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 the benefit of U.S. Provisional Patent Application No. 63 / 181,026, filed Apr. 28, 2021, which is hereby incorporated by reference in its entirety for all purposes.

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

Background Art

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

[0004] Patent Document 1 discloses a food container including a lubricating surface coating. This container may include a textured surface impregnated with a liquid coating that wets the textured surface and provides a lubricating surface. This can help remove the contents from the container. However, the impregnation liquid must be immiscible with the contents of the container and therefore must be adapted or customized to the contents. For example, an impregnation liquid used in a container for energy drinks may not work well with honey, salad dressing, or other liquids that have different properties (e.g., higher hydrophilicity, lower hydrophilicity, higher hydrophobicity, lower hydrophobicity, etc.) than energy drinks. Therefore, the use of coatings as described in Patent Document 1 may suffer from problems due to a lack of economies of scale, in the sense that container manufacturers may want to produce different containers for different contents. Recycling such coated containers may also cause further problems, considering that containers for different types of liquids may contain different impregnation liquid coatings and therefore may not be recycled together. Furthermore, impregnation liquid coatings may be toxic and / or difficult to remove from the bulk material (e.g., thermoplastic material) of the container. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent No. 9,371,173 [Overview of the project]

[0006] Discoveries have been made that offer solutions to at least some of the aforementioned problems. In one aspect, the solution involves the use of high-density polyethylene (HDPE) polymers combined with an injection stretch blow molding (ISBM) process to manufacture containers having surface properties that allow for efficient removal of contents (e.g., food) from the container. While we do not wish to be bound by theory, it is believed that the ISBM process, compared to the typically used extrusion blow molding (EBM) process, can, when combined with HDPE polymer compositions, provide better surface properties of the container across surface roughness, coefficient of friction, water contact angle, and / or surface uniformity, thereby making it easier to remove contents from the container. In one aspect, the HDPE polymer composition used to manufacture the ISBM container can have (1) a dispersion degree of 9 or higher (Mw / Mn) as measured by GPC, (2) an MI2 of 1 g / 10 min or higher as measured by ASTM D-1238 at 190°C / 2.16 kg, (3) a shear response of 40 or higher (HLMI / MI2) 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 by using less water or other liquid to remove the contents of the container during the recycling process. Another advantage is that the easier removal of contents reduces waste of the contents of the container, as the contents can be actually used before the container is "discarded" because it is "empty". Furthermore, another advantage of the container of the present invention is that the container can be mass-produced because the need to match the contents that the container holds with the container is reduced or eliminated. In other words, the container of the present invention can avoid or reduce the customization problems seen in currently available containers that are customized for specific contents (e.g., food contents). Furthermore, because no coating is used, the container of the present invention can be recycled together, whereas some currently available containers with different coatings are recycled separately due to the different types of coatings used.

[0007] One aspect of the present invention relates to an injection-stretched blow-molded (ISBM) container. This ISBM container may include a surface having a static coefficient of friction (COF) of 0.15 to 0.21 and a dynamic COF of 0.06 to 0.1. This surface can maintain a water contact angle of 76° or more for up to 3 minutes after being wetted with a water droplet of 14 to 16 mm, for example, about 15 mm. This surface may be an internal surface of the container, for example, a surface that comes into contact with the material inside the container. The material and contents can be used interchangeably throughout this specification. The container can be manufactured by injection-stretched blow molding of a polymer composition containing HDPE, the HDPE having a dispersion degree of 9 or greater (Mw / Mn) as measured by gel permeation chromatography (GPC); a melt index of 1 g / 10 min or greater as measured by ASTM D-1238, 190°C / 2.16 kg (MI2); a shear response of 40 or greater as measured by ASTM D-1238 (HLMI / MI2); and environmental stress crack resistance (ESCR) of >150 hours at 100% Igepal as measured by ASTM D-1693, B. Mw may be the weight-average molecular weight of the HDPE as measured by GPC. Mn may be the number-average molecular weight of the HDPE as measured by GPC. HLMI may be the high-load melt index. In some aspects, the surface of a container having the above surface properties is either uncoated or uncovered. In such aspects, the HDPE polymer composition forms the surface of the container.

