Thick parts and profiles with stone appearance using ionomer resins and BIO-fillers

Abstract

Molded articles exhibiting a stone-like decorative effect with a composition that includes at least 50% by weight of an ionomer, where the ionomer is an at least partially neutralized ethylene acid copolymer. Furthermore, the ethylene acid copolymer includes the reaction product of ethylene and carboxylic acid. The molded article further includes between 0.5% to 50% by weight of a bio-filler material and between 0.1% to 3% by weight of a liquid pigment.

Description

THICK PARTS AND PROFILES WITH STONE APPEARANCE USING IONOMER RESINS AND BIO-FILLERSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 599,133 filed November 15, 2023, the contents of which are incorporated in their entirety herein.FIELD

[0002] Embodiments disclosed herein generally relate to a molded article made from a mixture comprising an ionomer resin, a bio-filler, and a liquid pigment that exhibits a stonelike decorative effect while possessing both dimensional stability and chemical resistance.TECHNICAL BACKGROUND

[0003] Neutralized acid copolymers such as ionomer resins are materials well suited for use in injection-molded articles. This has made ionomer resins particularly useful for many consumer industries, including the cosmetics and infrastructure industries. Cosmetic goods, like perfume bottles, and infrastructure products, like building materials, are often made from molded articles and are designed to exhibit specific aesthetic properties depending on their application. The ability to customize these molded articles or to create molded articles with novel visual effects may present unique commercial opportunities.

[0004] In the cosmetics industry, injection molded articles have specific demands due to the nature in which they are used. Molded articles are often used as a component in cosmetic packaging that may expose the polymeric materials to fragrances or other chemicals. As such, these materials must not only exhibit dimensional stability but also chemical stability to avoid degradation. Additionally, these materials must be aesthetically desirable to enable creative marketing while remaining compatible with traditional injection molding techniques to remain economically feasible for cosmetic companies. Molded articles in the cosmetics industry often sacrifice one of these considerations. Traditional crystalline resins often lack dimensional stability, resulting in shrinkage and sink marks during the molding process that can affect the molded articles’ aesthetic features. Whereas, amorphous resins generally exhibit excellent dimensional stability while lacking chemical stability around cosmetic products.

[0005] Similarly, in the infrastructure industry, many companies have begun using injection- molded articles as replacements for traditional building materials due to their lower costs. Infrastructure companies have typically used polyolefins like polypropylene and polyethylene combined with wood to form a composite material to maintain the mechanical properties of these materials while seeking to emulate the appearance of traditional building materials. These composites are then coated with a thin layer of an ionomer resin. While this achieves good dimensional and chemical stability, it frustrates the typical injection molding process and prevents a single extrusion profile that would save companies both time and money.

[0006] A common desire among both consumers and businesses is for products that resemble marble or stone, exhibit dimensional and chemical stability, and remain cost-efficient. Though stone-like decorative effects have been previously achieved in molded articles by including pigmented polyamides into a copolymer blend, the resulting stone-like products have only exhibited streaked patterns or other results with poor aesthetic properties. Thus, there remains a need for easily produced molded articles that exhibit a stone-like appearance while possessing both dimensional stability and chemical resistance.SUMMARY

[0007] Accordingly, the present disclosure presents embodiments that meet this need, producing molded articles exhibiting a stone-like decorative effect while possessing both dimensional stability and chemical resistance. In embodiments, a molded article includes at least 50% by weight of an ionomer, where the ionomer is an at least partially neutralized ethylene acid copolymer. Furthermore, the ethylene acid copolymer includes a reaction product of ethylene and carboxylic acid. The molded article further includes between 0.5% to 50% by weight of a bio-filler material and between 0.1% to 3% by weight of a liquid pigment.

[0008] According to embodiments of the present disclosure, the bio-filler material comprises one or more of the following materials: wood flour, sawdust, filtered coffee, ground barley scull, agave fiber, ground rice scull, ground wheat scull, and coconut fiber. Further, in specific embodiments, the molded article may contain between 3% to 20% by weight of bio-filler. Additionally, the molded article may include a liquid pigment which comprises a solid colorant dispersed in a liquid carrier. The liquid pigment may include a liquid carrier. The liquid carrier may include one or more of mineral oil, polyethylene glycol(PEG), or polyisobutylene. The ionomer of the molded article may also have a melt index from 2 dg / min to 15 dg / min, as measured according to ASTM D1238.

