Low odor olefin-based polymer composition for flooring applications

Abstract

A composition comprising: A) a first ethylene / α-olefin interpolymer having a melt index I2 of 0.5 dg / min to 100 dg / min as measured at 190 °C and 2.16 kg; B) a second ethylene / α-olefin interpolymer having a Brinell viscosity BV of 3700 cP to 22000 cP as measured at 177 °C; C) ≥50% by weight of filler based on the total weight of the composition; and D) ≤7.5% by weight of tackifier based on the total weight of the composition.

Description

Background Technology

[0001] Typically, flooring applications (such as carpet backing) comprise about 19% to 21% polymer resin, about 7% tackifier, about 2% processing oil, and fillers. Therefore, fillers constitute the majority of the formulation, accounting for about 70% of the total weight of the formulation. There is a growing demand for recyclable, low-viscosity filler polymer compositions as alternatives to traditional bitumen carpet backing. Furthermore, there remains a need for formulations that reduce odor while maintaining the good mechanical and rheological properties required for flooring applications. These needs have been met by the following invention. Summary of the Invention

[0002] Embodiments of this disclosure relate to compositions comprising a first ethylene / α-interpolymer and a second ethylene / α-olefin interpolymer, fillers, and tackifiers. The compositions described herein are particularly suitable for flooring applications, including carpet tiles and carpet backing materials.

[0003] Some embodiments of this disclosure include a composition comprising: A) a first ethylene / α-olefin interpolymer having a melt index I2 of 0.5 dg / min to 100 dg / min as measured at 190 °C and 2.16 kg; B) a second ethylene / α-olefin interpolymer having a Brinell viscosity BV of 3700 cP to 22000 cP as measured at 177 °C; C) ≥50% by weight of filler based on the total weight of the composition; and D) ≤7.5% by weight of tackifier based on the total weight of the composition. Attached Figure Description

[0004] Figure 1 The TD-GCxGC-TOF MS plots of direct desorption from IE1 to IE3 and CE1 to CE3 are shown. Detailed Implementation

[0005] definition

[0006] All references to the periodic table in this document refer to the periodic table published and copyrighted by CRC Press, Inc. in 2003. Furthermore, any reference to one or more groups refers to one or more groups reflected in such a periodic table that uses the IUPAC system for group numbering.

[0007] Unless stated otherwise, implied by the context, or customary in the art, all parts and percentages are based on weight.

[0008] For the purposes of U.S. patent practice, any patent, patent application or publication mentioned herein is hereby incorporated in its entirety by reference (or its U.S. equivalent by reference), especially the disclosure of synthetic techniques, definitions (in case of any inconsistency with any definitions provided herein) and common knowledge in the art.

[0009] The numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and include both the lower and upper limits. For ranges containing exact values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7), any subranges between any two exact values ​​are included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.). The numerical ranges disclosed herein also include fractions between any two exact values.

[0010] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not specifically disclosed. Conversely, the term “consistently comprising” excludes any other component, step, or procedure from any subsequently listed scope, except those that are not essential for operability. The term “consisting of” excludes any component, step, or procedure not specifically described or listed. Unless otherwise stated, the term “or” refers to members listed individually and in any combination.

[0011] As used herein, the term "composition" includes the materials or mixtures of materials constituting the composition, as well as reaction products and decomposition products formed from the materials of the composition. Typically, any reaction products and / or decomposition products are present in trace amounts.

[0012] The term "polymer" refers to a material prepared by reacting (i.e., polymerizing) a group of monomers, wherein the group of monomers is either homogeneous (i.e., only one type) or heterogeneous (i.e., more than one type) monomers. As used herein, the term polymer includes the term "homogeneous polymer," which refers to a polymer prepared from a homogeneous group of monomers, and the term "interpolymer" as defined below. Trace impurities (e.g., catalyst residues) may be incorporated into and / or within the polymer.

[0013] The term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. This term includes "copolymers," which are polymers prepared from two different types of monomers, as well as polymers prepared from more than two different types of monomers, such as terpolymers, tetrpolymers, etc. This term also includes all forms of interpolymers, such as random, block, homogeneous, and heterogeneous polymers.

[0014] "Olefin polymers" refers to polymers that contain 50% by weight or most of an olefin monomer (e.g., ethylene or propylene) in polymeric form (based on the weight of the polymer), and optionally may contain at least one comonomer. Non-limiting examples of olefin polymers include ethylene polymers and propylene polymers.

[0015] "Propylene polymers" refers to polymers that contain a majority amount of propylene monomers (by weight of the polymer) in polymeric form, and optionally may contain one or more comonomers.

[0016] "Ethylene polymers" refers to polymers that contain a majority amount of ethylene monomers (by weight of the polymer) in polymeric form, and optionally may contain one or more comonomers.

[0017] "Ethylene interpolymers" refer to interpolymers that contain 50% by weight or most of ethylene monomers (based on the weight of the interpolymer) and at least one comonomer in polymeric form.

[0018] "Ethylene copolymers" refer to copolymers in which 50% by weight or most of the amount of ethylene monomer (based on the weight of the copolymer) and comonomer are the only two types of monomers.

[0019] "Ethylene / α-olefin interpolymer" refers to an interpolymer comprising 50% by weight or the majority of ethylene monomer (based on the weight of the interpolymer) and at least one α-olefin in polymeric form. Ethylene / α-olefin interpolymers can be random or block interpolymers.

