Thick components and profiles with a stone-like appearance using ionomer resins and bio-fillers

Abstract

A molded article exhibiting a stone-like decorative effect comprises at least 50% by weight of an ionomer, wherein the ionomer is at least partially neutralized ethylene copolymer. Furthermore, the ethylene copolymer comprises a reaction product of ethylene and carboxylic acid. The molded article also comprises between 0.5% and 50% by weight of a bio-filler and between 0.1% and 3% by weight of a liquid pigment.

Description

[0001] Cross-references to related applications

[0002] 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 herein by reference in their entirety. Technical Field

[0003] The embodiments disclosed herein generally involve molded articles made from a mixture comprising ionomer resin, biofiller and liquid pigment, which exhibit a stone-like decorative effect while also possessing dimensional stability and chemical resistance. Background Technology

[0004] Neutralized acid copolymers, such as ionomer resins, are ideal materials for injection molding. This makes ionomer resins particularly suitable for many consumer industries, including cosmetics and infrastructure industries. Cosmetics, such as perfume bottles, and infrastructure products, such as building materials, are often made from molded parts and designed to exhibit specific aesthetic characteristics depending on their application. The ability to customize these molded parts or produce molded parts with novel visual effects can present unique business opportunities.

[0005] In the cosmetics industry, injection-molded products have specific requirements due to their intended use. Molded products are often used as components in cosmetic packaging, potentially exposing polymer materials to fragrances or other chemicals. Therefore, these materials must exhibit not only dimensional stability but also chemical stability to prevent degradation. Additionally, these materials must be aesthetically pleasing for creative marketing purposes while remaining compatible with conventional injection molding techniques to maintain the economic viability of cosmetic companies. Molded products in the cosmetics industry often sacrifice one of these considerations. Conventional crystalline resins typically lack dimensional stability, leading to shrinkage and indentations during the molding process, which affects the aesthetic characteristics of the molded product. However, amorphous resins generally exhibit excellent dimensional stability but lack chemical stability in the cosmetic environment.

[0006] Similarly, in the infrastructure industry, many companies have begun using injection-molded products as alternatives to traditional building materials due to their lower cost. Infrastructure companies typically use polyolefins such as polypropylene and polyethylene combined with wood to form composites, aiming to retain the mechanical properties of these materials while mimicking the appearance of traditional building materials. These composites are then coated with a thin layer of ionomer resin. While this achieves good dimensional and chemical stability, it hinders typical injection molding processes and prevents the use of single-extrusion profiles that would save companies time and money.

[0007] Consumers and businesses alike desire marble- or stone-like products that exhibit dimensional and chemical stability while remaining cost-effective. Although previous attempts have achieved stone-like finishes in molded articles by incorporating colored polyamides into copolymer blends, the resulting stone-like products have often yielded less aesthetically pleasing results with striped patterns or other less desirable characteristics. Therefore, there remains a need for easily manufactured molded articles that achieve a stone-like appearance while also possessing dimensional stability and chemical resistance. Summary of the Invention

[0008] Therefore, this disclosure proposes embodiments that meet this need, producing molded articles that exhibit a stone-like decorative effect while also possessing dimensional stability and chemical resistance. In one embodiment, the molded article comprises at least 50% by weight of an ionomer, wherein the ionomer is at least partially neutralized ethylene copolymer. Furthermore, the ethylene copolymer comprises a reaction product of ethylene and carboxylic acid. The molded article also comprises between 0.5% by weight and 50% by weight of a bio-filler and between 0.1% by weight and 3% by weight of a liquid pigment.

[0009] According to embodiments of the present invention, the biofiller material comprises one or more of the following materials: wood flour, sawdust, filtered coffee, ground barley husks, agave fiber, ground rice husks, ground wheat husks, and coconut fiber. Furthermore, in specific embodiments, the molded article may contain between 3% and 20% by weight of the biofiller. Additionally, the molded article may contain a liquid pigment comprising a solid colorant dispersed in a liquid carrier. The liquid pigment may contain 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 of 2 dg / min to 15 dg / min as measured according to ASTM D1238.

