by reference herein.
[0052] In an embodiment, the ethylene / α-olefin multi-block copolymer consists of only (i) ethylene and (ii) a C4–C8 α-olefin.
[0053] In an embodiment, the ethylene / α-olefin multi-block copolymer has hard segments and soft segments, is styrene-free, consists of only (i) ethylene and (ii) a C4–C8 α-olefin, and is defined as having a Mw / Mn from 1.7 to 3.5.
[0054] In an embodiment, the ethylene / α-olefin multi-block copolymer used in the present disclosure has a density of between about 0.870 g / cc and about 0.920 g / cc, preferably between about 0.880 g / cc and 0.915 g / cc, more preferably between about 0.890 g / cc and about 0.910 g / cc, even more preferably between about 0.900 g / cc and about 0.905 g / cc.
[0055] Preferably, the ethylene / α-olefin multi-block copolymer used in the present disclosure has a MI of not greater than about 60 g / 10 min (at 190 ℃ / 2.16 kg) , preferably not greater than about 50 g / 10 min at 190 ℃ / 2.16 kg, more preferably not greater than about 40 g / 10 min at 190 ℃ / 2.16 kg, more preferably not greater than about 35 g / 10 min at 190 ℃ / 2.16 kg, even more preferably not greater than about 30 g / 10 min at 190 ℃ / 2.16 kg. Alternatively, the ethylene / α-olefin random copolymer used in the present disclosure has a MI from about 0.1 g / 10 min at 190 ℃ / 2.16 kg to about 60 g / 10 min at 190 ℃ / 2.16 kg, preferably about 1 g / 10 min at 190 ℃ / 2.16 kg to about 50 g / 10 min at 190 ℃ / 2.16 kg, more preferably about 1.5 g / 10 min at 190 ℃ / 2.16 kg to about 40 g / 10 min at 190 ℃ / 2.16 kg, still more preferably about 2 g / 10 min at 190 ℃ / 2.16 kg to about 35 / 10 min at 190 ℃ / 2.16 kg, and even more preferably about 3 g / 10 min at 190 ℃ / 2.16 kg to about 30 g / 10 min at 190 ℃ / 2.16 kg.
[0056] Suitable ethylene / α-olefin multi-block interpolymer can be INFUSETM from Dow, such as INFUSETM 9107, INFUSETM 9500, INFUSETM 9507, or INFUSETM 9807.
[0057] Ethylene / α-olefin random copolymer
[0058] An ethylene / α-olefin random copolymer (also called random POE or ethylene / α-olefin elastomer or POE) is an ethylene / propylene random copolymer or an ethylene / C4–C8 α-olefin random copolymer. In an embodiment, the ethylene / α-olefin copolymer is an ethylene / C4–C8 α-olefin copolymer. The ethylene / C4–C8 α-olefin copolymer is composed of, or otherwise consists of, ethylene and one copolymerizable C4–C8 α-olefin comonomer in polymerized form. The ethylene / C4–C8 α-olefin copolymer is composed of, or otherwise consists of, ethylene and one copolymerizable C4–C8 α-olefin comonomer in polymerized form. The C4-C8 α-olefin comonomer may be selected from 1-butene, methyl-l-butene, 1-pentene, 1-hexene, 4-hexene, 5-methyl-l-hexene, 4-ethyl-l-hexene, or 1-octene. In an embodiment, the ethylene / α-olefin copolymer is an ethylene / 1-octene copolymer.
[0059] In an embodiment, the ethylene / α-olefin random copolymer used in the present disclosure has a density of between about 0.870 g / cc and about 0.920 g / cc, preferably between about 0.880 g / cc and 0.915 g / cc, more preferably between about 0.890 g / cc and about 0.910 g / cc, even more preferably between about 0.900 g / cc and about 0.905 g / cc.
