Multi-layer PET bottle with low light transmittance

Abstract

Disclosed is a multilayer bottle comprising: a core layer having a first side and a second side, the core layer comprising a shading additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof; an inner layer on a first side of the core layer, the inner layer comprising a first polyester polymer; and an outer layer on a second side of the core layer, the outer layer comprising a second polyester polymer. These multilayer vials have a light transmittance of less than or equal to 1% at a wavelength in the range of 400 to 700 nm and an ash content of less than or equal to 1 wt.%.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application was filed on February 7, 2024 as a PCT International Patent Application and claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 484,220 filed on February 10, 2023, the disclosure of which is incorporated herein by reference in its entirety. Field of the Invention

[0003] The present disclosure relates generally to multilayer bottles comprising at least three layers, and more particularly to such bottles having low light transmittance and being substantially free of inorganic pigments or colorants. Background of the Invention

[0005] Bottles used as containers for dairy products or beverages have specific structural, light-barrier, and oxygen-barrier properties to ensure product quality and a desired shelf life. However, while meeting these requirements, ease of recyclability can be adversely affected. It would be beneficial if bottle structures and compositions could be designed to maintain current structural, light-barrier, and oxygen-barrier properties while exhibiting improved recyclability. Accordingly, the present disclosure generally relates to these objectives. SUMMARY OF THE INVENTION

[0007] This summary is provided to introduce a series of concepts in a simplified form, which are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter. This summary is also not intended to limit the scope of the claimed subject matter.

[0008] Multilayer bottles are disclosed and described herein. Representative multilayer bottles may include: (a) a core layer having a first side and a second side, the core layer comprising a light-blocking additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof, (b) an inner layer on the first side of the core layer, the inner layer comprising a first polyester polymer, and (c) an outer layer on the second side of the core layer, the outer layer comprising a second polyester polymer. The multilayer bottles may be characterized by a light transmittance of less than or equal to 1% at wavelengths in the range of 400 to 700 nm and an ash content of less than or equal to 1 wt.%. These multilayer bottles may contain or may be configured to contain dairy products or carbonated soft drinks, but are not limited thereto.

[0009] Both the foregoing summary and the following detailed description provide examples and are illustrative only. Therefore, the foregoing summary and the following detailed description should not be considered restrictive. In addition, features or variations other than those set forth herein may also be provided. For example, certain aspects may involve various feature combinations and sub-combinations described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 A diagrammatic representation of a 3-layer bottle structure according to one aspect of the present invention is presented.

[0011] Figure 2 A diagrammatic representation of a 4-layer bottle structure according to one aspect of the present invention is presented.

[0012] Figure 3 A diagrammatic representation of a 5-layer bottle structure according to one aspect of the present invention is presented.

[0013] Figure 4 A diagrammatic representation of a 7-layer bottle structure according to one aspect of the present invention is presented.

[0014] Figure 5 are photographs of the multilayer bottle and multilayer preform of Example 1.

[0015] Figure 6 is a photograph showing the location of the test panels for the multilayer bottle of Example 1.

[0016] Figure 7 is a graph of light transmittance (%) versus wavelength (nm) for the bottles of Example 1 and Comparative Example 2.

[0017] Figure 8 is a graph of light transmittance (%) versus wavelength (nm) for the bottles of Examples 3 to 6 and Comparative Example 7.

[0018] Figure 9 is a graph of light transmittance (%) versus wavelength (nm) for the bottles of Examples 3 to 4 and Comparative Example 7.

[0019] Figure 10 is a graph of light transmittance (%) versus wavelength (nm) for the bottles of Examples 8 and 9.

[0020] definition

[0021] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If term is used in this disclosure but is not specifically defined, the definition from the 2nd edition (1997) IUPAC Chemical Terminology Compendium (Compendium of ChemicalTerminology) can be applied, as long as the definition does not conflict with any other disclosure or the definition used herein, or does not make any claim using the definition uncertain or cannot be implemented. In any definition or usage provided by any document incorporated herein by reference and the definition or usage conflict provided herein, the definition or usage provided herein are main.

[0022] Herein, features of the subject matter are described such that within a particular aspect, combinations of different features are contemplated. For each aspect and each and every feature disclosed herein, all combinations that do not adversely affect the designs, compositions, processes, or methods described herein are contemplated, and such combinations are interchangeable, regardless of whether a particular combination is explicitly described. Thus, unless expressly stated otherwise, any aspect or feature disclosed herein may be combined to describe an inventive design, composition, process, or method consistent with the present disclosure.

[0023] Although compositions and methods are described herein as "comprising" various components or steps, unless otherwise indicated, these compositions and methods may also "consist essentially of" or "consist of" the various components or steps. For example, a multi-layer bottle consistent with aspects of the present invention may comprise a core layer, an inner layer, and an outer layer; alternatively, may consist essentially of the core layer, the inner layer, and the outer layer; or alternatively, may consist of the core layer, the inner layer, and the outer layer.

[0024] Unless otherwise stated, the terms "a," "an," and "the" are intended to include plural alternatives, such as at least one alternative. For example, unless otherwise stated, disclosure of "a first polyester polymer" or "a second polyester polymer" is intended to encompass one first polyester polymer or second polyester polymer, or a mixture or combination of more than one first polyester polymer or second polyester polymer.

[0025] The term "contacting" is used herein to refer to materials or components that can be blended, mixed, slurried, dissolved, reacted, treated, compounded, or otherwise combined in some other manner or by any suitable method. The materials or components can be contacted together in any order, in any manner, and for any length of time, unless otherwise indicated.

[0026] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the typical methods and materials are described herein.

[0027] All publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the concepts and methodologies that are described in the publications and patents, which might be used in connection with the invention described herein.

[0028] Several types of ranges are disclosed herein. When any type of range is disclosed or claimed, it is intended that every possible number that such range could reasonably encompass is disclosed or claimed individually, including the endpoints of the range and any subranges and combinations of subranges encompassed therein. As a representative example, the relative thickness of the core layer compared to the total thickness of the multi-layer bottle can be within certain ranges in various aspects of the present invention. By disclosing that the thickness of the core layer can be within the range of 1% to 25% of the total bottle thickness, it is intended to state that the thickness of the core layer can be any amount within that range, and for example, can be within any range or combination of ranges within the range of 1% to 25%, such as 3% to 20%, 5% to 15%, or 7% to 13%, etc. Similarly, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0029] In general, an amount, size, formulation, parameter, range, or other quantity or characteristic is "about" or "approximately," whether or not expressly stated as such. Claims, whether or not modified by the term "about" or "approximately," include equivalents to those quantities or characteristics.

[0030] Detailed Description of the Invention

[0031] Disclosed herein are multi-layer bottles with improved recyclability and substantially no inorganic pigments or colorants. These multi-layer bottles can have (a) a core layer having a first side and a second side, the core layer comprising a light-blocking additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof, (b) an inner layer located on the first side of the core layer, the inner layer comprising a first polyester polymer, and (c) an outer layer located on the second side of the core layer, the outer layer comprising a second polyester polymer. The multi-layer bottles can be characterized by a light transmittance of less than or equal to 1% at wavelengths in the range of 400 to 700 nm and an ash content of less than or equal to 1 wt.%.

[0032] While not wishing to be bound by the following theory, it is believed that a light-blocking multi-layer bottle structure in which the inner and outer layers contain, for example, clear PET and the core layer contains a light-blocking additive and a suitable PET or hydrolyzable polymer (or a combination of these polymers) but no inorganic pigments and colorants will enable such light-blocking bottles to be easily recycled along with the PET bottle stream in existing large-scale operating material recycling facilities (MRFs).