[0009] In other embodiments, the molded article includes between 75% and 95% by weight of the ionomer resin. Additionally, the carboxylic acid of the ionomer may be (meth)acrylic acid. The carboxylic acid may also be partially neutralized by sodium or zinc and the ionomer resin may include between 5% and 25% by weight of the carboxylic acid. Furthermore, the molded article may also optionally include between 1% to 3% by weight of a lubricant, where the lubricant is selected from one or more of calcium stearate, mineral oil, or fatty acid amide. The fatty acid amides may include but are not limited to examples such as erucamide, behenamide, oleamide, stearamide, oleyl palmitamide, stearyl erucamide, ethylene bisstearamide, and ethylene bis-oleamide. Further, the molded article may optionally include additional filler materials, for instance, between 5% and 10 % by weight of calcium carbonate and between 2% and 5% by weight of talc.

[0010] In some embodiments, the molded article described above may also include other polymers selected from the group including: ethylene / ethyl hydrogen maleate copolymer, ethylene / maleic acid monoester / methyl acrylate terpolymer, ethylene / maleic acid monoester / methyl methacrylate terpolymer, ethylene / maleic acid monoester / ethyl acrylate terpolymer, ethylene / maleic acid monoester / ethyl methacrylate terpolymer, ethylene / maleic acid monoester / n-butyl acrylate terpolymers, and ethylene / maleic acid monoester / n-butyl methacrylate terpolymer.

[0011] It is to be understood that both the preceding general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. Additional features and advantages of the embodiments will be set forth in the detailed description and, in part, will be readily apparent to persons of ordinary skill in the art from that description, which includes the accompanying claims, or recognized by practicing the described embodiments. However, the embodiments are illustrative and exemplary in nature and not intended to limit the claimed subject matter.DETAILED DESCRIPTION

[0012] In its broadest sense, the present disclosure pertains to embodiments of molded articles made from a mixture comprising ionomer resins, bio-fillers, and pigments, where theresulting molded articles exhibit a stone-like decorative effect while possessing both dimensional stability and chemical resistance.

[0013] As used herein, the term “polymer” means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer), and the term copolymer or interpolymer. Trace amounts of impurities (for example, catalyst residues) may be incorporated into and / or within the polymer. A polymer may be a single polymer, a polymer blend, or a polymer mixture, including mixtures of polymers that are formed in situ during polymerization.

[0014] As used herein, the term “polyethylene” or “ethylene-based polymer” shall mean polymers comprising greater than 50% by mole of units, which have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more co-monomers), including ethylene acid copolymers.

[0015] Molded articles, according to embodiments, may include at least 50% by weight of an ionomer resin, based on the total weight of the molded article. The ionomer resin includes one or more at least partially neutralized acid copolymers. In embodiments, the one or more at least partially neutralized acid copolymers are ethylene acid copolymers. The molded articles further include from 0.5% to 50% by weight of a bio-fdler material, based on the total weight of the molded article. The molded articles further include from 0.1% to 3% by weight of a liquid pigment, based on the total weight of the molded article. In embodiments, the molded articles further include from 0.1% to 3% by weight of a liquid pigment that comprises a colorant and a liquid carrier, based on the total weight of the molded article. Additionally, the molded articles may optionally include from 0% to 3% by weight of a lubricant, based on the total weight of the molded article. Furthermore, the molded articles may optionally include from 0% to 2% by weight of a coupling agent, based on the total weight of the molded article. In addition, the molded articles may optionally include from 5% to 10% by weight of the calcium carbonate, based on the total weight of the molded article. Fastly, the molded articles may optionally include from 2% to 5% by weight of talc, based on the total weight of the molded article.

[0016] Ionomer

[0017] According to embodiments, the ionomer may be one or more at least partially neutralized ethylene acid copolymers. The molded article may include at least 50% by weight, or at least 55% by weight, or at least 60% by weight, or at least 65% by weight, or at least 70% byweight, or at least 75% by weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, or at least 95% by weight of the ionomer, based on the total weight of the molded article.

[0018] Ionomer resins can be produced by any means known to one skilled in the art, such as by neutralization of an ethylene acid copolymer with one or more metal ions. An ethylene acid copolymer is a polymer that includes repeat units derived from ethylene and about 1% to about 50%, or about 5% to about 40%, or 5% to 25%, by weight of a carboxylic acid co-monomer, for example, a a,P-ethylenically unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, or combinations thereof, based on the total weight of the ethylene acid copolymer. Alternatively, the copolymerized units of the carboxylic co-monomer may comprise about 5 to about 20 wt%, or about 7 to about 15 wt%, or about 8 to about 12.5 wt%, of the total weight of the ionomer. In some embodiments, the carboxylic co-monomer of the ethylene-carboxylic acid copolymers is (meth)acrylic acid.