[0010] In other embodiments, the molded article comprises between 75% and 95% by weight of an ionomer resin. Additionally, the carboxylic acid of the ionomer may be (meth)acrylic acid. The carboxylic acid may also be partially neutralized with sodium or zinc, and the ionomer resin may comprise between 5% and 25% by weight of the carboxylic acid. Furthermore, the molded article may optionally comprise between 1% and 3% by weight of a lubricant selected from one or more of calcium stearate, mineral oil, or fatty acid amides. Fatty acid amides may include, but are not limited to, examples such as erucamide, betaine, oleamide, stearamide, oleyl palmitamide, stearyl erucamide, ethylene bis-stearamide, and ethylene bis-oleamide. Furthermore, the molded article may optionally comprise additional filler materials, such as between 5% and 10% by weight of calcium carbonate and between 2% and 5% by weight of talc.

[0011] In some embodiments, the molded article may further comprise other polymers selected from the group consisting of: ethylene / ethyl maleate copolymer, ethylene / monomethyl maleate / methyl acrylate terpolymer, ethylene / monomethyl maleate / methyl methacrylate terpolymer, ethylene / monomethyl maleate / ethyl acrylate terpolymer, ethylene / monomethyl maleate / ethyl methacrylate terpolymer, ethylene / monomethyl maleate / n-butyl acrylate terpolymer, and ethylene / monomethyl maleate / n-butyl methacrylate terpolymer.

[0012] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and characteristics 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 apparent to those skilled in the art from the description including the appended claims, or may be recognized by practice of the embodiments described. However, the embodiments are exemplary and illustrative in nature and are not intended to limit the claimed subject matter. Detailed Implementation

[0013] In its broadest sense, this disclosure relates to embodiments of molded articles made from mixtures comprising ionomer resins, biofillers, and pigments, wherein the resulting molded articles exhibit a stone-like decorative effect while also possessing dimensional stability and chemical resistance.

[0014] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Therefore, the general term polymer encompasses the term homopolymer (used to refer to a polymer prepared from only one type of monomer) and the term copolymer or interpolymer. Trace amounts of impurities (e.g., catalyst residues) may be incorporated into and / or within a polymer. A polymer can be a single polymer, a polymer blend, or a mixture of polymers, including mixtures of polymers formed in situ during polymerization.

[0015] As used herein, the terms "polyethylene" or "ethylene-based polymer" should mean a polymer comprising more than 50 mol% of units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers), including ethylene copolymers.

[0016] The molded article according to the embodiments may contain at least 50% by weight of an ionomer resin based on the total weight of the molded article. The ionomer resin contains one or more at least partially neutralized acid copolymers. In one embodiment, the one or more at least partially neutralized acid copolymers are ethylene glycol copolymers. The molded article also contains 0.5% to 50% by weight of a biofiller based on the total weight of the molded article. The molded article also contains 0.1% to 3% by weight of a liquid pigment based on the total weight of the molded article. In one embodiment, the molded article further contains 0.1% to 3% by weight of a liquid pigment based on the total weight of the molded article, the liquid pigment comprising a colorant and a liquid carrier. Additionally, the molded article may optionally contain 0% to 3% by weight of a lubricant based on the total weight of the molded article. Furthermore, the molded article may optionally contain 0% to 2% by weight of a coupling agent based on the total weight of the molded article. Additionally, the molded article may optionally contain 5% to 10% by weight of calcium carbonate based on the total weight of the molded article. Finally, the molded article also contains 2% to 5% talc based on the total weight of the molded article.

[0017] Isopolymer

[0018] According to the implementation scheme, the ionomer may be one or more at least partially neutralized vinyl acid copolymers. Based on the total weight of the molded article, the molded article may contain 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% by weight, 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.

[0019] Ionomer resins can be produced by any means known to those skilled in the art, such as by neutralizing ethylene-based copolymers with one or more metal ions. An ethylene-based copolymer is a polymer comprising repeating units derived from ethylene, and about 1% to about 50% by weight, or about 5% to about 40% by weight, or 5% to 25% by weight of a carboxylic acid comonomer, such as α,β-olefinically unsaturated carboxylic acids, like acrylic acid, methacrylic acid, or combinations thereof, based on the total weight of the ethylene-based copolymer. Alternatively, the copolymer units of the carboxylic acid comonomer may comprise about 5% to about 20% by weight, or about 7% to about 15% by weight, or about 8% to about 12.5% ​​by weight of the total weight of the ionomer. In some embodiments, the carboxylic acid comonomer of the ethylene-carboxylic acid copolymer is (meth)acrylic acid.