[0008] In some cases, HDPE showed a dispersion degree of 9-12 as measured by GPC; ASTM D-1238, MI2 at 190°C / 2.16kg at 1g / 10 min to 8g / 10 min; ASTM D-1693, ESCR at Igepal for 180-300 hours as measured by B. It may have 100%; or any combination thereof. In some cases, HDPE resin may 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 more as measured by GPC; or any combination thereof. In some aspects, HDPE can have a dispersion degree of 9-12 as measured by GPC; MI2 of 1 g / 10 min to 8 g / 10 min or 2 g / 10 min as measured by ASTM D-1238, 190°C / 2.16 kg; ESCR 100% at 180-300 hours in Igepal as measured by ASTM D-1693, B; density of 0.94 g / cc to 0.97 g / cc as measured by ASTM D792; 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. In some specific aspects, HDPE resin can have an MI2 of 2 g / 10 min as measured by ASTM D-1238, 190°C / 2.16 kg; and a tensile strength of 4,600 as measured by ASTM D-638, type IV test specimen, 2 inches / min. Yield point; >600% at break, measured at 2 inches / min on an ASTM D-638, Type IV specimen; Bending modulus of elasticity; 210 kpsi, measured on an ASTM D-790; ASTM Measured using D-1693, B, with ESCR 100% IVF for >200 hours; and measured using ASTM D-792, 0.958 g / cm³. 3 It can have a density of .

[0009] For example, the polymer composition used to produce the container of the present invention by ISBM may contain at least 99% by weight, or 99% to 99.9% by weight, or 99% to 100% by weight of HDPE and optionally one or more additives. The one or more additives may be selected from the group including acid scavengers, antioxidants, UV absorbers, nucleating agents, colorants, lubricants, processing aids, plasticizers, flow regulators, and any combination thereof. In some aspects, the one or more additives may include acid scavengers, nucleating agents, colorants, and / or lubricants. The nucleating agents may 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 may be disodium bicyclo[2.2.1]heptane-2,3-dicarboxylic acid; 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 may optionally contain 0.01% to 1% by weight of the nucleating agent. The coloring agent may 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 may optionally contain 0.01% to 1% by weight of the coloring agent. The lubricant may include oleoamide, erucamide, behenamide, silica-modified high molecular weight siloxane polymers dispersed in polyethylene; or any combination thereof. In some aspects, the polymer composition may optionally contain 0.01% to 1% by weight of a lubricant. In some aspects, the acid scavenger may include calcium stearate, zinc stearate, hydrotalcite, zinc oxide, or any combination thereof. In some aspects, the acid scavenger may include zinc stearate, hydrotalcite, zinc oxide, or any combination thereof.In some cases, the polymer composition may optionally contain 200-3000 ppm by weight of an acid scavenger, or 200-2000 ppm by weight.

[0010] The container of the present invention may have any suitable shape and size. In some aspects, the cross-section, for example, the cross-section of the container along a plane perpendicular to the longitudinal axis of the container. Lumen (hereinafter sometimes referred to as "lumen") The cross-section may be circular, oval, elliptical, triangular, square, rectangular, pentagonal, hexagonal, heptagonal, octagonal, nonagonal, decagonal, rounded triangle, rounded square, rounded rectangle, rounded pentagon, rounded hexagon, rounded heptagon, rounded octagon, rounded nonagon, or rounded decagon. In some specific aspects, the cross-section may be hexagonal or rounded hexagonal. Containers with other shapes and / or cross-sectional shapes can be easily manufactured. Along the plane perpendicular to the longitudinal axis of the container. lumen The cross-section may 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 of uniform or non-uniform thickness.