[0020] "Ethylene / α-olefin copolymer" refers to a copolymer in polymeric form containing 50% by weight or the majority of ethylene monomers (based on the weight of the copolymer) and α-olefins as the only two monomer types. Ethylene / α-olefin copolymers do not exclude residual amounts of other components. Ethylene / α-olefin copolymers can be random or block copolymers.

[0021] Unless stated to the contrary, all test methods are current methods as of the date of this disclosure.

[0022] Composition

[0023] Traditional flooring applications (such as carpet backing) contain approximately 19% to 21% polymer resin, approximately 7% tackifier, approximately 2% processing oil, and the remainder approximately 70% filler. These components must work in harmony to ensure the formulation is firmly bonded together and has good processability. Some key performance requirements for flooring formulations are: a premix viscosity of less than 30,000 cP at 165°C, high elongation at break (greater than 15%), and a tensile modulus of less than 400 MPa.

[0024] Besides good adhesion and processability of the formulation, a key concern in flooring applications is odor reduction. Depending on processing conditions with an average temperature of approximately 145°C to 205°C, significant amounts of volatile organic compounds (“VOCs”) can be generated due to the degradation of formulation components and / or the release of adsorbed molecules. These VOCs, including oxygenated substances, can cause quality concerns for consumers. One known source of VOCs is tackifier components, which have been identified as a major contributor to odor, accounting for approximately 60% to 70% of total VOCs. Despite this drawback, tackifiers play a crucial role in supporting good rheological properties during processing and mechanical properties during application. Therefore, any proposed solutions to odor affecting tackifier concentration must not sacrifice the overall performance of the carpet backing formulation.

[0025] As mentioned above, one potential solution to reduce odor is to decrease the tackifier content while increasing the filler content. High filler loading provides dimensional stability and cost reduction for the entire formulation. However, increasing the filler content above 70% by weight leads to a significant increase in system viscosity, which is detrimental to processability. Furthermore, using high filler loading in carpet backing applications results in deterioration of the formulation's mechanical properties, particularly elongation at break. Therefore, simply reducing the tackifier content by increasing the filler content is not advantageous.

[0026] Recently, the inventors of WO2020010052A1 disclosed the use of polyolefin elastomer (POE) blends comprising ethylene / α-olefin interpolymers in formulations for flooring applications. POE is well known for its high melt index (“MI”) properties and its use in hot melt adhesive applications. Introducing POE into carpet backing formulations provides an alternative feasible approach to ensure good carpet backing performance. Building on the success of formulations characterized by POE blends described in WO2020010052A1, the inventors of this application are committed to determining whether POE blends help maintain desired mechanical and rheological properties while reducing tackifier content to reduce odor.

[0027] As a result, the inventors developed formulations comprising high-MI ethylene / α-olefin interpolymer blends with reduced tackifier content, which are described herein. The inventors found that these formulations provided the desired mechanical and rheological properties in the formulation with reduced tackifier content. Furthermore, the inventors surprisingly found that formulations comprising ethylene / α-olefin interpolymers with a Brookfield viscosity (BV) of 3700 cP to 22000 cP (measured at 177°C) exhibited enhanced odor-reducing properties with reduced tackifier content. This result was determined by an odor panel and confirmed by thermal desorption of samples aged at 80°C for 21 days using the GCxGC-TOF MS method described herein. Compared to conventional formulations with a standard tackifier content (7 wt%, CE 1), the ethylene / α-olefin interpolymer blends of the present invention (containing less than 7.5 wt% tackifier) ​​improved the baseline performance of conventional formulations in both rheological and mechanical properties.

[0028] First ethylene / α-olefin interpolymer (EAO-1)

[0029] In one or a combination of embodiments described herein, the amount of the first ethylene / α-olefin interpolymer (“EAO-1”) included in the compositions of this disclosure may be from 1% to 20% by weight, 1% to 15% by weight, 5% to 12% by weight, or 8% to 14% by weight, based on the total weight of the composition. The first ethylene / α-olefin interpolymer is derived from ethylene and C3 to C4. 10 At least one of α-olefins. For example, the first ethylene / α-olefin interpolymer may be an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-hexene copolymer, and / or an ethylene-octene copolymer.

[0030] In one or more embodiments, the first ethylene / α-olefin interpolymer may have a content of 0.87 g / cm³. 3 Up to 0.911 g / cm 3 The density (according to ASTM D792). For example, the first ethylene / α-olefin interpolymer can have a density of 0.87 g / cm³. 3 Up to 0.875 g / cm 3 0.875g / cm 3 Up to 0.88 g / cm 3 0.88g / cm 3 Up to 0.885 g / cm 3 0.885g / cm 3 Up to 0.90 g / cm 3 0.90g / cm 3 Up to 0.905 g / cm 3 0.905g / cm 3 Up to 0.911 g / cm3 Or the density of any combination of these ranges.