[0020] To obtain an ionomer suitable for use in molded articles according to embodiments of this disclosure, the ionomer is neutralized with a base containing a metal cation, causing the acid groups (e.g., carboxylic acids) in the precursor acid copolymer to react and form acid salt groups (e.g., carboxylates). In the 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 of the α,β-ene unsaturated carboxylic acids derived from the precursor acid copolymer are neutralized. The level of neutralization of the acid groups of the α,β-ene unsaturated carboxylic acids derived from the precursor acid copolymer can be calculated based on the amount of alkali metal compound added or measured using infrared spectroscopy. The actual level of neutralization can be determined using infrared spectroscopy by comparing the levels at 1530 cm⁻¹. −1 Up to 1630cm −1 The absorption peak at 1690 cm⁻¹ can be attributed to the stretching vibration of the carboxylate anion. −1 Up to 1710cm −1 The location can be determined by the absorption peak attributable to the carbonyl stretching vibration. The amount of alkali metal compound capable of neutralizing acidic groups can be provided by adding a calculated stoichiometry of a basic compound to the target amount of the acid moiety in the neutralized acid copolymer.

[0021] It is believed that any stable cation, and any combination of two or more stable cations, is suitable as a counterion for the acid group in the ionomer. The counterion for the acid group in the ionomer can include, for example, divalent and monovalent cations, such as cations of alkali metals, alkaline earth metals, and some transition metals. For example, in some embodiments, the cation is a divalent cation, such as zinc, calcium, or magnesium. For example, in other embodiments, the cation is a monovalent cation, such as potassium or sodium. In further embodiments, the acid group of the α,β-olefinic unsaturated carboxylic acid derived from the precursor acid copolymer is neutralized by a sodium-containing base. The sodium-containing base can provide a sodium ionomer in which the hydrogen atom of the acid group of the precursor acid is replaced by a sodium cation. To obtain the ionomer of the acid copolymer used as neutralization in the embodiments, the precursor acid copolymer can be neutralized by any conventional procedure, such as those described in U.S. Patent Nos. 3,404,134 and 6,518,365.

[0022] The acid groups in the ionomer resin are at least partially neutralized. The neutralization of acid groups in the ionomer resin, based on the total carboxylic acid content, can, for example, range 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 the carboxylic acid groups in the ionomer resin neutralized with metal ions. The metal ion can be monovalent, divalent, trivalent, polyvalent, or a combination of two or more thereof. Examples include Li, Na, K, Ag, Hg, Cu, Be, Mg, Ca, Sr, Ba, Cd, Sn, Pb, Fe, Co, Zn, Ni, Al, Sc, Hf, Ti, Zr, Ce, and combinations of two or more thereof. If the metal ion is polyvalent, it may include a complexing agent, such as stearate, oleate, salicylate, and phenolic groups, as disclosed in U.S. Patent No. 3,404,134. Specific examples of neutralizing metal ions include Na, Zn, or combinations thereof. Other examples include sodium or zinc ions derived from, for example, salts such as: NaOH, NaHCO3, Na2CO3, NaHSO4, NaH2PO4, Na2HPO3, sodium stearate, sodium oleate, sodium salicylate, sodium phenolate, Zn(OH)2, ZnCO3, ZnCO3, ZnSO4, ZnHPO4, ZnHPO3, zinc oxide, zinc stearate, zinc oleate, zinc salicylate, zinc phenolate, Mg(OH)2, MgCO3, MgCO3, MgSO4, MgHPO4, MgHPO3, magnesium stearate, magnesium oleate, magnesium salicylate, magnesium phenolate, or combinations of two or more of these.

[0023] Examples of ethylene copolymers may include up to 25% by weight of optional comonomers based on the weight of the ethylene copolymer, such as carbon monoxide, sulfur dioxide, acrylonitrile, maleic anhydride, maleic diester, maleic acid, maleic monoester, itaconic acid, fumaric acid, fumaric monoester, salts of these acids, glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, amyl methacrylate, or combinations of two or more thereof, wherein the alkyl groups may be linear or branched.