[0011] One aspect relates to a process for manufacturing ISBM containers. ISBM containers can be manufactured by injection-stretch blow molding of a polymer composition. The injection-stretch blow molding process may include injection molding of a polymer composition to form a preform and stretch blow molding of the preform to form an ISBM container. In some aspects, the polymer composition may be melted at a melting temperature of 300-600°F, or 350-550°F, or 450-500°F, and / or the molten polymer composition may be... A preform can be formed by injecting a polymer composition into a preform mold at an injection pressure of 400-1000 psi. Injection molding of the polymer composition can be performed in an extruder. The melting temperature can depend on the polymer composition and can be sufficiently high so that the molten polymer composition flows freely within the extruder barrel, but relatively little decomposition of the molten polymer composition is observed. In some cases, the preform can have a tubular shape. The preform can include a neck of the formed ISBM vessel, which includes threads known as a finish. In some cases, the preform can be adjusted to form a preform with a desired temperature profile, and the ISBM vessel can be formed by stretch-blowing the preform with the desired temperature profile. In some cases, the ISBM vessel can be formed by stretch-blowing the preform, for example, a preform with a desired temperature profile, at a stretching speed of 25-150 cm / s and / or a stretching pressure of 150-500 psi. Although not intended to be limited by theory, it is thought that the stretching speed 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 resulting parts may not possess all the desired characteristics.

[0012] The ISBM process can be a one-stage ISBM process or a two-stage ISBM process. In a one-stage ISBM process, the steps of forming the preform, preparing the preform, and stretch-blowing the preform are typically performed in a single machine. In comparison, in a two-stage ISBM, the step of forming the preform is typically performed in a separate machine from the steps of preparing the preform and / or stretch-blowing the preform. In some aspects, the surface of the resulting container having the aforementioned surface properties is either without a coating or not covered by a coating. In such aspects, the HDPE polymer composition forms the surface of the container.

[0013] Other aspects of the present invention are discussed throughout this application. Any aspect discussed in relation to one aspect of the present invention is applicable to other aspects of the present invention, and vice versa. Each aspect described herein is understood to be an aspect of the present invention applicable to other aspects of the present invention. Any aspect or aspect discussed herein can be combined with any other aspect or aspect discussed herein and / or can be carried out in relation to any method or composition of the present invention, and vice versa. Furthermore, the methods of the present invention can be achieved using the compositions and systems of the present invention.

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

[0015] The terms “about” or “approximately” are defined as being close to what is understood by those skilled in the art. In one non-limiting aspect, the term is defined as being within 10%, or within 5%, or within 1%, and / or within 0.5%.

[0016] The terms "weight %", "volume %", and "mol %" refer to the weight percentage, volume percentage, and mole percentage of an ingredient, respectively, based on the total weight of the ingredient, the total volume of the material, and the total moles of the ingredient. In a non-restrictive example, 10 grams of an ingredient in 100 grams of material is 10 weight % of the ingredient.

[0017] The term “substantially” and its variations are defined as including a range of 10%, 5%, 1%, or 0.5%.

[0018] The terms “inhibit,” “reduce,” “prevent,” or “avoid,” or any variation thereof, when used in the claims and / or specification, include any measurable reduction or complete inhibition to achieve a desired result.

[0019] When the term "effective" is used in the specification and / or claims, it means sufficient to achieve a desired, expected, or intended result.

[0020] When used in conjunction with the terms "comprising," "including," "containing," or "having" in the claims or specification, the use of the word "a" or "an" may mean "one," but this 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, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include"), or "containing" (and any form of containing, such as "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 "include", "consist essentially of", or "consist of" the specific ingredients, components, compositions, steps, etc. disclosed throughout the specification. With respect to the transitional phrase "consist essentially of", in one non-limiting aspect, the basic and novel features of the containers and the container manufacturing processes of the present invention can include ISBM HDPE containers having surfaces 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 illustrate specific aspects of the present invention and are provided for illustrative purposes only and are not intended to be limiting. Further, it is contemplated that modifications and variations within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description. In a further aspect, the features of a particular aspect may be combined with the features of other aspects. For example, the features of one aspect may be combined with any of the features of other aspects. In a further aspect, additional features may be added to the particular aspects described herein.