[0031] In one embodiment or a combination of embodiments, the melt index I2 (measured at 190°C and 2.16 kg) of the first ethylene / α-olefin interpolymer can be at least 0.3 dg / min, such as 0.3 dg / min to 500 dg / min. For example, the melt index I2 of the ethylene / α-olefin interpolymer can be 0.3 dg / min to 500 dg / min, 0.3 dg / min to 250 dg / min, 0.5 dg / min to 100 dg / min, 0.5 dg / min to 80 dg / min, 0.5 dg / min to 75 dg / min, 0.5 dg / min to 50 dg / min, 0.5 dg / min to 30 dg / min, 0.5 dg / min to 25 dg / min, 0.5 dg / min to 15 dg / min, 0.5 dg / min to 10 dg / min, or any combination of these ranges. In one or a combination of embodiments described herein, the melt index I2 of the first interpolymer is <90 dg / min, or <80 dg / min, or <70 dg / min, or <60 dg / min, or <50 dg / min, or <40 dg / min, or <35 dg / min, or <30 dg / min, or <25 dg / min, or <20 dg / min, or <15 dg / min, or <10 dg / min, or <5.0 dg / min.

[0032] In one embodiment or a combination of embodiments, the melting point of the first ethylene / α-olefin interpolymer can be from 65°C to 100°C. For example, the melting point of the first ethylene / α-olefin interpolymer can be 65°C to 70°C, 70°C to 75°C, 75°C to 80°C, 80°C to 85°C, 85°C to 90°C, 90°C to 95°C, 95°C to 100°C, or any combination of these ranges.

[0033] In one or a combination of embodiments described herein, the molecular weight distribution (MWD) of the first ethylene / α-olefin interpolymer is >1.5, or >

[0034] 1.6, or >1.7, or >1.8. In one or a combination of embodiments described herein, the molecular weight distribution (MWD) of the first ethylene / α-olefin interpolymer is <2.5, or <2.4, or <2.3, or <2.2.

[0035] Some exemplary first ethylene / α-olefin interpolymers used in the compositions of this disclosure include those that can be used as ENGAGE ™Ethylene-octene polyolefin elastomers, 8100, 8003, 8400, 8401, 8411, 8480, 8842, 8200, 7447, or 7467, purchased from Dow Chemical Company.

[0036] Second ethylene / α-olefin interpolymer (EAO-2)

[0037] In one or a combination of embodiments described herein, the amount of the second ethylene / α-olefin interpolymer (EAO-2) included in the compositions of this disclosure may be from 1% to 20% by weight, 1% to 15% by weight, 5% to 12% by weight, or 8% to 14% by weight, based on the total weight of the composition. The second ethylene / α-olefin interpolymer has a composition derived from ethylene and C3 to C4. 10 A high melt flow interpolymer of at least one of α-olefins. For example, the second ethylene / α-olefin interpolymer may be an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-hexene copolymer, and / or an ethylene-octene copolymer.

[0038] The second ethylene / α-olefin interpolymer has a relatively high melt index, such that, according to ASTM D1238 and at 190°C / 2.16 kg, the melt index is from 10.0 dg / min to 200.0 dg / min. For example, the melt index can be from 10 dg / min to 150 dg / min, 20 dg / min to 120 dg / min, 30 dg / min to 70 dg / min, and / or 40 dg / min to 60 dg / min.

[0039] According to ASTM D792, the second ethylene / α-olefin interpolymer has a relatively low density, such that the density is from 0.860 g / cc to 0.900 g / cc, preferably from 0.860 g / cc to 0.885 g / cc, and more preferably from 0.860 g / cc to 0.875 g / cc.

[0040] The Brookfield viscosity (177°C) of the second ethylene / α-olefin interpolymer can be 1,000 cP to 30,000 cP, 2,500 cP to 25,000 cP, 3,700 cP to 22,000 cP, 5,000 cP to 20,000 cP and / or 10,000 cP to 15,000 cP.

[0041] The molecular weight distribution (MWD) of the second ethylene / α-olefin interpolymer can be <5, <4, or <3.

[0042] Some exemplary second ethylene / α-olefin interpolymers used in the compositions of this disclosure include the high melt flow ethylene-octene polyolefin elastomer AFFINITY, available from Dow Chemical Company. ™ GA 1875, 1900 and 1950.

[0043] Grafted ethylene polyolefins (GEBP-1 and GEBP-2)

[0044] In one or a combination of embodiments described herein, the amount of functionalized or grafted ethylene polyolefins (GEBP-1 and GEBP-2) included in the compositions of this disclosure may be from 1% to 5% by weight, from 1% to 3% by weight, from 2% to 4% by weight, or from 2% to 3% by weight, based on the total weight of the compositions.

[0045] Typically, grafted polyolefins are compatibilizers. Functionalized polyolefins can be polyethylene grafted with an olefinically unsubstituted dicarboxylic acid or its derivative, or polyolefins copolymerized with an olefinically unsubstituted dicarboxylic acid or its derivative. Grafted polyolefins may contain at least one α-olefin, such as C2-C... 14 α-olefins. Expected C2-C 14 α-olefins include, for example, but not limited to, C2, C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 Or C 14 In the implementation scheme, the α-olefin may be ethylene, and the grafted polyolefin may comprise functionalized polyethylene.