[0033] Multi-layer bottles

[0034] Aspects of the present invention relate to multi-layer bottles comprising (or consisting essentially of, or consisting of): (a) a core layer having a first side and a second side, the core layer comprising a sunscreen additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof, (b) an inner layer located on the first side of the core layer, the inner layer comprising a first polyester polymer, and (c) an outer layer located on the second side of the core layer, the outer layer comprising a second polyester polymer. In some aspects, the multi-layer bottle can have three layers generally described as an inner layer, a core layer, and an outer layer, while in other aspects, the multi-layer bottle can have four or more layers. Thus, the core layer is not limited to being an intermediate layer between the inner layer and the outer layer; i.e., other layers may be present. The inner layer and the outer layer are described as being located on the first and second sides of the core layer, respectively. One or more additional layers may be between the core layer and the inner layer, and similarly, between the core layer and the outer layer.

[0035] Various combinations of layers may be present in the multi-layer bottles according to the present invention. Figures 1 to 4 Representative 3-layer, 4-layer, 5-layer, and 7-layer multilayer bottle structures are shown, respectively. The following are these and other non-limiting layer configurations, where letters are used to represent bottle layers: 1 / C / O, 1 / M / C / O, 1 / C / M / O, 1 / M / M / C / O, 1 / M / C / M / O, 1 / C / M / M / O, 1 / M / M / C / M / O, 1 / M / C / M / M / O, 1 / M / M / M / C / O, 1 / M / M / C / M / O, 1 / M / M / M / C / M / O, and 1 / M / C / M / M / M / O. In these examples, "C" represents a core layer, "I" represents an inner layer, "O" represents an outer layer, and "M" represents a miscellaneous or intermediate layer. Optionally, the inner layer, the outer layer, or both can be coated with additional materials. Layers that are immediately adjacent to each other are described as being adhered to or adjacent to each other. For example, in the multi-layer structure I / M / C / O, the "O" layer is adjacent to or adhered to the second side of the "C" layer, and the "O" layer is also located on the second side of the "C" layer. Similarly, the "I" layer is not adjacent to or adhered to the first side of the "C" layer, but is located on the first side of the "C" layer. Thus, by referring to a given layer being located on one side of the core layer, the given layer may be adjacent to or adhered to the core layer, or one or more additional layers (e.g., "M") may be between the given layer and the core layer. There is no upper limit to the total number of layers in a multi-layer bottle according to the present invention, such as 7-layer and 9-layer structures, provided that an inner layer, a core layer, and an outer layer are present in the multi-layer bottle structure. Materials that can be used in the inner layer, the core layer, the outer layer, and the one or more miscellaneous layers are described herein, and these materials can be used in any combination without limiting the further description of the multi-layer bottle structure.

[0036] Figure 1A 3-layer bottle having an I / C / O layer configuration is shown. Specifically, in this multi-layer bottle, the inner layer is adjacent to a first side of the core layer, and the outer layer is adjacent to a second side of the core layer. Figures 2 to 4 As shown in , the multilayer bottles contemplated herein can have four or more layers, for example, the multilayer bottles can have five layers or seven layers. Thus, one (or more) miscellaneous or intermediate layers can be between the inner layer and the core layer and / or between the outer layer and the core layer.

[0037] In one aspect, the multi-layer bottle can be a 3-layer structure, wherein the inner layer is adjacent to the first side of the core layer, and the outer layer is adjacent to the second side of the core layer. In another aspect, the multi-layer bottle is a 5-layer structure (or a 7-layer structure, or a 9-layer structure), wherein one first intermediate layer (or two or more first intermediate layers) is located between the inner layer and the core layer, and one second intermediate layer (or two or more second intermediate layers) is located between the outer layer and the core layer.

[0038] The multilayer bottles described herein are not limited to any particular wall thickness; however, multilayer bottles useful in many end-use applications typically have an average wall thickness in the range of 100 to 500 microns. In certain aspects, the average wall thickness can be in the range of 150 to 400 microns, 175 to 350 microns, 200 to 400 microns, or 200 to 300 microns, among others.

[0039] In some aspects, the core layer of a multi-layer bottle may comprise, on average, 1% to 25% or 3% to 20% of the total wall thickness, while in other aspects, the core layer may comprise, on average, 5% to 15% or 7% to 13% of the total wall thickness. Similarly, the outer and inner layers of a multi-layer bottle may independently comprise, on average, 30% to 60% of the wall thickness; alternatively, 35% to 55%; alternatively, 35% to 50%; or alternatively, 40% to 50%. The sum of these layer percentages for the inner, core, and outer layers may not exceed 100%, but where the sum is less than 100%, the remaining thickness may come from one or more miscellaneous layers, as described herein. For example, an illustrative multi-layer bottle may comprise 10% core layer, 45% inner layer, and 45% outer layer. As another example, an illustrative multi-layer bottle may comprise 15% core layer, 30% inner layer, 40% outer layer, and 15% miscellaneous layers between the inner and core layers.

[0040] Advantageously, multi-layer bottles according to the present invention can have a relatively low oxygen transmission rate, resulting in reduced oxidative degradation of the contents of the bottle (for a particular set of storage conditions and shelf life). For example, the bottle can have an oxygen transmission rate of between 0.05 and 100 cc / m 2 More typically, the OTR of the bottle can be in one aspect from 0.1 to 50 cc / m 2 / day, in another aspect 1 to 30 cc / m 2 / day, in yet another aspect 2 to 25 cc / m 2 / day, and in yet another aspect 0.05 to 5 cc / m 2 Oxygen transmission rate (OTR) is measured at 25°C and 50% RH using any suitable breathability equipment (such as Mocon OX-TRN Model 2 / 61).

[0041] The multilayer bottles described herein can have a relatively high degree of light blocking to prevent UV / light-induced degradation of the bottle's contents (for a specific set of storage conditions and shelf life). In one aspect, for example, the bottle can have a light transmittance of less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) at a wavelength in the range of 400 to 700 nm. In another aspect, the bottle can have a light transmittance of less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) at a wavelength in the range of 400 to 670 nm. In yet another aspect, the bottle can have a light transmittance of less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) at any suitable wavelength range within the range of 400 to 700 nm (or the range of 400 to 670 nm) (e.g., 400 to 550 nm). In yet another aspect, the bottle can have a light transmittance of less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) at (all) wavelengths within the range of 400 to 670 nm. The light transmittance characteristics of the multilayer bottle are determined by UV-Vis as further described herein. Light transmittance is the ratio of the light intensity of radiation leaving the substrate (e.g., the bottle wall) to the light intensity of the radiation applied to the substrate as incident radiation. These intensities are measured perpendicular to the direction of radiation at the substrate surface.

[0042] Advantageously, the disclosed multilayer bottles are substantially free of inorganic pigments or colorants, such as titanium dioxide (TiO2). Thus, the aforementioned light transmittance characteristics can be achieved without the need for conventional high loadings of pigments or colorants. One measure of this characteristic is the ash content of the multilayer bottle, which can typically be less than 1 wt.%. In some aspects, the bottle can have a lower ash content, such as less than or equal to 0.5 wt.%, less than or equal to 0.3 wt.%, or less than or equal to 0.2 wt.%, while in other aspects, the bottle can have an even lower ash content, such as less than or equal to 0.1 wt.%, less than or equal to 0.05 wt.%, or less than or equal to 0.01 wt.%. Ash content is the amount of material (in weight percent) remaining at 800°C in a TGA test. A PerkinElmer Pyris 1 TGA unit was used with a sample size of approximately 25 mg, an air atmosphere (20 mL / min), and a heating rate of 10°C / min.