[0025] The advantages of the present invention may become apparent to those skilled in the art by virtue of the following detailed description and by referring to the accompanying drawings.

Brief Description of the Drawings

[0026] [Figure 1] A diagram of an ISBM HDPE container according to an embodiment of the present invention. [Figure 2] Visual comparison of an ISBM HDPE container of the present invention and an HDPE extrusion blow molding (EBM) container after emptying water from each container. [Figure 3] Comparison of the water contact angle over time of an ISBM HDPE container of the present invention and an EBM HDPE container after wetting the surface with water droplets having a diameter of approximately 15 mm. [Figure 4] A) Optical microscope images of the surfaces of EBM HDPE and B) ISBM HDPE containers. [Figure 5] A) Scanning electron microscope (SEM) images of the surface of EBM HDPE and B) ISBM HDPE containers. [Figure 6] Static and dynamic COF (Chemical Oxide Factor) on the surfaces of ISBM HDPE and EBM HDPE containers.

[0027] While various modifications and alternative forms are possible for this invention, specific embodiments are shown in the drawings as examples. The drawings may not be to scale. [Modes for carrying out the invention]

[0028] A discovery has been made that provides a solution to at least some of the aforementioned problems relating to removing contents from a container. In one aspect, this solution involves providing an ISBM container comprising a polymer composition containing HDPE. As illustrated in a non-limiting manner in the examples, an ISBM container made from HDPE having a dispersion degree of 9 or greater as measured by GPC (Mw / Mn); an MI2 of 1 g / 10 min or greater as measured by ASTM D-1238, 190°C / 2.16 kg; a shear response of 40 or greater as measured by ASTM D-1238 (HLMI / MI2); 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 to 0.21 and a dynamic COF of 0.06 to 0.1.

[0029] These aspects of the present invention, as well as other non-limiting aspects, will be discussed in more detail in the following sections.

[0030] A. Injection stretch blow molded (ISBM) container The ISBM HDPE container of the present invention can be manufactured by injection stretch blow molding of a polymer composition containing HDPE. The container may have any suitable shape and / or size. In some aspects, the container may be in sizes from 0.1 L to 10 L, or at least one of the sizes 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 a size between any two of these. The walls of the container may have a thickness of 0.05 mm to 2 mm, or 0.1 to 1 mm, or at least one of the following thicknesses: 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 may independently have uniform and / or non-uniform thicknesses.

[0031] In some aspects, the cross-section, for example, the lumen or bore of a container along a plane perpendicular to the longitudinal axis of the container, may be circular, oval, elliptical, star-shaped, triangular, square, rectangular, pentagonal, hexagonal, heptagonal, octagonal, nonagonal, decagonal, rounded star-shaped, rounded triangle, rounded square, rounded rectangle, rounded pentagon, rounded hexagon, rounded heptagon, rounded octagon, rounded nonagon, rounded decagon, or irregular in shape. The container may have a uniform or non-uniform shape. Referring to Figure 1, an ISBM container 100 according to one aspect of the present invention is shown. The container may have a longitudinal axis 101. The plane 102 may be a plane perpendicular to the longitudinal axis 101. 103 shows a cross-section of the lumen or bore 104 of the container 100 along the surface 102. Cross-sections of lumens along various surfaces perpendicular to the longitudinal axis 101 may have similar or different shapes and / or sizes. In some particular surfaces, the cross-section may be hexagonal or rounded hexagonal. When used herein, rounded polygon A shape, such as a rounded hexagon, can refer to a hexagon that has rounded corners / edges.