[0060] Preferably, the ethylene / α-olefin random copolymer used in the present disclosure has a MI of not greater than about 60 g / 10 min (at 190 ℃ / 2.16 kg) , preferably not greater than about 50 g / 10 min at 190 ℃ / 2.16 kg, more preferably not greater than about 40 g / 10 min at 190 ℃ / 2.16 kg, more preferably not greater than about 35 g / 10 min at 190 ℃ / 2.16 kg, even more preferably not greater than about 30 g / 10 min at 190 ℃ / 2.16 kg. Alternatively, the ethylene / α-olefin random copolymer used in the present disclosure has a MI from about 0.1 g / 10 min at 190 ℃ / 2.16 kg to about 60 g / 10 min at 190 ℃ / 2.16 kg, preferably about 1 g / 10 min at 190 ℃ / 2.16 kg to about 50 g / 10 min at 190 ℃ / 2.16 kg, more preferably about 1.5 g / 10 min at 190 ℃ / 2.16 kg to about 40 g / 10 min at 190 ℃ / 2.16 kg, still more preferably about 2 g / 10 min at 190 ℃ / 2.16 kg to about 35 / 10 min at 190 ℃ / 2.16 kg, and even more preferably about 3 g / 10 min at 190 ℃ / 2.16 kg to about 30 g / 10 min at 190 ℃ / 2.16 kg.
[0061] Suitable ethylene / α-olefin random copolymer can be ENGAGETM from Dow, such as ENGAGETM 8402, ENGAGETM 8450 from Dow Chemical Company.
[0062] The types of the polymer that can be used to prepare the neat 3D loop material are not limited in the present disclosure. Other polymers, such as thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) may be used to prepare the neat 3D loop material, as long as it can form a 3D loop material with good mechanical properties.
[0063] III. Coating composition
[0064] The coating of the present disclosure is prepared from a coating composition.
[0065] The coating composition may comprise 30-80 wt%, preferably 35-70 wt%, more preferably 40-60 wt%, most preferably 45-55wt%of at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof, based on the total weight of the composition.
[0066] The coating composition may further comprise 0-15 wt%, preferably 0.1-10 wt%, alternatively 0.5-8 wt%, alternatively 1-6 wt%, more preferably 2-6 wt%, most preferably 3-5 wt%of a foaming agent, based on the total weight of the composition. The at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber and an acrylic polymer and the foaming agent is in a weight ratio of from 10: 1 to 120: 1, preferably from 10: 1 to 80: 1, more preferably 10: 1 to 20: 1.
[0067] The foaming agent used in the present disclosure can comprise at least one physical foaming agent which is selected from a hydrocarbon, hydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon, dialkyl ether or fluorine-substituted dialkyl ether, or any combination thereof. Foaming agents of these types can comprise, but are not limited to, propane, isopentane, n-pentane, n-butane, isobutane, isobutene, cyclo-pentane, dimethyl ether, 1, 1-dichloro-l-fluoroethane (HCFC-141b) , chlorodifluoromethane (HCFC-22) , l-chloro-l, l-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) , hydrofluoroolefin (HCFO) , hydrofluoroolefin (HFO) , and any combination thereof. The coating composition may also comprise a chemical foaming agent, such as water, carboxylic acid, formic acid, and any combination thereof.
[0068] In one embodiment, a foaming bead can be used as a foaming agent. The foaming bead can be a core / shell structure. More preferably, the shell is made of acrylics and the core is filled with an alkane foaming agent. The foaming beads used in the coating composition can be activated at temperature below the melting point of polymer of the loop fibers. For example, the foaming bead is activated (also called foamed) at a temperature of less than 120 ℃, preferred less than 110 ℃, preferred less than100 ℃ and more preferred less than 90 ℃.
[0069] The coating composition comprises one or more additives selected from the groups consisting of a coalescent, a foaming agent and an antiblocker.
[0070] The coating composition may further comprise 0-6 wt%, preferably 0.5-5.5 wt%, more preferably 1-5 wt%, most preferably 2-4.5 wt%of a coalescent based on the total weight of the composition.
[0071] The coating composition may further comprise 0-4 wt%, preferably 0.1-3 wt%, more preferably 0.2-2 wt%, most preferably 0.3-1 wt%of an anti-blocker based on the total weight of the composition.
[0072] The coating composition may further comprise 0-3 wt%, preferably 0.05-2 wt%, more preferably 0.1-1 wt%, most preferably 0.15-0.5 wt%of a defoamer based on the total weight of the composition.
[0073] The coating composition may further comprise 0-3 wt%, preferably 0.05-2 wt%, more preferably 0.1-1 wt%, most preferably 0.15-0.5 wt%of a dispersant based on the total weight of the composition.
[0074] The loading amount of the coating, calculated based on the dry weight of the coating, on the 3D loop material can be in a range of 1-100wt%, preferably 2-90wt%, more preferably 2-50wt%, even more preferably 2-25wt%, still more preferably 5-15wt%, based on the dry weight of the 3D loop material before coated.