[0043] The multi-layer bottles described herein can be used in a variety of end-use applications.For example, the multi-layer bottles can contain (or can be configured to contain) dairy products or carbonated soft drinks.

[0044] The multilayer bottle can be produced using any suitable method. The multilayer bottle can be produced using an overmolding process, or the multilayer bottle can be produced by injection molding a multilayer preform and then blow molding the multilayer preform, or the multilayer bottle can be produced by blow molding a coextruded (multilayer) polymer stream. The present invention is not limited to any particular technique or method for producing the multilayer bottle.

[0045] In aspects where multilayer bottles are produced by injection molding a multilayer preform and then blow molding the multilayer preform, typically the average wall thickness of the preform is in the range of 2-5 mm, and the average wall thickness of the bottle is in the range of 200 to 500 microns. A typical drawdown ratio from preform thickness to bottle thickness can be about 10:1, although drawdown ratios in the range of 5:1 to 20:1 are also suitable.

[0046] While not necessarily limited thereto (particularly when the core layer contains a polymer other than polyester), in one aspect of the present invention, the multilayer bottle can contain at least 97 wt.% polyester. In another aspect, the multilayer bottle can contain at least 98 wt.% polyester, and in yet another aspect, the multilayer bottle can contain at least 99 wt.% polyester, and in yet another aspect, the multilayer bottle can contain at least 99.5 wt.% (or at least 99.7 wt.%) polyester. Additionally or alternatively, the multilayer bottle can generally contain less than or equal to 5 wt.% or less than or equal to 3 wt.% of an opacifying additive, and this can vary significantly based on the relative thickness of the core layer. However, in some aspects, the multilayer bottle can contain less than or equal to 2 wt.% of an opacifying additive; alternatively, less than or equal to 1.5 wt.% of an opacifying additive; alternatively, less than or equal to 1 wt.% of an opacifying additive; alternatively, less than or equal to 0.5 wt.% of an opacifying additive; or alternatively, less than or equal to 0.25 wt.% of an opacifying additive. Illustrative and non-limiting ranges for the amount of sunscreen additive in the multi-layer bottle can include 0.1 to 3 wt.%, 0.25 to 2 wt.%, 0.25 to 1.5 wt.%, 0.35 to 2 wt.%, 0.35 to 1.5 wt.%, 0.5 to 1.5 wt.%, or 0.5 to 1 wt.% of sunscreen additive.

[0047] core layer

[0048] The core layer of the multi-layer bottle can comprise an opacifying additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof. Thus, in one aspect, the core layer can comprise a core polyester polymer, while in another aspect, the core layer can comprise a hydrolyzable polymer, and in yet another aspect, the core layer can comprise any suitable relative amounts of the core polyester polymer and the hydrolyzable polymer. In certain aspects of the present invention, the core layer is free of pigments or colorants.

[0049] Referring first to the aspect wherein the core layer comprises a hydrolyzable polymer, any suitable hydrolyzable polymer may be present in the core layer. However, the hydrolyzable polymer is typically selected such that the bottle flakes will delaminate and / or the core layer will dissolve in a stirred solution of 1 wt.% NaOH in water at 85°C within a time period of less than or equal to 30 minutes, and advantageously less than or equal to 25 minutes, less than or equal to 20 minutes, or less than or equal to 15 minutes. The bottle flakes typically have any suitable size of less than or equal to 12 mm in diameter, or less than or equal to 9.5 mm in diameter. Additionally or alternatively, the hydrolyzable polymer present in the core layer may be any polymer such that the bottle flakes meet the PET-P-04 test (2019) of the Association of Plastic Recyclers.

[0050] The hydrolyzable polymer can include any suitable water-soluble polymer, and the polymer can be natural or synthetic and can be a homopolymer or a copolymer. Representative and non-limiting examples of hydrolyzable polymers that can be present in the core layer of the multi-layer bottle include polyvinyl alcohol (PVOH), partially hydrolyzed polyvinyl alcohol esters, partially hydrolyzed polyvinyl acetate, or polyglycolic acid (PGA), etc. A mixture or combination of two or more hydrolyzable polymers (or a mixture of a hydrolyzable polymer and a non-hydrolyzable polymer) can be used in the core layer. In some aspects, for example, the hydrolyzable polymer can include polyvinyl alcohol (PVOH), while in other aspects, the hydrolyzable polymer can include polyglycolic acid (PGA).

[0051] Regardless of the type of hydrolyzable polymer, such polymer can be further characterized by its degree of hydrolysis. Often, the degree of hydrolysis of a hydrolyzable polymer ranges from 50% to 99%, and more often, the degree of hydrolysis of a hydrolyzable polymer falls within the range of 60% to 95%, 70% to 90%, or 70% to 85%. If the degree of hydrolysis is too high, the bottle will not delaminate and / or the core layer will not dissolve quickly enough in the caustic solution during the recycling process.

[0052] While the inner and outer layers (and, if present, other intermediate or miscellaneous layers) can contribute to the light-blocking properties of the multilayer bottle, the vast majority of the light-blocking properties (and low light transmittance) come from the core layer. The light-blocking / light-transmittance properties can generally be caused by light scattering, light absorption, light reflection, or any combination thereof in the core layer. In one aspect, the light-blocking properties of the core layer can be at least partially caused by foaming a hydrolyzable polymer. Thus, in this aspect, the core layer can comprise a foamed hydrolyzable polymer.

[0053] Referring now to aspects wherein the core layer comprises a core polyester polymer, illustrative and non-limiting examples of polymers that can be used as the core polyester polymer can include polyethylene terephthalate (PET), glycol-modified PET (PET-G), recycled PET (R-PET), polybutylene terephthalate, polylactic acid (PLA), polyhydroxyalkanoate (PHA), or combinations thereof. In one aspect, the core polyester polymer can have a density of at least 1.05 g / cc, at least 1.1 g / cc, or at least 1.2 g / cc.

[0054] As described herein, in addition to the core polyester polymer and / or the hydrolyzable polymer, the core layer may also contain a sunscreen additive. Typically, the core layer contains at least 50 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, at least 95 wt.%, at least 98 wt.%, or at least 99 wt.% of the polymer component (polyester and / or one or more hydrolyzable polymers). Thus, the amount of sunscreen additive (or the sum of sunscreen additives if there is more than one) in the core layer is often less than or equal to 50 wt.%, less than or equal to 25 wt.%, less than or equal to 15 wt.%, less than or equal to 12 wt.%, less than or equal to 10 wt.%, less than or equal to 8 wt.%, less than or equal to 5 wt.%, or less than or equal to 2 wt.%. Typical ranges of sunscreen additives in the core layer can include, but are not limited to, 1 to 20 wt.%, 2 to 15 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, or 5 to 12 wt.% sunscreen additives.

[0055] Although not limited thereto, light-shielding additives can include any suitable organic light-shielding agent, that is, light-shielding additives are not minerals or pigments. As an example, light-shielding additives can include a polyolefin without colorant to provide light-shielding properties, which polyolefin may or may not be miscible or compatible with the one or more polymers in the core layer. Illustrative and non-limiting examples of light-shielding additives include polymethylpentene, cycloolefin copolymers, hydrogenated styrene polymers or copolymers, siloxanes, solid light-scattering pigments, cristobalite, etc., and any mixture or combination thereof. Representative cycloolefin copolymers include ethylene / norbornene copolymers, ethylene / tetracyclodecene copolymers, etc., and a combination of two or more cycloolefin copolymers can be used as light-shielding additives. Representative solid light-scattering pigments include, for example, titanium dioxide, metal oxide particles, barium sulfate, zinc sulfide, etc., and a combination thereof.