[0032] The container may have an inner surface having a static coefficient of friction (COF) of 0.15 to 0.21 and a dynamic COF of 0.06 to 0.1, for example, at least part or all of the inner surface. The outer surface opposite the inner surface may have the same or different COF. The coefficient of friction can be measured with respect to the steel by the normal force of 16.71 N applied to the surface. The COF between the inner surface and the steel plate can be measured by attaching a 2.5-inch x 2.5-inch thread to the wall of the container measuring 2.5 inches x 1 inch. The thread can be loaded such that the normal force applied to the wall of the container is 16.71 N. The thread can be pulled at a speed of 6 inches / minute. The static COF can be calculated from the force required at the start of movement, and the dynamic COF can be calculated from the average force required to pull a distance of 2 to 6 inches. The inner surface can maintain a water contact angle of 76° or greater, or 76° to 82°, for up to 3 minutes after being wetted with a water droplet of 14-16 mm or approximately 15 mm in diameter. The outer surface opposite the inner surface may have the same or different water contact angle values ​​or properties. In some surfaces, the inner and / or outer surfaces are not covered with a coating. In such surfaces, the HDPE polymer composition forms the surface of the container.

[0033] The ISBM HDPE container of the present invention may or may be used to contain food and / or consumer products. 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, toffee), cooking oil, fish oil, marshmallows, dough, coating, baked goods, chewing gum, bubblegum, butter, cheese, cream, cream cheese, mustard, yogurt, sour cream, curry, sauce, ajvar, curry wurst sauce. This includes, but is not limited to, sauces, 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 togarashi, ketchup, pasta sauces, Alfredo sauce, spaghetti sauce, icings, 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, grape seed oil, flaxseed oil, canola oil, peanut oil, safflower oil, sunflower oil), disinfectants, cosmetics, shampoos, lotions, creams, hair gels, toothpaste, and / or liquid soaps.

[0034] B. HDPE polymer composition The polymer composition or resin may contain at least 99% by weight of HDPE, or 99% to 99.9% by weight, or 99% to 100% by weight, or at least one of 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9 and 100%, or equal to any one of them, or between any two of them, and optionally, one or more additives having a total additive content of 0 to 1% by weight, or at least 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 equal to any one of them, or between any two of them.

[0035] i. HDPE HDPE may have a weight-average molecular weight (Mw) of 100,000 to 250,000 g / mol as measured by GPC. HDPE may have a dispersion degree (Mw / Mn) of 9 or greater, or 9 to 12 as measured by GPC. 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. 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 one of 1, 2, 3, 4, 5, 6, 7 and 8 g / 10 min, or equal to any one of them, or between any two of them, as measured by ASTM D-1238; 190°C / 2.16 kg. HDPE may have environmental stress tolerance (ESCR) of more than 150 hours, or more than 160 hours, or more than 170 hours, or more than 180 hours, or more than 180 hours to 300 hours at 100% Igepal as measured by ASTM D-1693. HDPE may have a density of 0.94 g / cc to 0.97 g / cc as measured by ASTM D792, or at least one of the densities of 0.94, 0.945, 0.95, 0.955, 0.96, 0.965 and 0.97 g / cc, or a density equal to any one of them, or a density between any two of them. HDPE can have a zero shear viscosity of 15,000 Pa·sec to 250,000 Pa·sec, or a zero shear viscosity of at least one of 15,000, 25,000, 50,000, 75,000, 100,000, 125,000, 150,000, 175,000, 200,000, 225,000, and 250,000 Pa·sec, or equal to any one of them, or between any two of them. HDPE can be metallocene or non-metallocene HDPE. HDPE can be unimodal or bimodal HDPE. In certain contexts, HDPE can be non-metallocene bimodal HDPE.

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

[0037] In some situations, for example, combinations of two or more HDPEs with different properties can be used. Non-limiting examples of commercially available HDPEs include 9260 and SB1359NA, available from TOTAL.

