Low friction isbm bottle

Abstract

An injection stretch blow molded (ISBM) container is disclosed having a static coefficient of friction (COF) of the surface of 0.15 to 0.21, a dynamic coefficient of friction of 0.06 to 0.1, wherein the surface retains a water contact angle of 76° or greater for up to three minutes after wetting the surface with a water droplet of 14 to 16 mm diameter, and the container is made from a polymer composition comprising a high density polyethylene (HDPE) having a dispersity (Mw / Mn) of 9 or greater as measured by GPC; an MI2 of 1 g / 10 min or greater as measured according to ASTM D-1238 at 190°C / 2.16 kg; and an environmental stress crack resistance (ESCR) of greater than 150 hours as measured according to ASTM D-1693, B at 100% Igepal.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 181,026, filed April 28, 2021, which is incorporated herein by reference in its entirety for all purposes. Background Technology

[0003] A. Technical Field

[0004] This invention generally relates to injection stretch blow molding (ISBM) containers. In some aspects, the invention relates to ISBM containers having the property of allowing efficient removal of food from the container without the use of a surface coating.

[0005] B. Description of related fields

[0006] Containers designed to retain minimal residue (such as food) after emptying. Advantages of such containers include reduced waste, ease of recycling, ease of use, reduced environmental impact, increased cost-effectiveness, and / or aesthetics.

[0007] US 9371173 discloses food containers containing a lubricating surface coating. The container may include a textured surface impregnated with a liquid coating that wets the textured surface and provides a lubricating surface. This facilitates the removal of contents from the container. However, the impregnating liquid needs to be immiscible with the contents of the container, thus requiring matching or customization to the contents. For example, an impregnating liquid used for energy drink containers may not work well with honey, salad dressing, or other liquids with properties different from energy drinks (e.g., more hydrophilic, less hydrophilic, more hydrophobic, less hydrophobic, etc.). Therefore, the use of coatings (such as those described in US 9371173) may encounter problems due to a lack of economies of scale, given that container manufacturers may want to manufacture different containers for different contents. The recycling of such coated containers may also present additional problems, as containers for different types of liquids may contain different impregnating liquid coatings and therefore may not be able to be recycled together. Furthermore, the impregnating liquid coating may be toxic and / or difficult to remove from the material constituting the container body (e.g., thermoplastic materials). Summary of the Invention

[0008] One discovery has provided a solution to at least some of the aforementioned problems. In one aspect, this solution involves producing containers using a combination of high-density polyethylene (HDPE) polymers and an injection stretch blow molding (ISBM) method, the containers possessing surface properties that allow for the efficient removal of contents (e.g., food) from the containers. Without wishing to be bound by theory, it is believed that the ISBM method combined with HDPE polymer compositions can provide superior container surface properties, including surface roughness, coefficient of friction, water contact angle, and / or surface uniformity, compared to the commonly used extrusion blow molding (EBM) method, thereby facilitating the removal of contents from the containers. In one particular aspect, the HDPE polymer composition used to manufacture ISBM containers may have (1) a dispersibility (Mw / Mn) of 9 or higher 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 (HLMI / MI2) of 40 or higher as measured by ASTM D-1238; and (4) an environmental stress cracking resistance (ESCR) greater than 150 hours as measured by ASTM D-1693,B at 100% Igepal. One advantage of the containers of the present invention is that they can be more easily recycled, for example by removing the contents of the container using less water or other liquids during the recycling process. Another advantage may be the reduction in waste of container contents, as easier removal of contents allows the contents to be actually used before the “empty” container is “thrown away.” Another advantage of the containers of the present invention is that they can be mass-produced and reduce or eliminate the need to match the container to the contents to be contained. In other words, the container of the present invention can avoid or reduce the customization problems that arise from the customization of currently available containers for specific contents (e.g., food contents). Furthermore, the containers of the present invention can be recycled together without the use of a coating; however, due to the different types of coatings used, some currently available containers with different coatings need to be recycled separately.

[0009] One aspect of the invention relates to an injection stretch blow molding (ISBM) container. The 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. After wetting the surface with water droplets of 14 to 16 mm diameter (e.g., about 15 mm), the surface maintains a water contact angle of 76° or higher for up to three minutes. This surface may be an inner surface of the container, such as a surface in contact with the material inside the container. The material and contents are interchangeable throughout the specification. The container can be manufactured by injection stretch blow molding of a polymer composition containing HDPE, wherein the HDPE has a dispersibility (Mw / Mn) of 9 or higher as measured by gel permeation chromatography (GPC); a melt index (MI2) of 1 g / 10 min or higher as measured by ASTM D-1238 at 190°C / 2.16 kg; a shear response (HLMI / MI2) of 40 or higher as measured by ASTM D-1238; and an environmental stress cracking resistance (ESCR) greater than 150 hours as measured by ASTM D-1693,B at 100% Igepal. Mw can be the weight-average molecular weight of HDPE as measured by GPC, and Mn can be the number-average molecular weight of HDPE as measured by GPC. HLMI can be the high-load melt index. In some aspects, the container surface having the above-described surface properties is either uncoated or not coated. In these aspects, the HDPE polymer composition forms the surface of the container.