[0075] The coating composition may also comprise one or more conventional additives such as foam stabilizers, tackifiers, plasticizers, rheology modifiers, antioxidants, UV-absorbents, light-stabilizers, catalysts, fillers, colorants, pigments, water scavengers, surfactants, solvents, diluents, flame retardants, antistatic agents, preservatives, biocides and any combinations thereof. Besides, in addition to the above stated components, the coating composition may comprise balance amount of water, such as having a water content of about 30 wt%to 75 wt%.
[0076] Polyurethane elastomer
[0077] The polyurethane elastomer useful in the present disclosure may be an aqueous polyurethane (PU) dispersion. Polyurethane is an alternating copolymer generally prepared by reacting di or tri-isocyanates with suitable polyols such as, for the sake of example, an alkylene polyol as depicted below, or a polyether polyol, a polyester polyol, or a polycarbonate polyol. The respective isocyanate and polyol, polymerize through the formation of carbamate / urethane links, such as shown below:
[0078] For the avoidance of doubt, polyurethanes herein do not include polyureas. The isocyanates used to make polyurethane have at least two isocyanate groups per molecule and may be aromatic and / or aliphatic. They may be selected from diphenylmethane diisocyanates (MDIs) , polymeric diphenylmethane diisocyanates (pMDIs) , toluene diisocyanates (TDIs) , hexamethylene diisocyanates (HDIs) , isophorone diisocyanates (IPDIs) , naphthalene diisocyanates (NDIs) , and combinations thereof. Aromatic diisocyanates such as toluene diisocyanate (TDI) and methylene diphenyl diisocyanate, (MDI) are most commonly used because they are generally less expensive and more reactive than other isocyanates. However, they are generally supplied as mixtures of isomers such as in the case of TDI 2, 4-and 2, 6-toluenediisocyanate and in the case of MDI 4, 4'-, 2, 4'-and 2, 2'-diphenylmethanediisocyanates as well as the polymeric equivalent (pMDI) . Aliphatic and cycloaliphatic isocyanates may also be utilised. These may include 1, 6-hexamethylene diisocyanate (HDI) , isophorone diisocyanate (IPDI) and 4, 4-diisocyanato dicyclohexylmethane (otherwise known as hydrogenated MDI) .
[0079] Hence, exemplary polyisocyanates which may be used to make the polyurethane herein include m-phenylene diisocyanate, 2, 4-and / or 2, 6-toluene diisocyanate (TDI) , the various isomers of diphenylmethanediisocyanate (MDI) , hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, cyclohexane-1, 4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI (H12 MDI) , naphthylene-1, 5-diisocyanate, methoxyphenyl-2, 4-diisocyanate, 4, 4′-biphenylene diisocyanate, 3, 3′-dimethyoxy-4, 4′-biphenyl diisocyanate, 3, 3′-dimethyldiphenylmethane-4, 4′-diisocyanate, 4, 4′, 4″-triphenylmethane diisocyanate, polymethylene polyphenylisocyanates, hydrogenated polymethylene polyphenyl polyisocyanates, toluene-2, 4, 6-triisocyanate and 4, 4′-dimethyldiphenylmethane-2, 2′, 5, 5′-tetraisocyanate. However, toluene diisocyanates (TDIs) and methylene diphenyl diisocyanates, (MDIs) are preferred.
[0080] The polyols used to make polyurethane are typically compounds having at least two hydroxyl groups. They may comprise alkylene polyols include for the sake of example, but not limited to ethylene glycol, propylene glycol, 1, 3-dihydroxypropane, 1, 4-dihydroxybutane and 1, 6 dihydroxyhexane; triols such as glycerol, 1, 2, 4-trihydroxybutane, 1, 2, 6-trihydroxyhexane and 1, 1, 1-trimethylolpropane; tetrols such as pentaerythritol, pentols such as xylitol and arabitol and hexols such as sorbitol and mannitol. The polyols may alternatively be polyether glycols such as polyethylene glycol (PEG) and polypropylene glycol (PPG) or polyester glycols such as polycaprolactone. Whilst less common, polyols can be replaced, in the preparation of polyurethanes by compounds having at least two amine groups such as Polyamines and amine-terminated polyethers.