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

[0039] The nucleating agent may 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 may be hexahydrophthalic acid (HHPA) salts, e.g., calcium, strontium, lithium, or monobasic aluminum salts of HHPA; bicyclo[2.2.1]heptane-2,3-dicarboxylate; 1,2-cyclohexanedicarboxylate salts, e.g., calcium salts of 1,2-cyclohexanedicarboxylate; lithium, sodium, calcium, barium, magnesium, aluminum, or zinc salts of fatty acids, e.g., zinc stearate or calcium stearate; 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol; talc; sodium benzoate; or any combination thereof. While we do not wish to be bound by theory, it is thought that by adding a nucleating agent, compositions with relatively high crystallinity and a uniform crystalline structure can be obtained. In some aspects, the polymer composition may optionally contain 0.01% to 1% by weight, or at least 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 any of these. It may contain a nucleating agent that is equal to one of them, or between any two of them.

[0040] The colorants may be organic pigments, inorganic pigments, carbon black, white pigments, and / or aluminum pigments. Organic pigments may be organic dyes such as polycyclic mono-azo metal complexes and / or polycyclic di-azo metal complexes. Inorganic pigments may be metal salts or metal oxides such as titanium dioxide. In some aspects, the polymer composition may optionally contain a colorant in an amount of 0.01% to 1% by weight, or at least 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 any one of them, or between any two of them.

[0041] The lubricant may include oleoamide, erucamide, behenamide, silica-modified high molecular weight siloxane polymers dispersed in polyethylene, available from Dow Corning under trade name MB50-802, or any combination thereof. In some aspects, the polymer composition may optionally contain 0.01% to 1% by weight of the lubricant, or at least 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 an amount equal to or between any two of these.

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

[0043] C. Method for preparing ISBM HDPE containers The ISBM HDPE container of the present invention can be prepared by injection stretch blow molding of an HDPE polymer composition. The injection stretch blow molding process may include injection molding of the HDPE polymer composition to form a preform, and stretch blow molding of the preform to form an ISBM container. In some aspects, the injection molding process may include mixing, for example, dry blending, the components of the polymer composition, such as HDPE and one or more optional additives, melting the polymer composition, and injecting the molten polymer composition into a preform mold. The injection molding process may be carried out using an extruder. The extruder used may be a suitable extruder known in the art. The temperature of the molten HDPE polymer composition may be sufficiently high so that the molten HDPE polymer composition flows freely within the extruder barrel, but is low enough that relatively little decomposition of the polymer composition is observed. In some aspects, the HDPE polymer composition can be melted at a melting temperature of 300-600°F, or 350-550°F, or 450-500°F, or at least one of 300, 350, 400, 450, 500, 550, and 600°F, or equal to any one of them, or between any two of them. The injection pressure of the injection molding process may be 400-1000 psi, or at least one of 400, 500, 600, 700, 800, 900, and 1000 psi, or equal to any one of them, or between any two of them. The preform mold may be a multi-cavity type, for example, in which case multiple preforms can be formed together. The preform may 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 a form of ISBM HDPE container that includes threads, also known as a finish. This may include a neck. In some aspects, the preform formed by injection molding can be adjusted to form a preform having a desired temperature profile, and the preform having the desired temperature profile can be stretch-blown to form an ISBM HDPE container. In some aspects, the adjustment process may include heating the preform with a suitable device, such as a radiant heat oven or air knife, and optionally dispersing heat through the preform.

[0044] The stretch blowing process may include blowing air into the preform. In some aspects, a preform, for example, a preform having a desired temperature profile, can be stretch blown with pressurized air at a stretching speed of 25 to 150 cm / sec, or at least one of 25, 50, 75, 100, 125, and 150 cm / sec, or equal to or between any two of them, and / or at a stretching pressure of 150 to 500 psi, or at least 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 them. In certain situations, before stretch-blowing with pressurized air, a preform, for example, a preform having a desired temperature profile, can optionally be stretched axially by a central rod to form an axially stretched preform, and the axially stretched preform can be stretch-blowed with pressurized air to form an ISBM container.