[0010] In some aspects, HDPE can have a dispersibility of 9 to 12 as measured by GPC; an MI 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 h as measured by ASTM D-1693,B at 100% Igepal; or any combination thereof. In some aspects, 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 15000 Pa·s to 250000 Pa·s; a peak molecular weight of 20000 g / mol or greater as measured by GPC; or any combination thereof. In some respects, HDPE can have a dispersibility of 9 to 12 as measured by GPC; an MI2 of 1 g / 10 min to 8 g / 10 min or 2 g / 10 min as measured by ASTM D-1238 at 190 °C / 2.16 kg; an ESCR of 180 to 300 h as measured by ASTM D-1693,B at 100% Igepal; a density of 0.94 g / cc to 0.97 g / cc as measured by ASTM D792; a zero-shear viscosity of 15000 Pa·s to 250000 Pa·s; and a peak molecular weight of 20000 g / mol or greater as measured by GPC. In certain specific aspects, HDPE resin may have an MI2 of 2 g / 10 min measured at 190°C / 2.16 kg according to ASTM D-1238; a yield tensile strength of 4600 psi measured at 2 in / min using Type IV specimens according to ASTM D-638; an elongation at break greater than 600% measured at 2 in / min using Type IV specimens according to ASTM D-638; a flexural modulus of 210 kpsi measured according to ASTM D-790; an environmental stress cracking resistance (ESCR) greater than 200 hours measured at 100% Igepal according to ASTM D-1693,B; and an elongation at break of 0.958 g / cm³ measured according to ASTM D-792. 3 The density.

[0011] The polymer composition (e.g., a polymer composition for manufacturing the containers of the present invention via 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. One or more additives may be selected from the group consisting of: acid removers, antioxidants, UV absorbers, nucleating agents, colorants, lubricants, processing aids, plasticizers, flow modifiers, or any combination thereof. In some aspects, one or more additives may include acid removers, nucleating agents, colorants, and / or lubricants. Nucleating agents may include carboxylates (e.g., dicarboxylates and / or fatty acid salts), sorbitol derivatives, nonanol derivatives, or any combination thereof. In some aspects, nucleating agents may be disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; calcium salt of 1,2-cyclohexanedicarboxylate; zinc stearate; calcium stearate; 1,3:2,4-di(3,4-dimethylbenzyl)sorbitol; talc; sodium benzoate; or any combination thereof. In some aspects, the polymer composition may optionally contain 0.01% to 1% by weight of a nucleating agent. The colorant may contain titanium dioxide; carbon black; organic dyes such as polycyclic monoazo metal complexes and / or polycyclic diazo metal complexes; or any combination thereof. In some aspects, the polymer composition may optionally contain 0.01% to 1% by weight of a colorant. The lubricant may contain a silica-modified high molecular weight siloxane polymer dispersed in polyethylene, oleamide, erucamide, behenamide, 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 remover may contain calcium stearate, zinc stearate, hydrotalcite, zinc oxide, or any combination thereof. In some aspects, the acid remover may contain zinc stearate, hydrotalcite, zinc oxide, or any combination thereof. In some aspects, the polymer composition may optionally contain 200 to 3000 ppm, or 200 to 2000 ppm by weight of an acid remover.

[0012] The container of the present invention can be of any suitable shape and size. In some aspects, the cross-section of the container's lumen along a transverse plane (e.g., a plane perpendicular to the container's longitudinal axis) can 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 can be hexagonal or rounded hexagonal. Containers having other shapes and / or cross-sectional shapes can be readily manufactured. The cross-section of the lumen along a plane perpendicular to the container's longitudinal axis can vary in shape and size along the length of the longitudinal axis. The container wall can have a thickness of 0.05 to 2 mm or 0.1 to 1 mm. The container wall can have a uniform or non-uniform thickness.