[0019] To obtain ionomers useful in the molded articles according to embodiments of this disclosure, the ionomers are neutralized with a base comprising a metal cation such that the acid groups (for example, carboxylic acid) in the precursor acid copolymer react to form acid salt groups (for example, carboxylate salts). In embodiments herein, about 25% to about 65%, or about 30% to about 60%, or about 35% to about 60%, or about 30% to about 55%, or about 35% to about 55% of the acid groups derived from the a,P-ethylenically unsaturated carboxylic acid of the precursor acid copolymer are neutralized. The neutralization level of the acid groups derived from the a,P-ethylenically unsaturated carboxylic acid of the precursor acid copolymer may be calculated based on the amount of basic metal compound added or measured using infrared spectroscopy. Actual neutralization levels may be determined using infrared spectroscopy by comparing an absorption peak attributable to carboxylate anion stretching vibrations at 1530 cm-1to 1630 cm-1and an absorption peak attributable to carbonyl stretching vibrations at 1690 cm-1to 1710 cm-1. The amount of basic metal compound capable of neutralizing acidic groups may be provided by adding the stoichiometric amount of the basic compound calculated to neutralize a target amount of acid moieties in the acid copolymer.

[0020] Any stable cation and any combination of two or more stable cations are believed to be suitable as counterions to the acid groups in the ionomer. The counterions to the acid groups in the ionomer may include, for example, divalent and monovalent cations, such as cations of alkali metals, alkaline earth metals, and some transition metals. In some embodiments, the cation is adivalent cation, such as zinc, calcium, or magnesium, for example. In other embodiments, the cation is a monovalent cation, such as potassium or sodium, for example. In further embodiments, the acid groups derived from the a,P-ethylenically unsaturated carboxylic acid of the precursor acid copolymer are neutralized by a base containing sodium ions. The base containing sodium ions can provide a sodium ionomer wherein the hydrogen atoms of the acid groups of the precursor acid are replaced by sodium cations. To obtain the ionomers useful as the neutralized acid copolymer in embodiments, the precursor acid copolymers may be neutralized by any conventional procedure, such as those described in U.S. Pat. Nos. 3,404,134 and 6,518,365.

[0021] Acid groups of an ionomer resin are at least partly neutralized. The neutralization of acid groups in ionomer resins can range, for example, from about 0.1% to about 100%, or about 10% to about 90%, or about 20% to about 80%, or about 30% to about 60%, or about 20% to about 40% of carboxylic acid groups in the ionomer resin being neutralized with a metallic ion, based on the total carboxylic acid content. The metallic ions may be monovalent, divalent, trivalent, multivalent, or combinations of two or more thereof. Examples include Ei, Na, K, Ag, Hg, Cu, Be, Mg, Ca, Sr, Ba, Cd, Sn, Ph, Fe, Co, Zn, Ni, Al, Sc, Hf, Ti, Zr, Ce, and combinations of two or more thereof. If the metallic ion is multivalent, a complexing agent, such as stearate, oleate, salicylate, and phenolate radicals, can be included, as disclosed in U.S. Pat. No. 3,404,134. Specific examples of neutralizing metal ions include Na, Zn, or combinations thereof. Further examples include sodium or zinc ions derived from salts such as NaOH, NaHCOs, Na2COs, NaHSC , NaEEPC , Na2HPO3, sodium stearate, sodium oleate, sodium salicylate, sodium phenolate, Zn(OH)2, ZnCOs, ZnCOs, ZnSC , ZnHPC , ZnHPCh, zinc oxide, zinc stearate, zinc oleate, zinc salicylate, zinc phenolate, Mg(OH)2, MgCC , MgCCb, MgSC , MgHPC , MgHPCh, magnesium stearate, magnesium oleate, magnesium salicylate, magnesium phenolate, or combinations of two or more thereof.

[0022] Examples of ethylene acid copolymers may include up to 25 wt.% of an optional comonomer based on the weight of the ethylene acid copolymer, such as carbon monoxide, sulfur dioxide, acrylonitrile, maleic anhydride, maleic acid diesters, maleic acid, maleic acid monoesters, itaconic acid, fumaric acid, fumaric acid monoester, a salt of these acids, glycidyl acrylate, glycidyl methacrylate, and glycidyl vinyl ether, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, pentyl methacrylate, or combinations of two or more thereof where the alkyl group can be linear or branched.