[0024] Resin properties

[0025] The ionomer resin for the molded articles has a melt index I2 of 2 dg / min to 15 dg / min, as measured according to ASTM D1238 (190°C, 2.16 kg). Melt index I2 is determined according to ASTM D1238 at 190°C, 2.16 kg. This document includes and discloses all individual values ​​and sub-ranges from 2 dg / min to 15 dg / min. For example, in some embodiments, the partially neutralized precursor acid copolymer may have a melt index I2 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.

[0026] biological packing

[0027] Molded articles may also contain organic fillers or biofillers. Biofillers can be plant-based granular or fibrous materials. In some embodiments, the filler may be a cellulose, hemicellulose, or lignocellulose material. Biofillers may include granular, fibrous organic materials, or a combination of both. Suitable biofillers include organic materials that can withstand temperatures up to 220°C without degradation. In some embodiments, the biofiller is a granular material, such as in the form of powder, dust, slurry, broken fibers, flakes, or fragments. In other embodiments, the filler is a fibrous material, such as fibrous organic materials like flax, linen, or hemp. In some embodiments, the biofiller may be a mixture of granular and fibrous materials.

[0028] Molded articles may contain 0.5 wt% to 50 wt% of biological filler based on the total weight of the molded article. This document includes and discloses all individual values ​​and sub-ranges from 0.5 wt% to 50 wt%. For example, in some embodiments, the molded article may contain 0.5 wt% to 40 wt% of biological filler, 1 wt% to 30 wt% of biological filler, 2 wt% to 25 wt% of biological filler, 3 wt% to 20 wt% of biological filler, 5 wt% to 20 wt% of biological filler, or 7 wt% to 15 wt% of biological filler.

[0029] Biofillers may comprise particles or fibers with dimensions ranging from 0.1 mm to 1000 mm. This document includes and discloses all individual values ​​and sub-ranges of 0.1 mm to 1000 mm. For example, in some embodiments, the biofiller size 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 biofiller material comprises one or more organic materials from the following: wood flour, sawdust, filtered coffee, ground barley husks, agave fibers, ground rice husks, ground wheat husks, coconut fiber, or any other suitable organic material.

[0030] liquid pigments

[0031] The molded article also includes a liquid pigment added to the molded article to achieve a stone-like decorative effect. The liquid pigment can be any organic or inorganic colorant formulation in liquid form and comprises a colorant and a liquid carrier. The liquid carrier must be chemically compatible with at least partially neutralized acid copolymers and stable at typical temperatures of extrusion or injection molding processes. In some embodiments, the liquid pigment also comprises titanium dioxide.

[0032] Examples of suitable liquid pigments for inclusion in molded articles include, but are not limited to, organic or inorganic pigments. Such organic or inorganic pigments may be selected from black, yellow, magenta, red, purple, cyan, blue, green, orange, brown, and white pigments. In some cases, the organic or inorganic pigment may include spot color pigments, which are formed by combining two or more primary color pigments in a predetermined proportion. In a preferred embodiment, the liquid pigment is an organic oil-based white pigment. Such liquid pigments may be traded under the name HiFormer. ™ Purchased from Avient.

[0033] Molded articles may contain 0.1% to 3% by weight of liquid pigment based on the total weight of the molded article. This document includes and discloses all individual values ​​and sub-ranges from 0.1% to 3%. For example, in some embodiments, the molded article may contain 0.1% to 2.5% by weight of liquid pigment, 0.5% to 2.5% by weight of liquid pigment, 0.5% to 2% by weight of liquid pigment, or 0.5% to 1.5% by weight of liquid pigment.

[0034] Liquid pigments may include 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 glycol, or polyisobutylene. Oil-based liquid carriers may also include one or more of cyclopentasiloxane, cyclohexylsiloxane, or isoparaffin fluids. In a specific embodiment, the liquid carrier is mineral oil. In another specific embodiment, the liquid carrier is polyethylene glycol. In another specific embodiment, the liquid carrier is polyisobutylene. In another specific embodiment, the liquid carrier is a mixture of polyethylene glycol and mineral oil. In another specific embodiment, the liquid carrier is a mixture of polyisobutylene and mineral oil.

[0035] Molded articles may contain 0.1 wt% to 3 wt% liquid pigment based on the total weight of the molded article. This document includes and discloses all individual values ​​and sub-ranges from 0 wt% to 3 wt%. For example, in some embodiments, the molded article may contain 0.1 wt% to 3 wt% liquid pigment, 0.1 wt% to 2.5 wt% liquid pigment, 0.5 wt% to 2.5 wt% liquid pigment, 0.5 wt% to 2 wt% liquid pigment, or 0.5 wt% to 1.5 wt% liquid pigment.