[0013] One aspect relates to a method for manufacturing an ISBM container. The ISBM container can be manufactured by injection stretch blow molding a polymer composition. The injection stretch blow molding method may include injection molding the polymer composition to form a preform, and stretch blow molding the preform to form an ISBM container. In some aspects, the polymer composition may be melted at a melt temperature of 300 to 600°F, 350 to 550°F, or 450 to 500°F, and / or the molten polymer composition may be injected into a preform die at an injection pressure of 400 to 1000 psi to form a preform. The polymer composition may be injection molded in an extruder. The melt temperature may depend on the polymer composition, and may be high enough to allow the molten polymer composition to flow freely in the extruder barrel, but low enough to result in relatively little observed decomposition of the molten polymer composition. In some aspects, the preform may have a tubular shape. The preform may include a threaded neck of the ISBM container to be formed, referred to as the finish. In some aspects, preforms can be tuned to form preforms with a desired temperature distribution, and preforms with a desired temperature distribution can be stretch blow molded to form ISBM containers. In some aspects, preforms (e.g., preforms with a desired temperature distribution) can be stretch blow molded at stretch rates of 25 to 150 cm / s and / or stretch pressures of 150 to 500 psi to form ISBM containers. Without theoretical limitations, it is believed that the stretch rate affects the material distribution in the final part, while the pressure affects the detail and fullness of the part. If the pressure is too low, the produced part may not possess all the desired characteristics.

[0014] 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, conditioning the preform, and stretch blow molding the preform are typically performed in a single machine. In contrast, in a two-stage ISBM, the steps of forming the preform and conditioning and / or stretch blow molding the preform are typically performed in separate machines. In some aspects, the surface of the resulting container, having the aforementioned surface characteristics, is either uncoated or not coated. In these aspects, the HDPE polymer composition forms the surface of the container.

[0015] Other embodiments of the invention are also discussed in this application. Any embodiment discussed with respect to one aspect of the invention is also applicable to other aspects of the invention, and vice versa. All embodiments described herein can be understood as embodiments of the invention applicable to other aspects of the invention. It is contemplated that any embodiment or aspect discussed herein can be combined with other embodiments or aspects discussed herein and / or implemented using any method or composition of the invention, and vice versa. Furthermore, the compositions and systems of the invention can be used to implement the methods of the invention.

[0016] The following includes definitions of various terms and phrases used in this specification.

[0017] The term “about” or “approximately” is defined as close to the understanding of those skilled in the art. In a non-limiting embodiment, the term is defined as within ±10%, or within ±5%, or within ±1%, or within ±0.5%.

[0018] The terms “weight%”, “volume%”, or “molar%” refer to the percentage of a component by weight, volume, or mole, respectively, based on the total weight, volume, or number of moles of the material containing the component. In a non-limiting example, 10 grams of a component in 100 grams of material is 10% by weight of the component.

[0019] The term “basically” and its variations are defined as including ranges within ±10%, ±5%, ±1%, or ±0.5%.

[0020] The terms “suppress” or “reduce” or “prevent” or “avoid” or any variations thereof, when used in the claims and / or specification, include any measurable reduction or complete suppression to achieve the desired result.

[0021] When used in the specification and / or claims, the term "effective" means sufficient to achieve the desired, desired, or anticipated result.

[0022] When “a” or “an” is used with any of the terms “comprising,” “including,” “containing,” or “having” in the claims or description, it may mean “a”, but it is also consistent with the meaning of “a or more,” “at least one,” and “a or more than one.”

[0023] The phrase “and / or” can include “and” or “or”. To illustrate this, 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.

[0024] The words “contains” (and any form of inclusion, such as “contains” and “containing”), “have” (and any form of having, such as “have” and “possess”), “includes” (and any form of inclusion, such as “includes” and “encompasses”), or “contains” (and any form of containing, such as “includes” and “includes”) are inclusive or open-ended and do not exclude other elements or method steps not cited.

[0025] The methods and systems of the present invention may be described as "comprising," "substantially comprising," or "consisting of specific ingredients, components, compositions, steps, etc. disclosed throughout the specification." Regarding the transitional phrase "substantially comprising," in a non-limiting aspect, the essential and novel features of the containers and methods of manufacturing containers of the present invention may include ISBM HDPE containers having a static coefficient of friction (COF) of 0.15 to 0.21 and a dynamic COF of 0.06 to 0.1.

[0026] Other objects, features, and advantages of the present invention will become apparent from the following accompanying drawings, detailed description, and embodiments. However, it should be understood that while these figures, detailed descriptions, and embodiments illustrate specific embodiments of the invention, they are given by way of illustration only and are not intended to be limiting. Furthermore, it is contemplated that changes and modifications within the spirit and scope of the invention will be apparent to those skilled in the art from the detailed description. In further embodiments, features of specific embodiments may be combined with features of other embodiments. For example, a feature from one embodiment may be combined with features from any other embodiment. In further embodiments, additional features may be added to the specific embodiments described herein.

