Low friction ISBM bottle

Abstract

Disclosed is an injection stretch blow molded (ISBM) container comprising a surface having a static coefficient of friction (COF) of 0.15-0.21, a dynamic COF of 0.06-0.1, the surface retaining a water contact angle of 76° or greater for up to 3 minutes after wetting the surface with a water drop having a diameter of 14-16 mm, the container being made of a polymer composition comprising high density polyethylene (HDPE) having a polydispersity (Mw / Mn) of 9 or greater as measured by GPC; a MI2 of 1 g / 10 min or greater as measured by ASTM D-1238; and an environmental stress crack resistance (ESCR) of >150 hours at 100% Igepal as measured by ASTM D-1693, B.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 181,026, filed April 28, 2021, which is incorporated by reference in its entirety for all purposes.

[0002] 2. Background of the Invention A. Field of the Invention The present invention relates generally to injection stretch blow molded (ISBM) containers. In some aspects, the present invention relates to ISBM containers having properties that allow for efficient removal of food from the container without the use of a surface coating. [Background technology]

[0003] B. Description of Related Art There is a need for containers that retain less residual contents (e.g., food) after the container's contents have been emptied. Advantages of such containers include reduced waste, ease of recycling, ease of use, reduced environmental impact, increased value for money, and / or aesthetic appearance.

[0004] US Patent No. 5,399,663 discloses a food container comprising a lubricating surface coating. The container may comprise a textured surface impregnated with a liquid coating that wets the textured surface and provides a lubricating surface. This may aid in the removal of the contents from the container. However, the impregnating liquid needs to be immiscible with the contents of the container and therefore needs to be matched or customized with the contents. For example, an impregnating liquid used for a container for an energy drink may not work well with honey, salad dressing, or other liquids that have different properties (e.g., more hydrophilic, less hydrophilic, more hydrophobic, less hydrophobic, etc.) than an energy drink. Thus, the use of coatings as described in US Patent No. 5,399,663 may suffer from problems due to lack of economies of scale in terms of container manufacturers wanting to make different containers for different contents. Recycling of such coated containers may also cause further problems, considering that containers for different types of liquids may contain different impregnating liquid coatings and therefore may not be recycled together. Furthermore, the impregnating liquid coating may be toxic and / or difficult to remove from the materials (e.g., thermoplastic materials) that make up the bulk of the container. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Pat. No. 9,371,173 Summary of the Invention

[0006] A discovery has been made that provides a solution to at least some of the problems discussed above. In one aspect, the solution involves the use of a high density polyethylene (HDPE) polymer in combination with an injection stretch blow molding (ISBM) process to produce a container having surface properties that allow for efficient removal of contents (e.g., food) from the container. Without wishing to be bound by theory, it is believed that the ISBM process, in combination with an HDPE polymer composition, can provide better surface properties for the container across surface roughness, coefficient of friction, water contact angle, and / or surface uniformity, compared to the typically used extrusion blow molding (EBM) process, thereby making it easier to remove contents from the container. In one aspect, the HDPE polymer composition used to make the ISBM container can have (1) a polydispersity (Mw / Mn) of 9 or greater as measured by GPC, (2) an MI2 of 1 g / 10 min or greater as measured by ASTM D-1238, 190° C. / 2.16 kg, (3) a shear response (HLMI / MI2) of 40 or greater as measured by ASTM D-1238, and (4) an environmental stress crack resistance (ESCR) of >150 hours at 100% Igepal as measured by ASTM D-1693, B. An advantage of the container of the present invention is that it can be recycled more easily, for example, by using less water or other liquids to remove the contents of the container during the recycling process. Another advantage is that the easier removal of the contents can reduce waste of the contents of the container, since the contents can actually be used before the container is "thrown away" because it is "empty". Yet another advantage of the container of the present invention is that the container can be mass-produced, since there is a reduced or no need to match the container with the contents it will contain. That is, the containers of the present invention can avoid or reduce customization issues found in currently available containers that are customized for a particular content (e.g., food content).Furthermore, because no coating is used, the containers of the present invention can be recycled together, whereas some currently available containers that have different coatings are recycled separately due to the different types of coatings used.

[0007] One aspect of the invention relates to an injection stretch blow molded (ISBM) container. The ISBM container can include a surface having a static coefficient of friction (COF) of 0.15-0.21 and a dynamic COF of 0.06-0.1. The surface can maintain a water contact angle of 76° or greater for up to 3 minutes after wetting the surface with a water drop of 14-16 mm, e.g., about 15 mm. The surface can be an interior surface of the container, e.g., a surface that contacts a material inside the container. Material and contents can be used interchangeably throughout this specification. The container can be made by injection stretch blow molding of a polymer composition comprising HDPE, the HDPE having a polydispersity (Mw / Mn) of 9 or greater as measured by gel permeation chromatography (GPC); a melt index (MI2) of 1 g / 10 min or greater as measured by ASTM D-1238, 190° C. / 2.16 kg; a shear response (HLMI / MI2) of 40 or greater as measured by ASTM D-1238; and an environmental stress crack resistance (ESCR) of >150 hours at 100% Igepal as measured by ASTM D-1693, B. Mw can be the weight average molecular weight of the HDPE as measured by GPC. Mn can be the number average molecular weight of the HDPE as measured by GPC. HLMI can be the high load melt index. In some aspects, the surface of the container having the above surface characteristics does not include a coating or is not coated with a coating. In such aspects, the HDPE polymer composition forms the surface of the container.