[0036] lubricant

[0037] According to the embodiments, the molded article may optionally contain a lubricant to facilitate efficient flow and handling within the extruder or injection unit. The lubricant may include one or more of calcium stearate, mineral oil, or erucamide. In a specific embodiment, the lubricant is mineral oil. In another specific embodiment, the lubricant is calcium stearate. In another specific embodiment, the lubricant is erucamide. In another specific embodiment, the lubricant is a mixture of calcium stearate and mineral oil. In yet another specific embodiment, the lubricant is a mixture of erucamide and mineral oil.

[0038] Molded articles may contain 0% to 3% by weight of lubricant based on the total weight of the molded article. This document includes and discloses all individual values ​​and sub-ranges from 0% to 3% by weight. For example, in some embodiments, the molded article may contain 0.1% to 3% by weight of lubricant, 0.1% to 2.5% by weight of lubricant, 0.5% to 2.5% by weight of lubricant, 0.5% to 2% by weight of lubricant, or 0.5% to 1.5% by weight of lubricant.

[0039] Additional packing

[0040] According to the embodiments, the molded article may optionally contain calcium carbonate as a filler to increase the weight of the molded article and achieve a more realistic stone-like decorative effect. The molded article may contain 0% to 10% calcium carbonate based on the total weight of the molded article. All individual values ​​and sub-ranges from 0% to 10% are included and disclosed herein. In a preferred embodiment, the molded article may contain 5% to 10% calcium carbonate. In other embodiments, the molded article may contain 5% to 8% calcium carbonate, 5% to 6.5% calcium carbonate, 7% to 10% calcium carbonate, or 8.5% to 10% calcium carbonate.

[0041] According to the embodiments, the molded article may optionally contain talc as a filler to promote the distribution of the filler within the molded article and optimize the outer surface of the molded article to produce an attractive tactile feel. The molded article may contain 0% to 5% talc based on the total weight of the molded article. All individual values ​​and sub-ranges of 0% to 5% talc are included and disclosed herein. In a preferred embodiment, the molded article may contain 2% to 5% talc. In other embodiments, the molded article may contain 2% to 4% talc, or 2% to 3% talc.

[0042] In addition to the materials described so far, the molded article may also contain additional polymeric materials. In one embodiment, the anhydride is grafted onto an ethylene-based polymer. Alternatively, in another embodiment, the anhydride is copolymerized with an ethylene monomer and optionally additional comonomers. In some embodiments, the at least partially neutralized ethylene copolymer may be blended with additional polymers selected from the group consisting of: ethylene / ethyl maleate copolymer, ethylene / monomethyl maleate / methyl acrylate terpolymer, ethylene / monomethyl maleate / methyl methacrylate terpolymer, ethylene / monomethyl maleate / ethyl acrylate terpolymer, ethylene / monomethyl maleate / ethyl methacrylate terpolymer, ethylene / monomethyl maleate / n-butyl acrylate terpolymer, and ethylene / monomethyl maleate / n-butyl methacrylate terpolymer. In another specific embodiment, maleic anhydride-functionalized polyethylene or ethyl-monoethyl maleate may be included in the molded article as a filler coupling agent.

[0043] Preparation and article formation

[0044] The components of the molded article can be prepared by dry mixing. Alternatively, the components of the molded article can be prepared by compounding. In some embodiments, the compounding method is an extrusion method. Some preparation methods may also optionally include compounding and dry mixing steps. In some embodiments, the initial composite material can be compounded via an extrusion method and then granulated. The granulated composite material can then be dry-mixed with additional components to form a mixture supplied to the molding equipment.

[0045] Molded articles can be formed under standard processing conditions using any suitable manufacturing technique. In some embodiments, the molded article is formed by injection molding. Alternatively, the molded article can be formed by plastic extrusion. In other non-limiting embodiments, the molded article can be formed by rotational molding, compression molding, vacuum casting, or any other suitable manufacturing technique. The resulting molded article may have a wall thickness greater than or equal to 3 mm. In some embodiments, the molded article may have a wall thickness greater than or equal to 5 mm. In other embodiments, the molded article may have a wall thickness greater than or equal to 7 mm. In yet another embodiment, the molded article may have a wall thickness greater than or equal to 9 mm. Depending on the embodiment, the molded article may have any shape or size.