[0027] Brief description of the attached figures

[0028] The advantages of the present invention will be apparent to those skilled in the art from the following detailed description and with reference to the accompanying drawings.

[0029] Figure 1 : A schematic diagram of an ISBM HDPE container according to an embodiment of the present invention.

[0030] Figure 2 Visual comparison of the ISBM HDPE container and the HDPE extruded blow molded (EBM) container of the present invention after the water has been drained from each container.

[0031] Figure 3 Comparison of the water contact angle of the ISBM HDPE container and the EBM HDPE container of the present invention over time after wetting the surface with water droplets of approximately 15 mm in diameter.

[0032] Figure 4: Optical microscope images of the surfaces of EBM HDPE and ISBM HDPE containers, A) and B) respectively.

[0033] Figure 5: Scanning electron microscope (SEM) images of the surfaces of EBM HDPE and ISBM HDPE containers, A) and B) respectively.

[0034] Figure 6 Static COF and dynamic COF of ISBM HDPE and EBM HDPE container surfaces.

[0035] While the invention can be modified and substituted in various ways, specific embodiments of the invention are shown by way of example in the accompanying drawings. The drawings may not be drawn to scale. Detailed Implementation

[0036] One discovery has provided a solution to at least some of the aforementioned problems in removing contents from containers. In one aspect, the solution includes providing an ISBM container containing a polymer composition comprising HDPE. As shown in a non-limiting manner in the examples, the ISBM container made of HDPE has a dispersibility (Mw / Mn) of 9 or higher as measured by GPC; an MI2 of 1 g / 10 min or higher as measured by ASTM D-1238 at 190°C / 2.16 kg; a shear response (HLMI / MI2) of 40 or higher as measured by ASTM D-1238; and an environmental stress cracking resistance (ESCR) of greater than 150 hours as measured by ASTM D-1693,B at 100% Igepal, and its surface may have relatively low friction, for example, a static COF of 0.15 to 0.21 and a dynamic COF of 0.06 to 0.1.

[0037] These and other non-limiting aspects of the invention will be discussed in further detail in the following sections.

[0038] A. Injection stretch blow molding (ISBM) containers

[0039] The ISBM HDPE container of the present invention can be manufactured by injection stretch blow molding of a polymer composition containing HDPE. The container can have any suitable shape and / or size. In some aspects, the size of the container can be at least any of the following values, equal to any of the following values, or between any two of the following values: 0.1L to 10L, or 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 10L. The thickness of the container wall can be from 0.05 mm to 2 mm, or from 0.1 mm to 1 mm, or at least any of the following values, equal to any of the following values, or between any two of the following values: 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 mm. The container wall can independently have a uniform and / or non-uniform thickness.

[0040] In some respects, the cross-section of the container's lumen or orifice along a transverse plane (e.g., a plane perpendicular to the container's longitudinal axis) can be circular, oval, elliptical, star-shaped, triangular, square, rectangular, pentagonal, hexagonal, heptagonal, octagonal, nonagonal, decagonal, rounded-corner star, rounded-corner triangle, rounded-corner square, rounded-corner rectangle, rounded-corner pentagon, rounded-corner hexagon, rounded-corner heptagon, rounded-corner octagon, rounded-corner nonagon, rounded-corner decagon, or irregular in shape. The container can have a uniform or non-uniform shape. (See reference...) Figure 1 The image illustrates an ISBM container 100 according to one embodiment of the invention. The container may have a longitudinal axis 101. Plane 102 may be a plane perpendicular to the longitudinal axis 101. Image 103 shows a cross-section of the lumen or aperture 104 of the container 100 along plane 102. The cross-sections of the lumen along various planes perpendicular to the longitudinal axis 101 may have similar or different shapes and / or dimensions. In some specific aspects, the cross-section may be hexagonal or rounded hexagonal in shape. As used herein, a rounded polygon, such as a rounded hexagon, may refer to a hexagon with rounded corners / sides.

[0041] The inner surface of the container (e.g., at least a portion or the entire inner surface) can have a static coefficient of friction (COF) of 0.15 to 0.21 and a dynamic coefficient of friction of 0.06 to 0.1. The outer surface opposite the inner surface can have the same or different COF. The coefficient of friction can be measured by applying a normal force of 16.71 N relative to the steel surface. The COF between the inner surface and the steel plate can be measured by attaching a portion of the container wall measuring 2.5” x 1” to a 2.5” x 2.5” slider. The slider can be loaded such that the normal force applied to the container wall surface is 16.71 N. The slider can be pulled at a rate of 6 inches per minute. The static COF can be calculated based on the force required to start the movement, and the dynamic COF can be calculated by the average force required to pull a distance of 2” to 6”. After wetting the surface with water droplets of 14 to 16 mm in diameter or about 15 mm, the inner surface can maintain a water contact angle of 76° or higher, or 76° to 82°, for up to three minutes. The outer surface opposite the inner surface may have the same or different water contact angle values ​​or properties. In some aspects, the inner and / or outer surfaces are not coated. In these aspects, the HDPE polymer composition forms one or more surfaces of the container.