[0008] In some aspects, HDPE has a polydispersity of 9 to 12 as measured by GPC; an MI2 of 1 g / 10 min to 8 g / 10 min as measured by ASTM D-1238, 190°C / 2.16 kg; an ESCR of 180 to 300 hours in Igepal as measured by ASTM D-1693, B; In some aspects, the HDPE resin can have a density of 0.94 g / cc to 0.97 g / cc as measured by ASTM D792, a zero shear viscosity of 15,000 Pa·sec to 250,000 Pa·sec, a peak molecular weight of 20,000 g / mol or greater as measured by GPC, or any combination thereof. In some aspects, the HDPE can have a dispersity of 9 to 12 as measured by GPC; an MI2 of 1 g / 10 min to 8 g / 10 min or 2 / 10 min as measured by ASTM D-1238, 190°C / 2.16 kg; an ESCR of 100% in Igepal 180 to 300 hours as measured by ASTM D-1693, B; a density of 0.94 g / cc to 0.97 g / cc as measured by ASTM D792; a zero shear viscosity of 15,000 Pa·sec to 250,000 Pa·sec; and a peak molecular weight of 20,000 g / mol or greater as measured by GPC. In some particular aspects, the HDPE resin can have an MI2 of 2 g / 10 min as measured by ASTM D-1238, 190°C / 2.16 kg; a tensile strength of 4,600 @ 100% as measured by ASTM D-638, Type IV specimen, 2 in / min. Yield point;>600% elongation at break measured per ASTM D-638, Type IV specimen, 2 in / min; Flexural modulus of 210 kpsi measured per ASTM D-790; ASTM ESCR 100% lgepal >200 hours as measured by D-1693, B; and 0.958 g / cm as measured by ASTM D-792 3 The density of the powder may be 0.01 to 0.01.

[0009] For example, the polymer composition used to make the container of the present invention by ISBM can include at least 99% by weight, or 99% to 99.9% by weight, or 99% to 100% by weight HDPE and optionally one or more additives. The one or more additives can be selected from the group including acid scavengers, antioxidants, UV absorbers, nucleating agents, colorants, lubricants, processing aids, plasticizers, flow control agents, and any combination thereof. In some aspects, the one or more additives can include acid scavengers, nucleating agents, colorants, and / or lubricants. The nucleating agents can include carboxylate salts, such as dicarboxylate salts and / or fatty acid salts, sorbitol derivatives, nonitol derivatives, or any combination thereof. In some aspects, the nucleating agent can be disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; calcium salt of 1,2-cyclohexanedicarboxylic acid; zinc stearate; calcium stearate; 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol; talc; sodium benzoate; or any combination thereof. In some aspects, the polymer composition can optionally include 0.01% to 1% by weight of the nucleating agent. The colorant can include titanium dioxide; carbon black; organic dyes such as polycyclic mono-azo metal complexes and / or polycyclic di-azo metal complexes; or any combination thereof. In some aspects, the polymer composition can optionally include 0.01% to 1% by weight of the colorant. The lubricant can include oleamide, erucamide, behenamide, silica modified high molecular weight siloxane polymer dispersed in polyethylene, or any combination thereof. In some aspects, the polymer composition can optionally include 0.01 wt% to 1 wt% of a lubricant. In some aspects, the acid scavenger can include calcium stearate, zinc stearate, hydrotalcite, zinc oxide, or any combination thereof. In some aspects, the acid scavenger can include zinc stearate, hydrotalcite, zinc oxide, or any combination thereof.In some aspects, the polymer composition can optionally include from 200 to 3000 ppm, alternatively from 200 to 2000 ppm, by weight, of an acid scavenger.

[0010] The container of the present invention can be of any suitable shape and size. In some aspects, the cross-section, for example, the cross-section of the lumen of the container along a plane perpendicular to the longitudinal axis of the container, can be circular, oval, elliptical, triangular, square, rectangular, pentagonal, hexagonal, heptagonal, octagonal, nonagonal, decagonal, rounded triangle, rounded square, rounded rectangle, rounded pentagonal, rounded hexagonal, rounded heptagonal, rounded octagonal, rounded nonagonal, or rounded decagonal. In some particular aspects, the cross-section can be hexagonal or rounded hexagonal. Containers having other shapes and / or cross-sectional shapes can be easily made. The cross-section of the lumen along a plane perpendicular to the longitudinal axis of the container can vary in shape and size along the length of the longitudinal axis. The walls of the container may have a thickness of 0.05 to 2 mm or 0.1 to 1 mm. The container may have walls with a uniform or non-uniform thickness.