[0046] Polyolefins can be functionalized with olefinically unsubstituted dicarboxylic acids or their derivatives. Functionalized polyolefins can be formed by copolymerizing an α-olefin with an olefinically unsubstituted dicarboxylic acid or by grafting an olefinically unsubstituted dicarboxylic acid onto an already formed polyolefin. The olefinically unsubstituted dicarboxylic acid or its derivatives can be selected from maleic anhydride, itaconic anhydride, maleic acid diester, fumarate diester, maleic acid monoester or fumarate monoester, esters of C1 to C4 alcohols, maleic acid, itaconic acid, fumarate, or mixtures thereof. For example, functionalized polyolefins (such as functionalized polyethylene) can include anhydride-functionalized polyolefins, such as maleic anhydride-functionalized polyolefins, such as maleic anhydride-functionalized polyethylene, such as maleic anhydride-grafted polyolefins. The functionalization level of the olefinic unsubstituted dicarboxylic acid or its derivative can be from 0.5 wt% to 3.0 wt%, such as 1.0 wt% to 2.0 wt%, 0.5 wt% to 1.0 wt%, 1.0 wt% to 1.5 wt%, 1.5 wt% to 2.0 wt%, 2.0 wt% to 2.5 wt%, 2.5 wt% to 3.0 wt%, or any combination of two or more of these ranges. Preferred ethylene polymers used as grafted ethylene polyolefins include low-density polyethylene (LDPE), high-density polyethylene (HDPE), non-uniformly branched linear low-density polyethylene (LLDPE), uniformly branched linear ethylene polymers, and substantially linear ethylene polymers.

[0047] The grafted polyolefin can have a density, and the elastomer can have a density from 0.850 g / cc to 0.925 g / cc, such as 0.855 g / cc to 0.920 g / cc, 0.865 g / cc to 0.915 g / cc, 0.875 g / cc to 0.910 g / cc, 0.885 g / cc to 0.905 g / cc, 0.895 g / cc to 0.900 g / cc, or any combination of two or more of these ranges. Preferably, the polymer density of the host ethylene polymer is greater than or equal to 0.915 g / cc, and most preferably greater than or equal to 0.920 g / cc.

[0048] Some exemplary functionalized vinyl polyolefins include FUSABOND, available from Dow Chemical Company, Midland, Michigan. ™ E204 and E528

[0049] Tackifier

[0050] In one or a combination of embodiments described herein, the amount of tackifier included in the composition of this disclosure may be less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, or less than 3 wt%, based on the total weight of the composition. In one or a combination of embodiments, the amount of tackifier included in the composition may be from 1 wt% to 7 wt%, from 1 wt% to 5 wt%, from 1 wt% to 4 wt%, from 5 wt% to 7 wt%, from 3 wt% to 5 wt%, from 2 wt% to 4 wt%, or from 1 wt% to 3 wt%, based on the total weight of the composition.

[0051] The compositions disclosed herein comprise a tackifier or a tackifying resin or a tackifying resin. The tackifier can modify the properties of the composition, such as viscoelastic properties (e.g., tanδ), rheological properties (e.g., viscosity), and tackiness (i.e., adhesion).

[0052] Any tackifier known to those skilled in the art may be used in the adhesive compositions disclosed herein. Tackifiers suitable for the compositions disclosed herein may be solid, semi-solid, or liquid at room temperature. Non-limiting examples of tackifiers include (1) natural and modified rosins (e.g., resin rosin, wood rosin, tarro oil rosin, distilled rosin, hydrogenated rosin, dimer rosin, and polymerized rosin); (2) glycerides and pentaerythritol esters of natural and modified rosins (e.g., glycerides of light-colored wood rosin, glycerides of hydrogenated rosin, glycerides of polymerized rosin, pentaerythritol esters of hydrogenated rosin, and phenol-modified pentaerythritol esters of rosin); and (3) copolymers and terpolymers of natural terpenes (e.g., styrene / terpenes and α-methyl rosin). (4) Polyterpene resins and hydrogenated polyterpene resins; (5) Phenolic modified terpene resins and their hydrogenated derivatives (e.g., resin products produced by the condensation reaction of bicyclic terpenes and phenols in an acidic medium); (6) Aliphatic or cycloaliphatic hydrocarbon resins and their hydrogenated derivatives (e.g., resins obtained by polymerization of monomers mainly composed of olefins and dienes); (7) Aromatic hydrocarbon resins and their hydrogenated derivatives; (8) Aromatic modified, aliphatic or cycloaliphatic hydrocarbon resins and their hydrogenated derivatives; and combinations thereof.

[0053] In some implementations, the tackifier is an aliphatic hydrocarbon resin having at least five carbon atoms (e.g., PICCOTAC from Synthomer Chemicals Company, Essex UK). ™ 1095). In other embodiments, the tackifier includes rosin-based tackifiers (e.g., AQUATAC from Arizona Chemical, Jacksonville, FL). ® 9027, AQUATAC ® 4188, SYLVALITE ®SYLVATAC ® and SYLVAGUM ® Rosin ester). In other embodiments, the tackifier includes polyterpenes or terpene resins (e.g., SYLVARES from Arizona Chemical, Jacksonville, FL). ® Terpene resins). In other embodiments, the tackifier includes aliphatic hydrocarbon resins, such as resins produced by the polymerization of monomers consisting of olefins and dienes (e.g., ESCOREZ from ExxonMobil Chemical Company, Houston, Tex.). ® 1310LC, ESCOREZ ® 2596) and its hydrogenated derivatives; alicyclic petroleum hydrocarbon resins and their hydrogenated derivatives (e.g., ESCOREZ from ExxonMobil Chemical Company). ® 5300 and 5400 series; EASTOTAC from Eastman Chemical, Kingsport, Tenn. ® (Resin). In another embodiment, the tackifier is modified with a tackifier modifier, which includes aromatic compounds (e.g., ESCOREZ from ExxonMobil Chemical Company). ® 2596) and low softening point resins (e.g., AQUATAC 5527 from Arizona Chemical, Jacksonville, FL).