[0042] The ISBM HDPE container of this invention can be used or is capable of being 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, but are not limited to, ketchup / seasoned ketchup, mustard, mayonnaise, syrup, honey, jelly, peanut butter, butter, chocolate syrup, shortening, butter, margarine, artificial cream, animal fats, dips, yogurt, sour cream, ice cream, sticky foods (e.g., candy, chocolate syrup, fermented rice, yeast fermented rice, beer fermented rice, toffee), edible oils, fish oil, marshmallows, dough, batter, baked goods, chewing gum, bubble gum, butter, cheese, cream, cream cheese, mustard, yogurt, sour cream, curry, sauces, Balkan-style sweet pepper sauce (AJvar), curry sausage sauce, spicy ketchup (Salsa Lizano), chutney, Pebre, fish sauce, yogurt cucumber sauce (Tzatziki), Sriracha sauce. Sauces, including: Vegemite, Chimichurri, HP / Brown Sauce, Harissa, Kochujang, Hoisan Sauce, Kimchi, Cholulah Hot Sauce, Tartar Sauce, Tahini, Hummus, Shichimi, Tomato Sauce, Pasta Sauce, Alfredo Sauce, Pasta Sauce, Icing Sugar, Dessert Toppings, Cream, Food Additives (such as ethyl oleate), Fatty Acids, Proteins, Vegetable Oils (such as olive oil, light olive oil, corn oil, soybean oil, rapeseed oil, flaxseed oil, grapeseed oil, linseed oil, canola oil, peanut oil, safflower oil, sunflower oil), Disinfectants, Cosmetics, Shampoos, Lotions, Creams, Hairspray, Toothpaste, and / or Liquid Soaps.

[0043] B. HDPE polymer composition

[0044] The polymer composition or resin may contain: at least 99% by weight, 99% to 99.9% by weight, 99% to 100% by weight, or 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9, and 100% HDPE, equal to any one of them, or between any two of them, and optionally one or more additives, wherein the total additive content is 0 to 1% by weight, or at least 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1% by weight, equal to any one of them, or between any two of them.

[0045] i.HDPE

[0046] The weight-average molecular weight (Mw) of HDPE, as measured by GPC, can be from 100,000 to 250,000 g / mol. The dispersibility (Mw / Mn) of HDPE, as measured by GPC, can be 9 or higher, or 9 to 12. The peak molecular weight of HDPE, as measured by GPC, can be 20,000 g / mol or higher, or 20,000 to 5,000 g / mol. The MI2 of HDPE, as measured according to ASTM D-1238 at 190°C / 2.16 kg, can be 1 g / 10 min or higher, or 1 g / 10 min to 8 g / 10 min, or at least one, equal to, or between any two of the following: 1, 2, 3, 4, 5, 6, 7, and 8 g / 10 min. The environmental stress cracking resistance (ESCR) of HDPE, measured with 100% Igepal according to ASTM D-1693, may be greater than 150 hours, or greater than 160 hours, or less than 170 hours, or greater than 180 hours, or 180 hours to 300 hours. The density of HDPE, measured according to ASTM D792, may be from 0.94 g / cc to 0.97 g / cc, or at least one, equal to, or between any two of the following: 0.94, 0.945, 0.95, 0.955, 0.96, 0.965, and 0.97 g / cc. The zero-shear viscosity of HDPE can be from 15,000 Pa·s to 250,000 Pa·s, or at least one, equal to, or between any two of the following: 15,000, 25,000, 50,000, 75,000, 100,000, 125,000, 150,000, 175,000, 200,000, 225,000, and 250,000 Pa·s. HDPE can be metallocene or non-metallocene HDPE. HDPE can be monomodal or bimodal. In some respects, HDPE can be non-metallocene bimodal HDPE.

[0047] The HDPE used may have at least one, any combination of, or all of the properties mentioned herein.

[0048] In some respects, a combination of two or more HDPEs (e.g., HDPEs with different properties) may be used. Non-limiting examples of commercially available HDPEs include 9260 and SB1359NA, which are available from TOTAL.

[0049] ii. Additives

[0050] The polymer composition may optionally contain one or more additives. The optional additives may be selected from the group consisting of: acid removers, antioxidants, ultraviolet absorbers, nucleating agents, colorants, lubricants, processing aids, plasticizers, flow modifiers, or any combination thereof.