[0023] Resin Properties

[0024] The ionomer resin of the molded articles has a melt index, 12, from 2 dg / min to 15 dg / min, as measured according to ASTM D1238 (190 °C, 2.16 kg). The melt index, 12, is determined according to ASTM D1238 at 190°C, 2.16 kg. All individual values and subranges of 2 dg / min to 15 dg / min are included and disclosed herein. For example, in some embodiments, the partially neutralized precursor acid copolymer may have a melt index, 12, of 2 g / 10 min to 12 g / 10 min, 2 dg / min to 10 dg / min, 4 dg / min to 10 dg / min, 4 dg / min to 8 dg / min, or 5 dg / min to 7 dg / min.

[0025] Bio-Filler

[0026] The molded article further includes an organic fdler material or bio-fdler. The biofiller may be a plant-based particulate or fibrous material. In some embodiments, the filler may be a cellulosic, hemicellulosic, or lignocellulosic material. The bio-filler may comprise particulates, fibrous organic materials, or a combination of the two. Suitable bio-fillers include organic materials that can withstand up to 220°C without degradation. In some embodiments, the bio-filler is a particulate material, e.g., in the form of powder, dust, pulp, broken fibers, flakes, or chips. Additionally, in other embodiments, the filler is a fibrous material, e.g., fibrous organic materials like flax, linen, or hemp, etc. In some embodiments, the bio-filler may be a mixture of both particulate and fibrous materials.

[0027] The molded article may include from 0.5% to 50% by weight of bio-filler, based on the total weight of the molded article. All individual values and subranges of 0.5% to 50% by weight are included and disclosed herein. For example, in some embodiments, the molded article may include from 0.5% to 40% bio-filler by weight, 1% to 30% bio-filler by weight, 2% to 25% bio-filler by weight, 3% to 20% bio-filler by weight, 5% to 20% bio-fdler by weight, or 7% to 15% bio-fdler by weight.

[0028] The bio-filler may comprise particulates or fibers with sizes ranging from 0.1 mm to 1000 mm. All individual values and subranges of 0.1 mm to 1000 mm are included and disclosed herein. For example, in some embodiments, the bio-fdler sizes may range from 0.1 mm to 800 mm, 50 mm to 800 mm, 100 mm to 750 mm, 100 mm to 500 mm, 100 mm to 300 mm, or 100 mm to 200 mm. In some non-limiting embodiments, the bio-fdler material comprises one or more organic materials from the following: wood flour, sawdust, filtered coffee, ground barley scull, agave fiber, ground rice scull, ground wheat scull, coconut fiber or any other suitable organic material.

[0029] Liquid Pigment

[0030] The molded article further includes a liquid pigment added to the molded article to achieve stone-like decorative effect. The liquid pigment may be any organic or inorganic colorant formulation that is in liquid form and comprises a colorant and a liquid carrier. The liquid carrier must be chemically compatible with the at least partially neutralized acid copolymer and be stable at typical temperatures of extrusion or injection molding processes. In embodiments, the liquid pigment further includes titanium dioxide.

[0031] Examples of liquid pigments suitable for inclusion in the molded article include, without limitation, organic or inorganic pigments. Such organic or inorganic pigments may be selected from black pigments, yellow pigments, magenta pigments, red pigments, violet pigments, cyan pigments, blue pigments, green pigments, orange pigments, brown pigments, and white pigments. In some instances, the organic or inorganic pigments may include spot-color pigments, which are formed from a combination of a predefined ratio of two or more primary color pigments. In a preferred embodiment, the liquid pigment is an organic, oil-based, white pigment. Such liquid pigments are commercially available from Avient under the tradename HiFormer™.

[0032] The molded article may include from 0.1% to 3% by weight of liquid pigment, based on the total weight of the molded article. All individual values and subranges of 0.1% to 3% by weight are included and disclosed herein. For example, in some embodiments, the molded article may include from 0.1% to 2.5% liquid pigment by weight, 0.5% to 2.5% liquid pigment by weight, 0.5% to 2% liquid pigment by weight, or 0.5% to 1.5% liquid pigment by weight.

[0033] The liquid pigment may comprise a liquid carrier. The liquid carrier is chemically compatible with the liquid pigment. In embodiments where the liquid pigment is oil based, the liquid pigment may be an oil-based carrier. Preferred oil-based liquid carriers include one or more of mineral oil, polyethylene glycols, or polyisobutylene. The oil-based liquid carriers may further include one or more of cyclopentasiloxane, cyclohexasiloxane, or isoparaffinic fluids. In specific embodiments, the liquid carrier is mineral oil. In further specific embodiments, the liquid carrier is polyethylene glycol. In further specific embodiments, the liquid carrier is polyisobutylene. In further specific embodiments, the liquid carrier is a mixture of a polyethylene glycol and mineral oil. In further specific embodiments, the liquid carrier is a mixture of polyisobutylene and mineral oil.