[0054] Oil

[0055] In one or a combination of embodiments described herein, the amount of oil included in the compositions of this disclosure may be from 1% to 5% by weight, 1% to 3% by weight, 2% to 4% by weight, or 2% to 3% by weight, based on the total weight of the composition. Oils that can be used in embodiments of the invention include, for example, paraffin oils, aromatic oils, naphthenic oils, hydrogenated (white) oils (such as Kaydol oil), vegetable oils and animal oils and their derivatives, petroleum-derived oils, or combinations thereof.

[0056] filler

[0057] In one or a combination of embodiments described herein, the amount of filler included in the compositions of this disclosure may be less than 70% by weight, less than 60% by weight, less than 50% by weight, less than 40% by weight, or 10% to 50% by weight, or 20% to 60% by weight, or 30% to 70% by weight, based on the total weight of the composition. In other embodiments, the compositions disclosed herein may optionally contain filler. Any filler known to those skilled in the art may be used in the adhesive compositions disclosed herein. Non-limiting examples of suitable fillers include sand, talc, dolomite, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass beads, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, and combinations thereof. In one embodiment, the filler is selected from talc, carbon black, or calcium carbonate, more specifically carbon black or calcium carbonate, and more specifically calcium carbonate (CaCO3).

[0058] Compositions and Articles

[0059] In one or a combination of embodiments described herein, the composition comprises one or more additives. Additives include, but are not limited to, antioxidants, UV absorbers, antistatic agents, colorants (e.g., titanium dioxide, carbon black, and pigments), viscosity modifiers, flame retardants, odor modifiers / absorbents, and any combination thereof. In one or a combination of embodiments described herein, the composition further comprises a thermoplastic polymer that differs in one or more properties from the first ethylene / α-olefin interpolymer and the second ethylene / α-olefin interpolymer. Illustrative polymers include, but are not limited to, propylene polymers, ethylene polymers, and olefin multiblock interpolymers. Suitable vinyl polymers include, but are not limited to, high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ultra-low-density polyethylene (ULDPE), uniformly branched linear ethylene polymers, and uniformly branched substantially linear ethylene polymers (i.e., uniformly branched long-chain branched ethylene polymers).

[0060] The compositions disclosed herein can be used to prepare various articles or components thereof. The compositions of this invention can be transformed into final articles by any of a variety of conventional methods and equipment. Illustrative methods include, but are not limited to, adhesives, injection molding, extrusion, calendering, compression molding, and other typical thermosetting material forming methods. Articles include, but are not limited to, sheets, foams, molded goods, and extruded parts. Other articles include flooring materials such as resilient bricks and sheets, rigid boards and laminates, bricks, carpet tiles, carpets, and carpet backing materials.

[0061] The specific implementation schemes disclosed herein include, but are not limited to, the following:

[0062] A composition comprising:

[0063] A) The first ethylene / α-olefin interpolymer, wherein the melt index I2 of the first ethylene / α-olefin interpolymer is 0.5 dg / min to 100 dg / min as measured at 190 °C and 2.16 kg;

[0064] B) Second ethylene / α-olefin interpolymer, wherein the Brookfield viscosity (BV) of the second ethylene / α-olefin interpolymer measured at 177°C is 3700 cP to 22000 cP.

[0065] C) ≥50% by weight of filler, wherein the filler is based on the total weight of the composition;

[0066] D) ≤7.5% by weight of thickener based on the total weight of the composition.

[0067] The composition according to any one of the embodiments, wherein the density of the first ethylene α-olefin interpolymer is from 0.860 g / cc to 0.910 g / cc, and the density of the second ethylene α-olefin interpolymer is from 0.860 g / cc to 0.910 g / cc.

[0068] The composition according to any one of the embodiments, wherein the first ethylene / α-olefin interpolymer is selected from the group consisting of: ethylene / butene interpolymer, ethylene / hexene interpolymer or ethylene / octene interpolymer.

[0069] The composition according to any one of the embodiments, wherein the second ethylene / α-olefin interpolymer is selected from the group consisting of: ethylene / butene interpolymer, ethylene / hexene interpolymer or ethylene / octene interpolymer.

[0070] The composition according to any one of the embodiments, wherein the weight ratio of the first ethylene / α-olefin interpolymer to the second ethylene / α-olefin interpolymer is 9:1 to 1:9.

[0071] The composition according to any one of the embodiments, wherein the weight ratio of the first ethylene / α-olefin interpolymer to the second ethylene / α-olefin interpolymer is 1:1 to 1:1.

[0072] The composition according to any one of the embodiments, wherein the weight ratio of the first ethylene / α-olefin interpolymer to the second ethylene / α-olefin interpolymer is 6:4 to 4:6.