[0011] One aspect relates to a process for making an ISBM container. The ISBM container can be made by injection stretch blow molding of a polymeric composition. The injection stretch blow molding process can include injection molding the polymeric composition to form a preform and stretch blowing the preform to form the ISBM container. In some aspects, the polymeric composition can be melted at a melt temperature of 300-600°F, or 350-550°F, or 450-500°F, and / or the molten polymeric composition can be melted at a melt temperature of 300-600°F, or 350-550°F, or 450-500°F. The preform can be injected into a preform mold at an injection pressure of 400-1000 psi to form a preform. Injection molding of the polymer composition can be performed in an extruder. The melt temperature can depend on the polymer composition, and the melt temperature can be high enough so that the molten polymer composition flows freely through the extruder barrel, but low enough that relatively little degradation of the molten polymer composition is observed. In some aspects, the preform can have a tubular shape. The preform can include a neck of the ISBM container to be formed, including a thread, known as a finish. In some aspects, the preform can be tailored to form a preform with a desired temperature profile, and the preform with the desired temperature profile can be stretch-blown to form an ISBM container. In some aspects, the preform, for example, the preform with the desired temperature profile, can be stretch-blown at a stretch speed of 25-150 cm / s and / or a stretch pressure of 150-500 psi to form an ISBM container. Without intending to be limited by theory, it is believed that the stretch rate affects the material distribution in the final part, and the pressure affects the detail and fullness of the part. If the pressure is too low, the part produced may not have all the desired features.

[0012] The ISBM process may be a one-stage ISBM process or a two-stage ISBM process. In a one-stage ISBM process, the steps of forming the preform, conditioning the preform, and stretch-blowing the preform are typically performed on a single machine. In comparison, a two-stage ISBM process, in which the steps of forming the preform are typically performed on a separate machine from the steps of conditioning the preform and / or stretch-blowing the preform. In some aspects, the surface of the produced container having the aforementioned surface characteristics does not include or is not covered with a coating. In such aspects, the HDPE polymer composition forms the surface of the container.

[0013] Other aspects of the invention are discussed throughout this application. Any aspect discussed with respect to one aspect of the invention also applies to other aspects of the invention, and vice versa. Each aspect described herein is understood to be an aspect of the invention that is applicable to other aspects of the invention. It is contemplated that any aspect or aspect discussed herein can be combined with other aspects or aspects discussed herein and / or implemented with respect to any method or composition of the invention, and vice versa. Furthermore, the compositions and systems of the invention can be used to achieve the methods of the invention.

[0014] The following contains definitions of various terms and phrases used throughout this specification.

[0015] The term "about" or "approximately" is defined as close to what would be understood by a person of ordinary skill in the art. In one non-limiting aspect, the term is defined as within 10%, or within 5%, or within 1%, and / or within 0.5%.

[0016] The terms "wt. %, "vol. %, "or "mol %" refer to the weight percentage, volume percentage, or mole percentage of a component based on the total weight including the component, based on the total volume of the material, or based on the total moles, respectively. In a non-limiting example, 10 grams of a component in 100 grams of a material is 10% by weight of the component.

[0017] The term "substantially" and variations thereof are defined to include within 10%, within 5%, within 1%, or within 0.5%.

[0018] The terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms, as used in the claims and / or specification, include any measurable reduction or complete inhibition to achieve a desired result.

[0019] The term "effective," as that term is used in the specification and / or claims, means sufficient to accomplish a desired, expected, or intended result.

[0020] When used in conjunction with the terms "comprising," "including," "containing," or "having" in a claim or specification, the use of the words "a" or "an" may mean "one," but is also consistent with "one or more," "at least one," and "one or more than one."

[0021] The phrase "and / or" can include "and" or "or." By way of example, A, B, and / or C can include A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B and C.

[0022] The words "comprising" (and any form of comprising, e.g., "comprise" and "comprises"), "having" (and any form of "having", e.g., "have" and "has"), "including" (and any form of including, e.g., "includes" and "include"), or "containing" (and any form of containing, e.g., "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0023] The processes and systems of the present invention can "comprise," "consist essentially of," or "consist of" certain ingredients, components, compositions, steps, etc. disclosed throughout the specification. With respect to the transitional phrase "consist essentially of," in one non-limiting aspect, basic and novel features of the containers and container manufacturing processes of the present invention can include an ISBM HDPE container having a surface with a static coefficient of friction (COF) of 0.15 to 0.21 and a dynamic COF of 0.06 to 0.1.