[0051] Nucleating agents may include carboxylates (e.g., dicarboxylates and / or fatty acid salts), sorbitol derivatives, nonanol derivatives, or any combination thereof. In some aspects, nucleating agents may be hexahydrophthalic acid (HHPA) salts, such as calcium, strontium, lithium, or monoaluminum salts of HHPA; disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; 1,2-cyclohexanedicarboxylate, such as calcium salts of 1,2-cyclohexanedicarboxylate; lithium, sodium, calcium, barium, magnesium, aluminum, or zinc salts of fatty acids, such as zinc stearate or calcium stearate; 1,3:2,4-di(3,4-dimethylbenzyl)sorbitol; talc; sodium benzoate; or any combination thereof. Where it is not desired to be bound by theory, it is believed that compositions with relatively high crystallinity and uniform crystal structures can be obtained by adding nucleating agents. In some aspects, the polymer composition may optionally contain 0.01% by weight to 1% by weight or at least, equal to, or between any two of the following amounts: 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.

[0052] The colorant can be an organic pigment, an inorganic pigment, carbon black, a white pigment, and / or an aluminum pigment. Organic pigments can be organic dyes, such as polycyclic monoazo metal complexes and / or polycyclic diazo metal complexes. Inorganic pigments can be metal salts or metal oxides, such as titanium dioxide. In some aspects, the polymer composition may optionally contain at least, equal to, or between any two of the following: 0.01% by weight to 1% by weight, or 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 of the colorant.

[0053] The lubricant may include a silica-modified high molecular weight siloxane polymer dispersed in polyethylene, commercially available from Dow Corning under the trade name MB50-802, oleamide, erucamide, behenamide, or any combination thereof. In some aspects, the polymer composition may optionally contain at least, equal to, or between any two of the following: 0.01% by weight to 1% by weight, or 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.

[0054] The acid scavenger may contain calcium stearate, zinc stearate, hydrotalcite, or 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 aspects, the polymer composition may contain at least one, equal to one, or between two of the following amounts: 200 to 3000 ppm, or 200 to 2000 ppm, or 200, 400, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, and 3000 ppm.

[0055] C. Methods for preparing ISBM HDPE containers

[0056] 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 method 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 method may include mixing, for example, dry mixing of the components of the polymer composition (such as HDPE and optionally one or more additives), melting the polymer composition, and injecting the molten polymer composition into a preform die. The injection molding process can be performed 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 high enough to allow the molten polymer composition to flow freely in the extruder barrel, but low enough to result in relatively little observed decomposition of the polymer composition. In some aspects, the melt temperature of the molten HDPE polymer composition may be 300 to 600°F, or 350 to 550°F, or 450 to 500°F, or at least any one of 300, 350, 400, 450, 500, 550, and 600°F, equal to any one of them, or between any two of them. The injection pressure of the injection molding process may be 400 to 1000 psi, or at least any one of 400, 500, 600, 700, 800, 900, and 1000 psi, equal to any one of them, or between any two of them. The preforming mold may be a multi-cavity mold, for example, capable of forming multiple preforms simultaneously. The wall thickness of the preform may be 1 mm to 8 mm, the length may be 8 cm to 15 cm, and the cross-sectional diameter or width may be 30 mm to 40 mm. The preform may include the neck of an ISBM HDPE container (to be formed, including threads), referred to as the finished product. In some aspects, preforms formed by injection molding can be tempered to form preforms with a desired temperature distribution, and preforms with a desired temperature distribution can be stretch blow molded to form ISBM HDPE containers. In some aspects, the tempering process may include heating the preform with a suitable device (e.g., a reflective radiation heating oven, an air knife, etc.) and optionally allowing heat to be dispersed through the preform.

[0057] Stretch blow molding methods may include blowing air into a preform. In some aspects, compressed air may be used to stretch blow mold a preform (e.g., a preform with a desired temperature distribution) at a stretch rate of 25 to 150 cm / s, or at least any one of 25, 50, 75, 100, 125, and 150 cm / s, equal to any one of them, or between any two of them; and / or a stretch pressure of 150 to 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, equal to any one of them, or between any two of them. In some aspects, a preform (e.g., a preform with a desired temperature distribution) can optionally be axially stretched by a central rod to form an axially stretched preform before stretch blow molding with pressurized air, and the axially stretched preform can be stretch blow molded with pressurized air to form an ISBM container.

[0058] 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, conditioning the preform, and stretching the blow-molded preform are typically performed in one machine. In contrast, in a two-stage ISBM process, the steps of forming the preform and conditioning and / or stretching the blow-molded preform are typically performed in separate machines.