[0056] In one aspect, suitable opacifying additives for use in the core layer can have a DSC melting point in the range of 200° C. to 250° C., such as 210° C. to 250° C., 225° C. to 240° C., or 230° C. to 235° C., etc. Additionally or alternatively, the opacifying additive can have a glass transition temperature (Tg) in the range of 115° C. to 145° C. in one aspect, 120° C. to 140° C. in another aspect, 120° C. to 135° C. in yet another aspect, and 125° C. to 130° C. in yet another aspect. As disclosed herein, the opacifying additive can be a polymer that is immiscible or incompatible with the one or more polymers used in the core layer.

[0057] Inner and outer layers

[0058] The multi-layer bottles described herein may include: (a) a core layer having a first side and a second side, the core layer comprising a sunscreen additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof, (b) an inner layer positioned on the first side of the core layer, the inner layer comprising a first polyester polymer, and (c) an outer layer positioned on the second side of the core layer, the outer layer comprising a second polyester polymer. In some aspects, the inner and outer layers can have the same composition, comprising the same polymer or the same polymer blend, or alternatively, the inner and outer layers can have different compositions, comprising different polymers or different polymer blends.

[0059] Illustrative and non-limiting examples of polymers that can be used as the first polyester polymer and / or the second polyester polymer can include polyethylene terephthalate (PET), glycol-modified PET (PET-G), recycled PET (R-PET), polybutylene terephthalate, polylactic acid (PLA), polyhydroxyalkanoate (PHA), or combinations thereof. In one aspect, the first polyester polymer and the second polyester polymer can comprise the same polymer, although this is not required, and alternatively, the first polyester polymer and the second polyester polymer can independently have a density of at least 1.05 g / cc, at least 1.1 g / cc, or at least 1.2 g / cc. In certain aspects of the present invention, the inner and outer layers are free of pigments or colorants other than the first polyester polymer in the inner layer and the second polyester polymer in the outer layer.

[0060] As an example, a typical bottle structure can be PET / core / PET, where the core layer is selected as described above. The PET can be from any source (e.g., virgin, recycled, enhanced recycled) or any combination of sources in varying relative amounts. Enhanced recycled refers to PET that has been depolymerized into one or more of its monomers and then repolymerized into PET.

[0061] Typically, the inner layer contains at least 90 wt.%, at least 95 wt.%, at least 98 wt.%, or at least 99 wt.% of the first polyester polymer, and the outer layer contains at least 90 wt.%, at least 95 wt.%, at least 98 wt.%, or at least 99 wt.% of the second polyester polymer.

[0062] Other layers and additives

[0063] In some aspects of the present invention, the multi-layer bottle may include miscellaneous layers or intermediate layers. Any miscellaneous layer or intermediate layer (one or more than one) that may be present in the multi-layer bottle may comprise any of the polymers discussed above as polymers selected for the core layer, inner layer, and / or outer layer. Optionally, the miscellaneous layer or intermediate layer may be a tie layer, and / or the miscellaneous layer or intermediate layer may be a layer comprising regrind. A tie layer may be used to promote adhesion between any two layers, such as between a core layer and an inner layer.

[0064] Additives are often used in polymer bottles and formulations to improve the processing or manufacturing ease of the one or more polymers and multilayer bottles. Another use of additives is to impart certain properties or characteristics to multilayer bottles. In various aspects of the present invention, one or more additives may be employed in any of the inner layer, and / or outer layer, and / or core layer, and / or any miscellaneous or intermediate layers that may be present. Suitable additives that may be used in the multilayer structures or formulations disclosed herein may include, but are not limited to, antioxidants, acid scavengers, antiblocking additives, slip additives, colorants, fillers, polymer processing aids, UV inhibitors, and the like, including combinations thereof. Such materials are well known to those skilled in the art and are described, for example, in Modern Plastics Encyclopedia, Vol. 72, No. 12, mid-November 1995; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992.

[0065] Examples

[0066] The present invention is further illustrated by the following examples, which are not to be construed in any way as limiting the scope of the present invention. After reading the description herein, one of ordinary skill in the art can conjure up various other aspects, modifications, and their equivalents without departing from the spirit of the present invention or the scope of the appended claims.

[0067] Example 1 and Comparative Example 2

[0068] Figure 5The following are photographs of the multilayer bottle and multilayer preform of Example 1, produced as follows. Multilayer A / B / A injection molded preforms were first prepared using an Arburg injection molding unit with 165 tons of clamping force and a 2-cavity mold tooling to produce 21.2 g preforms with a 38 mm finish, 69.1 mm total length, 3.4 mm maximum wall thickness, and a 4 mm gate mark diameter. The extrusion system was configured to produce preforms with a 45 / 10 / 45 layer ratio (thus, a 10% core layer). The inner and outer layers ("A") were 100 wt.% PET (DAK B90A), and the core layer was a mixture of 92.5 wt.% PET (DAK B90A) and 7.5 wt.% opacifying additive. Thus, the amount of opacifying additive in the entire multilayer bottle structure was 0.75 wt.%. All PET materials were dried to a level of less than 20 ppm H2O prior to molding. TGA testing of the opacifying additive showed no significant amount of ash (less than 0.5 wt.%), which equates to less than 50 ppm in the entire multi-layer bottle structure. The opacifying additive had two DSC melting points at temperatures of approximately 230°C and 234°C, and a glass transition temperature (Tg) of approximately 130°C.

[0069] The extruders feeding the inner and outer layers had a 30 mm screw diameter and an L / D ratio of 25:1, while the extruder feeding the core layer had a 16 mm screw diameter and an L / D ratio of 25:1. All melt channels (feed zone, metering zone, sprue, manifold and nozzle temperature) in the injection unit and hot runner unit were set to 280°C. Injection unit A had a fill position of 58 mm and a fill speed of 21.2 mm / sec, and injection unit B had a fill position of 27 mm and a fill speed of 25 mm / sec. Injection unit B filled the core layer (10 wt.%) with a length of 55 mm, located between the bottle mouth and the end cap of the preform. The holding phase process time was 8.5 sec, the cooling phase process time was 6 sec, and the tooling mold cooling circuit was 10°C. The total injection molding process time was 25.7 sec.

[0070] The injection molded preforms were blow molded using a Sidel blow molding unit at a preform temperature of 138°C. The blow molding process parameters included a pre-blowing time of 0.14 sec, a blowing time of 0.912 sec, a compensation time of 1.34 sec, and an exhaust time of 0.2 sec. The blow molding unit was equipped with a 14 mm flat stretch rod, and a cooling shield was set 2 mm from the preform and 2 mm above the neck support flange. The pre-blowing pressure set point was 8 bar, and the flow limiter was set at 150. The pre-blowing delay was 2.50 / 10. The high blow pressure used was 35 bar. The stretching speed was 1.9 m / s. The mold cooling circuit was set at 12°C.

[0071] The wall thickness and light transmittance properties of the multilayer bottles of Example 1 and Comparative Example 2 were tested. The multilayer bottle of Example 1 was configured to hold approximately 11.5 fluid ounces. Comparative Example 2 was a white pigmented single-layer bottle (containing approximately 3 wt.% TiO2 throughout the structure) and was configured to hold approximately 14 fluid ounces. Figure 6 This photograph shows the location of the test plate for the multilayer bottle of Example 1. This test plate is the second plate from the top of the bottle. Therefore, bottle thickness and light transmittance were tested on this portion of the multilayer bottle. The average bottle thickness for both Example 1 and Comparative Example 2 was 0.30 mm (300 microns).

