Multilayer thermoplastic articles with unique visual effects and recycled thermoplastic materials

Abstract

The present invention discloses a blow-molded multilayer article having a hollow body and a wall formed from at least three layers, including a first skin layer, a second skin layer, and a core sandwiched between the first and second skin layers. The skin layers may comprise a first thermoplastic material and an effect pigment and / or a pore-forming agent. The core may comprise a recycled thermoplastic material and a pigment and / or dye. The article may contain greater than 30% recycled thermoplastic material.

Description

Technical Field

[0001] The present invention relates to multilayer thermoplastic articles having unique visual effects, in particular multilayer articles having a core layer comprising recycled thermoplastic material. The present invention also relates to preforms for making such articles and methods for making such preforms and articles. Background Art

[0002] Many consumers prefer to purchase products, particularly hair and beauty products, in packaging that is both attractive and functional. With regard to hair and beauty products, many consumers find plastic packaging particularly desirable because, unlike glass, plastic packaging is typically lightweight while still offering good mechanical properties, ease of use, and drop resistance, properties that are particularly important for hair and beauty products that users often handle with wet hands while barefoot in the bathroom, bathtub, or shower. Many consumers also prefer plastics, particularly polyethylene terephthalate (PET), high-density polyethylene (HDPE), and polypropylene (PP), because plastics are recyclable.

[0003] It may be desirable to package hair and beauty products in containers made from at least some recycled plastic material. However, chemically recycled plastics, which may have physical properties similar to virgin plastic, are currently in limited supply. In some cases, mechanical recycling may be preferred because it is more readily available than chemically recycled plastics. However, mechanically recycled plastics can only be made into bottles with poor structural integrity and poor color. For example, the most popular recycled PET is mechanically recycled PET sold in a "clear" state, which produces bottles with a gray tint, which is generally undesirable for consumers when packaging hair and beauty products. Less popular recycled PET may be green or variegated, which often produces unattractive, poorly colored containers. Furthermore, there are many opportunities to obtain even more colorful PET from materials such as carpet and non-beverage containers, which, when recycled, will have very dark and / or dark colors. These materials are not currently collected for recycling because the current market for this material is very limited.

[0004] Therefore, there remains a need for visually appealing blow-molded articles comprising recycled materials, in particular mechanically recycled plastic materials including pigmented recycled PET, having good mechanical properties. Summary of the Invention

[0005] A blow molded multilayer article comprising: (a) a hollow body defined by a wall comprising an inner surface and an outer surface, the wall being formed in at least one region from three or more layers comprising: (i) a first skin layer and a second skin layer comprising: a first thermoplastic material; and effect pigments and / or pore formers; wherein the first skin layer constitutes the outer surface of the wall in the region and the second skin layer constitutes the inner surface of the wall in the region; (ii) a core sandwiched between the first skin layer and the second skin layer, wherein the core comprises: about 90% to about 99% recycled thermoplastic material, comprising a second thermoplastic material and greater than 200 ppm of impurities; pigments and / or dyes; wherein the article comprises greater than 30% recycled thermoplastic material.

[0006] A blow molded multilayer article comprising: (a) a hollow body defined by a wall comprising an inner surface and an outer surface, the wall being formed in at least one region from three or more layers comprising: (i) a first skin layer and a second skin layer comprising: a thermoplastic material; and an effect pigment and / or a pore former; wherein the first skin layer constitutes the outer surface of the wall in the region and the second skin layer constitutes the inner surface of the wall in the region; (ii) an opaque core sandwiched between the first skin layer and the second skin layer, wherein the core comprises: about 90% to about 99% recycled thermoplastic material comprising the second thermoplastic material and having an L* value less than or equal to 80; pigments and / or dyes; wherein the first skin layer and the core slightly interpenetrate at the interface between the first skin layer and the core.

[0007] An array of articles, wherein each article comprises (a) a hollow body defined by a wall comprising an inner surface and an outer surface, the wall being formed in at least one region from three or more layers comprising: (i) a first skin layer and a second skin layer comprising: a thermoplastic material; and an effect pigment and / or a pore former; wherein the first skin layer constitutes the outer surface of the wall in the region and the second skin layer constitutes the inner surface of the wall in the region; (ii) a core sandwiched between the first skin layer and the second skin layer, wherein the core comprises: a mechanically recycled thermoplastic material comprising a second thermoplastic material; a pigment and / or a dye; wherein each article has the following parameters: ΔE*, ΔL*, and average C* at -15° to 45° when using 45° illumination; and the ΔE* and ΔL* at -15° to 45° vary by less than 6 units across the array. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0009] While the specification concludes with claims which particularly point out and distinctly claim the subject matter of the invention, it is believed the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings, in which:

[0010] Figure 1 are photos of preforms and bottles made from different recycled PET materials;

[0011] Figure 2 A bottle having three layers is schematically represented according to a schematic cross section showing an enlargement;

[0012] Figure 3 Describes the measurement nomenclature system for determining ΔE, a*, b*, C*, and h° at various viewing angles when illuminated at 45°;

[0013] Figure 4A is a schematic diagram of a syringe arrangement in which the nozzle is a concentric nozzle;

[0014] Figure 4B is a schematic cross section of an off-center syringe arrangement;

[0015] Figure 4C is a schematic cross section of an off-center injector arrangement;

[0016] Figure 5A is a photograph of a multilayer PET bottle having mechanically recycled PET in the core and chemically recycled PET in the skin layers;

[0017] Figure 5B is a photograph of a multilayer PET bottle having mechanically recycled PET and opaque pigments in the core layer and chemically recycled PET and effect pigments in the surface layers;

[0018] Figure 5C is a photograph of a multilayer PET bottle having virgin PET and opaque pigment in the core and virgin PET and effect pigment in the skin layers;

[0019] Figure 6A is a photograph of Example 1, which is a multi-layer PET bottle having a PCR of 66.8%;

[0020] Figure 6B is a photograph of a cross section of a preform that can be blown into the bottle of Example 1;

[0021] Figure 6C is a photograph of Example 3, which is a single-layer bottle with a PCR of 66.8%;

[0022] Figure 6D is a photograph of a cross section of a preform that can be blown into the bottle of Example 3;

[0023] Figure 6E is a photograph of Example 5, which is a multi-layer PET bottle with 67% PCR;

[0024] Figure 6F is a photograph of a cross section of a preform that can be blown into the bottle of Example 5;

[0025] Figure 6G is a photograph of Example 6, which is a single-layer PET bottle with a PCR of 67%;

[0026] Figure 6H is a photograph of a cross section of a preform that can be blown into the bottle of Example 6;

[0027] Figure 6I is a photograph of Example 9, which is a multi-layer PET bottle with 65% PCR;

[0028] Figure 6J is a photograph of a cross section of a preform that can be blown into the bottle of Example 9;

[0029] Figure 6K is a photograph of Example 10, which is a multi-layer PET bottle having a PCR of 65%;

[0030] Figure 6L is a photograph of a cross section of a preform that can be blown into the bottle of Example 10. DETAILED DESCRIPTION

[0031] Many consumers desire beauty products packaged in attractive, lightweight, shatter-resistant plastic packaging that is at least partially made from recycled materials. However, manufacturing such packaging can be challenging. Consumers are increasingly interested in understanding the actual percentage of recycled plastic used in packaging. For example, many current PET (Insulated Plastic) (ISBM) bottles for beverages marketed in North America contain only 11% recycled content and those in Western Europe contain only 27% recycled content.