[0081] Any suitable polyurethane may be utilized as the aqueous polyurethane dispersion (PUD) or polyurethane elastomer herein. In one embodiment the aqueous polyurethane dispersion has a solids content of from 40 to 60 wt. %. The polyurethane particles in the PUD comprise particles having an average particle size in the range of from 75nm to 1μm, alternatively from 200 nm to 1μm, alternatively from 250nm to 900nm. As used herein, unless otherwise indicated, the term “average particle size, ” with regard to the polyurethane particles in the PUD, means the particle size as determined by light scattering (LS) using a BI-90 particle size analyzer, Brookhaven Instruments Corp. (Holtsville, N. Y. ) .
[0082] The polyurethane herein typically has a number average molecular weight (Mn) of at least about 5000g / mole. In certain embodiments, the polyurethane has an Mn of from 5,000 to 5,000,000 g / mole, alternatively of from 10,000 to 1,000,000 g / mole, alternatively of from 10,000 to 750,000 g / mole, alternatively of from 15,000 to 250,000 g / mole, alternatively of from 15,000 to 200,000 g / mole, alternatively of from 15,000 to 100,000 g / mole.
[0083] The number average molecular weight may be readily determined using Gel Permeation Chromatography (GPC) techniques based on polystyrene standards or using end group analysis by nuclear magnetic resonance spectroscopy.
[0084] When preparing the polyurethane herein, the isocyanate monomer (s) and polyol monomer (s) are typically reacted in an isocyanate monomer: polyol monomer molar ratio of from 5: 1 to 1: 5; alternatively, from 4: 1 to 1: 4; alternatively, from 3: 1 to 1: 3; alternatively, from 2: 1 to 1: 2; alternatively from 1.1: 1 to 1: 1.1.
[0085] The polyurethane may have a glass transition temperature (Tg) in the range of from -50 to 100 ℃., for example from -50 to 75 ℃., or alternatively from -40 to 50 ℃. As used herein, unless otherwise indicated, the term “Tg” or “glass transition temperature” of a polymer, with regard to the (meth) acrylic emulsion and components thereof, refers to the Tg of a polymer calculated by using the Fox equation (T.G. Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956) .
[0086] Representative, non-limiting examples of commercially produced PUDs useful in the present disclosure include those sold under the tradenames (all available from DOW, Inc. ) DOW SYNTEGRA and BAYDERM series PUDs including aliphatic and aromatic polyurethane dispersions. Examples are SYNTEGRA YS3000, SYNTEGRA YS3018, BAYDERM FINISH 91UD.
[0087] Styrene-butadiene rubber
[0088] The styrene-butadiene rubber useful in the present disclosure may be a carboxylic styrene butadiene latex formed by polymerizing a vinyl or vinylidene monoaromatic monomer, a C4-6 conjugated diene, a C3-6 ethylenically unsaturated mono-or di-carboxylic acid or a mixture thereof and a C1-8 alkyl ester of acrylic or methacrylic acid.
[0089] In making the polymer in accordance with the present disclosure, the amount of vinyl or vinylidene monoaromatic monomer is from about 10 to about 40 weight percent based on the total monomer. Preferably this monomer is used in an amount from about 15 to about 30 weight percent. Some monomer examples are styrene unsubstituted or substituted by a C1-4 alkyl radical or a chlorine or bromine atom, e.g. styrene, α-methyl styrene, and chlorostyrene.
[0090] The C4-6 conjugated diene is used in an amount from about 45 to about 70 weight per cent based on total monomer. Preferably, the conjugated diene is used in an amount from about 55 to about 70 weight percent. Preferred aliphatic C4-6 conjugated dienes are well known to those skilled in the art. Examples of the aliphatic C4-6 conjugated diene are, for example, 1, 3 butadiene and isoprene. Butadiene is especially preferred.
[0091] The mono-or di-carboxylic acid or mixture thereof is used in an amount from about 1 to about 5 weight per cent based on the total monomer. The preferred amount is from about 2 to about 4 weight per cent. Some examples of the C3-6 acids are maleic, fumaric, itaconic, butenoic, pentenoic, hexenoic, acrylic, and methacrylic acids. Mixtures of one or more of these acids may also be used.
[0092] The alkyl ester is used in an amount from about 5 to about 30 weight percent based on the weight of the total monomer. Preferably the ester is used in an amount from about 10 to about 25 percent by weight. The C1-8 alkyl ester of acrylic acid or methacrylic acid may be a simple straight chain ester such as butyl acrylate or a branched ester such as ethyl hexyl acrylate. The ester may be a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl or octyl ester of acrylic or methacrylic acid.