[0024] Other objects, features and advantages of the present invention will become apparent from the following drawings, detailed description and examples. However, it should be understood that the drawings, detailed description and examples, while showing certain aspects of the present invention, are given for illustration only and are not intended to be limiting. Furthermore, it is contemplated that changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description. In further aspects, features of a particular embodiment may be combined with features of other embodiments. For example, features of one embodiment may be combined with any feature of the other embodiments. In further aspects, further features may be added to the particular embodiments described herein.

[0025] Advantages of the present invention may become apparent to those skilled in the art having the benefit of the following detailed description and by reference to the accompanying drawings. [Brief description of the drawings]

[0026] [Figure 1] 1 is a diagram of an ISBM HDPE container according to an embodiment of the present invention. [Diagram 2] A visual comparison of an ISBM HDPE container of the present invention with an HDPE extrusion blow molded (EBM) container after the water was emptied from each container. [Diagram 3] A comparison of water contact angles over time for an ISBM HDPE container of the present invention and an EBM HDPE container after wetting the surfaces with a water droplet approximately 15 mm in diameter. [Figure 4] Optical microscope images of A) EBM HDPE and B) ISBM HDPE container surfaces. [Diagram 5] Scanning electron microscope (SEM) images of A) EBM HDPE and B) ISBM HDPE container surfaces. [Figure 6] Static and dynamic COF of ISBM HDPE and EBM HDPE container surfaces.

[0027] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings. The drawings may not be to scale. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] A discovery has been made that provides a solution to at least some of the above-mentioned problems associated with removing contents from a container. In one aspect, the solution includes providing an ISBM container that includes a polymer composition that includes HDPE. As illustrated in a non-limiting manner in the Examples, ISBM containers made from HDPE having a polydispersity (Mw / Mn) of 9 or greater as measured by GPC; a MI2 of 1 g / 10 min or greater as measured by ASTM D-1238, 190° C. / 2.16 kg; a shear response (HLMI / MI2) of 40 or greater as measured by ASTM D-1238; and an Environmental Stress Crack Resistance (ESCR) of >150 hours at 100% Igepal as measured by ASTM D-1693, B, can have a surface with relatively low friction, such as a static COF of 0.15-0.21 and a dynamic COF of 0.06-0.1.

[0029] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

[0030] A. Injection stretch blow molding (ISBM) containers The ISBM HDPE container of the present invention can be made by injection stretch blow molding of a polymer composition comprising HDPE. The container can have any suitable shape and / or size. In some aspects, the container can have a size between 0.1 L and 10 L, or at least any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 L, or a size equal to any one of these, or between any two of these. The walls of the container can have a thickness of 0.05 mm to 2 mm, or 0.1 to 1 mm, or a thickness of at least any one of 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2, or a thickness equal to any one of these, or a thickness between any two of these. The walls of the container can independently have a uniform and / or non-uniform thickness.

[0031] In some aspects, a cross-section, e.g., a cross-section of a lumen or bore of a container along a plane perpendicular to the longitudinal axis of the container, can be circular, oval, elliptical, star-shaped, triangular, square, rectangular, pentagonal, hexagonal, heptagonal, octagonal, nonagonal, decagonal, rounded star, rounded triangle, rounded square, rounded rectangle, rounded pentagon, rounded hexagon, rounded heptagon, rounded octagon, rounded nonagon, rounded decagon, or irregularly shaped. The container can have a uniform or non-uniform shape. Referring to FIG. 1, an ISBM container 100 according to one embodiment of the present invention is shown. The container can have a longitudinal axis 101. A surface 102 can be a plane perpendicular to the longitudinal axis 101. 103 denotes a cross-section of the lumen or bore 104 of the container 100 along the plane 102. The cross-sections of the lumen along the various planes perpendicular to the longitudinal axis 101 can have similar or different shapes and / or sizes. In some particular aspects, the cross-section can be hexagonal or rounded hexagonal. As used herein, rounded polygonal is also used. A shape, e.g., a rounded hexagon, can refer to a hexagon with rounded corners / edges.

[0032] The container can have an inner surface, e.g., at least a portion of the inner surface or the entire inner surface, with a static coefficient of friction (COF) of 0.15 to 0.21 and a dynamic COF of 0.06 to 0.1. The outer surface opposite the inner surface can have the same or a different COF. The coefficient of friction can be measured with a normal force of 16.71 N applied to the surface against steel. The COF between the inner surface and the steel plate can be measured by attaching a container wall of size 2.5" x 1" to a 2.5" x 2.5" sled. The sled can be loaded such that the normal force applied to the container wall is 16.71 N. The sled can be pulled at a rate of 6 inches per minute. The static COF can be calculated from the force required at the start of the movement and the dynamic COF can be calculated from the average force required to pull a distance of 2 inches to 6 inches. The inner surface may maintain a water contact angle of 76° or greater, or 76°-82°, for up to 3 minutes after wetting the surface with a water drop having a diameter of 14-16 mm or about 15 mm. The outer surface opposite the inner surface may have the same or different water contact angle value or property. In some aspects, the inner surface and / or the outer surface are not covered with a coating. In such aspects, the HDPE polymer composition forms a surface of the container.