[0032] Chemically recycled plastic can resemble virgin plastic, but currently there isn't enough raw material for large-scale manufacturing. Mechanically recycled material is more readily available but can have an unattractive appearance, including low gloss, high haze, and / or poor color, and may not provide sufficient structural integrity for bottles containing beauty care products.

[0033] Figure 1 Photos of preforms 100, 101 and 102 and bottles 110, 111 and 112 made via ISBM are shown. Preform 100 and bottle 110 contain 100% virgin PET in the core (transparent pellets, purchased from DAK (Richmond, Indiana, USA) and contains virgin PET in the skin layer. Both preform 100 and bottle 110 are transparent for comparison. Beauty care consumers often prefer packaging with this transparency because it implies sophistication and quality, but this transparency may be diminished by any change in color.

[0034] Furthermore, the availability of truly "clear" mechanically recycled PET is limited due to additives used in the processing or stabilization of PET bottles, as well as chemicals absorbed during product use. PET ISBM bottles commonly used in the beverage industry are primarily clear and transparent, and use "almost clear" mechanically recycled PET in their packaging containing recycled material. Due to color shifts caused by fading, these bottles typically have only a small amount of recycled content.

[0035] The preform 101 and bottle 111 contained 75% "virgin" PET in the core and 25% chemically recycled PET (available from London The preform 101 and bottle 111 have a grey hue, which is less attractive to beauty care consumers.

[0036] The preforms 102 and bottles 112 contained 40% "green" recycled PET in the core (green pellets, available from Evergreen, Ohio, USA). ), and contains 25% chemically recycled PET and 75% virgin PET in the skin layer. Using "green" recycled PET is advantageous because it is readily available. However, the preform 102 and bottle 112 have a swampwater green color that is unattractive to consumers, especially those purchasing beauty care products.

[0037] It has been discovered that articles having a high-quality appearance and strong structural properties can be made using a wide range of recycled thermoplastic materials, including mechanically recycled PET that is clear, green, or has other colors, including dark colors such as brown, gray, and black. Figure 2A hollow article 1 is shown, which in this example is a container, specifically an opaque bottle. The hollow article 1 comprises a hollow body 25 defined by a wall 3 having an inner surface 5 and an outer surface 6. As shown in the enlarged cross-section, the article wall 3 has three layers. The wall can be formed by injection stretch blow molding (ISBM) without (or substantially without) an adhesive. The surface layer (A) may contain effect pigments. The core layer (C) may be opaque and may comprise: a recycled thermoplastic material, particularly a mechanically recycled thermoplastic material, including but not limited to clear, green, or other colored PET; a pigment, including an opaque pigment; a toner; and / or a dye. When the core is a separate opaque layer, it can absorb a complementary color that is transmitted and can allow for enhanced color and / or bright, angle-dependent color to be observed. The core can be any color. If a dark or black color is placed behind the effect pigment (such as a pigmented core), this absorbs most of the transmitted light, resulting in a large color response, thereby attracting consumers' attention as they pass by the article on a store shelf.

[0038] It has been discovered that in the articles described herein, the effect pigment particles in the surface layer can be primarily oriented so that their faces are parallel to the surface of the article. Without being bound by theory, it is believed that the higher ratio of oriented to unevenly oriented flakes may be due to a combination of factors, including the fact that the interface between each stream experiences higher shear relative to similar locations in a single-layer article where the effect pigment is dispersed throughout the entire wall of the article, which is thicker than the surface layer of a multilayer article (at the same mechanical strength of the article). In a single-layer article, the particles are less concentrated in high-shear areas, so they have more free space to tumble / rotate 360° during the injection molding process. In a multilayer article, the surface layers are much thinner because each surface layer represents only a portion of the total thickness of the article wall, resulting in the injection molding and stretching steps providing a greater percentage of optimally oriented flake-shaped pigment particles. Furthermore, the dispersion of the effect pigment within the surface layer can result in better spatial overlap between adjacent flakes, resulting in a higher percentage of incident light being reflected closer to the outer surface compared to a single-layer article.

[0039] It has also been found that platelet-shaped effect pigments maintain a tendency to orient parallel to the surface of the article even when the article is irregularly shaped. Therefore, the shape of the article can also be used to modify the visual effect produced by the article from the perspective of a person viewing the article, depending on the orientation of the article when viewed.

[0040] The core layer may have from about 0.1% to about 6%, from about 0.3% to about 4%, and / or from about 0.5% to about 2% pigments and / or dyes. The core layer may comprise from about 94% to about 99.9%, from about 96% to about 99.7%, from about 98% to about 99.5% recycled thermoplastic material by weight of the core layer. The recycled thermoplastic material may include thermoplastic material and optional impurities such as colorants / dyes, additives, catalysts, and / or other non-thermoplastic elements and / or compounds from the source material. The recycled thermoplastic material may contain more than 1000 ppm, more than 500 ppm, and / or more than 200 ppm of impurities by weight of the core layer. The recycled thermoplastic material may contain less than 2%, less than 1.5%, less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, and less than 0.05% impurities by weight of the core layer. The recycled thermoplastic material may comprise impurities from about 0.01% to about 2%, from about 0.05% to about 1%, and / or from about 0.1% to about 0.75%, by weight of the core layer.

[0041] The thermoplastic material may be PET. The core may comprise less than 99%, less than 98%, less than 96%, less than 95%, and / or less than 94% PET, based on the weight of the core layer. The core may comprise from about 90% to about 99%, from about 92% to about 98%, from about 93% to about 97%, and / or from about 94% to about 96% PET, based on the weight of the core layer. In some examples, substantially all of the thermoplastic material in the core is recycled thermoplastic resin, while in other examples, substantially all of the thermoplastic material in the core is mechanically recycled thermoplastic resin. As used herein, "substantially all" may mean at least 97%, alternatively at least 98%, alternatively at least 98.5%, alternatively at least 99%, alternatively at least 99.25%, alternatively at least 99.5%, alternatively at least 99.75%, alternatively at least 99.9%, and alternatively at least 99.99%.

[0042] The skin layer may contain a thermoplastic material and an additional ingredient selected from the group consisting of pigments (including effect pigments), tints, dyes, pore formers, and combinations thereof. The skin layer may contain from about 0.1% to about 6%, from about 0.3% to about 4%, and / or from about 0.5% to about 2% of the additional material, based on the weight of the skin layer.

[0043] In some examples, the surface layer may comprise a recycled thermoplastic material, which may comprise a thermoplastic material and optional impurities, as described herein. In some examples, substantially all of the thermoplastic material in the surface layer is recycled thermoplastic resin, while in other examples, substantially all of the thermoplastic material in the surface layer is mechanically recycled thermoplastic resin. The surface layer may comprise, by weight of the surface layer, approximately 94% to approximately 99.9%, approximately 96% to approximately 99.7%, approximately 98% to approximately 99.5% recycled thermoplastic material. The surface layer may comprise, by weight of the surface layer, approximately 94% to approximately 99.9%, approximately 96% to approximately 99.7%, approximately 98% to approximately 99.5% thermoplastic material. The thermoplastic material may be selected from the group consisting of, but not limited to, virgin thermoplastic material, recycled thermoplastic material, and combinations thereof. The recycled thermoplastic material may contain less than 2%, less than 1.5%, less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, and less than 0.05% impurities by weight of the surface layer. The recycled thermoplastic material may contain from about 0.01% to about 2%, from about 0.05% to about 1%, and / or from about 0.1% to about 0.75% impurities by weight of the surface layer.