[0034] The molded article may include from 0.1% to 3% by weight of liquid pigment, based on the total weight of the molded article. All individual values and subranges of 0% to 3% byweight are included and disclosed herein. For example, in some embodiments, the molded article may include from 0.1% to 3% liquid pigment by weight, 0.1% to 2.5% liquid pigment by weight, 0.5% to 2.5% liquid pigment by weight, 0.5% to 2% liquid pigment by weight, or 0.5% to 1.5% liquid pigment by weight.

[0035] Lubricant

[0036] The molded article, according to embodiments, may also optionally include a lubricant to encourage efficient flow and handling within an extruder or injection unit. The lubricant may include one or more of calcium stearate, mineral oil, or erucamide. In specific embodiments, the lubricant is mineral oil. In further specific embodiments, the lubricant is calcium stearate. In further specific embodiments, the lubricant is erucamide. In further specific embodiments, the lubricant is a mixture of calcium stearate and mineral oil. In further specific embodiments, the lubricant is a mixture of erucamide and mineral oil.

[0037] The molded article may include from 0% to 3% by weight of a lubricant, based on the total weight of the molded article. All individual values and subranges of 0% to 3% by weight are included and disclosed herein. For example, in some embodiments, the molded article may include from 0.1% to 3% lubricant by weight, 0.1% to 2.5% lubricant by weight, 0.5% to 2.5% lubricant by weight, 0.5% to 2% lubricant by weight, or 0.5% to 1.5% lubricant by weight.

[0038] Additional Fillers

[0039] The molded article, according to embodiments, may also optionally include calcium carbonate as a filler to increase the weight of the molded article and achieve a more realistic looking stone-like decorative effect. The molded article may include from 0% to 10% by weight of calcium carbonate, based on the total weight of the molded article. All individual values and subranges of 0% to 10% by weight are included and disclosed herein. In a preferred embodiment, the molded article may include from 5% to 10% calcium carbonate by weight. In other embodiments, the molded article may include from 5% to 8% calcium carbonate by weight, 5% to 6.5% calcium carbonate by weight, 7% to 10% calcium carbonate by weight, or 8.5% to 10% calcium carbonate by weight.

[0040] The molded article, according to embodiments, may also optionally include talc as a filler to facilitate filler distribution within the molded article and to optimize the exterior surface of the molded article to create an appealing sense of touch. The molded article may include from 0% to 5% by weight of talc, based on the total weight of the molded article. All individual values and subranges of 0% to 5% by weight are included and disclosed herein. In apreferred embodiment, the molded article may include from 2% to 5% talc by weight. In other embodiments, the molded article may include from 2% to 4% talc by weight, or 2% to 3% talc by weight.

[0041] Additionally, the molded article may further include additional polymeric materials beyond those described thus far. In one embodiment, the anhydride is grafted to an ethylene-based polymer. As an alternative, in another embodiment, the anhydride is copolymerized with an ethylene monomer and optionally additional co-monomers. In some embodiments, the at least partially neutralized ethylene copolymer may be mixed with additional polymers selected from the group consisting of ethylene / ethyl hydrogen maleate copolymer, ethylene / maleic acid monoester / methyl acrylate terpolymer, ethylene / maleic acid monoester / methyl methacrylate terpolymer, ethylene / maleic acid monoester / ethyl acrylate terpolymer, ethylene / maleic acid monoester / ethyl methacrylate terpolymer, ethylene / maleic acid monoester / n-butyl acrylate terpolymers, and ethylene / maleic acid monoester / n-butyl methacrylate terpolymer. In further specific embodiments, maleic anhydride functionalized polyethylene or an ethyl-maleic acid monoethyl ester may be included in the molded article as a filler coupling agent.

[0042] Preparation and Article Formation

[0043] The components of the molded article may be prepared via a dry-blending method. Alternatively, the components of the molded article may be prepared through a compounding method. In some embodiments, the compounding method is an extrusion method. Some preparation methods may also optionally include both a compounding and a dry-blending step. In some embodiments, an initial composite may be compounded via an extrusion method and then pelletized. The pelletized composite may then be dry blended with additional components to form a mixture supplied to a molding apparatus.