[0033] The ISBM HDPE containers of the present invention may be used or can be used to contain food and / or consumer products. The food and / or consumer products may include liquid or semi-solid products. Semi-solid products typically have a higher viscosity than liquid products. Non-limiting examples of food and / or consumer products include ketchup, mustard, mayonnaise, syrup, honey, jelly, peanut butter, butter, chocolate syrup, shortening, butter, margarine, Oreo, grease, dip, yogurt, sour cream, ice cream, sticky foods (e.g., candy, chocolate syrup, mash, yeast mash, beer mash, taffy), food oil, fish oil, marshmallow, dough, batter, baked goods, chewing gum, bubble gum, butter, cheese, cream, cream cheese, mustard, yogurt, sour cream, curry, sauce, ayvar, curry wurst sauce, etc. sauce), salsa lisano, chutney, pebre, fish sauce, tzatziki, sriracha sauce, vegemite, chimichurri, HP sauce / brown sauce, harissa, gochujang, hoisin sauce, kimchi, cholula hot sauce, tartar sauce, tahini, hummus, shichimi pepper, ketchup, pasta sauce, alfredo sauce, spaghetti sauce, icing, dessert toppings, whipped cream, food additives (e.g., ethyl oleate), fatty acids, proteins, vegetable oils (e.g., olive oil, light olive oil, corn oil, soybean oil, rapeseed oil, linseed oil, grapeseed oil, flaxseed oil, canola oil, peanut oil, safflower oil, sunflower oil), disinfectants, cosmetics, shampoos, lotions, creams, hair gels, toothpastes, and / or liquid soaps.

[0034] B. HDPE Polymer Composition The polymer composition or resin can comprise at least 99% by weight, or between 99% by weight and 99.9% by weight, or between 99% by weight and 100% by weight, or at least any one of 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9 and 100%, or between any two of them, HDPE, and optionally one or more additives having a total additive content between 0 and 1% by weight, or at least any one of 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1% by weight, or between any two of them.

[0035] HDPE The HDPE may have a weight average molecular weight (Mw) of 100,000 to 250,000 g / mol as measured by GPC. The HDPE may have a polydispersity (Mw / Mn) of 9 or greater, or 9 to 12 as measured by GPC. The HDPE may have a peak molecular weight of 20,000 g / mol or greater, or 20,000 to 50,000 g / mol as measured by GPC. The HDPE may have an MI2 of 1 g / 10 min or greater, or 1 g / 10 min to 8 g / 10 min, or at least any one of 1, 2, 3, 4, 5, 6, 7, and 8 g / 10 min, or between any two of them, as measured by ASTM D-1238; 190°C / 2.16 kg. The HDPE may have an Environmental Stress Resistance Rating (ESCR) of greater than 150 hours, or greater than 160 hours, or greater than 170 hours, or greater than 180 hours, or between 180 hours and 300 hours on 100% Igepal as measured by ASTM D-1693. The HDPE may have a density of 0.94 g / cc to 0.97 g / cc, or a density of at least one of, or equal to, any one of, 0.94, 0.945, 0.95, 0.955, 0.96, 0.965, and 0.97 g / cc as measured by ASTM D792, or a density between any two of, 0.94, 0.945, 0.95, 0.955, 0.96, 0.965, and 0.97 g / cc. The HDPE can have a zero shear viscosity of 15000 Pa·sec to 250000 Pa·sec, or at least any one of 15000, 25000, 50000, 75000, 100000, 125000, 150000, 175000, 200000, 225000, and 250000 Pa·sec, or a zero shear viscosity equal to or between any two of any one of them. The HDPE can be a metallocene or non-metallocene HDPE. The HDPE can be a unimodal or bimodal HDPE. In certain aspects, the HDPE can be a non-metallocene bimodal HDPE.

[0036] The HDPE used can have at least one of the properties described herein, or any combination thereof, or all of them.

[0037] In some aspects, a combination of two or more HDPEs, e.g., having different properties, can be used. Non-limiting examples of commercially available HDPEs include 9260, SB1359NA available from TOTAL.

[0038] ii. Additives The polymer composition may optionally include one or more additives, which may be selected from the group including acid scavengers, antioxidants, UV absorbers, nucleating agents, colorants, lubricants, processing aids, plasticizers, flow control agents, and any combination thereof.