[0044] The article may comprise, by weight of the article, more than 20%, more than 30%, more than 35%, more than 40%, more than 45%, more than 50%, more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, more than 92%, more than 94%, more than 95% recycled thermoplastic material, including chemically recycled material, mechanically recycled thermoplastic material, and combinations thereof. In one example, the skin layer comprises less than 25%, less than 20%, less than 15%, less than 10%, less than 5% mechanically recycled thermoplastic material or chemically recycled thermoplastic material, by weight of the skin layer. In some examples, substantially all of the thermoplastic resin used in the container is mechanically recycled thermoplastic resin. In other examples, the thermoplastic resin used in the container is a recycled thermoplastic material, which may include a chemically recycled material and / or a mechanically recycled thermoplastic material.

[0045] The articles described herein not only comprise recycled thermoplastic materials (which may include mechanically recycled materials and / or chemically recycled materials), but they also have improved aesthetics and improved structural integrity compared to other articles comprising recycled materials.

[0046] The article may have a relatively high gloss compared to other articles made from recycled thermoplastic materials. At least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, and / or at least 95% of the area of ​​the exterior surface of the article may have a 20° gloss of 65 GU or greater, 68 GU or greater, 70 GU or greater, 71 GU or greater, 73 GU or greater, 75 GU or greater, 80 GU or greater, 85 GU or greater, 90 GU or greater, and / or 95 GU or greater. To determine the % of area having a 20° gloss as specified in this paragraph, select a vertical line across the sample (from the side initially closest to the shoulder to the side initially closest to the base), make 10 measurements equally spaced along the line, and confirm that they have the required number of gloss units.

[0047] The article may include an area on the outer surface having a haze of ≤30, alternatively ≤20, alternatively ≤15, alternatively ≤10, alternatively ≤5, alternatively ≤3, and alternatively ≤2. The article may include an area on the outer surface that may have a haze of from about 0 to about 30, alternatively from about 0 to about 20, alternatively from about 0.5 to about 15, alternatively from about 0.8 to about 10, and alternatively from about 1 to about 5. Haze can be measured by the haze and reflectance methods described below.

[0048] The article may comprise regions on the exterior surface having a haze anisotropy of <1, alternatively ≤0.9, alternatively ≤0.8, alternatively ≤0.7, and alternatively ≤0.6. Haze may be measured by the haze and reflectance methods described below.

[0049] In addition, the articles described herein may be less prone to delamination than other articles, including single-layer and multi-layer articles containing recycled thermoplastic materials, particularly mechanically recycled thermoplastic materials. Delamination is a common problem in the manufacture of blow-molded multi-layer hollow articles, such as bottles and containers. Delamination can occur immediately or over time due to thermal or mechanical stresses caused by mechanical handling of the container. It usually manifests as bubbles on the surface of the container (which is actually the separation of the two layers at the interface, which can be seen by the bubble-like appearance), but it can also be the source of container damage. Without being bound by theory, it is believed that due to the long-term contact of the layers of material that are still in a molten or partially molten state, parallel flow co-injection leads to the formation of interfacial regions between the layers, in which the layers slightly interpenetrate each other at the interface. The joining area creates good adhesion between the layers, thus making it more difficult to separate them.

[0050] The presence and thickness of the interface between the skin layer and the core (also known as the tie layer) is determined by the Tie Layer Thickness Method described below. The thickness of the interface is the distance perpendicular to the interface where the composition of a unique pigment, additive, or resin varies between a maximum concentration and a minimum concentration.

[0051] The thickness of the interface (i.e., bonding layer or transition layer or interpenetration region) may be from about 500 nm to about 125 μm, alternatively from 1 μm to about 100 μm, alternatively from about 3 μm to about 75 μm, alternatively from about 6 μm to about 60 μm, alternatively from about 10 μm to about 50 μm, as determined by the Bonding Layer Thickness Method described below.

[0052] These articles may have a critical nominal load of greater than or equal to 30 N, greater than or equal to 50 N, greater than or equal to 60 N, greater than or equal to 70 N, greater than or equal to 80 N, greater than or equal to 90 N, greater than or equal to 95 N, greater than or equal to 100 N, greater than or equal to 104 N, greater than or equal to 105 N, greater than or equal to 110 N, and / or greater than or equal to 120 N. These articles may have a critical nominal load of about 30 N to about 170 N, alternatively about 50 N to about 160 N, alternatively about 60 N to about 155 N, alternatively about 90 N to about 145 N, and alternatively about 100 N to about 140 N. The critical nominal load can be measured using the critical nominal load method described below.

[0053] As used herein, " goods " refers to a single blow-molded hollow object for use by a consumer, for example, a container suitable for containing a composition. Non-limiting examples may include bottles, cans, cups, lids, vials, tottles, etc. The goods can be used for storage, packaging, transportation / shipment, and / or for dispensing the composition in a container. The non-limiting volume that can be accommodated in the container is about 10 mL to about 1000 mL, about 100 ml to about 900 mL, about 200 mL to about 860 mL, about 260 mL to about 760 mL, about 280 mL to about 720 mL, about 350 mL to about 500 mL. Alternatively, the container can have a volume of 5 L or 20 L at the most.

[0054] The composition contained in the article can be any of a variety of compositions and include detergents (such as laundry detergents or dishwashing detergents), fabric softeners, and fragrance enhancers (such as and / or skin care products), food products (including but not limited to liquid beverages and snacks), paper products (such as facial tissues, wipes), beauty care compositions (such as cosmetics, lotions, shampoos, conditioners, hair styling agents, deodorants and antiperspirants, as well as personal cleansing products including washing, cleaning, washing and / or peeling of the skin (including the face, hands, scalp and body)), oral care products (such as toothpaste, mouthwash, dental floss), medications (fever reducers, analgesics, nasal vasoconstrictors, antihistamines, cough suppressants, supplements, antidiarrheals, proton pump inhibitors and other heartburn formulations, antiemetics, etc.), etc. The composition can have a variety of forms, non-limiting examples of which can include liquids, gels, powders, beads, solid sticks, packets (such as Tide ), flakes, pastes, tablets, capsules, ointments, filaments, fibers and / or sheets (including paper such as toilet paper, facial tissue and wipes).

[0055] The article may be a bottle for containing a product, for example a liquid product such as shampoo and / or conditioner and / or body wash.

[0056] As used herein, the term "blow molding" refers to a manufacturing process that forms a hollow thermoplastic article containing a cavity suitable for containing a composition. Generally speaking, there are three main types of blow molding: extrusion blow molding (EBM), injection blow molding (IBM), and injection stretch blow molding (ISBM).

[0057] As used herein, the term "color" includes any color, such as white, black, red, orange, yellow, green, blue, purple, brown, and / or any other color, or variations thereof.