[0046] Example

[0047] The implementation of the molded articles will be better understood by referring to the following examples, which are provided in an illustrative manner and will be recognized by those skilled in the art of molded articles as not being restrictive.

[0048]

[0049] The ionomers of the present invention can be prepared by standard neutralization and techniques, as disclosed in U.S. Patent No. 3,264,272 (Rees), which is incorporated herein by reference. Other neutralization and techniques are described in U.S. Patent Nos. 3,404,134 (Rees) and 3,649,578 (Bush et al.), which are incorporated herein by reference.

[0050] All ethylene / MAA copolymers are prepared by standard free radical copolymerization, using high pressure and operated continuously. Monomers are fed into the reaction mixture in proportions related to their reactivity and the desired incorporation amount. In this manner, a uniform, nearly random distribution of monomer units along the chain is achieved. Polymerization in this manner is well known and described in U.S. Patent No. 4,351,931 (Armitage), which is incorporated herein by reference. Other polymerization techniques are described in U.S. Patent Nos. 5,028,674 (Hatch et al.) and 5,057,593 (Statz), which are incorporated herein by reference.

[0051] To achieve a stone-like appearance in molded articles, an initial composition is prepared by compounding and / or dry-blending a mixture of ionomer A resin, biofiller, and at least one liquid-based pigment. The resulting composition is then fed into an injection molding machine to produce molded articles. The following exemplary embodiment is molded using a Demag Ergotech 80-400 Viva molding machine. This injection molding machine uses a 40mm diameter screw extruder and employs a clamping force of 80 tons.

[0052] Table 2 below summarizes the parameters of the injection molding process used in all embodiments:

[0053]

[0054]

[0055] Comparative Example 1

[0056] Comparative Example 1 was prepared according to a standard dry-mixing method. The formulation contained 95% by weight of ionomer A resin and 5% by weight of filtered coffee grounds. The resulting mixture was then molded using the injection molding method described above to produce a molded article. Unlike the claimed embodiment, Comparative Example 1 did not contain any liquid pigments. The resulting molded article, containing only 5% by weight of biofiller, did not exhibit a stone-like appearance but instead presented a relatively transparent polymer matrix with an inconsistent and unattractive appearance due to scattered suspended biofiller particles.

[0057] Comparative Example 2

[0058] Comparative Example 2 was also prepared according to the standard dry-mixing method. This formulation contained 95.5% by weight of ionomer A resin and 4.5% by weight of agave fiber. The resulting mixture was then molded using the injection molding method described above to produce a molded article. Similar to Comparative Example 1, Comparative Example 2 did not contain any liquid pigments. The resulting molded article contained only 4.5% by weight of biofiller and did not exhibit a stone-like appearance, but it did show a more consistent appearance than Example 1 due to the difference in size and shape between the fibrous agave biofiller and the filtered coffee particles, despite its lower concentration of biofiller material.

[0059] Comparative Example 3

[0060] Comparative Example 3 was also prepared according to the standard dry-mix method. This formulation contained 87.5% by weight of ionomer A resin and 12.5% ​​by weight of wood flour particles. The resulting mixture was then injection molded using the injection molding method described above to produce a molded article. Similar to Comparative Examples 1 and 2, Comparative Example 3 did not contain any liquid pigments. The resulting molded article with 12.5% ​​by weight of bio-filler exhibited an almost uniform appearance, even though it did not perfectly resemble stone. The large wood flour particles and high concentration of bio-filler present in the mixture had a significant impact on the appearance of the molded article.

[0061]

[0062] Example 1

[0063] Example 1 was prepared according to a standard dry-mixing method. The mixture of Example 1 contained 94 wt% ionomer A resin, 1 wt% white liquid pigment, and 5 wt% biofiller containing agave fibers. The mixture was molded using the injection molding method described above. The resulting molded article exhibited a more stone-like appearance than any comparative example, but contained limited marble patterns, which would produce a more realistic appearance.