[0045] The ISBM process can 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, preparing the preform, and stretch-blowing the preform can be performed by a single machine. In comparison, in a two-stage ISBM process, typically the preform forming step is performed by a separate machine from the preform preparation and / or stretch-blowing steps. [Examples]

[0046] The present invention will be described in more detail by specific embodiments. The following embodiments are provided solely for illustrative purposes and are not intended to limit the invention in any way. Those skilled in the art will readily recognize a variety of non-essential parameters that can be changed or modified to obtain essentially the same results.

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

[0048] An injection-stretched blow-molded (ISBM) container with a hexagonal cross-section and a size of 0.5 liters, similar to a typical Gatorade-type bottle, was manufactured by injection-stretched blow molding of HDPE resin SB1359NA (Table 1), available from TOTAL. In a comparative experiment, a square extrusion-blown (EBM) bottle was prepared by extrusion-blown molding of HDPE resin 5502 (Table 1), also available from TOTAL. The ISBM conditions used are provided in Table 2. The EBM bottles were manufactured using a UNILOY 250R1 blow molding machine. Figure 2 shows the geometric shapes of the manufactured bottles, with bottles 1-5 in the front row being EBM bottles and bottles 1-5 in the back row being ISBM bottles. [Table 1] [Table 2]

[0049] The bottles were tested for water retention. Five bottles were taken from each set, for both ISBM and EBM bottles. Clean, dry bottles were labeled and weighed individually. The bottles were filled with water and allowed to stand for 5 minutes. Then, the bottles were emptied. Care was taken to prevent water from splashing onto the outside of the bottles during emptiness. The bottles were gently shaken once and then immediately weighed. Table 3 shows the initial weight, final weight, and the weight of residual water remaining after the water in the bottles was emptied. The data in Table 3 shows that the EBM bottles retained approximately twice as much residual water after emptiness compared to the ISBM bottles (0.42g for EBM vs. 0.20g for ISBM). [Table 3]

[0050] To compensate for the residual water phenomenon, the internal bottle surface was investigated in detail. The water contact angle of the inner surface of the bottle was measured using an optical microscope and a precision dropping device. The inner surface of the bottle was moistened with a water droplet approximately 15 mm in diameter, and the water contact angle was monitored for 4 minutes in 1-minute increments. The experiment was repeated 5 times for each bottle type. Figure 3 shows the water contact angle of the bottle surface over 4 minutes after initial wetting. As shown in Figure 3, the contact angle of both surfaces gradually decreases as the water droplet spreads. The ISBM surface shows a larger contact angle (approximately 5-6° larger than the EBM surface) and indicates a more hydrophobic surface. Since the ISBM surface is more hydrophobic, it is reasonable to expect easier water flow on the surface during emptying.

[0051] Furthermore, the inner surface of the bottles was studied using optical and scanning electron microscopy (SEM). Figures 4A and 4B show optical microscope images of the inner surface of the EBM bottle and the ISBM bottle, respectively. As can be seen in Figure 4, the EBM surface exhibits a more disordered surface, while the ISBM surface is more oriented and uniform. The phenomena observed by optical spectroscopy can be observed in more detail with surface SEM images. Figures 5A and 5B show SEM images of the inner surfaces of the EBM bottle and the ISBM bottle, respectively. As can be seen in Figure 5, the EBM surface appears to contain random aggregates of the 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 2.5-inch x 1-inch bottle wall was attached to a 2.5-inch x 2.5-inch thread, and the COF between the bottle's inner surface and the steel plate was measured by pulling it across a stationary steel plate. The thread was loaded so that the total normal force applied to the bottle surface was 16.71 N. The thread was pulled at a speed of 6 inches / minute. The force was then measured at the start of the movement (used to calculate the static COF) and averaged over a tensile distance of 2 inches to 6 inches (used to calculate the dynamic COF). This process was repeated three times with good reproducibility. The obtained static and dynamic COFs for 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 COFs compared to the inner surface of the EBM bottle.