[0058] As used herein, "effect pigments" refers to one of the two broad categories of pigments: metallic effect pigments and special effect pigments. Metallic effect pigments are composed of metallic particles. When aligned parallely in their application system, they produce a metallic-like luster by reflecting light from the surface of a metallic flake. Incident light is completely reflected at the surface of a metallic flake, which lacks any transmissive components. When the metal flakes are well aligned and closely spaced, incident light can be completely reflected from the first few tens of microns of the surface. In a blow-molded article, if the article contains metallic flakes throughout its thickness distribution, those metal flakes extending beyond the surface by a few tens of microns have no opportunity to interact with the incident light and are therefore unimportant to the optical response. Furthermore, metallic effect pigments can be expensive to manufacture and purchase, and may impact recycling streams and environmental sustainability. To reduce the total amount of metallic effect pigment used, it may be desirable to confine the metallic effect pigment to a thin layer of the blow-molded article, with the remainder of the article thickness containing no or substantially no metallic effect pigment. Due to the high reflectivity and hiding strength of many metallic effect pigments combined with the good arrangement and spacing of the platelets, the color of the material behind the layer containing the metallic effect pigments is less critical, so a variety of colored materials can be used, such as previously unpopular colors and color-changing resins, including resins from one or more recycling streams.

[0059] Metallic effect pigments typically have a metal such as aluminum, copper or bronze as the flake substrate. The thickness, shape and aspect ratio of the flakes can vary from thick and irregular shapes commonly known as "corn flakes" to smoother, pancake-shaped "dollars" to ultra-thin, flat flakes with an extremely high aspect ratio. "Corn flake" and "dollar" flakes are produced by grinding or atomization processes, while ultra-thin flakes are produced by physical vapor deposition. The metal flakes are often coated with an additional material to passivate the aluminum so that they are stable to processing under thermoplastic processing conditions. In addition, a variety of color effects can be achieved by coating with dielectric materials, such as metal oxides with a specific refractive index, and / or absorbing substances such as dyes or pigments attached to the surface. Commercial examples of metallic effect pigments are: product line, and Mastersafe from Eckart (a subsidiary of Altana), and

[0060] Special effect pigments may include all other flake-shaped effect pigments that cannot be classified as "metallic effect pigments". These pigments are generally based on a substrate with flake-shaped crystals (or particles), such as mica, (natural or synthetic) borosilicate glass, aluminum oxide flakes and / or silicon dioxide flakes. These flake-shaped particles may be coated with metal oxides such as titanium dioxide, iron oxide, silicon dioxide, tin oxide, and combinations thereof. Special effect pigments (including pearlescent pigments) are made of materials including and Vendor included selling as is.

[0061] Special effect pigments can be transparent / translucent, based on coating one or more layers onto a platelet substrate such as mica, silica, borosilicate glass, aluminum oxide, and the like. The layers coating the platelet are typically oxides such as titanium dioxide, iron oxide, silicon dioxide, or combinations thereof. Effect pigments based on this structure can reflect a portion of incident light while allowing a complementary portion of the spectrum to be transmitted through the coated platelet. Interference color effects due to reflected light from the translucent effect pigments are best observed when viewed against a dark background, as the background absorbs the transmitted complementary spectrum as well as any other incident light that passes through or around the coated platelet. Against a white or light-colored background, the complementary transmitted spectrum can be diffusely scattered and reappear to the viewer, resulting in a lower colorimetric response.

[0062] In one example, the effect pigment can be titanium dioxide coated onto mica platelets, which can achieve a silver pearlescent luster with a thickness of approximately 40 to 60 nm. When the titanium dioxide is applied as a thicker layer, a range of interference colors can be achieved due to the difference in refractive index between the layer and the mica platelets. For example, as the thickness of the titanium dioxide layer increases from approximately 60 to 160 nm, the interference colors progress from yellow to red, to blue, and then to green. Due to the nature of the pigment, interference colors are only observable at specific angles relative to the observer, the incident light, and the platelet surface. In other words, for titanium dioxide / mica-based special effect pigments with parallel alignment in their application system, the interference colors will appear bright near one angle and transparent, making the surrounding material or background visible at other angles. The interference color effects due to reflected light from the translucent effect pigment are best observed when viewed against a dark background, as the background absorbs the transmitted complementary spectrum as well as any other incident light. In this case, a titanium dioxide / mica pigment with a blue interference color will appear to float between a lustrous blue and black as the angle changes. Against a white background, the complementary transmission spectra can be diffusely scattered and reappear to the observer, resulting in a lower chromatic response. In this case, a titanium dioxide / mica pigment with a blue interference color will appear to fluctuate between a less brilliant blue and a pale yellow as the angle changes. Against different colored backgrounds, the background color can be hidden at certain angles but visible at others. This creates a variety of angle-dependent color effects. Furthermore, curved surfaces can enhance the appearance of the article, as both effects can be observed simultaneously across the entire article.

[0063] While a black background can improve the appearance of titanium dioxide / mica effect pigments, the interference color effect can be limited due to the uneven and impure nature of the mica used as the platelet substrate. Without wishing to be bound by theory, two general approaches have been used to improve the interference color effect of mica coated with a single titanium dioxide layer (the structure is actually three layers—A / B / A, where B = mica and A = titanium dioxide). First, additional layers with alternating refractive indices and appropriate layer thicknesses can be added to the A / B / A structure, resulting in a final structure with an A / C / A / B / A / C / A architecture, where C = silicon dioxide, B = mica, and A = titanium dioxide. The additional interfaces created by the multilayered structure can contribute to increased reflectivity and higher chromaticity compared to a three-layer A / B / A structure. The second approach relies on improving the quality of the substrate used to manufacture the effect pigment platelets. Mica flakes produced via commercial milling and sorting methods have high thickness variation. Furthermore, such mica flakes suffer from surface defects that can lead to diffuse scattering. Natural micas may also contain iron impurities that impart a yellowish hue to effect pigments. Synthetic platelets based on borosilicate glass, aluminum oxide, or silicon dioxide can improve the achievable color floating effects, such as high chroma (color purity) and sparkle, due to their smooth surface, uniform thickness, and lack of a yellow hue due to elemental impurities.

[0064] The color shift / goniochromatic effect is defined by the ability of the article to change color (i.e., green to purple, gold to purple, blue to violet, red to blue) with viewing angle. Without being bound by theory, highly transparent special effect pigments that exhibit color shift / goniochromatic effects can be produced in a variety of ways. In general, for most substrates including mica, borosilicate glass, aluminum oxide, and silicon dioxide, increasing the number of layers in the basic A / B / A structure can produce color shift / goniochromatic effects if the layer thicknesses and refractive index differences are appropriately chosen. A commercial example of this is BASF Corporation's BASF GLASS® from BASF Corporation. The Colormotion product line relies on a 7-layer structure that starts with a borosilicate platelet substrate and then alternates TiO2 / SiO2 / TiO2 on either side of the substrate. Alternatively, a synthetically produced substrate such as silica with uniform and controllable thickness can produce color-shifting / goniochromatic effects with only 3 layers of an A / B / A structure (where A=TiO2 and B=SiO2). A commercial example is the VISION from Merck KGaA (Darmstadt, Germany). product line.