[0064] Example 2

[0065] Example 2 was prepared according to a standard dry-mixing method. The mixture of Example 2 contained 89% by weight of ionomer A resin, 1% by weight of white liquid pigment, and 10% by weight of a bio-filler containing wood flour. The mixture was molded using the injection molding method described above. The resulting molded article exhibited an appearance similar to that of Example 1, but contained slightly more marble-like patterns / spots.

[0066] Example 3

[0067] Example 3 was prepared according to a standard dry-mixing method. The mixture of Example 3 contained 89% by weight of ionomer A resin, 1% by weight of white liquid pigment, and 10% by weight of biofiller containing colored sawdust. The mixture was molded using the injection molding method described above. The resulting molded articles exhibited an appearance similar to that of Examples 1 and 2, but with a significantly darker overall appearance and a marbled / spotted texture similar to that of Example 2.

[0068] Example 4

[0069] Example 4 was prepared according to a standard dry-mixing method. The mixture of Example 4 contained 92% by weight of ionomer A resin, 1% by weight of white liquid pigment, and 7% by weight of biofiller containing filtered coffee particles. The mixture was molded using the injection molding method described above. The resulting molded article exhibited an appearance similar to that of Example 3, but with a slightly lighter color and more marble-like patterns / spots, thus producing the most stone-like appearance among the four examples.

[0070] Additional examples were prepared using a pre-mixing step. Ionomer resins, biofillers, lubricants, and coupling agents were compounded using a twin-screw extruder with a counter-rotating screw, venting barrel, and an L / D ratio of 30. The resulting extrudate was then dry-mixed with additional ionomer resins and liquid-based pigments to form the final composition. While pre-mixing of the components is preferred, the initial mixture may contain ionomers, biofillers, lubricants, and coupling agents prepared by dry mixing.

[0071] Table 5 below summarizes the parameters of the compounding processes used in Examples 5-7:

[0072]

[0073] An exemplary molded article was formed by compounding an initial mixture of ionomer B (partially neutralized ethylene-methacrylic acid copolymer), Eclec-INH20, E / MAME, and Hydrobrite 550 PO in an extruder. The compounded material was then dry-blended with ionomer A (another alternatively partially neutralized ethylene-methacrylic acid copolymer) and white pigment HiFormerOM00606537, and then molded into the desired article using the injection molding parameters described above. The molded article has a composition according to the table below:

[0074]

[0075] Composite materials that are easily mixed with ionomer resins were developed. In these trials, the final molded articles contained two ionomers (Ionomer A and Ionomer B), which constituted the total ionomer weight percentage in the molded articles. These articles also contained wood fibers (Eclec-IN H2O) with fiber sizes between 500 nm and 800 nm. The dry-mixed mixture was pre-dried in a desiccant hopper for more than 5 hours prior to injection molding. The white pigment, being liquid, was found to be a good additive in this method due to its oil-based nature (Avient's HiFormer code OM00613043-LA). Lower percentages of white pigments or other colored pigments can also be used. The molding trials proceeded smoothly, and the molded articles achieved the desired stone-like appearance.

[0076] Example 5

[0077] Example 5 was prepared according to the above preparation method. The composition of Example 5 contained 84.5% by weight of ionomer resins (ionomers A and B), 1% by weight of white liquid pigment, and 12.5% ​​by weight of a biofiller containing wood flour particles. In addition, the composition of Example 5 also contained 1% by weight of a coupling agent composed of monoethyl maleate and 1% by weight of a mineral oil lubricant. The resulting article was molded by the above injection molding method. The resulting molded article exhibited a light gray, stone-like appearance with a more natural marble-like texture / spotting than that of Examples 1-4.

[0078] Example 6

[0079] Example 6 was prepared according to the above preparation method. The composition of Example 6 contained 77.25% by weight of ionomer resins (ionomers A and B), 1% by weight of white liquid pigment, and 18.75% by weight of a biofiller containing wood flour particles. In addition, the composition of Example 6 also contained 1.5% by weight of a coupling agent composed of monoethyl maleate and 1.5% by weight of a mineral oil lubricant. The resulting article was molded by the above injection molding method. The resulting molded article exhibited an appearance similar to that of Example 5.