[0073] The composition according to any one of the embodiments, wherein the weight ratio of the first ethylene / α-olefin interpolymer to the second ethylene / α-olefin interpolymer is 7:3 to 3:7.

[0074] The composition according to any one of the embodiments further comprises maleic anhydride-grafted ethylene polymer in an amount of 0.5% to 5% by weight based on the total weight of the composition.

[0075] The composition according to any one of the embodiments further comprises paraffin oil in an amount of 0.5% to 5% by weight based on the total weight of the composition.

[0076] The composition according to any one of the embodiments, wherein the complex shear viscosity of the composition at a shear rate of 100 rad / s and 190°C is 250 Pa s to 1000 Pa s, 300 Pa s to 950 Pa s, 400 Pa s to 800 Pa s, or 500 Pa s to 800 Pa s.

[0077] The composition according to any one of the embodiments, wherein the concentration of volatile organic compounds in the composition, as measured by TD–GC×GC–TOF MS, is less than 2000 µg / g.

[0078] An article comprising the composition according to any one of the embodiments.

[0079] A floor structure comprising articles according to any one of the embodiments.

[0080] In one or a combination of embodiments described herein, the growth tension of the composition at 40°C is less than 50 PSI, less than 45 PSI, less than 40 PSI, less than 35 PSI, or less than 30 PSI. In one or a combination of embodiments described herein, the growth tension of the composition at 40°C is 10 PSI to 50 PSI, 20 PSI to 40 PSI, or 30 PSI to 40 PSI.

[0081] In one or a combination of embodiments described herein, the rheological ratio of the composition is greater than 160, greater than 170, greater than 180, greater than 190, greater than 200, or greater than 250. In one or a combination of embodiments described herein, the rheological ratio of the composition is 175 to 300, 180 to 275, or 190 to 300, wherein the rheological ratio is defined as the ratio of the complex shear viscosity at 0.1 rad / s to the complex shear viscosity at 100 rad / s.

[0082] In one or a combination of embodiments described herein, the average hardness (Shore A) is greater than 75, greater than 80, greater than 85, greater than 90, greater than 95, greater than 97, or greater than 100. In one or a combination of embodiments described herein, the average hardness (Shore A) is 75 to 100, 80 to 99, 85 to 97, 90 to 97, or 90 to 100.

[0083] In one or a combination of embodiments described herein, the elongation at break of the composition is greater than or equal to 10%, or greater than or equal to 20%, or greater than or equal to 25%, or greater than or equal to 30%, or greater than or equal to 40%, or greater than or equal to 50%. In one or a combination of embodiments described herein, the elongation at break of the composition is from 10% to 45%.

[0084] Test methods

[0085] density

[0086] Density was measured according to ASTM D-792.

[0087] Melt index (I2) and melt flow rate (MFR)

[0088] Melt index of ethylene polymers (2.16 kg, 190 °C) was measured according to ASTM D-1238.

[0089] GPC molecular weight and molecular weight distribution

[0090] Molecular weight was determined using gel permeation chromatography (GPC) on a Waters 150°C high-temperature chromatography unit equipped with three mixed porous columns (Polymer Laboratories 103, 104, 105, and 106) operated at a system temperature of 140°C. 1,2,4-Trichlorobenzene was used as the solvent, and a 0.3 wt% sample solution was prepared from 1,2,4-trichlorobenzene for injection. The flow rate was 1.0 mL / min, and the injection volume was 100 μL.

[0091] Molecular weight determinations were inferred using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes. The equivalent polyethylene molecular weight was determined using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described in T. Williams & IMWard, The Construction of a Polyethylene Calibration Curve for Gel Permeation Chromatography Using Polystyrene Fractions, 6 J. Polymer Sci. Pt. B: Polymer Letter 621, 621–624 (1968)), leading to the following formula:

[0092] In this formula, a = 0.4316 and b = 1.0.

[0093] The number-average molecular weight Mn of a polymer is expressed as the first moment of a plot of the number of molecules per molecular weight range against the molecular weight. In practice, this is the total molecular weight of all molecules divided by the number of molecules, and is typically calculated using the following formula:

[0094]

[0095] Where ni = the number of molecules with molecular weight Mi,

[0096] wi = weight fraction of material with molecular weight Mi.

[0097] And ∑ ni = the total number of molecules.

[0098] The weight-average molecular weight Mw is calculated in the conventional manner according to the following formula: Mw = ∑ wi x Mi, where wi and Mi are the weight fraction and molecular weight of the i-th fraction eluted from the GPC column, respectively. The ratio of these two averages (molecular weight distribution (MWD or Mw / Mn)) defines the breadth of the molecular weight distribution.

[0099] Micro-stretch test

[0100] Micro-tensile testing measures the properties of a specimen when tested under uniaxial extension. These properties include yield strength and yield strain, tensile strength and tensile strength at break, strain at break, fracture energy (sometimes referred to as toughness), and elastic modulus (derived from the initial portion of the stress-strain curve, commonly referred to as Young's modulus). Micro-tensile testing is performed using an INSTRON 5565 equipped with a "100 force sensor". In preparation, the test specimen is compressed and molded according to ASTM D4703 (Program C, Appendix A1). After 24 hours of molding, the micro-tensile specimen is cut using a NAEF press with an ASTM die head D1708. The test specimen is conditioned for at least 40 hours at 23°C (+ / -2°C) and 50% RH (+ / -10) according to ASTM standards. Standard test conditions are 23°C (+ / -2°C) and 50% RH (+ / -10) according to ASTM standards. During testing, the prepared specimen is subjected to a strain rate of 5 inches per minute. Based on this measurement, the average fracture stress is reported here; the reported value is the average of up to five measurements.