[0044] A molded article may be formed by any suitable manufacturing technique with standard processing conditions. In some embodiments, the molded article is formed through an injection molding method. Alternatively, the molded article may be formed by a plastic extrusion method. In other non-limiting embodiments, the molded article may be formed by rotational molding, compression molding, vacuum casting, or any other suitable manufacturing technique. The resulting molded article may possess a wall thickness greater than or equal to 3 mm. In some embodiments, the molded article may possess a wall thickness greater than or equal to 5 mm. In other embodiments, the molded article may possess a wall thickness greater than or equal to 7mm. In further embodiments, the molded article may possess a wall thickness greater than or equal to 9 mm. The molded article, according to embodiments, may have any shape or size.EXAMPLES

[0045] Embodiments of the molded articles will be better understood by reference to the following examples, which are offered by way of illustration and which one skilled in the art of molded articles will recognize are not meant to be limiting.

[0046] Table 1 : Ionomer Properties

[0047] The ionomers of this invention may be prepared by standard neutralization techniques, as disclosed in U.S. Pat. No. 3,264,272 (Rees), which is hereby incorporated by reference. Other neutralization techniques are described in U.S Pat. No. 3,404,134 (Rees) and U.S. Pat. No. 3,649,578 (Bush et al.), which is hereby incorporated by reference.

[0048] All ethylene / MAA copolymers were prepared by standard free-radical copolymerization methods, using high pressure, operating in a continuous manner. Monomers are fed into the reaction mixture in a proportion, which relates to the monomer’s reactivity, and the amount desired to be incorporated. In this way, a uniform, near-random distribution of monomer units along the chain is achieved. Polymerization in this manner is well known and is described in U.S. Pat. No. 4,351,931 (Armitage), which is hereby incorporated by reference. Other polymerization techniques are described in U.S. Pat. No. 5,028,674 (Hatch et al.) and U.S. Pat. No. 5,057,593 (Statz), both of which are also hereby incorporated by reference.

[0049] To demonstrate the stone-like appearance that may be attained in molded articles, initial compositions were prepared by compounding and / or dry-blending a mixture of Ionomer A resin, a bio-fdler, and at least one liquid-based pigment. The resulting compositions were then fed into an injection molding apparatus to produce the molded articles. The following exemplary embodiments were molded using a Demag Ergotech 80-400 Viva. The injection moldingapparatus utilized a screw extruder with a diameter of 40 mm and used a clamping force of 80 tons.

[0050] The following Table 2 summarizes the parameters of the injection molding process that was applied in all examples:

[0051] Table 2: General Injection Molding Parameters

[0052] Table 3: Comparative Examples 1-3

[0053] Comparative Example 1

[0054] Comparative example 1 was made according to a standard dry-blending process. The formulation included 95% by weight of Ionomer A resin and 5% by weight of fdtered coffee grounds. The resulting mixture was then molded via the injection molding method discussed above to create a molded article. Unlike the claimed embodiments, comparative example 1 did not include any liquid pigment. The resulting molded article, including only 5% by weight of biofiller, did not exhibit a stone-like appearance but instead appeared as a relatively clear polymer matrix with an inconsistent and non-aesthetically pleasing appearance due to the sporadic, suspended bio-fdler particulates.

[0055] Comparative Example 2

[0056] Comparative example 2 was also made according to a standard dry-blending process. The formulation included 95.5% by weight of Ionomer A resin and 4.5% by weight of agave fibers. The resulting mixture was then molded via the injection molding method discussed above to create a molded article. As in example 1, comparative example 2 did not include any liquid pigment. The resulting molded article with only 4.5% by weight of bio-filler and did not exhibit a stone-like appearance, but it did demonstrate a more consistent appearance than example 1 despite its lower concentration of bio-filler material due to the size and shape of the fibrous agave biofiller compared to the filtered coffee particulates.

[0057] Comparative Example 3

[0058] Comparative example 3 was also made according to a standard dry-blending process. The formulation included 87.5% by weight of Ionomer A resin and 12.5% by weight of wood flour particulates. The resulting mixture was then injection molded via the injection molding method discussed above to create a molded article. As in comparative examples 1 and 2, comparative example 3 did not include any liquid pigment. The resulting molded article with 12.5% by weight of bio-fdler exhibited an almost uniform appearance even though it was not quite stone like. The large wood flour particles and higher concentration of bio-fdler present in the mixture had a substantial effect on the appearance of the molded article.

[0059] Table 4: Inventive Examples 1-4

[0060] Example 1

[0061] Example 1 was prepared according to a standard dry-blending process. The example 1 mixture included 94% by weight of Ionomer A resin, 1% by weight of a white liquid pigment, and 5% by weight of bio-fdler comprising agave fibers. The resulting mixture was molded via the injection molding method described above. The resulting molded article demonstrated a morestone-like appearance than any of the comparative examples but contained limited marbling that would create a more authentic appearance.