[0059] Example

[0060] The present invention will be described in more detail through specific embodiments. The embodiments provided below are for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily identify various non-critical parameters that can be changed or modified to produce substantially the same results.

[0061] Example 1

[0062] Injection stretch blow molding (ISBM) and extrusion blow molding (EBM) containers

[0063] Injection stretch blow molding (ISBM) containers with a hexagonal cross-section, similar in size to standard Gatorade bottles, were produced by injection stretch blow molding of HDPE resin SB1359NA (Table 1), available from TOTAL. In a comparative experiment, extrusion blow molding (EBM) bottles with a square shape were prepared by extrusion blow molding of HDPE resin 5502 (Table 1), also available from TOTAL. The ISBM conditions used are provided in Table 2. The EBM bottles were produced using a UNILOY 250R1 blow molding machine. Figure 2The geometry of the produced bottles is shown, where the front row bottles 1-5 are EBM bottles and the back row bottles 1-5 are ISBM bottles.

[0064] Table 1: HDPE Resin

[0065]

[0066]

[0067] Table 2: ISBM Conditions

[0068]

[0069] Water retention tests were performed on the bottles. Five bottles were taken for each group of ISBM and EBM bottles. Clean and dry bottles were labeled and weighed individually. The bottles were filled with water and left undisturbed for 5 minutes. Then the bottles were emptied. Care was taken not to splash the water onto the outer surface of the bottles. The bottles were shaken rapidly and weighed immediately. Table 3 lists the initial weight, final weight, and weight of residual water after emptying the bottles. The data in Table 3 show that the EBM bottles retained approximately twice the amount of residual water after emptying compared to the ISBM bottles (0.42 g for EBM and 0.20 g for ISBM).

[0070] Table 3: Water Holding Capacity of SBM and EBM Containers

[0071]

[0072]

[0073] To investigate the presence of residual water, the inner surface of the bottle was examined in detail. The water contact angle of the inner surface was measured using an optical microscope and a precision dropper. The inner surface of the bottle was wetted with water droplets approximately 15 mm in diameter, and the water contact angle was monitored every minute for 4 minutes. The experiment was repeated 5 times for each bottle type. Figure 3 The water contact angle of the bottle surface is shown within 4 minutes after initial wetting. Figure 3 As shown, the contact angles of the two surfaces gradually decrease as the water droplet diffuses. The ISBM surface exhibits a higher contact angle (approximately 5-6° larger than the EBM), indicating that its surface is more hydrophobic. Due to the greater hydrophobicity of the ISBM surface, it is reasonable to expect water to flow more easily across the surface during the drainage process.

[0074] The inner surface of the bottle was also studied using optical and scanning electron microscopy (SEM). Figure 4A and 4BOptical microscopic images of the inner surfaces of EBM and ISBM bottles are shown, respectively. As can be seen from Figure 4, the EBM surface exhibits a more disordered surface, while the ISBM surface is more oriented and homogeneous. The phenomena observed in the optical spectrum can be observed in more detail through SEM images of the surfaces. Figure 5A and 5B SEM images of the inner surfaces of the EBM bottle and the ISBM bottle are shown, respectively. As can be seen from Figure 5, the EBM surface appears to contain random aggregates of material, while the ISBM surface appears to contain highly oriented polymer chains.

[0075] The static and dynamic coefficients of friction (COF) of the bottle surface relative to steel were measured. The COF between the inner surface of the bottle and the steel plate was measured by attaching a 2.5” x 1” bottle wall section to a 2.5” x 2.5” slider and pulling it against a fixed steel plate. The slider was loaded with a total normal force applied to the bottle surface of 16.71 N. The slider was pulled at a rate of 6 inches / minute. The force was then measured at the start of the movement (for calculating the static COF) and averaged over a pulling distance from 2” to 6” (for calculating the dynamic COF). The procedure was repeated three times with good repeatability. The static and dynamic COFs obtained for ISBM and EBM surfaces are shown below. Figure 6 As shown. From Figure 6 As can be seen, the inner surface of the ISBM bottle exhibits significantly lower static and dynamic COF compared to the inner surface of the EBM bottle.

[0076] While embodiments and advantages thereof have been described in detail, it should be understood that various changes, substitutions, and modifications may be made herein without departing from the spirit and scope of the embodiments as defined in the appended claims. Furthermore, the scope of this application is not intended to be limited to the specific embodiments of the processes, machines, manufactures, material compositions, means, methods, and steps described in the specification. As will be readily understood by those skilled in the art from the foregoing disclosure, existing or future processes, machines, manufactures, material compositions, means, methods, or steps that perform substantially the same function or achieve substantially the same result as the corresponding embodiments herein can be utilized. Therefore, the appended claims are intended to include such processes, machines, manufactures, material compositions, means, methods, or steps within their scope.