[0072] The transmittance was measured using a Thermo Fisher Scientific Evolution 300 UV-Vis spectrophotometer with the following test parameters: baseline correction of 100% T baseline, % transmittance data mode, wavelength range of 200-800 nm, bandwidth of 2 nm, scan speed of 240 nm / min, data interval of 1 nm, xenon lamp change, 1 cycle, and cycle time set to automatic. The results of the transmittance tests of the bottles of Example 1 and Comparative Example 2 are summarized in Figure 7 Note that both bottles have transmittance values ​​of well below 1% (and well below 0.25%) at all wavelengths between 200 and 800 nm. While the Example 1 bottle does not offer transmittance values ​​as low as the Comparative Example 2 bottle, the Example 1 bottle exhibits transmittance values ​​within the very low range of 0.1%-0.15% between 400 and 700 nm. Furthermore, the Example 1 bottle advantageously has an ash content (e.g., from inorganic pigments or colorants) of less than 50 ppm.

[0073] In summary, it is surprising that such low light transmittance values ​​are achieved with only 7.5 wt.% of sunscreen additive in the core layer of the multilayer bottle of Example 1 (and only 0.75 wt.% of sunscreen additive in the entire multilayer bottle structure). This extremely high light protection at a much lower additive loading (compared to monolayer bottles) is achieved by placing the sunscreen additive only in the core layer and subjecting the bottle to sufficient orientation during molding during manufacturing to significantly increase its light blocking properties.

[0074] Examples 3 to 6 and Comparative Example 7

[0075] Examples 3 to 6 were produced in the same manner as Example 1, but with the following layer configurations and compositions. Example 3 had a 47.5 / 5 / 47.5 layer ratio (thus, a 5% core layer). The inner and outer layers ("A") were 100 wt.% PET (B90A from DAK), and the core layer was a mixture of 90 wt.% PET (B90A from DAK) and 10 wt.% of the same opacifying additive as in Example 1. Thus, the amount of opacifying additive in the overall multilayer bottle structure of Example 3 was 0.5 wt.%.

[0076] Example 4 had a 46.25 / 7.5 / 46.25 layer ratio (thus, 7.5% core layer). The inner and outer layers ("A") were 100 wt.% PET (B90A from DAK), and the core layer was a mixture of 90 wt.% PET (B90A from DAK) and 10 wt.% of the same opacifying additive as in Example 1. Thus, the amount of opacifying additive in the entire multilayer bottle structure of Example 4 was 0.75 wt.%.

[0077] Example 5 had a 47.5 / 5 / 47.5 layer ratio (thus, a 5% core layer). The inner and outer layers ("A") were 100 wt.% PET (B90A from DAK), and the core layer was a mixture of 95 wt.% PET (B90A from DAK) and 5 wt.% of the same opacifying additive as in Example 1. Thus, the amount of opacifying additive in the entire multilayer bottle structure of Example 5 was 0.25 wt.%.

[0078] Example 6 had a 46.25 / 7.5 / 46.25 layer ratio (thus, 7.5% core layer). The inner and outer layers ("A") were 100 wt.% PET (B90A from DAK), and the core layer was a mixture of 95 wt.% PET (B90A from DAK) and 5 wt.% of the same opacifying additive as in Example 1. Thus, the amount of opacifying additive in the entire multilayer bottle structure of Example 6 was 0.375 wt.%.

[0079] The multilayer bottles of Examples 3 to 6 and Comparative Example 7 were tested for their wall thickness and light transmittance properties. The multilayer bottles of Examples 3 to 6 were configured to hold approximately 11.5 fluid ounces. Comparative Example 7 was a white-colored, single-layer bottle similar to Comparative Example 2 (containing approximately 3 wt.% TiO2 throughout the entire structure) and configured to hold approximately 14 fluid ounces. Bottle thickness and light transmittance were tested on the same portion of the multilayer bottles as in Examples 1 and Comparative Example 2. The bottles of Examples 3 to 6 had an average bottle thickness of 0.26-0.27 mm (260-270 microns), and the bottles of Comparative Example 7 had an average bottle thickness of 0.30 mm (300 microns).

[0080] The results of the light transmittance tests on the bottles of Examples 3 to 6 and Comparative Example 7 are summarized in Figures 8 and 9 Although the transmittance values ​​of the bottles of Examples 5 and 6 are less than 1% at lower wavelengths, the transmittance values ​​at all wavelengths within the range of 200 to 800 nm are not less than 1%, as shown in FIG. Figure 8 Note that Examples 5-6 have the lowest amount of sunscreen additive in the entire multi-layer bottle structure, ranging from 0.25 wt.% to 0.375 wt.%.

[0081] The results of the light transmittance test of the bottles of Examples 3 to 4 and Comparative Example 7 are shown in Figure 9 (where the maximum transmittance (y-axis) is 1%). Beneficially, all bottles had transmittance values ​​significantly less than 1% at all wavelengths within the 200 to 800 nm range. While the bottles of Examples 3 and 4 did not offer transmittance values ​​as low as those of Comparative Example 7, the transmittance values ​​of the bottles of Examples 3 and 4 within the 400 to 670 nm range were in the very low ranges of 0.3%-0.5% and 0.1%-0.2%, respectively. Furthermore, the bottles of Examples 3 and 4 were substantially free of ash content (e.g., from inorganic pigments or colorants).

[0082] In summary, it is surprising that only 0.5 wt.% and 0.75 wt.% of the sunscreen additive in the entire multilayer bottle structures of Examples 3 and 4 resulted in such low light transmittance values. The extremely high light protection at much lower additive loadings (compared to monolayer bottles) was achieved by placing the sunscreen additive only in the core layer and subjecting the bottles to sufficient orientation during molding during manufacturing to significantly increase their light blocking properties.

[0083] Example 8 to Example 9

[0084] Examples 8 and 9 were produced in the same manner as Example 1, but with the following layer configurations and compositions. Example 8 had a 45 / 10 / 45 layer ratio (thus, a 10% core layer). The inner and outer layers ("A") were 100 wt.% PET (B90A from DAK), and the core layer was a mixture of 92.5 wt.% PET (B90A from DAK) and 7.5 wt.% of the same opacifying additive as in Example 1. Thus, the amount of opacifying additive in the entire multilayer bottle structure of Example 8 was 0.75 wt.%.

[0085] Example 9 has a 46.5 / 7 / 46.5 layer ratio (thus, a 7% core layer). The inner and outer layers ("A") are 100 wt.% PET (B90A from DAK), and the core layer is a mixture of 85 wt.% PVOH (Mowilex M-05 from Kuraray) and 15 wt.% of the same opacifying additive as in Example 1. Therefore, the amount of opacifying additive in the entire multilayer bottle structure of Example 9 is 1.05 wt.%. PVOH is used as a representative hydrolyzable polymer in the core layer instead of PET.

[0086] The multilayer bottles of Examples 8 and 9 were tested for wall thickness, oxygen transmission rate, and light transmittance properties. The multilayer bottles of Examples 8 and 9 were configured to hold approximately 11.5 fluid ounces. Bottle thickness and light transmittance were tested on the same portion of the multilayer bottles as in Example 1 and Comparative Example 2. The average bottle thickness of the bottles of Examples 8 and 9 ranged from 0.26 to 0.31 mm (260 to 310 microns). The oxygen transmission rate of Examples 8 and 9 at 25°C and 50% RH was 1.6 cc / m², respectively. 2 / day and 0.23cc / m 2 / day. Unexpectedly, the OTR of Example 9 is almost an order of magnitude less than that of Example 8. These transmission rates were calculated by measuring the oxygen transmission rate of the entire bottle and then converting to cc / m based on the surface area of ​​the bottle. 2 / day to determine.