[0101] Shore A hardness

[0102] The test material was compressed into a sheet for micro-tensile testing. Compression molding was performed according to ASTM D4703 to prepare a 4" × 4" × 0.125" sheet. The molding temperature was 190°C, with controlled cooling at 15°C / min. Shore A hardness was tested using a hardness tester according to ASTM D2240. For each measurement, the indenter was held against the sample for 5 seconds before recording the hardness value. The Shore A hardness value for each sample reported here is the average of 5 measurements.

[0103] Brinell viscosity

[0104] According to the standard test of apparent viscosity for hot melt adhesives and coatings in ASTM D1986, an LVDV-1 Prime Brinell digital viscometer with thermosel was used. Compositions containing fillers were measured using rotor SC4-27. Compositions without fillers were measured using rotor SC4-31.

[0105] Capillary rheology

[0106] Capillary tests were performed on either a Rheotester 2000 or a Rheograph 25 capillary rheometer, both manufactured by Göttfert. The die used for testing had a diameter of 1 mm and an entry angle of 180 degrees (also known as a "flat die"). The die used in the Rheograph 25 capillary was 30 mm long (20 mm effective length), while the Rheotester used a 20 mm long die (also 20 mm effective length). Each test was performed isothermally at 190 °C.

[0107] Before starting the test, a sample, preferably in granular form, is loaded into a capillary cylinder and equilibrated at the test temperature for 10 minutes. After a 10-minute waiting period, the test begins. During the test, a piston inside the cylinder applies force to the molten sample to achieve a range of approximately 150 seconds. -1 Up to 10,000s -1 The apparent shear rate is determined. As the test proceeds, a pressure drop across the capillary die is measured using sensors. This pressure drop is used to determine the apparent shear stress near the wall relative to the apparent shear rate. Other calculations provided by the capillary test include apparent viscosity, Rabinowitsch corrected shear rate, and Rabinowitsch corrected viscosity. Apparent viscosity is obtained by dividing the apparent wall shear stress by the corresponding apparent shear rate. The Rabinowitsch corrected shear rate is obtained by applying the Weissenberg-Rabinowitsch correction to the apparent shear rate and shear stress datasets. Furthermore, the Rabinowitsch corrected viscosity is calculated by dividing the apparent wall shear stress by the Rabinowitsch corrected shear rate. Note: Bagley correction is not used in the calculations.

[0108] The software used to facilitate capillary measurements and calculations is Lab Rheo and Win Rheo. These software packages were developed by Göttfert.

[0109] Growth tension

[0110] Growth tension is a key parameter for understanding stress relaxation in test samples. It was measured using a TA Instrument Rheometric Solids Analyzer III. Compression-molded sheets with a thickness of 0.8 mm to 1 mm were cut into rectangular shapes with a width of 12.7 mm and loaded into the instrument. During testing, strain and tension were set such that the clamp distance was fixed at 20 mm. The temperature was increased from room temperature at a rate of 20 °C / min until melting. The force was recorded during the temperature rise, and the growth tension was calculated from this, as defined by Equation 1 below.

[0111]

[0112] In Equation 1, F is the growth force, "area" is the cross-sectional area of ​​the test sample, t is the thickness of the test sample, and w is the width of the test sample. In this study, growth tension values ​​at 40°C were used uniformly to facilitate simpler comparisons at higher temperatures sometimes encountered in applications. Each composition was tested at least three times, and the average values ​​were reported. The molding conditions used for preparing growth tension samples were: preheating at 130°C for 15 minutes, at 3,000 lbs for 3 minutes, at 10,000 lbs for 3 minutes, and at 20,000 lbs for 1 minute, followed by cooling at 20,000 lbs pressure for 1 to 2 minutes.

[0113] Scent Group

[0114] In preparation, each sample in this study was placed in two separate 20 mL vials. Each vial was aged in an oven at 80°C for 21 days. A panel of five participants was assembled to perform a qualitative odor comparison of the formulations produced in the study. Panel members were asked to subjectively rank the test samples on a scale of 1 to 5, where 5 represents the strongest odor and 1 represents the weakest odor.

[0115] Thermal desorption was performed using two-dimensional gas chromatography-TOF-MS.

[0116] Thermal desorption of the compositions, combined with integrated two-dimensional gas chromatography and time-of-flight mass spectrometry (TD–GC×GC–TOF MS), was performed to determine the amount of VOCs present in each composition. This was done using Agilent... ™ The Markes Centrifuge is coupled with the Markes 8860 GC and the Markes benchtop TOF mass spectrometer. ™ This analysis was performed using 360 Autosampler. ChromSpace was used. ® (SepSolve analysis) Version 2.1.7 software was used for data collection and analysis.