[0065] The particle size of the effect pigment in its longest dimension may be from about 1 μm to about 200 μm, from about 2 μm to about 150 μm, from about 3 μm to about 100 μm, from about 4 μm to about 75 μm, and / or from about 5 μm to about 50 μm. The thickness of the effect pigment may be less than 5 μm, less than 3 μm, less than 1 μm, less than 800 nm, less than 700 nm, and / or less than 600 nm. The thickness of the effect pigment may be from about 25 nm to about 5 μm, from about 100 nm to about 3 μm, from about 150 nm to about 1 μm, from about 200 nm to about 700 nm, from about 250 nm to about 600 nm, and / or from about 300 nm to about 560 nm. The size of the effect pigment may be determined by the Platelet Size Test Method described below.

[0066] Effect pigments can have a relatively high aspect ratio (i.e., the ratio of the major axis divided by the minor axis). For example, the aspect ratio can be greater than 1:1, greater than 5:1, greater than 10:1, greater than 15:1, greater than 20:1, greater than 30:1, greater than 40:1, greater than 60:1, greater than 80:1, and / or greater than 100:1.

[0067] The materials comprising any one or more layers of the preform and / or article may include one or more effect pigments or other materials, such as pore formers, including but not limited to the domain-forming liquids, domain-forming solids, microvoid-forming solids, and foaming agents described herein. As used herein, the term "pore former" refers to a material that can induce the appearance of gas-filled or vapor-filled domains or pores within a polymer matrix. Examples of pore formers include porous solid particles that retain at least some porosity during processing to form the container. Other pore formers include solid particles that at least partially separate from the matrix upon stretching the thermoplastic material, thereby causing micropore formation. Examples of such solid particles include calcium carbonate particles that can be coated with a fatty acid or its salt. Pore formers also include foaming agents that evaporate or release gas to form micropores. Such materials can be added to provide a variety of visual effects in the preform and / or finished product, such as pearlescence, shimmer, reflection, color change, and the like. Surprisingly, however, as described in more detail herein, it has been discovered that the inclusion of effect pigments and / or pore formers, when combined with etching, texturing, or otherwise modifying the outer surface of the preform, can provide unique aesthetic properties in the final article. For example, the article can have unique aesthetic features that impart depth, texture, and / or a three-dimensional appearance. Furthermore, in addition to the novel features and methods described herein, these aesthetic properties can be provided using conventional blow molding equipment and techniques. Furthermore, these unique aesthetic properties can be provided in articles having a smooth, relatively smooth, or substantially smooth outer surface, which can itself be a beneficial effect. Having a smooth, relatively smooth, or substantially smooth outer surface can be desirable for a number of reasons, including that it can allow the outer surface to be easier to print on, easier to label, easier to handle, and have a better tactile feel, among other benefits.

[0068] The preform may contain from about 0.01% to about 5.0%, from about 0.05% to about 1.5%, and / or from about 0.1% to about 0.5% of a domain-forming liquid. Without being bound by theory, it is believed that the liquid is finely dispersed in the thermoplastic material due to the high shear conditions during compounding of the masterbatch and / or injection molding of the preform. Because the liquid is immiscible with the thermoplastic material, finely dispersed droplets or phase-separated domains are formed within the thermoplastic material. To minimize interfacial energy, domains are often spherical when formed. However, during the injection and blow molding processes, domains can change shape. If the thermoplastic material is subjected to uniaxial shear or stretching in a specific zone or region, the domains can become rod-shaped, sausage-shaped, or ellipsoidal in that zone or region. If the thermoplastic material is subjected to biaxial stretching in a specific zone or region, the domains can become disc-shaped or plate-shaped in that zone or region. These and other different shapes can be formed depending on the elongation or stretching properties of the thermoplastic material. Different fluid-containing domain shapes may be provided in different regions or zones within a preform or article.

[0069] The microdomain forming liquid may include silicone oil, hydrocarbon oil, liquid polyfluorinated compound, liquid oligomer, polyfluorinated compound, ethylene glycol, propylene glycol water, ionic liquid, and mixtures thereof. Some or all of the molecules of the microdomain forming liquid may be linear, cyclic or branched. Some or all of the molecules of the microdomain forming liquid may contain functional groups. Examples of such functional groups include esters, ethers, amines, phenyls, hydroxyls, carboxylic acids, vinyls and halogen groups. The molecule may contain one or more functional groups, and the microdomain forming liquid may contain molecules with different functional groups. Specific examples of microdomain forming liquids include linear, branched and cyclic polydimethylsiloxanes or other polydialkyl or polydiarylsiloxanes. Suitable silicone liquids include linear or branched polydimethylsiloxane homopolymers. Hydrocarbon oils include mineral oil (C15-C40) or liquid paraffin. Polyfluorinated compounds include perfluorocarbons (such as perfluorooctane) and fluorinated polyethers (such as Oil). Liquid oligomers include low molecular weight hydrocarbon compounds such as polyisoprene or polyisobutylene. Other liquid oligomers include polyalkylene glycols such as low molecular weight polyethylene glycol. An exemplary thermoplastic material is polyethylene terephthalate (PET), and an exemplary domain-forming liquid is hydroxyl-terminated polydimethylsiloxane.

[0070] The preform may comprise from about 0.10% to about 20%, preferably from about 1.0% to about 10%, and more preferably from about 1.0% to about 5.0% of a microdomain-forming solid material or a microvoid-forming solid material. The material is dispersed in the thermoplastic material in the form of small solid particles, these particles typically having a number average maximum dimension of about 1 micron or less. The particles may comprise inorganic materials such as calcium carbonate, or organic materials such as poly(methyl methacrylate). Without being bound by theory, it is believed that due to the high shear conditions during compounding of the masterbatch and / or injection molding of the preform, the microvoid-forming solid particles are finely dispersed in the thermoplastic material. The solid material may melt to form droplets during compounding of the masterbatch, but resolidify upon cooling to 25°C to form phase-separated, finely dispersed solid particles within the thermoplastic material.

[0071] It is believed that when the thermoplastic material is stretched, for example, during blow molding, the micropore-forming solid is at least partially separated from the thermoplastic matrix to form dispersed microvoids within the thermoplastic material. As used herein, microvoids can encompass air-filled microvoids and any solid microvoid-forming particles therein. The micropore-forming solid particles can be treated or coated to facilitate separation from the thermoplastic polymer matrix during stretching. For example, the particles can be at least partially coated with a relatively thin layer of a fatty acid or its salt, such as stearic acid or calcium stearate. Examples of other treating agents or coating materials include fluorochemicals and silicone compounds. Examples of inorganic micropore-forming solid particles include calcium carbonate, silica (including ground, precipitated and / or fumed silica), aluminum oxide, titanium dioxide, clay, barium sulfate, etc., and mixtures thereof. Examples of organic or organosilicon microvoid-forming solid particles include polysiloxane waxes, hydrocarbon waxes, polyalkylene oxide waxes, polystyrene, polyesters such as polycarbonates, polyolefins, poly(meth)acrylates, polymethylpentene, liquid crystal polymers (LCPs), and other solid or waxy polymers, and mixtures thereof. An exemplary embodiment includes a microvoid-forming solid, namely calcium carbonate in polyethylene terephthalate (PET).