[0087] The results of the light transmittance testing of the bottles of Examples 8 and 9 (with 95% confidence limits) are shown in Figure 10 (wherein the maximum transmittance (y-axis) is 0.6%). Beneficially, both bottles have transmittance values ​​well below 1% at all wavelengths within the 200 to 800 nm range. The transmittance values ​​of the bottles of Examples 8 and 9 are in the very low range of less than 0.5% within the 400 to 670 nm range. Beneficially, the bottles of Examples 8 and 9 are essentially free of ash content (e.g., from inorganic pigments or colorants).

[0088] Reference is made to Example 9, which demonstrates that very low light transmittance in combination with very low inorganic / ash content can be achieved with polymers other than PET, such as PVOH. Furthermore, although not tested, it is expected that, due to the core layer containing a PVOH hydrolyzable polymer, the flakes of the bottle will delaminate and / or the core layer will dissolve in a stirred solution of 1 wt.% NaOH in water at 85°C in 30 minutes or less, as described herein and in the Association of Plastics Recyclers' PET-P-04 test (2019).

[0089] aspect

[0090] The present invention has been described above with reference to numerous aspects and specific examples. In view of the above detailed description, many variations will occur to those skilled in the art. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following (aspects are described as "comprising", but alternatively, may be "consisting essentially of" or "consisting of"):

[0091] Aspect 1. A multi-layer bottle comprising: (a) a core layer having a first side and a second side, the core layer comprising a sunscreen additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof; (b) an inner layer located on the first side of the core layer, the inner layer comprising a first polyester polymer; and (c) an outer layer located on the second side of the core layer, the outer layer comprising a second polyester polymer; wherein the bottle is characterized by a light transmittance of less than or equal to 1% at a wavelength in the range of 400 to 700 nm; and an ash content of less than or equal to 1 wt.%.

[0092] Aspect 2. The bottle of aspect 1, wherein the inner layer is adjacent to the first side of the core layer.

[0093] Aspect 3. The bottle of aspect 1, wherein a first intermediate layer (or two or more first intermediate layers) is located between the inner layer and the core layer.

[0094] Aspect 4. The bottle of any one of aspects 1 to 3, wherein the outer layer is adjacent to the second side of the core layer.

[0095] Aspect 5. The bottle of any of aspects 1 to 3, wherein a second intermediate layer (or two or more second intermediate layers) is located between the outer layer and the core layer.

[0096] Aspect 6. The bottle of any one of aspects 1 to 5, wherein the inner layer and the outer layer have the same composition (eg, the same polymer or the same polymer blend).

[0097] Aspect 7. The bottle of any one of aspects 1 to 5, wherein the inner layer and the outer layer have different compositions (eg, different polymers or different polymer blends).

[0098] Aspect 8. The bottle of any one of Aspects 1 to 7, wherein the transmittance is less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) at a wavelength in the range of 400 to 670 nm.

[0099] Aspect 9. The bottle of any one of Aspects 1 to 7, wherein the transmittance is less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) at a wavelength range (e.g., 400 to 550 nm) within the range of 400 to 700 nm (or the range of 400 to 670 nm).

[0100] Aspect 10. The bottle of any one of Aspects 1 to 7, wherein the transmittance is less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) in the (all) wavelength range from 400 to 670 nm.

[0101] Aspect 11. The bottle of any one of aspects 1 to 10, wherein the ash content is less than or equal to 0.5 wt.%, less than or equal to 0.3 wt.%, less than or equal to 0.2 wt.%, less than or equal to 0.1 wt.%, less than or equal to 0.05 wt.%, or less than or equal to 0.01 wt.%.

[0102] Aspect 12. The bottle of any of Aspects 1 to 11, wherein the bottle has a wall thickness (average) within any range disclosed herein, such as 100 to 500 microns, 150 to 400 microns, 175 to 350 microns, 200 to 400 microns, or 200 to 300 microns.

[0103] Aspect 13. The bottle of any of Aspects 1 to 12, wherein the core layer is any (average) percentage of the wall thickness of the bottle disclosed herein, for example 1% to 25%, 3% to 20%, 5% to 15%, or 7% to 13%.

[0104] Aspect 14. The bottle of any of Aspects 1 to 13, wherein the outer layer is any (average) percentage of the wall thickness of the bottle disclosed herein, for example, 30% to 60%, 35% to 55%, 35% to 50%, or 40% to 50%.

[0105] Aspect 15. The bottle of any of Aspects 1 to 14, wherein the inner layer is any (average) percentage of the wall thickness of the bottle disclosed herein, for example, 30% to 60%, 35% to 55%, 35% to 50%, or 40% to 50%.

[0106] Aspect 16. The bottle of any one of Aspects 1 to 15, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes any polymer that causes the flakes of the bottle (less than or equal to 12 mm or 9.5 mm in diameter) to delaminate and / or the core layer to dissolve in a stirred solution of 1 wt.% NaOH in water at 85° C. in less than or equal to 30 min, less than or equal to 25 min, less than or equal to 20 min, or less than or equal to 15 min.

[0107] Aspect 17. The bottle of any one of Aspects 1 to 16, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes any polymer that causes the flakes of the bottle to meet the PET-P-04 test (2019) of the Association of Plastics Recyclers.

[0108] Aspect 18. The bottle of any one of aspects 1 to 17, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer comprises any suitable water-soluble polymer, which may be natural or synthetic and a homopolymer or a copolymer.

[0109] Aspect 19. The bottle of any one of Aspects 1 to 18, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer comprises polyvinyl alcohol (PVOH), partially hydrolyzed polyvinyl alcohol ester, partially hydrolyzed polyvinyl acetate, polyglycolic acid (PGA), or any combination thereof.

[0110] Aspect 20. The bottle of any one of aspects 1 to 19, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer comprises polyvinyl alcohol (PVOH).

[0111] Aspect 21. The bottle of any one of aspects 1 to 19, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer comprises polyglycolic acid (PGA).

[0112] Aspect 22. The bottle of any one of Aspects 1 to 21, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer has any suitable degree of hydrolysis, such as 50% to 99%, 60% to 95%, 70% to 90%, or 70% to 85%.

[0113] Aspect 23. The bottle of any one of aspects 1 to 22, wherein the core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer comprises a foamed hydrolyzable polymer.

[0114] Aspect 24. The bottle of any of aspects 1 to 23, wherein the core layer comprises the core polyester polymer.

[0115] Aspect 25. The bottle of any one of aspects 1 to 24, wherein the bottle comprises at least 97 wt.% polyester, at least 98 wt.% polyester, at least 99 wt.% polyester, at least 99.5 wt.% or at least 99.7 wt.% polyester.

[0116] Aspect 26. The bottle of any one of Aspects 1 to 25, wherein the core polyester polymer, the first polyester polymer, and the second polyester polymer independently comprise polyethylene terephthalate (PET), glycol-modified PET (PET-G), recycled PET (R-PET), polybutylene terephthalate, polylactic acid (PLA), polyhydroxyalkanoate (PHA), or a combination thereof.

[0117] Aspect 27. The bottle of any one of Aspects 1 to 26, wherein the core polyester polymer, the first polyester polymer, and the second polyester polymer independently comprise polyethylene terephthalate (PET), glycol-modified PET (PET-G), recycled PET (R-PET), or a combination thereof.