[0093] The carboxylic styrene-butadiene latex in the present disclosure may be prepared by well-known conventional emulsion polymerization techniques using the monomers herein disclosed and conventional additives for emulsion polymerization. The emulsifiers may be either anionic or non-ionic. Conventional initiators or initiator systems of either the redox or the free radical type may be used to start the polymerization. Electrolytes and chelating agents may be used in accordance with known emulsion polymerization art.
[0094] Acrylic polymer
[0095] The acrylic polymer useful in the present disclosure may comprise structural units of one or more ethylenically unsaturated nonionic monomers. The term “nonionic monomers” refers to monomers that do not bear an ionic charge between pH=1-14. Suitable ethylenically unsaturated nonionic monomers may include an alkyl ester of (meth) acrylic acid; a hydroxy-functional alkyl (meth) acrylate; a cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate, vinyl aromatic monomers such as styrene and substituted styrene (including for example D-methyl styrene, p-methyl styrene, t-butyl styrene, vinyltoluene) ; glycidyl (meth) acrylate; α-olefins such as ethylene, propylene, and 1-decene; vinyl compounds such as vinyl (meth) acrylate, vinyl butyrate, vinyl versatate and other vinyl esters; nitrile-containing monomers such as acrylonitrile (AN) ; or mixtures thereof. “Alkyl” means a linear or branched alkyl group. The alkyl ester of (meth) acrylic acid may be selected from C1-C2-alkyl (meth) acrylates, C4-C20-alkyl (meth) acrylates, or mixtures thereof. The C4-C20-alkyl (meth) acrylates refer to alkyl esters of (meth) acrylic acid containing an alkyl with from 4 to 20 carbon atoms, or from 4 to 18 carbon atoms. Examples of C4-C20-alkyl (meth) acrylates include butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, or mixtures thereof. Desirably, the C4-C20-alkyl (meth) acrylate is selected from 2-ethylhexyl acrylate (EHA) , butyl (meth) acrylate, or mixtures thereof. Suitable C1-C2-alkyl (meth) acrylates may include methyl (meth) acrylate, ethyl (meth) acrylate, or mixtures thereof. Suitable hydroxy-functional alkyl (meth) acrylates may include hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, hydroxybutyl (meth) acrylates, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-2-ethylhexyl (meth) acrylate, or mixtures thereof. Desirably, the hydroxy-functional alkyl (meth) acrylate is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA) , 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and mixtures thereof. Desirably, the ethylenically unsaturated nonionic monomers are selected from styrene, HEMA, acrylonitrile, methyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, butyl methacrylate, butyl acrylate (BA) , EHA, vinyl acrylate or mixtures thereof. Desirably, the ethylenically unsaturated nonionic monomers are selected from styrene, alkyl ester of (meth) acrylic acid, vinyl acrylate or mixtures thereof. More desirably, the ethylenically unsaturated nonionic monomers are selected from styrene, butyl methacrylate, butyl acrylate (BA) , or mixtures thereof.
[0096] The acrylic polymer useful in the present disclosure may comprise or be free of structural units of one or more ethylenically unsaturated acid monomers, salts thereof, or mixtures thereof. The acid monomers and / or their salts may include a, β-ethylenically unsaturated carboxylic acids including an acid-bearing monomer such as methacrylic acid (MAA) , acrylic acid (AA) , itaconic acid, maleic acid, or fumaric acid; or a monomer bearing an acid-forming group which yields or is subsequently convertible to, such an acid group (such as anhydride, (meth) acrylic anhydride, or maleic anhydride) ; phosphorous-containing monomers such as vinyl phosphonic acid, allyl phosphonic acid, phosphoalkyl (meth) acrylates such as phosphoethyl (meth) acrylate, phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate, SIPOMER PAM-100, SIPOMER PAM-200, and SIPOMER PAM-300 all available from Solvay, phosphoalkoxy (meth) acrylates such as phospho ethylene glycol (meth) acrylate, phospho di-ethylene glycol (meth) acrylate, phospho tri-ethylene glycol (meth) acrylate, phospho propylene glycol (meth) acrylate, phospho di-propylene glycol (meth) acrylate, phospho tri-propylene glycol (meth) acrylate; sulfonic acid monomers and salts thereof including, for example, 2-acrylamido-2-methyl-1-propanesulfonic acid; sodium salt of 2-acrylamido-2-methyl-1-propanesulfonic acid; and ammonium salt of 2-acrylamido-2-methyl-1-propane sulfonic acid; sodium p-styrene sulfonate (SSS) ; sodium vinyl sulfonate (SVS) ; sodium salt of allyl ether sulfonate; salts thereof; and mixtures thereof. Desirably, the acid monomer is an D, β-ethylenically unsaturated carboxylic acid. More desirably, the acid monomer includes acrylic acid, methyl acrylic acid, SSS, or mixtures thereof, and more desirably, the acid monomer is AA. The acrylic polymer may comprise structural units of the acid monomer at a concentration of 0%to 20%, and can be 0.1%to 15%, 0.3%to 12%, 0.5%to 10%, or 0.7%to 8%, by weight based on the weight of the acrylic polymer.