[0053] While the aspects of this application and their advantages have been described in detail, it should be understood that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of the aspects defined by the appended claims. Furthermore, the scope of this application is not limited to specific aspects of the processes, machines, manufactures, material compositions, means, methods, and procedures described herein. As will be readily apparent to those skilled in the art from the above disclosure, processes, machines, manufactures, material compositions, means, methods, or procedures that exist today or are later developed, performing substantially the same functions or achieving substantially the same results as the corresponding aspects described herein, can be used. Accordingly, the appended claims are intended to include such processes, machines, manufactures, material compositions, means, methods, or procedures within their scope.

Claims

1. Injection stretch blow molded (ISBM) container: Static friction coefficient (COF) of 0.15 to 0.21; and Dynamic COF of 0.06 to 0.1; A surface having, A variance of 9 or higher (Mw / Mn) measured by GPC; ASTM D-1238; MI2 of 1 g / 10 min or more measured at 190°C / 2.16 kg; and Environmental stress crack resistance (ESCR) of >150 hours in 100% igel, as measured by ASTM D-1693, B. A polymer composition containing high-density polyethylene (HDPE) is included, The aforementioned surface is an injection-stretched blow-molded (ISBM) container having a water contact angle of 76° or more for up to 3 minutes after the surface is wetted with water droplets with a diameter of 14 to 16 mm.

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

3. HDPE resin: Density measured by ASTM D792: 0.94 g / cc to 0.97 g / cc; Zero shear viscosity of 15,000 Pa·sec to 250,000 Pa·sec; and Peak molecular weight of 20,000 g / mol or higher as measured by GPC An ISBM container according to claim 1, having the following features.

4. HDPE resin: ASTM D-1238; MI2 measured at 190°C / 2.16 kg, 2.0 g / 10 min; ASTM D-638, Type IV specimen, tensile strength of 4,600 psi at yield point, measured at 2 inches / min; ASTM D-638, Type IV test specimen, measured at 2 inches / min, >600% elongation at break; The flexural modulus was measured at 210 kpsi using an ASTM D-790; Environmental stress crack resistance (ESCR) of 100% (as measured by ASTM D-1693, B) for >200 hours (Igepal) Vicar softening point of 260°F; and Measured with ASTM D-792, the result was 0.959 g / cm³. 3 density An ISBM container according to claim 1, having the following features.

5. The ISBM container according to claim 1, wherein the cross-section of the inner cavity of the container along the cross-section 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. The ISBM container according to claim 5, wherein the cross-section is hexagonal or rounded hexagonal.

7. The ISBM container according to claim 1, wherein the polymer composition contains an additive.

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

9. The ISBM container according to 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. The ISBM container according to claim 8, wherein the nucleating agent comprises 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, or any combination thereof.

11. The ISBM container according to claim 8, wherein the coloring agent comprises titanium dioxide, carbon black, a polycyclic mono-azo metal complex, a polycyclic diazo metal complex, or any combination thereof.

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

13. Including the outer surface and the opposing inner surface, the inner surface is: Static friction coefficient (COF) of 0.15 to 0.21; and Dynamic COF of 0.06 to 0.1 An ISBM container according to claim 1, having the following features.

14. The ISBM container according to claim 1, wherein food is contained within the container and in contact with at least a portion of its inner surface.

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

16. The process according to claim 15, wherein a preform is heated and adjusted to form a preform having a desired temperature profile, and the preform having the desired temperature profile is stretch-blown to form an ISBM container.

17. The process according to claim 15, which is a one-stage or two-stage injection stretch blow molding process.

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

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

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