[0118] Aspect 28. The bottle of any of aspects 1 to 27, wherein the core polyester polymer, the first polyester polymer, and the second polyester polymer independently have a density of at least 1.05 g / cc, at least 1.1 g / cc, or at least 1.2 g / cc.

[0119] Aspect 29. The bottle of any one of aspects 1 to 28, wherein the light transmittance of the bottle is caused by light scattering, light absorption, light reflection, or any combination thereof in the core layer.

[0120] Aspect 30. The bottle of any one of Aspects 1 to 29, wherein the core layer comprises less than or equal to 50 wt.%, less than or equal to 25 wt.%, less than or equal to 15 wt.%, less than or equal to 12 wt.%, less than or equal to 10 wt.%, less than or equal to 8 wt.%, less than or equal to 5 wt.%, less than or equal to 2 wt.%, 1 to 20 wt.%, 2 to 15 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, or 5 to 12 wt.% of an opacifying additive.

[0121] Aspect 31. The bottle of any one of Aspects 1 to 30, wherein the bottle comprises less than or equal to 5 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1.5 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, less than or equal to 0.25 wt.%, 0.1 to 3 wt.%, 0.25 to 2 wt.%, 0.25 to 1.5 wt.%, 0.35 to 2 wt.%, 0.35 to 1.5 wt.%, 0.5 to 1.5 wt.%, or 0.5 to 1 wt.% of a sunscreen additive.

[0122] Aspect 32. The bottle of any of aspects 1 to 31, wherein the sunscreen additive comprises any suitable sunscreen additive or any sunscreen additive disclosed herein.

[0123] Aspect 33. The bottle of any one of aspects 1 to 32, wherein the opacifying additive comprises polymethylpentene, cyclic olefin copolymer, hydrogenated styrene polymer or copolymer, siloxane, solid light scattering pigment, cristobalite, or any combination thereof.

[0124] Aspect 34. The bottle of any of aspects 1 to 33, wherein the opacifying additive has a DSC melting point in the range of 200°C to 250°C, 210°C to 250°C, 225°C to 240°C, or 230°C to 235°C.

[0125] Aspect 35. The bottle of any one of aspects 1 to 34, wherein the opacifying additive has a glass transition temperature (Tg) in the range of 115°C to 145°C, 120°C to 140°C, 120°C to 135°C, or 125°C to 130°C.

[0126] Aspect 36. The bottle of any one of aspects 33 to 35, wherein the solid light scattering pigment comprises titanium dioxide, metal oxide particles, barium sulfate, zinc sulfide, or any combination thereof.

[0127] Aspect 37. The bottle of any one of aspects 33 to 36, wherein the cyclic olefin copolymer comprises an ethylene / norbornene copolymer, an ethylene / tetracyclodecene copolymer, or a combination thereof.

[0128] Aspect 38. The bottle of any one of aspects 1 to 37, wherein the bottle is characterized by a volumetric density of 0.05 to 100, 0.1 to 50, 1 to 30, 2 to 25, or 0.05 to 5 cc / m 2 Oxygen transmission rate within the range of / day.

[0129] Aspect 39. The bottle of any of aspects 1 to 38, wherein the first polyester polymer and the second polyester polymer comprise the same polymer.

[0130] Aspect 40. The bottle of any one of aspects 1 to 39, wherein the inner layer and the outer layer are free of pigments or colorants.

[0131] Aspect 41. The bottle of any one of aspects 1 to 40, wherein the core layer is free of pigments or colorants.

[0132] Aspect 42. The bottle of any one of aspects 1 to 41, wherein the bottle contains (or is configured to contain) a dairy product or a carbonated soft drink.

[0133] Aspect 43. The bottle of any one of aspects 1 to 42, wherein the bottle is produced using an overmolding process.

[0134] Aspect 44. The bottle of any one of aspects 1 to 42, wherein the bottle is produced by injection molding a multilayer preform and then blow molding the multilayer preform.

[0135] Aspect 45. The bottle of any one of aspects 1 to 42, wherein the bottle is produced by blow molding a coextruded (multi-layer) polymer stream.

[0136] Aspect 46. A multi-layer bottle comprising: (a) a core layer having a first side and a second side, the core layer comprising a sunscreen additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof; (b) an inner layer located on the first side of the core layer, the inner layer comprising a first polyester polymer; and (c) an outer layer located on the second side of the core layer, the outer layer comprising a second polyester polymer; wherein the bottle is characterized by a light transmittance of less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) at a wavelength in the range of 400 to 700 nm; and an ash content of less than or equal to 1 wt.% (or less than or equal to 0.5 wt.%, or less than or equal to 0.3 wt.%, or less than or equal to 0.2 wt.%, or less than or equal to 0.1 wt.%, or less than or equal to 0.05 wt.%, or less than or equal to 0.01 wt.%).

[0137] Aspect 47. The bottle of aspect 46, wherein the light transmittance is less than or equal to 1% (or less than or equal to 0.8%, or less than or equal to 0.6%, or less than or equal to 0.4%, or less than or equal to 0.2%) within the (all) wavelength range of 400 to 670 nm; the core layer is an average percentage of 1% to 25%, 3% to 20%, 5% to 15%, or 7% to 13% of the wall thickness of the bottle; and The core layer comprises 1 to 20 wt.%, 2 to 15 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, or 5 to 12 wt.% of the sunscreen additive and / or the bottle comprises 0.1 to 3 wt.%, 0.25 to 2 wt.%, 0.25 to 1.5 wt.%, 0.35 to 2 wt.%, 0.35 to 1.5 wt.%, 0.5 to 1.5 wt.%, or 0.5 to 1 wt.% of the sunscreen additive.

[0138] Aspect 48. The bottle of Aspect 46 or 47, wherein the core layer comprises the hydrolyzable polymer and the hydrolyzable polymer comprises polyvinyl alcohol (PVOH); or the core layer comprises the core polyester polymer and the bottle comprises at least 97 wt.% polyester, at least 98 wt.% polyester, at least 99 wt.% polyester, at least 99.5 wt.% or at least 99.7 wt.% polyester.

Claims

1. A multi-layer bottle comprising: (a) a core layer having a first side and a second side, the core layer comprising a sunscreen additive and a core polyester polymer, a hydrolyzable polymer, or a combination thereof; (b) an inner layer on the first side of the core layer, the inner layer comprising a first polyester polymer; and (c) an outer layer on the second side of the core layer, the outer layer comprising a second polyester polymer; The bottle is characterized in that: a light transmittance of less than or equal to 1% at wavelengths in the range of 400 to 700 nm; and Ash content less than or equal to 1 wt.%.

2. The bottle according to claim 1, wherein The inner layer is adjacent to the first side of the core layer.

3. The bottle according to claim 1, wherein A first intermediate layer, or two or more first intermediate layers, are located between the inner layer and the core layer.

4. The bottle according to any one of claims 1 to 3, wherein The outer layer is adjacent to the second side of the core layer.

5. The bottle according to any one of claims 1 to 3, wherein A second intermediate layer, or two or more second intermediate layers, are located between the outer layer and the core layer.

6. The bottle according to any one of claims 1 to 5, wherein The inner layer and the outer layer have the same composition.

7. The bottle according to any one of claims 1 to 5, wherein The inner layer and the outer layer have different compositions.

8. The bottle according to any one of claims 1 to 7, wherein At a wavelength within a range of 400 to 670 nm, the light transmittance is less than or equal to 1%, less than or equal to 0.8%, less than or equal to 0.6%, less than or equal to 0.4%, or less than or equal to 0.2%.