[0072] It is believed that domain-forming solids (unlike microvoid-forming solids) soften during the blow molding process. Therefore, they tend not to separate from the thermoplastic polymer matrix in which they are embedded and do not create microvoids. Examples of domain-forming solids include, but are not limited to, elastomers and other cross-linked polymers, as well as PET.

[0073] The preform may contain from about 0.01% to about 5.0%, preferably from about 0.05% to about 1.5%, and more preferably from about 0.1% to about 0.5% of a microvoid-forming blowing agent. The blowing agent may be a solid or liquid under ambient conditions. Without being bound by theory, it is believed that the blowing agent becomes finely dispersed or dissolved in the thermoplastic material due to the high pressure and high shear conditions during compounding of the masterbatch and / or injection molding of the preform. The blowing agent may or may not be miscible with the thermoplastic material. Upon a triggering event such as heating, reduced pressure, or a change in pH, the blowing agent releases vapor or gas to form microvoids within the thermoplastic matrix. When formed, the microvoids are often spherical in shape. However, during the blow molding process, the microvoids can change shape. If the thermoplastic material undergoes uniaxial stretching in a specific zone or region, the microvoids can become rod-shaped, sausage-shaped, or elliptical in that zone or region. If the thermoplastic material undergoes biaxial stretching in a specific zone or zones, the microvoids can become disc-shaped or plate-shaped in that zone or zones. Depending on the elongation or stretching properties of the thermoplastic material, different shapes can be formed, and the preform and / or article can have different fluid-containing microvoid shapes in different zones or zones.

[0074] The blowing agent may include compounds such as pentane or hexane that are volatile liquids under ambient conditions but boil or evaporate under process conditions that may include elevated temperatures and / or reduced pressures. Alternatively, the warping agent may be a solid under ambient conditions but release a vapor or gas when heated or subjected to other triggering events. Examples of such materials include pentane, sodium bicarbonate, azo compounds such as azobisisobutyronitrile, peroxide compounds such as dibenzoic acid peroxide, and the like.

[0075] Effect pigments, domain-forming materials, microvoid-forming solids, and microvoid-forming blowing agents may comprise or form platelet-shaped shaped particles or regions (hereinafter referred to as "effect structures") in one or more layers of the preform. Additional information regarding pore formers (including domain-forming liquids, domain-forming solids, microvoid-forming solids, and microvoid-forming blowing agents) can be found in U.S. Patent Application No. 16 / 720,052, which is incorporated herein by reference.

[0076] As used herein, "opaque" means that a layer or wall has a total light transmittance of less than 50%.Total light transmittance is measured according to the Total Light Transmittance Test Method described below.

[0077] As used herein, a "preform" is a unit that has undergone preliminary (usually incomplete) shaping or molding, and is typically further processed to form an article. A preform is typically generally "test tube" shaped.

[0078] As used herein, "substantially free" means less than 3%, alternatively less than 2%, alternatively less than 1%, alternatively less than 0.5%, alternatively less than 0.25%, alternatively less than 0.1%, alternatively less than 0.05%, alternatively less than 0.01%, alternatively less than 0.001%, and / or alternatively free. As used herein, "free" means 0%.

[0079] As used herein, the terms "include," "comprising," and "including" are intended to be non-limiting, and are understood to mean "having," "having," and "including," respectively.

[0080] Unless otherwise specified, all percentages, parts and ratios are based upon the total weight of the compositions of the present invention. All weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials.

[0081] Unless otherwise indicated, all component or composition levels are in reference to the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

[0082] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range falling within such wider numerical range, as if such narrower numerical ranges were all expressly written herein.

[0083] Where content ranges are given, these should be understood to refer to the total amount of the stated ingredient in the composition, or where more than one substance falls within an ingredient definition, the total amount of all ingredients in the composition that meet that definition.

[0084] The article may have a total light transmittance of 50% or less, alternatively 40% or less, alternatively 30% or less, alternatively 20% or less, alternatively 10% or less, and alternatively 0% or less. The total light transmittance may be from about 0% to about 50%, alternatively from about 0% to about 40%, alternatively from about 0% to about 30%, alternatively from about 0% to about 20%, and alternatively from about 0% to about 10%, as measured according to the Total Light Transmittance test method described below.

[0085] The core layer may have a total light transmittance of less than or equal to 50%, alternatively less than or equal to 40%, alternatively less than or equal to 30%, alternatively less than or equal to 20%, alternatively less than or equal to 10%, alternatively less than or equal to 5%, as measured according to the Total Light Transmittance test method described below.

[0086] The core layer may have a dark or black color with an L* less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, alternatively less than or equal to 40, alternatively less than or equal to 30, alternatively less than or equal to 20, alternatively less than or equal to 10, alternatively less than or equal to 5. The core may have an L* of about 0 to about 80, about 0 to about 75, about 0 to about 65, about 0 to about 55, about 0 to about 50, about 0 to about 45, and / or about 0 to about 40. In some examples, effect pigments, particularly special effect pigments, that can provide a goniochromatic effect (i.e., where the bottle has an angle-dependent color shift) may be used.

[0087] The color change ΔE of the same area but between two different detection angles, such as between steep and gentle viewing angles (Color45as45 and Color45as-15), can be calculated. *, to determine the magnitude of the color shift. The larger the magnitude, the more color shift there is on the bottle. The measurement nomenclature system used here is written where the first angle provided is the illumination angle defined from the surface normal and the second angle is the retroreflective detection angle. This is in Figure 3 Further described in .

[0088] ΔE * Mathematically it is expressed by the following formula:

[0089] ΔE*=[(L* X -L* Y ) 2 +(a* X -a* Y ) 2 +(b* X -b* Y ) 2 ] 1 / 2

[0090] “X” represents the first measurement point (eg, Color45as45), and “Y” represents the second measurement point (eg, Color45as-15).

[0091] When using 45° illumination, the multi-layered structure may have a ΔE* at -15° to 45° of greater than 20, greater than 30, greater than 40, greater than 50, greater than 60, greater than 75, greater than 80, greater than 85, greater than 90, greater than 95, greater than 100, and / or greater than 105. The multi-layered structure may have a ΔE* at -15° to 45° of about 25 to about 150, about 35 to about 145, about 45 to about 140, about 50 to about 135, about 55 to about 130, about 60 to about 130, about 75 to about 130, about 90 to about 125, about 95 to about 130, about 100 to about 125, and / or about 105 to about 120.

[0092] ΔL* is the difference between the maximum and minimum values ​​of the following six angles: Color45as-15, Color45as15, Color45as25, Color45as45, Color45as75, and Color45as110. The ΔL* of the multi-layered structure may be greater than 45, greater than 50, greater than 55, greater than 60, greater than 65, and / or greater than 70. The ΔL* of the multi-layered structure may be from about 10 to about 100, from about 25 to about 90, from about 40 to about 85, and / or from about 50 to about 80.

[0093] Average C* is the average chromaticity at six angles: Color45as-15, Color45as15, Color45as25, Color45as45, Color45as75, and Color45as110. The average *C of the multi-layered structure can be greater than 10, greater than 15, greater than 20, greater than 25, and / or greater than 30. The average *C of the multi-layered structure can be from about 10 to about 50, from about 15 to about 45, from about 20 to about 40, and / or from about 25 to about 35.