[0039] The nucleating agent can include a carboxylate salt, such as a dicarboxylate salt and / or a fatty acid salt, a sorbitol derivative, a nonitol derivative, or any combination thereof. In some aspects, the nucleating agent can be a hexahydrophthalic acid (HHPA) salt, such as a calcium, strontium, lithium, or monobasic aluminum salt of HHPA; a bicyclo[2.2.1]heptane-2,3-dicarboxylate; a 1,2-cyclohexanedicarboxylate salt, such as a calcium salt of 1,2-cyclohexanedicarboxylate; a lithium, sodium, calcium, barium, magnesium, aluminum, or zinc salt of a fatty acid, such as zinc stearate or calcium stearate; 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol; talc; sodium benzoate; or any combination thereof. Without wishing to be bound by theory, it is believed that the addition of a nucleating agent can provide a composition with a relatively high degree of crystallinity and a uniform crystal structure. In some aspects, the polymer composition optionally comprises 0.01 wt % to 1 wt %, or at least any one of 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1 wt %, or any of them. The nucleating agent may be equal to or between any two of the above.

[0040] The colorant can be an organic pigment, an inorganic pigment, carbon black, a white pigment, and / or an aluminum pigment. The organic pigment can be an organic dye, such as a polycyclic mono-azo metal complex and / or a polycyclic di-azo metal complex. The inorganic pigment can be a metal salt or a metal oxide, such as titanium dioxide. In some aspects, the polymer composition can optionally include 0.01% to 1% by weight of a colorant, or at least any one of, or equal to, or between any two of, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1% by weight.

[0041] The lubricant can include oleamide, erucamide, behenamide, silica modified high molecular weight siloxane polymer dispersed in polyethylene available from DOW CORNING under the tradename MB50-802, or any combination thereof. In some aspects, the polymer composition can optionally include 0.01% to 1% by weight of the lubricant, or at least any one of 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1% by weight, or equal to or between any two of these.

[0042] The acid scavenger can include calcium stearate, zinc stearate, hydrotalcite, or zinc oxide, or any combination thereof. In some aspects, the acid scavenger can include zinc stearate, hydrotalcite, zinc oxide, or any combination thereof. In some aspects, the polymer composition can include 200-3000 ppm, or 200-2000 ppm, or at least any one of 200, 400, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, and 3000 ppm, or equal to or between any two of these.

[0043] C. Preparation method of ISBM HDPE container The ISBM HDPE container of the present invention can be prepared by injection stretch blow molding of the HDPE polymer composition. The injection stretch blow molding process can include injection molding the HDPE polymer composition to form a preform and stretch blowing the preform to form the ISBM container. In some aspects, the injection molding process can include mixing, e.g., dry blending, the components of the polymer composition, e.g., HDPE and optional one or more additives, melting the polymer composition, and injecting the molten polymer composition into a preform mold. The injection molding process can be carried out using an extruder. The extruder used can be any suitable extruder known in the art. The temperature of the molten HDPE polymer composition can be high enough so that the molten HDPE polymer composition flows freely through the extruder barrel, but low enough that relatively little degradation of the polymer composition is observed. In some aspects, the HDPE polymer composition can be melted at a melt temperature of 300-600°F, or 350-550°F, or 450-500°F, or at least any one of 300, 350, 400, 450, 500, 550, and 600°F, or equal to or between any two of them. The injection pressure of the injection molding process can be 400-1000 psi, or at least any one of 400, 500, 600, 700, 800, 900, and 1000 psi, or equal to or between any two of them. The preform mold can be a multi-cavity mold, e.g., multiple preforms can be formed together. The preforms can have a wall thickness of 1 mm to 8 mm, a length of 8 cm to 15 cm, and / or a cross-sectional diameter or width of 30 mm to 40 mm. The preform is then molded into the ISBM HDPE container, including the threads, known as the finish. In some aspects, the preform formed by injection molding can be conditioned to form a preform having a desired temperature profile, and the preform having the desired temperature profile can be stretch blown to form the ISBM HDPE container. In some aspects, the conditioning process can include heating the preform with a suitable device, such as a reflective radiant heat oven, air knife, or the like, and optionally dispersing heat through the preform.

[0044] The stretch blow process can include blowing air into the preform. In some aspects, the preform, e.g., a preform having a desired temperature profile, can be stretch blown with pressurized air at a stretch speed of 25-150 cm / sec, or at least any one of 25, 50, 75, 100, 125, and 150 cm / sec, or equal to or between any two of these, and / or at a stretch pressure of 150-500 psi, or at least any one of 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, and 500 psi, or equal to or between any two of these. In certain aspects, prior to stretch blowing with pressurized air, a preform, for example a preform having a desired temperature profile, can be optionally axially stretched by a central rod to form an axially stretched preform, which can be stretch blown with pressurized air to form an ISBM container.