Claims

1. An injection stretch blow molded (ISBM) container, comprising: Surface, which has: The static coefficient of friction (COF) ranges from 0.15 to 0.

21. and Dynamic COF ranging from 0.06 to 0.1; and A polymer composition comprising high-density polyethylene (HDPE), said high-density polyethylene having: Dispersion of 9 or higher (Mw / Mn) as measured by GPC; According to ASTM D-1238, MI2 of 1 g / 10 minutes or higher, measured at 190°C / 2.16 kg; and According to ASTM D-1693, the environmental stress cracking resistance (ESCR) is greater than 150 hours, measured with 100% Igepal. Specifically, after wetting the surface with water droplets of 14 to 16 mm in diameter, the surface maintains a water contact angle of 76° or higher for up to three minutes. MI2 refers to the melt index.

2. The ISBM container as claimed in claim 1, wherein, HDPE resin has a dispersibility of 9 to 12 as measured by GPC; an MI 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 h as measured by ASTM D-1693 at 100% Igepal.

3. The ISBM container as described in claim 1 or 2, wherein, HDPE resin has the following characteristics: Density ranging from 0.94 g / cc to 0.97 g / cc, as measured according to ASTM D792; Zero-shear viscosity from 15000 Pa·s to 250000 Pa·s; and Molecular weight at peak position of 20,000 g / mol or higher, as measured by GPC.

4. The ISBM container as described in claim 1 or 2, wherein, HDPE resin has the following characteristics: MI2 of 2.0 g / 10 min, measured at 190 °C / 2.16 kg according to ASTM D-1238; Yield tensile strength of 4600 psi measured at 2 inches per minute using a Type IV specimen, according to ASTM D-638; Elongation at break greater than 600% as measured with Type IV specimens at 2 inches per minute, according to ASTM D-638; The flexural modulus is 210 kpsi, as measured by ASTM D-790. Environmental stress cracking resistance (ESCR) greater than 200 hours as measured by 100% Igepal according to ASTM D-1693; Vicat softening point at 260°F; and 0.959 g / cm³ as measured according to ASTM D-792 3 The density.

5. The ISBM container as claimed in claim 1 or 2, wherein, The cross-section of the container's lumen along the container's transverse plane 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 as claimed in claim 5, wherein, The cross-section is hexagonal or rounded hexagonal.

7. The ISBM container as claimed in claim 1 or 2, wherein, The polymer composition contains additives.

8. The ISBM container as claimed in claim 7, wherein, The additive is an acid remover, antioxidant, ultraviolet absorber, nucleating agent, colorant, lubricant, processing aid, plasticizer, flow modifier, or any combination thereof.

9. The ISBM container as claimed in claim 8, wherein, The nucleating agent includes carboxylates, dicarboxylates, fatty acid salts, sorbitol derivatives, nonanol derivatives, or any combination thereof.

10. The ISBM container as claimed in any one of claims 8 to 9, wherein, The nucleating agent includes 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-di(3,4-dimethylbenzyl)sorbitol or any combination thereof.

11. The ISBM container as claimed in claim 8 or 9, wherein, The colorant includes titanium dioxide, carbon black, polycyclic monoazo metal complexes, polycyclic diazo metal complexes, or any combination thereof.

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

13. The ISBM container as claimed in claim 1 or 2, wherein, The container includes an outer surface and an opposing inner surface, wherein the inner surface includes: The static coefficient of friction (COF) ranges from 0.15 to 0.21; and Dynamic COF ranging from 0.06 to 0.

1.

14. The ISBM container as claimed in claim 13, wherein, Food is contained in the container and is in contact with at least a portion of the inner surface.

15. The ISBM container as claimed in claim 13, wherein, Liquid or semi-solid food is contained in the container and is in contact with at least a portion of the inner surface.

16. A method for manufacturing an ISBM container according to any one of claims 1 to 15, the method comprising: The polymer composition is injection molded to form a preform; and The preform is stretched and blow-molded to form an ISBM container.

17. The method of claim 16, wherein, The preform is thermally tempered to form a preform with a desired temperature distribution, and the preform with the desired temperature distribution is stretched and blow-molded to form an ISBM container.

18. The method of claim 16, wherein, The method is a one-stage or two-stage injection stretch blow molding method.

19. The method of claim 16, wherein, The injection molding conditions for the polymer composition include a melt temperature of 350 to 550°F and / or an injection pressure of 400 to 1000 psi.

20. The method of claim 16, wherein, Stretch blow molding conditions include stretch rates of 25 to 150 cm / s and / or stretch pressures of 150 to 500 psi.

Images