[0062] Example 2

[0063] Example 2 was prepared according to a standard dry-blending process. The example 2 mixture included 89% by weight of Ionomer A resin, 1% by weight of a white liquid pigment, and 10% by weight of bio-filler comprising wood flour. The resulting mixture was molded via the injection molding method described above. The resulting molded article demonstrated a similar appearance to example 1 but contained slightly more marbling / speckling.

[0064] Example 3

[0065] Example 3 was prepared according to a standard dry-blending process. The example 3 mixture included 89% by weight of Ionomer A resin, 1% by weight of a white liquid pigment, and 10% by weight of bio-fdler comprising colored sawdust. The resulting mixture was molded via the injection molding method described above. The resulting molded article demonstrated a similar appearance to examples 1 and 2 but had a substantially darker overall appearance with similar marbling / speckling to example 2.

[0066] Example 4

[0067] Example 4 was prepared according to a standard dry-blending process. The example 4 mixture included 92% by weight of Ionomer A resin, 1% by weight of a white liquid pigment, and 7% by weight of bio-fdler comprising fdtered coffee particulates. The resulting mixture was molded via the injection molding method described above. The resulting molded article demonstrated a similar appearance to example 3 but had a slightly lighter color with more marbling / speckling to produce the most stone-like appearance of the four examples.

[0068] Additional examples were also prepared using a pre- compounding step. An ionomer resin, bio-fdler, lubricant, and coupling agent were compounded using a twin-screw extruder with counter rotating screws, a vented barrel, and an E / D ratio of 30. Additionally, the resulting extrudate was dry-blended with an additional ionomer resin and the liquid-based pigment to form the final composition. Though it is preferable to pre-compound the components, an initial mixture can comprise an ionomer, bio-fdler, lubricant, and a coupling agent prepared by dry blending.

[0069] The following Table 5 summarizes the parameters of the compounding process that was applied in examples 5-7:

[0070] Table 5: General Compounding Parameters

[0071] Exemplary molded articles were created by compounding an initial mixture of Ionomer B (a partially neutralized ethylene-methacrylic acid copolymer), Eclec-IN H20, E / MAME, and Hydrobrite 550 PO in the extruder. The compounded composites were dry blended with Ionomer A (an alternative partially neutralized ethylene-methacrylic acid copolymer) and White Pigment HiFormer OM00606537, and then molded into desired articles using the injection molding parameters discussed above. The molded articles had compositions according to the following table:

[0072] Table 6 - Inventive Examples 5-7

[0073] The composites were developed to be easily mixed with an ionomer resin. In these trials, the final molded articles comprise two ionomers (Ionomers A & B) that made up the total ionomer weight percentage in the molded article. These articles also comprised wood fibers (Eclec-IN H20) with fiber sizes between 500 and 800 nm. The dry-blended mixtures were pre-dried in a desiccant hopper for over 5 hours prior to injection molding. The white pigment was liquid, which was found to be a good aid in the process because of its oil base (Avient’s HiFormer code OM00613043-EA). A lower percentage of white pigment or other colored pigments can be used as well. The molding trials ran smoothly, and the molded articles achieved a desired stone-like appearance.

[0074] Example 5

[0075] Example 5 was prepared according to the preparation process discussed above. The example 5 composition included 84.5% by weight of ionomer resin (Ionomers A & B), 1% by weight of a white liquid pigment, and 12.5% by weight of bio-fdler comprising wood flour particulates. In addition, the example 5 composition also included 1% by weight of a coupling agent consisting of an ethyl-maleic acid monoethyl ester and 1% by weight of a mineral oil lubricant. The resulting article was molded via the injection molding method described above. The resulting molded article demonstrated a light gray, stone-like appearance, with marbling / speckling that looked more natural than examples 1-4.

[0076] Example 6

[0077] Example 6 was prepared according to the preparation process discussed above. The example 6 composition included 77.25% by weight of ionomer resin (Ionomers A & B), 1% by weight of a white liquid pigment, and 18.75% by weight of bio-fdler comprising wood flour particulates. In addition, the example 6 composition also included 1.5% by weight of a coupling agent consisting of an ethyl-maleic acid monoethyl ester and 1.5% by weight of a mineral oil lubricant. The resulting article was molded via the injection molding method described above. The resulting molded article demonstrated a similar appearance to example 5.

[0078] Example 7

[0079] Example 7 was prepared according to the preparation process discussed above. The example 7 composition included 85.5% by weight of ionomer resin (Ionomers A & B), 1% by weight of a white liquid pigment, and 12.5% by weight of bio-fdler comprising wood flour particulates. Unlike examples 5 and 6, the composition of example 7 did not include a coupling agent, but it did include 1 % by weight of a mineral oil lubricant. The resulting article was molded via the injection molding method described above. The resulting molded article demonstrated a similar appearance to examples 5 and 6 but had a slightly darker color and slightly larger marbling / speckling. Additionally, examples 5 and 6 had a noticeably smoother surface. Example 6 was slightly rougher due to the lack of a coupling agent, which caused a more homogenous distribution of the bio-fdler in examples 5 and 6.