[0097] The acrylic polymer useful in the present disclosure may comprise or be free of structural units of one or more ethylenically unsaturated monomers carrying at least one functional group selected from an amide, ureido, carbonyl, or silane group, or combinations thereof (hereinafter “functional monomer” ) . Suitable functional monomers may include, for example, carbonyl-containing functional monomers such as acetoacetoxyethyl methacrylate (AAEM) and diacetone acrylamide (DAAM) , acrylamide, methacrylamide, vinyltrialkoxysilanes such as vinyltrimethoxysilane, (meth) acryloxyalkyltrialkoxysilanes such as (meth) acryloxyethyltrimethoxysilane and (meth) acryloxypropyltrimethoxysilane, or mixtures thereof. Desirably, the functional monomer comprises acrylamide, DAAM, ureido-containing monomers, or mixtures thereof. The acrylic polymer may comprise structural units of the functional monomer at a concentration of 0%to 20%, and can be 0.1%to 15%, 0.3%to 12%, 0.5%to 10%, or 0.7%to 8%, by weight based on the weight of the acrylic polymer.
[0098] Desirably, the acrylic polymer may comprise structural units of the alkyl ester of (meth) acrylic acid at a concentration of zero to 90%, 2%to 80%, 3%to 70%, or 4%to 60%, or 5%to 50%or 10%to 45%by weight based on the weight of the acrylic polymer. The acrylic polymer may comprise structural units of styrene at a concentration of 20%to 99%, 25%to 95%, 30%to 90%, 35%to 85%, 40%to 80%, or 50%to 70%, or 55%to 65%, by weight based on the weight of the acrylic polymer. The acrylic polymer may comprise structural units of vinyl (meth) acrylate at a concentration of 20%to 99%, 25%to 95%, 30%to 90%, 35%to 85%, 40%to 80%, or 50%to 70%, or 55%to 65%, by weight based on the weight of the acrylic polymer. The acrylic polymer may comprise or be free of structural units of a multifunctional nonionic monomer such as butadiene, divinylbenzene, and allyl (meth) acrylate, typically at a concentration of zero to 5%, zero to 2%, 0.1%to 1%, or 0.1%to 0.5%, by weight based on the weight of the acrylic based polymer.
[0099] Desirably, the acrylic polymer may comprise structural units of the ethylenically unsaturated nonionic monomer at a total concentration of 80%to 100%, 85%to 99.6%, 90%to 99.4%, 92%to 99.2%, or 95%to 99%, by weight based on the weight of the acrylic polymer. Preferably, the ethylenically unsaturated nonionic monomer is selected from butyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, vinyl (meth) acrylate.
[0100] The acrylic polymer useful in the present disclosure may have a Tg of below 5 ℃, or a Tg of below 0℃, or a Tg of below -5 ℃, or a Tg of below -10 ℃ or a Tg of below -15 ℃ or within a numerical range obtained by combining any two of the following values: 5 ℃, 0 ℃, -5 ℃, -10 ℃, -15 ℃, -20 ℃, -25 ℃, -30 ℃, -35 ℃, -40℃, -45 ℃.
[0101] IV. Production of three-dimensional loop material
[0102] The present disclosure also provides a method for producing the three-dimensional loop material disclosed herein, comprising the steps of:
[0103] i) providing loop fibers made from polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof; and
[0104] ii) 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, and
[0105] iii) coating the three-dimensional loop material with a coating composition comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof.
[0106] The term “coating” used herein comprises making the loop fibers or 3D loop materials exposure to the coating composition, 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.