[0094] The ΔE*, ΔL* and average C* of a multilayer structure having a core comprising mechanically recycled polymer material can differ by about 6 units, about 5 units, about 4 units, about 3 units, about 2 units and / or about 1 unit compared to a multilayer structure having a similar construction except that the core comprises virgin thermoplastic material instead of mechanically recycled polymer material.

[0095] Another issue with using recycled thermoplastic materials, particularly mechanically recycled thermoplastic materials such as PET, is that different raw materials may have inconsistent colors, resulting in products appearing different when displayed in an array on a store shelf. Noticeable variations can make the product look cheap and unappealing, which is unacceptable to beauty product consumers. The articles described herein may include an array of two or more articles that may have varying ΔE*, ΔL*, average C*, gloss, and haze, but such variations are not visually detectable to an observer. The ΔE*, ΔL*, and average C* across each article in the array vary by less than 6 units, less than 5 units, less than 4 units, less than 3 units, less than 2 units, and / or less than 1 unit across the array. The ΔE*, ΔL*, and average C* measured on the outer wall of the bottles across the array vary by less than 10%, less than 7%, less than 5%, less than 3%, less than 2%, and / or less than 1% across the array. The term “visually perceptible” means that the indented element can be visually distinguished by a human observer with the naked eye (excluding standard corrective lenses suitable for correcting myopia, hyperopia or astigmatism, or other vision correction) at a distance of 1 meter under illumination at least equal to that of a standard 100-watt incandescent bulb.

[0096] The average panel wall thickness may be from about 200 μm to about 5 mm, alternatively from about 250 μm to about 2.5 mm, alternatively from about 300 μm to about 2 mm, alternatively from about 350 μm to about 1.5 mm, alternatively from about 375 μm to about 1.4 mm, and alternatively from about 400 μm to about 1 mm. The average panel wall thickness may be determined using the local wall thickness method described below. The average local wall thickness may vary by less than 20%, alternatively by less than 15%, alternatively by less than 10%, and alternatively by less than 10% over the entire volume.

[0097] The thickness of the skin layer constituting the outer surface and / or the skin layer constituting the inner surface and / or the core may be about 50 μm to about 800 μm, alternatively about 75 μm to about 600 μm, alternatively 85 μm to about 500 μm, alternatively 100 μm to about 450 μm, and alternatively about 120 μm to about 250 μm.

[0098] The surface layer comprising the outer surface of the article can be thicker than other layers, including the surface layer comprising the inner surface of the article. The surface layer comprising the outer surface can be 10%, 20%, 25%, 30%, 40%, and / or 50% thicker than the surface layer comprising the inner surface. The surface layer comprising the outer surface can be two, three, four, and / or five times as thick as the surface layer comprising the inner surface. The thickness of a layer can be determined using the layer thickness method described herein.

[0099] The average panel wall thickness may constitute from about 30% to about 80% of the core, from about 35% to about 75% of the core, from about 40% to about 70% of the core, from about 45% to about 65% of the core, and / or from about 50% to about 60% of the core. The average panel wall thickness may constitute greater than 33% of the core, greater than 40% of the core, greater than 45% of the core, greater than 50% of the core, greater than 55% of the core, and / or greater than 60% of the core.

[0100] The article may feel smooth and may have a root mean square roughness Sq of less than 50 μin (1.27 μm), less than 45 μin (1.12 μm), less than 40 μin (1.016 μm), less than 35 μin (0.89 μm), and / or less than 32 μin (0.8128 μm). The article may have a root mean square roughness Sq of about 20 μin (0.508 μm) to about 42 μin (1.0668 μm), about 25 μin (0.635 μm) to about 40 μin (1.016 μm), about 28 μin (0.7112 μm) to about 38 μin (0.9652 μm), and / or about 30 μin (0.762 μm) to about 36 μin (0.9144 μm). The root mean square roughness Sq can be measured by the root mean square roughness Sq measurement method described below.

[0101] The article may comprise a thermoplastic material selected from the group consisting of polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene naphthalate (PEN), polycyclohexanedimethanol terephthalate (PCT), glycol-modified PCT copolymer (PCTG), copolyester of cyclohexanedimethanol and terephthalic acid (PCTA), polybutylene terephthalate (PBCT), acrylonitrile-styrene (AS), styrene-butadiene copolymer (SBC) or polyolefin (e.g., one of low density polyethylene (LDPE), linear low density polyethylene (LLPDE), high density polyethylene (HDPE), polypropylene (PP), polymethylpentene (PMP), liquid crystal polymer (LCP), cyclic olefin copolymer (COC)), and combinations thereof. The thermoplastic material may be selected from the group consisting of: PET, HDPE, LDPE, PP, PVC, PETG, PEN, PS, and combinations thereof. The thermoplastic material may be selected from the group consisting of: PET, PP, HDPE, LDPE, and combinations thereof. In one example, the thermoplastic material may be PET.

[0102] Recycled thermoplastic materials may also be used, such as post-consumer recycled ("PCR") materials, post-industrial recycled ("PIR") materials, and regrind materials, such as polyethylene terephthalate (PCRPET), high-density polyethylene (PCRHDPE), low-density polyethylene (PCRLDPE), polyethylene terephthalate (PIRPET), high-density polyethylene (PIRHDPE), regrind polyethylene terephthalate, low-density polyethylene (PIRLDPE), and others.

[0103] The thermoplastic materials described herein can be formed by using a combination of monomers or oligomers derived from renewable resources and monomers derived from non-renewable (e.g., petroleum) resources. For example, the thermoplastic material can include polymers made entirely from biologically derived monomers or oligomers, polymers made in part from biologically derived monomers or oligomers and in part from petroleum-derived monomers or oligomers, or can also be derived from enzyme-derived methods.

[0104] The core layer and the skin layer may comprise the same or different thermoplastic materials. The skin layer and the core layer may be based on the same type of thermoplastic material (e.g. PET), which may allow the layers to better interpenetrate at the interface due to their chemical compatibility, resulting in a stronger wall. "Based on the same type of resin" means that the skin layer and the core layer may comprise at least 50%, at least 70%, at least 90% and / or at least 95% of the same type of resin. Resins of the "same type" are intended to be resins belonging to the same chemical class, i.e., PET is considered to be a single chemical class. For example, two different PET resins having different molecular weights are considered to be of the same type. However, a PET resin and a PP resin are not considered to be of the same type. Different polyesters are also not considered to be of the same type.

[0105] The skin and core layers can comprise similar resins, such as the same grade of PET, different grades of PET, or virgin PET / recycled PET (rPET). The use of rPET is desirable due to potential cost reductions and sustainability considerations. The skin and core layers can also comprise different resins that can be alternated within the article, such as PET / cyclic olefin copolymer, PET / PEN, or PET / LCP. The resin pairs are selected to have optimal properties, such as appearance, mechanical properties, and vapor and / or moisture barriers.

[0106] The article may comprise at least three layers in one or more regions. The region formed by the three layers may comprise more than about 60%, more than about 80%, more preferably more than 90%, and / or more than 95% of the weight of the article. The region formed by the three layers (referred to herein as two skin layers and a core) may comprise substantially the entire length of the article and / or comprise the entire length of the article.