[0080] It will be apparent to persons of ordinary skill in the art that various modifications and variations can be made without departing from the scope disclosed herein. Since modifications, combinations, sub-combinations, and variations of the disclosed embodiments, which incorporate the spirit and substance disclosed herein, may occur topersons of ordinary skill in the art, the scope disclosed herein should be construed to include everything within the scope of the appended claims and their equivalents.

[0081] For the purposes of defining the present technology, the transitional phrase “consisting of’ may be introduced in the claims as a closed preamble term limiting the scope of the claims to the recited components or steps and any naturally occurring impurities. For the purposes of defining the present technology, the transitional phrase “consisting essentially of’ may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non-recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transitional phrases “consisting of’ and “consisting essentially of’ may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open-ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of’ and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of’ components A, B, and C as well as a composition “consisting essentially of’ components A, B, and C. Any quantitative value expressed in the present application may be considered to include open-ended embodiments consistent with the transitional phrases “comprising” or “including,” as well as closed or partially closed embodiments consistent with the transitional phrases “consisting of’ and “consisting essentially of.”

[0082] As used in the Specification and appended Claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly indicates otherwise. The verb “comprises” and its conjugated forms should be interpreted as referring to elements, components, or steps in a non-exclusive manner. The referenced elements, components, or steps may be present, utilized, or combined with other elements, components, or steps not expressly referenced.

[0083] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. The subject matter disclosed herein has been described in detail and by reference to specific embodiments. Itshould be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

CLAIMS1. A molded article comprising: at least 50% by weight of an ionomer, the ionomer being an at least partially neutralized ethylene acid copolymer, wherein the ethylene acid copolymer comprises a polymerized reaction product of ethylene and carboxylic acid; from 0.5% to 50% by weight of a bio-filler material; and from 0.1% to 3% by weight of a liquid pigment.

2. The molded article of claim 1, wherein the bio-filler material comprises one or more of wood flour, sawdust, filtered coffee, ground barley scull, agave fiber, ground rice scull, ground wheat scull, and coconut fiber.

3. The molded article of claim 1 or 2, wherein the molded article comprises 3% to 20% by weight of the bio-filler material.

4. The molded article of any one of claims 1 to 3, wherein the liquid pigment comprises a liquid carrier, wherein the liquid carrier comprises mineral oil, polyethylene glycol (PEG), polyisobutylene, or combinations thereof.

5. The molded article of any one of claims 1 to 4, wherein the ionomer has a melt index (12) from 2 dg / min to 15 dg / min, as measured according to ASTM D1238 (190 °C, 2.16 kg).

6. The molded article of any one of claims 1 to 5, wherein the molded article comprises from 75% to 95% by weight of the ionomer.

7. The molded article of any one of claims 1 to 6, wherein the carboxylic acid of the ionomer comprises (meth)acrylic acid.

8. The molded article of any one of claims 1 to 7, wherein the ionomer comprises 5% to 25% of carboxylic acid co-monomer which is at least partially neutralized by sodium or zinc cations.

9. The molded article of any one of claims 1 to 8, wherein the molded article further comprises from 1% to 3% by weight of a lubricant.

10. The molded article of claim 9, wherein the lubricant comprises calcium stearate, mineral oil, or erucamide.

11. The molded article of any one of claims 1 to 10, wherein the molded article comprises calcium carbonate.

12. The molded article of claim 11, wherein the molded article comprises from 5% to 10% by weight of the calcium carbonate.

13. The molded article of any one of claims 1 to 12, wherein the molded article comprises additional polymers selected from the group consisting of ethylene / ethyl hydrogen maleate copolymer, ethylene / maleic acid monoester / methyl acrylate terpolymer, ethylene / maleic acid monoester / methyl methacrylate terpolymer, ethylene / maleic acid monoester / ethyl acrylate terpolymer, ethylene / maleic acid monoester / ethyl methacrylate terpolymer, ethylene / maleic acid monoester / n-butyl acrylate terpolymers, and ethylene / maleic acid monoester / n-butyl methacrylate terpolymer.

14. The molded article of any one of claims 1 to 13, wherein the molded article is formed by an extrusion or injection molding process and comprises one or more walls, each wall having a thickness of at least 5 mm.

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