[0045] The ISBM process may be a one-stage ISBM process or a two-stage ISBM process. In a one-stage ISBM process, typically the steps of forming the preform, conditioning the preform, and stretch-blowing the preform can be performed by a single machine. In comparison, in a two-stage ISBM process, typically the steps of forming the preform are performed by a different machine than the steps of conditioning the preform and / or stretch-blowing the preform. EXAMPLES

[0046] The present invention will be described in more detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the present invention in any way. Those skilled in the art will easily recognize various non-critical parameters that can be changed or modified to obtain essentially the same results.

[0047] Example 1 Injection stretch blow molded (ISBM) and extrusion blow molded (EBM) containers

[0048] Injection stretch blow molded (ISBM) containers with a hexagonal cross section similar to a typical Gatorade type bottle, size 0.5 liters, were produced by injection stretch blow molding of HDPE resin SB1359NA (Table 1) available from TOTAL. In a comparative experiment, square extrusion blow molded (EBM) bottles were prepared by extrusion blow molding of HDPE resin 5502 (Table 1) available from TOTAL. The ISBM conditions used are provided in Table 2. EBM bottles were produced on a UNILOY 250R1 blow molding machine. Figure 2 shows the geometry of the produced bottles, where bottles 1-5 in the front row are EBM bottles and bottles 1-5 in the back row are ISBM bottles. [Table 1] [Table 2]

[0049] The bottles were tested for water retention. Five bottles were taken for each set, ISBM and EBM bottles. Clean, dry bottles were labeled and individually weighed. The bottles were filled with water and allowed to sit for 5 minutes. The bottles were then emptied. Care was taken not to splash the emptying water onto the exterior of the bottle. The bottles were gently shaken once and then immediately weighed. The initial weight, final weight, and weight of residual water remaining after emptying the water in the bottle are shown in Table 3. The data shown in Table 3 indicate that the EBM bottles retain approximately twice as much residual water after emptying compared to the ISBM bottles (0.42 g for EBM vs. 0.20 g for ISBM). [Table 3]

[0050] To compensate for the residual water phenomenon, the internal bottle surfaces were investigated in detail. The water contact angle of the inner surface of the bottle was measured using an optical microscope and a precision dropper. The inner surface of the bottle was wetted with a water drop of approximately 15 mm in diameter, and the water contact angle was monitored for 4 minutes at 1 min increments. For each bottle type, the experiment was repeated 5 times. Figure 3 shows the water contact angle of the bottle surface over a 4 minute period after initial wetting. As shown in Figure 3, both surfaces show a gradual decrease in contact angle as the water drop spreads. The ISBM surface exhibits a larger contact angle (approximately 5-6° larger than the EBM), indicating a more hydrophobic surface. Since the ISBM surface is more hydrophobic, it is reasonable to expect an easier flow of water over the surface during emptying.

[0051] The bottle inner surfaces were also studied using optical and scanning electron microscopy (SEM). Figures 4A and 4B show optical microscopy images of the inner surfaces of the EBM and ISBM bottles, respectively. As can be seen in FIG. 4, the EBM surface exhibits a more disordered surface, while the ISBM surface is more oriented and uniform. The phenomenon seen in optical spectroscopy can be observed in more detail in SEM images of the surfaces. FIGS. 5A and 5B show SEM images of the inner surface of an EBM bottle and an ISBM bottle, respectively. As can be seen in FIG. 5, the EBM surface appears to contain random aggregates of material, while the ISBM surface appears to contain highly oriented polymer chains.

[0052] The static and dynamic coefficients of friction (COF) of the bottle surface against steel were measured. A bottle wall of size 2.5" x 1" was attached to a 2.5" x 2.5" sled and pulled across a stationary steel plate to measure the COF between the inner surface of the bottle and the steel plate. The sled was loaded such that the normal force applied to the bottle surface was a total of 16.71 N. The sled was pulled at a rate of 6 in / min. The force was then measured at the start of the travel (used to calculate the static COF) and averaged over a pull distance of 2" to 6" (used to calculate the dynamic COF). This process was repeated three times with good repeatability. The static and dynamic COFs obtained for the ISBM and EBM surfaces are shown in Figure 6. As can be seen from Figure 6, the inner surface of the ISBM bottle shows significantly lower static and dynamic COF compared to the inner surface of the EBM bottle.

[0053] Although the aspects of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the aspects as defined by the appended claims. Moreover, the scope of the present application is not limited to the particular aspects of the processes, machines, manufacture, compositions of matter, means, methods, and steps described herein. As one skilled in the art will readily appreciate from the above disclosure, currently existing or later developed processes, machines, manufacture, compositions of matter, means, methods, or steps that perform substantially the same function or achieve substantially the same result as the corresponding aspects described herein can be used. It is therefore intended that the appended claims include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

1. 1. An injection stretch blow molded (ISBM) container comprising: A static coefficient of friction (COF) of 0.15 to 0.21; and Dynamic COF of 0.06-0.1; and a surface having A dispersity (Mw / Mn) of 9 or more as measured by GPC; ASTM D-1238; MI2 of 1 g / 10 min or greater measured at 190° C. / 2.16 kg; and Environmental Stress Crack Resistance (ESCR) >150 hours at 100% Igepal as measured by ASTM D-1693, B and a polymer composition comprising high density polyethylene (HDPE) having An injection stretch blow molded (ISBM) container, wherein the surface has a water contact angle of 76° or greater for up to 3 minutes after wetting the surface with a water drop of 14-16 millimeters in diameter.