[0117] Samples were prepared by adding 1.00 g of resin composition to a weighed headspace vial. VOCs were extracted using a Markes Centri 360 autosampler (Markes International) operating in headspace mode via multiple headspace extractions. The sample was incubated at a desorption temperature of 120 °C for 45 min. The desorbed VOCs were collected / concentrated in a -30 °C cold trap and injected into an Agilent 8890 gas chromatograph for separation (1D column: VF-200 ms phase, dimensions 30 m × 250 μm × 1 μm, helium as carrier gas; 2D column: VF-1 ms phase, dimensions 2.5 m × 320 μm × 0.5 μm, helium as carrier gas). The gas chromatograph was operated in GCxGC mode with a reverse pack / wash modulator (modulation cycle (Pm) = 1.8 s). Samples were quantified using internal standard calibration with a concentration of one part per million (ppm; μg / mL) of deuterated toluene gaseous standard added to a cold trap after sample collection and concentration, and detected on a Markes Bench TOF2 time-of-flight mass spectrometer (mass range: m / z 30-600).

[0118] The obtained 2D-GC chromatogram is provided in Figure 1 In the middle. For example Figure 1 In this scheme, aliphatic compounds retain longer in the second-dimensional column, thus eluting along a strong peak at the top of the graph. Conversely, odor-active compounds (such as oxygen-containing substances or VOCs) elute earlier in the second dimension, thus separating these compounds from aliphatic compounds. This region is... Figure 1 The area is defined as the "integration region" and is bounded by the upper hydrocarbon and lower tower emission areas. The minimum peak area used for integration is set to 10,000 peak areas, and the total peak area in the "integration region" is used to determine the concentration of oxygen-containing substances, in parts per million (ppm; μg / g).

[0119] Example

[0120] The following examples are intended to illustrate some embodiments of the present invention and should not be construed as limiting the scope of the invention as described in the claims.

[0121] Material

[0122] The materials used in this section are shown in Table 1 below. Polymer properties are shown in Table 2.

[0123] Table 1 :

[0124] Table 1. Materials

[0125]

[0126] Table 2 :

[0127] Table 2: Summary of Polymer Properties

[0128]

[0129] Mixing

[0130] Blending (with fillers) :

[0131] All sample formulations (compositions) were mixed with the filler material in a rotary Haake Rheomix 3000 at 180°C. Raw materials, except for the filler material, were added sequentially and mixed at 180°C and 20 rpm until homogeneous (approximately five minutes). The filler material was then added within five minutes. After the final addition of the filler material, the mixture was mixed at 35 rpm for 35 minutes.

[0132] Samples and Results

[0133] Table 3: Examples and Comparative Examples of the Invention with 70% by weight of filler

[0134]

[0135] Table 4: Physical characteristics of the embodiments

[0136]

[0137] *The unit for 2D-GC data is μg / g volatiles in the polymer eluted in the integration region.

[0138] As shown in the figure, the blends IE 1-3 of the present invention exhibit enhanced rheological properties, good growth tension, and hardness characteristics comparable to the conventional formulation CE 1. Furthermore, all IE 1-3 contain a second ethylene / α-olefin interpolymer with a Brookfield viscosity (BV) of 3700 cP to 22000 cP measured at 177°C; compared to CE 2 and CE 3, these formulations exhibit enhanced odor reduction properties with reduced thickener content. These formulations also possess good growth tension and hardness comparable to existing formulations.

Claims

1. A composition comprising: A) The first ethylene / α-olefin interpolymer, wherein the melt index I2 of the first ethylene / α-olefin interpolymer is 0.5 dg / min to 100 dg / min as measured at 190 °C and 2.16 kg; B) Second ethylene / α-olefin interpolymer, wherein the Brookfield viscosity (BV) of the second ethylene / α-olefin interpolymer measured at 177°C is 3700 cP to 22000 cP. C) ≥50% by weight of filler, wherein the filler is based on the total weight of the composition; D) ≤7.5% by weight of tackifier based on the total weight of the composition.

2. The composition according to claim 1, wherein the density of the first ethylene α-olefin interpolymer is from 0.860 g / cc to 0.910 g / cc, and the density of the second ethylene α-olefin interpolymer is from 0.860 g / cc to 0.910 g / cc.

3. The composition according to any one of the preceding claims, wherein the first ethylene / α-olefin interpolymer is selected from the group consisting of: ethylene / butene interpolymer, ethylene / hexene interpolymer, or ethylene / octene interpolymer.

4. The composition according to any one of the preceding claims, wherein the weight ratio of the first ethylene / α-olefin interpolymer to the second ethylene / α-olefin interpolymer is 9:1 to 1:

9.

5. The composition according to any one of the preceding claims, wherein the composition further comprises 0.5% to 5% by weight of maleic anhydride-grafted ethylene polymer based on the total weight of the composition.

6. The composition according to any one of the preceding claims, wherein the composition further comprises paraffin oil in an amount of 0.5% to 5% by weight based on the total weight of the composition.

7. The composition according to any one of the preceding claims, wherein the composition has a complex shear viscosity of 250 Pa s to 1000 Pa s at a shear rate of 100 rad / s and a temperature of 190°C.

8. The composition according to any one of the preceding claims, wherein the concentration of volatile organic compounds in the composition, as measured by TD-GC×GC-TOF MS, is less than 2000 µg / g.

9. An article comprising the composition according to any one of the preceding claims.

10. A floor structure comprising the article of claim 9.

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