[0107] In some embodiments, the method further comprises iv) a step of foaming the formed three-dimensional loop material, when the coating composition comprises a foaming agent. The foaming step is activated at a temperature below the melting point of polymer of the loop fibers. After the foaming step, the foamed coating layer has a density of 0.1-0.8 g / cm3, preferably 0.2-0.6 g / cm3, more preferably 0.3-0.5 g / cm3and a pore size of 25-120 μm, preferably 30-90 μm, more preferably 40-80 μm.
[0108] In some embodiments, the method further comprises v) a step of drying the formed three-dimensional loop material before use or storage.
[0109] In further embodiments of the present disclosure, the method further comprises the steps of:
[0110] (a) melting a polymer selected from polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof as well as optional additives to form a molten composition; and
[0111] (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;
[0112] (c) cooling the loop fibers.
[0113] 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 ℃.
[0114] 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 ℃.
[0115] VIII. Applications and uses
[0116] The present disclosure also provides use of the three-dimensional loop material as a cushioning material or a bedding material.
[0117] 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.
[0118] In some embodiments, the three-dimensional loop material can be covered with an outerwrap.
[0119] The present disclosure further provides an article comprising the three-dimensional loop material disclosed herein.
[0120] In some embodiments, the article can be a pillow or a mattress.
[0121] The present disclosure further provides use of a coating layer comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof in reducing noise creation of a three-dimensional loop material.
[0122] The present disclosure further provides use of a coating layer comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof in improving hand-feeling of a three-dimensional loop material.
[0123] 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
[0124] Some embodiments of the invention will now be described in the following Examples, wherein all parts and percentages are by weight unless otherwise specified.
[0125] Materials / Ingredients
[0126] Table 1: Raw materials
[0127] A. The production of the 3D Loop structure
[0128] The polymer resin ENGAGETM 8402 and ENGAGETM 8450 were dry blended in a weight ratio of 1: 1 to form polymer resin pellets with a density of 0.902 g / cc and a melting index of 15. The polymer resin pellets were fed in the single screw extruder and melt was then extruded though the T-die with 80 × 5 nozzles. The fiber diameter was around 0.8 mm, and the extruder and die temperature was set at 200 ℃, fiber melt dropped to cold water (25 ℃) and fiber curling and bonding with each other and cooled to form 3D loop samples. The resulting 3DL cushion sample thickness was controlled at 50 mm, and each formulation was prepared with a bulk density of 35 kg / m3. Samples were stabilized at room temperature for 24 hours and then cut into 100 x 100 mm square 3D Loop samples for further use.
[0129] B. Coating Process
[0130] A coating emulsion was prepared by simply mixing the ingredients in weight percentage according to the formulation shown in Table 2. The 100 x 100 mm square 3D Loop sample (thickness 50 mm) was immersed in the coating emulsion, then taken out of the emulsion and slightly shaken to remove extra liquid. The sample was then dried in air at room temperature to obtain a coated article as shown in Figure 1.
[0131] C. Foaming process of the coating layer
[0132] The samples, which were coated with a coating emulsion comprising the foaming agent, were placed in an oven at 90℃ for 30 minutes to allow for the complete foaming of the added foaming beads in the coating layer.
[0133] After drying, the loading of the coating was obtained via the equation below:
[0134] Where Mafter coating refers to the mass of the 3DL article after coating with the coating emulsion; and Mbefore coating refers to the mass of the 3DL article before coating.
[0135] Table 2: Coating formulation
[0136] C. Property tests
[0137] 1) Noise test
[0138] As shown in Figure 2, the microphone of the sound level meter was put 2 cm away from 3DL sample. The coated 100 x 100 mm 3D Loop samples were pressed and rubbed repeatedly. The noise was recorded for 30 seconds in a silent environment. The maximum decibel value was recorded and shown in Table 3. The control 3D Loop sample without coating showed noise of 49.8 dB. The background noise was 36.0 dB. As 3 dB is a critical difference level by human ear, “a noticeable improvement” and “a significant noticeable improvement” are defined as follows:
[0139] *represents a noticeable improvement: when sound level test value difference of two samples is > 3 dB, the intensity of sound can be technically distinguished by the human ear. In this table, noise test result of < 46.8 dB (i.e., the reduction of ≥ 3 dB from the control sample without coating) is considered as a noticeable improvement.
[0140] **represents a significantly noticeable improvement: the sound level of ≤ 39.0 dB is close to the background noise level (36.0 dB) , which is considered as very quiet in noise creation.
[0141] 2) Hand feeling test
[0142] The hand feeling of the coated 3D Loop sample was recorded by an experienced technician and shown in Table 3.