9. The bottle according to any one of claims 1 to 7, wherein Within a wavelength range of 400 to 700 nm or within a wavelength range of 400 to 670 nm, the transmittance is less than or equal to 1%, less than or equal to 0.8%, less than or equal to 0.6%, less than or equal to 0.4%, or less than or equal to 0.2%.

10. The bottle according to any one of claims 1 to 7, wherein In all wavelength ranges within the range of 400 to 670 nm, the transmittance is less than or equal to 1%, less than or equal to 0.8%, less than or equal to 0.6%, less than or equal to 0.4%, or less than or equal to 0.2%.

11. The bottle according to any one of claims 1 to 10, wherein The ash content is less than or equal to 0.5 wt.%, less than or equal to 0.3 wt.%, less than or equal to 0.2 wt.%, less than or equal to 0.1 wt.%, less than or equal to 0.05 wt.%, or less than or equal to 0.01 wt.%.

12. The bottle according to any one of claims 1 to 11, wherein The bottle has an average wall thickness in a range of 100 to 500 microns, 150 to 400 microns, 175 to 350 microns, 200 to 400 microns, or 200 to 300 microns.

13. The bottle according to any one of claims 1 to 12, wherein The core layer is 1% to 25%, 3% to 20%, 5% to 15%, or 7% to 13% of the average wall thickness of the bottle.

14. The bottle according to any one of claims 1 to 13, wherein The outer layer is 30% to 60%, 35% to 55%, 35% to 50%, or 40% to 50% of the average wall thickness of the bottle.

15. The bottle according to any one of claims 1 to 14, wherein The inner layer is 30% to 60%, 35% to 55%, 35% to 50%, or 40% to 50% of the average wall thickness of the bottle.

16. The bottle according to any one of claims 1 to 15, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes any polymer that causes flakes having a bottle diameter of less than or equal to 12 mm or less than or equal to 9.5 mm to delaminate and / or the core layer to dissolve in a stirred solution of 1 wt.% NaOH in water at 85° C. in 30 minutes or less, 25 minutes or less, 20 minutes or less, or 15 minutes or less.

17. The bottle according to any one of claims 1 to 16, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes any polymer that causes the flakes of the bottle to meet the PET-P-04 test of the Association of Plastics Recyclers (2019).

18. The bottle according to any one of claims 1 to 17, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes a water-soluble polymer.

19. The bottle according to any one of claims 1 to 18, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes polyvinyl alcohol (PVOH), partially hydrolyzed polyvinyl alcohol ester, partially hydrolyzed polyvinyl acetate, polyglycolic acid (PGA), or any combination thereof.

20. The bottle according to any one of claims 1 to 19, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes polyvinyl alcohol (PVOH).

21. The bottle according to any one of claims 1 to 19, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer includes polyglycolic acid (PGA).

22. The bottle according to any one of claims 1 to 21, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer has a degree of hydrolysis ranging from 50% to 99%, 60% to 95%, 70% to 90%, or 70% to 85%.

23. The bottle according to any one of claims 1 to 22, wherein The core layer comprises the hydrolyzable polymer, and the hydrolyzable polymer comprises a foamed hydrolyzable polymer.

24. The bottle according to any one of claims 1 to 23, wherein The core layer comprises the core polyester polymer.

25. The bottle according to any one of claims 1 to 24, wherein The bottle comprises at least 97 wt.% polyester, at least 98 wt.% polyester, at least 99 wt.% polyester, at least 99.5 wt.%, or at least 99.7 wt.% polyester.

26. The bottle according to any one of claims 1 to 25, wherein The core polyester polymer, the first polyester polymer, and the second polyester polymer independently include polyethylene terephthalate (PET), glycol-modified PET (PET-G), recycled PET (R-PET), polybutylene terephthalate, polylactic acid (PLA), polyhydroxyalkanoate (PHA), or a combination thereof.

27. The bottle according to any one of claims 1 to 26, wherein The core polyester polymer, the first polyester polymer, and the second polyester polymer independently include polyethylene terephthalate (PET), glycol-modified PET (PET-G), recycled PET (R-PET), or a combination thereof.

28. The bottle according to any one of claims 1 to 27, wherein The core polyester polymer, the first polyester polymer, and the second polyester polymer independently have a density of at least 1.05 g / cc, at least 1.1 g / cc, or at least 1.2 g / cc.

29. The bottle according to any one of claims 1 to 28, wherein The light transmittance of the bottle is caused by light scattering, light absorption, light reflection, or any combination thereof in the core layer.

30. The bottle according to any one of claims 1 to 29, wherein The core layer contains less than or equal to 50 wt.%, less than or equal to 25 wt.%, less than or equal to 15 wt.%, less than or equal to 12 wt.%, less than or equal to 10 wt.%, less than or equal to 8 wt.%, less than or equal to 5 wt.%, less than or equal to 2 wt.%, 1 to 20 wt.%, 2 to 15 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, or 5 to 12 wt.% of the sunscreen additive.

31. The bottle according to any one of claims 1 to 30, wherein The bottle contains less than or equal to 5 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1.5 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, less than or equal to 0.25 wt.%, 0.1 to 3 wt.%, 0.25 to 2 wt.%, 0.25 to 1.5 wt.%, 0.35 to 2 wt.%, 0.35 to 1.5 wt.%, 0.5 to 1.5 wt.%, or 0.5 to 1 wt.% of the sunscreen additive.

32. The bottle according to any one of claims 1 to 31, wherein The sunscreen additive includes any suitable sunscreen additive or any sunscreen additive disclosed herein.

33. The bottle according to any one of claims 1 to 32, wherein The sunscreen additive includes polymethylpentene, cyclic olefin copolymer, hydrogenated styrene polymer or copolymer, silicone, solid light scattering pigment, cristobalite, or any combination thereof.

34. The bottle according to any one of claims 1 to 33, wherein The sunscreen additive has a DSC melting point in the range of 200°C to 250°C, 210°C to 250°C, 225°C to 240°C, or 230°C to 235°C.

35. The bottle according to any one of claims 1 to 34, wherein The sunscreen additive has a glass transition temperature (Tg) in the range of 115°C to 145°C, 120°C to 140°C, 120°C to 135°C, or 125°C to 130°C.

36. The bottle according to any one of claims 33 to 35, wherein The solid light scattering pigment includes titanium dioxide, metal oxide particles, barium sulfate, zinc sulfide, or any combination thereof.

37. The bottle according to any one of claims 33 to 36, wherein The cyclic olefin copolymer includes an ethylene / norbornene copolymer, an ethylene / tetracyclodecene copolymer, or a combination thereof.

38. The bottle according to any one of claims 1 to 37, wherein The bottle is characterized by a range of 0.05 to 100, 0.1 to 50, 1 to 30, 2 to 25, or 0.05 to 5 cc / m 2 Oxygen transmission rate within the range of / day.

39. The bottle according to any one of claims 1 to 38, wherein The first polyester polymer and the second polyester polymer comprise the same polymer.

40. The bottle according to any one of claims 1 to 39, wherein The inner layer and the outer layer contain no pigments or colorants.

41. The bottle according to any one of claims 1 to 40, wherein The core layer contains no pigments or colorants.

42. The bottle according to any one of claims 1 to 41, wherein The bottle contains a dairy product or a carbonated soft drink, or the bottle is configured to contain a dairy product or a carbonated soft drink.

43. The bottle according to any one of claims 1 to 42, wherein The bottles are produced using an overmolding process.

44. The bottle according to any one of claims 1 to 42, wherein The bottle is produced by injection molding a multilayer preform and then blow molding the multilayer preform.

45. The bottle according to any one of claims 1 to 42, wherein The bottles are produced by blow molding of coextruded or multilayer polymer streams.

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