[0080] Example 7

[0081] Example 7 was prepared according to the preparation method described above. The composition of Example 7 contained 85.5% by weight of ionomer resins (ionomers A and B), 1% by weight of white liquid pigment, and 12.5% ​​by weight of biofiller containing wood flour particles. Unlike Examples 5 and 6, the composition of Example 7 did not contain a coupling agent, but it did contain 1% by weight of mineral oil lubricant. The resulting article was molded by the injection molding method described above. The resulting molded article exhibited a similar appearance to Examples 5 and 6, but with a slightly darker color and slightly larger marbled / spotted patterns. In addition, Examples 5 and 6 had a significantly smoother surface. Due to the lack of a coupling agent, Example 6 was slightly rougher, which resulted in a more uniform distribution of the biofiller in Examples 5 and 6.

[0082] It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope disclosed herein. Because modifications, combinations, sub-combinations, and variations of the disclosed embodiments can be made by those skilled in the art that incorporate the spirit and substance of the disclosure herein, the scope of this disclosure should be interpreted as including all things within the scope of the appended claims and their equivalents.

[0083] For the purpose of defining the technology of the invention, the transitional phrase "consisting of..." may be introduced in the claims as a closing preamble, which limits the scope of the claims to the listed components or steps and any naturally occurring impurities. For the purpose of defining the technology of the invention, the transitional phrase "consisting substantially of..." may be introduced in the claims to limit the scope of one or more claims to the stated elements, components, materials, or method steps and any non-stated elements, components, materials, or method steps that do not substantially affect the novelty of the claimed subject matter. The transitional phrases "consisting of..." and "consisting substantially of..." may be interpreted as open-ended transitional phrases, such as subsets of "comprising" and "including", such that any use of an open-ended phrase to introduce a statement of a series of elements, components, materials, or steps should be interpreted as also disclosing a statement of that series of elements, components, materials, or steps using the closing terms "consisting of..." and "consisting substantially of...". For example, a statement of a composition "comprising" components A, B, and C should be interpreted as also disclosing compositions "consisting of components A, B, and C" and compositions "consisting substantially of components A, B, and C". Any quantitative value expressed in this application may be considered to include open-ended embodiments conforming to the transitional phrases “comprising” or “including”, as well as closed or partially closed embodiments conforming to the transitional phrases “consisting of” and “substantially consisting of”.

[0084] As used in the specification and appended claims, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural references. The verb “comprising” and its homologous forms should be interpreted as referring to an element, component, or step in a non-exclusive manner. The referenced element, component, or step may exist, be used, or be combined with other elements, components, or steps not expressly referenced.

[0085] It should be understood that any two quantitative values ​​assigned to a characteristic may constitute a range for that characteristic, and all combinations of ranges formed by all stated quantitative values ​​of a given characteristic are considered in this disclosure. The subject matter described herein has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that such component or feature is necessary for a particular embodiment or any other embodiment. Furthermore, it will be apparent to those skilled in the art that various modifications and changes may be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

1. A molded article, the molded article comprising: At least 50% by weight of an ionomer, said ionomer being at least partially neutralized ethylene copolymer, wherein said ethylene copolymer comprises polymerization products of ethylene and carboxylic acid; 0.5% to 50% by weight of biofilled materials; and Liquid pigments ranging from 0.1% to 3% by weight.

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

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

4. The molded article according to 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 a combination thereof.

5. The molded article according to any one of claims 1 to 4, wherein the ionomer has a melt index (I2) of 2 dg / min to 15 dg / min as measured according to ASTM D1238 (190°C, 2.16 kg).

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

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

8. The molded article according to any one of claims 1 to 7, wherein the ionomer comprises 5% to 25% of a carboxylic acid comonomer, said carboxylic acid comonomer being at least partially neutralized by sodium or zinc cations.

9. The molded article according to any one of claims 1 to 8, wherein the molded article further comprises 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 according to 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 5% to 10% by weight of the calcium carbonate.

13. The molded article according to any one of claims 1 to 12, wherein the molded article comprises an additional polymer selected from the group consisting of: ethylene / ethyl maleate copolymer, ethylene / monomethyl maleate / methyl acrylate terpolymer, ethylene / monomethyl maleate / methyl methacrylate terpolymer, ethylene / monomethyl maleate / ethyl acrylate terpolymer, ethylene / monomethyl maleate / ethyl methacrylate terpolymer, ethylene / monomethyl maleate / n-butyl acrylate terpolymer, and ethylene / monomethyl maleate / n-butyl methacrylate terpolymer.

14. The molded article according to 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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