[0143] Table 3: Test result of the coated 3D Loop sample *represents a noticeable improvement; **represents a significantly noticeable improvement.
[0144] The properties of cushion samples are shown in Table 3. For Sample 1 (CE-1) , the noise test value was 49.8 dB. All the inventive samples showed less noise compared to neat 3D loop. Significantly quiet products with improved hand-feeling were obtained.
[0145] The coated 3D Loop sample showed even better quiet property and hand-feeling after foaming. Samples 6 and 12 (IE-7 and IE-8) having high loading of coating had slightly higher noise, indicating the total loading of the coating was not the higher the better. When the level of foaming agents of more than 3 wt%was used to get higher foaming ratio, higher loading of coating may be adopted.
[0146] Such coated 3D loop materials can be used in a quiet and comfortable bedding design.
[0147] D. Measurement information
[0148] 1. Hardness
[0149] Hardness of the 3D loop article was measured in accordance with ASTM D3574.
[0150] 2. Density of the 3D loop material
[0151] The mass and the dimensions of the specimen were determined, and the volume (in kilograms per cubic meter) was calculated:
[0152] Density = M / V
[0153] where: M = mass of specimen, kg, and V = volume of specimen, m3.
[0154] 3. Density of the foamed coating layer
[0155] Due to the coating layer is difficult to be removed from the 3DL without destroying the structure, to calculate the density, the formulated emulsion was first casted to an independent film (40 um before foaming) , then heat-treated at 90 ℃ for 30 minutes, and the density of foamed film was then measured on density balance with GB / T 4472-2011.
[0156] 4. Thickness
[0157] The thickness at different positions of the article was measured with a vernier caliper. The thickness values were recorded and averaged to provide the thickness of the article.
[0158] 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 made from polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof, wherein the three-dimensional loop material is coated with a coating layer comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof.2.The three-dimensional loop material according to claim 1, wherein the loading of the coating layer, calculated based on the dry weight of the coating, on the 3D loop material is in a range of 1-100wt%based on the dry weight of the 3D loop material before coated.3.The three-dimensional loop material according to claim 1, wherein the coating layer is made from a coating composition, wherein the coating composition comprises 30-80 wt%of the at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof.4.The three-dimensional loop material according to claim 1, wherein the coating composition further comprises a foaming agent, wherein the at least one polymer and the foaming agent is in a weight ratio of from 10: 1 to 120: 1.5.The three-dimensional loop material according to claim 4, wherein the three-dimensional loop material is coated with a foamed coating layer, wherein the foamed coating layer has a density of 0.1-0.8 g / cm3 and a pore size of 25-120 μm.6.The three-dimensional loop material according to claim 3, wherein the coating composition further comprises at least one additive selected from the group consisting of foam stabilizer, defoamer, coalescent, dispersant, tackifier, plasticizer, rheology modifier, antioxidant, UV-absorbent, light-stabilizer, catalyst, filler, colorant, pigment, water scavenger, surfactant, solvent, diluent, flame retardant, antistatic agent, preservative, biocide and any combinations thereof.7.A method for making the three-dimensional loop material according to claim 1, comprising the steps of:(i) providing loop fibers made from polyethylene (PE) , ethylene / α-olefin elastomers (POE) , olefin block copolymers (OBC) , thermoplastic polyester elastomers (TPEE) , thermoplastic polyamide elastomers (TPAE) , thermoplastic polyurethanes (TPU) , or the blends thereof to form a 3D loop material;(ii) 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, and(iii) coating the three-dimensional loop material with a coating composition comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and an optional foaming agent.8.The method for making the three-dimensional loop material according to claim 7, wherein the step (iii) is performed by dipping the 3D loop material in the coating composition or by spaying the coating composition on the 3D loop material.9.The method for making the three-dimensional loop material according to claim 7, wherein the method further comprises (iv) a step of foaming the three-dimensional loop material.10.The method for making the three-dimensional loop material according to claim 9, wherein the step (iv) is performed at a temperature below the melting point of polymer of the loop fibers to activate the foaming agent.11.An article comprising the three-dimensional loop material according to claim 1.12.Use of a coating composition comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof in reducing noise creation of a three-dimensional loop material.13.Use of a coating composition comprising at least one polymer selected from the group consisting of a polyurethane elastomer, a styrene-butadiene rubber, an acrylic polymer and any combinations thereof in improving hand-feeling of a three-dimensional loop material.
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