2. 2. The ISBM container of claim 1, wherein the HDPE resin has a dispersity of 9-12 as measured by GPC; an MI2 of 1-8 g / 10 min as measured by ASTM D-1238; 190° C. / 2.16 kg; and an ESCR of 180-300 hours at 100% Igepal as measured by ASTM D-1693, B.

3. HDPE resin: A density of 0.94 g / cc to 0.97 g / cc as measured by ASTM D792; A zero shear viscosity of 15,000 Pa·sec to 250,000 Pa·sec; and Peak molecular weight of 20,000 g / mol or more as measured by GPC 2. The ISBM container of claim 1, comprising:

4. HDPE resin: ASTM D-1238; MI2 of 2.0 g / 10 min measured at 190°C / 2.16 kg; ASTM D-638, Type IV specimen, tensile strength @ yield point of 4,600 psi measured at 2 in / min; ASTM D-638, Type IV specimen, elongation at break >600% measured at 2 in / min; Flexural modulus of 210 kpsi as measured by ASTM D-790; Environmental Stress Crack Resistance (ESCR) 100% lgepal >200 hours as measured by ASTM D-1693, B; Vickers at 260° F.; and 0.959 g / cm as measured by ASTM D-792 3 Density of 2. The ISBM container of claim 1, comprising:

5. 2. The ISBM container of claim 1, wherein a cross-section of the container lumen along a transverse plane of the container is circular, oval, elliptical, square, rectangular, pentagonal, hexagonal, heptagonal, octagonal, nonagonal, decagonal, rounded square, rounded rectangle, rounded pentagon, rounded hexagon, rounded heptagon, rounded octagon, rounded nonagon, or rounded decagon.

6. 6. The ISBM container of claim 5, wherein the cross section is a hexagon or a rounded hexagon.

7. The ISBM container of claim 1 , wherein the polymer composition comprises an additive.

8. 8. The ISBM container of claim 7, wherein the additive is an acid scavenger, an antioxidant, a UV absorber, a nucleating agent, a colorant, a lubricant, a processing aid, a plasticizer, a flow control agent, or any combination thereof.

9. 9. The ISBM container of claim 8, wherein the nucleating agent comprises a carboxylate salt, a dicarboxylate salt, a fatty acid salt, a sorbitol derivative, a nonitol derivative, or any combination thereof.

10. 9. The ISBM container of claim 8, wherein the nucleating agent comprises disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; a calcium salt of 1,2-cyclohexanedicarboxylic acid; zinc stearate, calcium stearate, 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol, or any combination thereof.

11. 9. The ISBM container of claim 8, wherein the colorant comprises titanium dioxide, carbon black, a polycyclic mono-azo metal complex, a polycyclic di-azo metal complex, or any combination thereof.

12. 9. The ISBM container of claim 8, wherein the lubricant comprises oleamide, erucamide, behenamide, a silica modified high molecular weight siloxane polymer dispersed in polyethylene, or any combination thereof, and the acid scavenger comprises calcium stearate, zinc stearate, hydrotalchite, zinc oxide, or any combination thereof.

13. The housing includes an outer surface and an opposing inner surface, the inner surface comprising: A static coefficient of friction (COF) of 0.15 to 0.21; and Dynamic COF of 0.06 to 0.1 2. The ISBM container of claim 1, comprising:

14. 10. The ISBM container of claim 1, wherein a food product, such as a liquid or semi-solid food product, is contained within the container and in contact with at least a portion of the interior surface.

15. A process for manufacturing an ISBM container according to any one of claims 1 to 14, comprising the steps of: injection molding the polymer composition to form a preform; and stretch blowing the preform to form an ISBM container.

16. 16. The process of claim 15, wherein the preform is heat conditioned to form a preform having a desired temperature profile, and the preform having the desired temperature profile is stretch blown to form the ISBM container.

17. 16. The process of claim 15 which is a one-stage or two-stage injection stretch blow molding process.

18. 16. The process of claim 15, wherein the injection molding conditions of the polymer composition include a melt temperature of 350-550° F. and / or an injection pressure of 400-1000 psi.

19. The process of claim 15, wherein the stretch-blowing conditions include a stretch speed of 25 to 150 cm / s and / or a stretch pressure of 150 to 500 psi.

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