[0107] The article may include one or more sublayers having various functions. For example, the article may include a barrier material sublayer or a recycled material sublayer between an outer thermoplastic material layer and an inner thermoplastic material layer. Such layered containers may be made from multilayer preforms using common techniques employed in the thermoplastic manufacturing art. The barrier material sublayer and the recycled material sublayer may be used in the core layer and / or in the additional C layer. In one example, the article wall may include an inner surface having a skin layer, adjacent to which may be a core, adjacent to which may be a C layer, adjacent to which may be another core, and adjacent to which may be a skin layer forming the outer surface.

[0108] The article may contain additives in any of its layers (as long as the desired properties of the layer are maintained) in an amount generally from about 0.0001% to about 9%, from about 0.001% to about 5%, and / or from about 0.01% to about 1% by weight of the article. Non-limiting examples of additives may include fillers, curing agents, antistatic agents, lubricants, UV stabilizers, antioxidants, antiblocking agents, catalyst stabilizers, nucleating agents, and combinations thereof.

[0109] The core and / or the skin layer may contain opacifying pigments. The opacifying pigments may include opacifiers, opaque absorbing pigments, and combinations thereof. The skin layer forming the outer surface of the article may be free or substantially free of opacifying pigments to avoid diminishing the effect of the effect pigment.

[0110] Non-limiting examples of opacifiers can include titanium dioxide, calcium carbonate, silica, mica, clay, minerals, and combinations thereof. The opacifier can be any domain / particle having a refractive index suitably different from that of a thermoplastic material, such as PET (which can include poly(methyl methacrylate)), silicone, liquid crystal polymer (LCP), polymethylpentene (PMP), air, gas, etc. Additionally, the opacifier can have an appearance that is white due to scattering of light or black due to absorption of light, as well as tones intermediate thereto, as long as they prevent most light from being transmitted to the underlying layers. Non-limiting examples of black opacifying pigments include carbon black and organic black pigments such as Black L 0086 (BASF).

[0111] Opaque absorbing pigments can include particles that provide color and opacity for the materials in which they are present. Opaque absorbing pigments can be inorganic or organic particulate materials. If the average particle size of all absorbing pigments is large enough or if they have a high extinction coefficient, they can be opaque. The particle size of the absorbing pigment is generally greater than 15nm, alternatively greater than 100nm, alternatively greater than 500nm, and alternatively greater than 1 micron. The absorbing pigment can be an organic pigment and / or an inorganic pigment. The non-limiting example of organic absorbing pigments can include azo and diazo pigments, such as azo and diazo lakes, Hansa, benzimidazolone, diaryl compounds, pyrazolone, pigment yellow and red; polycyclic pigments, such as phthalocyanine, quinacridone, perylene, naphthoxycyclone, dioxazine, anthraquinone, isoindoline, thioindigo, diaryl or quinoline yellow pigment, nigrosine and their combination. Non-limiting examples of inorganic pigments may include titanium yellow, iron oxide, ultramarine blue, cobalt blue, chromium oxide green, lead yellow, cadmium yellow and cadmium red, carbon black pigment, mixed metal oxides, and combinations thereof. Organic pigments and inorganic pigments may be used alone or in combination.

[0112] Another aspect of the present invention relates to a hollow preform that can be blow molded to produce an article as described above. The hollow preform may include a wall, wherein the wall has an inner surface and an outer surface, and the preform wall is formed in at least one region from three layers: two preform skin layers forming the inner surface of the wall region and the outer surface of the wall region, and a preform core layer located between the two preform skin layers. Together, these three layers form the entire wall of the preform in this region.

[0113] The preform may be manufactured by co-injecting two or more streams in parallel, with one or more streams constituting the skin layers and the remaining streams constituting the core layer, wherein the skin layers comprise effect pigments and thermoplastic material, and the core layer may comprise recycled thermoplastic material and pigment.

[0114] Two uniform streams of hot polymer melt merge at the injector nozzle before entering the mold cavity, and this initiates multi-stream co-flow. These injectors can be arranged in a number of different ways, including Figures 4A to 4C Arrangement shown.

[0115] Figure 4A The syringe nozzle arrangement can form two concentric streams of molten thermoplastic components produced by concentric nozzles B and A. The outer nozzle A can distribute stream I, which can contain the thermoplastic composition and effect pigments that will eventually form the skin. The inner nozzle B corresponds to stream II, which can contain the molten combination of recycled thermoplastic material and pigments that will eventually form the core, such as Figure 2 An enlarged schematic cross section is shown.

[0116] Different nozzle arrangements can result in different flow patterns for streams I and II. Figure 4B and Figure 4C Shown are off-center (non-concentric or offset) syringe nozzles A and B. The outer nozzle A can dispense stream I, and the inner nozzle B can dispense stream II. Figure 4B In the embodiment, the syringe nozzle A is positioned in such a way that a thicker surface layer is achieved, which forms the outer surface of the bottle (which forms the outer surface of the product). Figure 3 In Figure C, the syringe nozzle A is positioned in a manner that creates a thinner skin layer (which forms the outer surface of the bottle) and a thicker skin layer (which forms the inner surface of the product). To achieve this flow pattern, several approaches can be used. Processes with non-concentric nozzles require positioning the central nozzle off-center, while processes with valve pin plates adjust the profile to create an offset preferential flow. Figure 4B The offset position in may allow more A material to flow to the exterior of the preform, which may result in an article having an improved visual effect, in particular an improved appearance of the recessed elements.

[0117] It is obvious to the skilled person that such a preform, once blown, will form an article according to the invention having a skin layer and a core layer, wherein the layers of the preform will form the corresponding layers of the article, i.e. the skin layer of the preform will form the skin layer of the article and the core layer of the preform will form the core layer of the article.

[0118] A preform suitable for blow molding can be formed by the following steps:

[0119] a) providing a co-injection mold for preparing a preform;

[0120] b) substantially simultaneously co-injecting (parallel co-injection) two or more streams of molten resin to form a complete preform as described above, wherein one or more streams form the preform skin layer containing effect pigments and the opaque preform core layer; optionally, additional streams may be added to form one or more C layers.

[0121] The preforms obtained using this method can then be blow molded using IBM or ISBM. Specifically, the articles can be produced using ISBM. Articles produced using the ISBM process (and their respective preforms produced by injection molding) can be distinguished from similar articles produced using different processes, such as extrusion blow molding, by the presence of a gate mark, a small raised spot that indicates the "gate" where the injection molding took place. Typically, in the case of containers and bottles, the "gate mark" is present at the bottom of the article.

[0122] Test Method

[0123] When the article is a container or bottle, critical nominal load, opacity, and goniospectrophotometry measurements are performed on panel wall samples removed from the article. Unless otherwise specified, the outer surface of the panel wall sample is tested. A sample having dimensions of 100 mm in length and approximately 50 mm in width is cut from the main portion of the article wall and at least 50 mm away from the shoulder / neck and base areas.

[0124] When the product does not allow for removal of such a large sample, a shorter sample with a width:length ratio of 1:2 may be used, as described in further detail below. For containers and bottles, the sample is preferably removed from the label panel of the bottle at least 50 mm away from the shoulder / neck or base area. Cut with a suitable razor blade or utility knife to remove the larger area, and then further cut to the appropriate size with a new single-edge razor blade.

[0125] If possible, the sample should be flat or made flat by using a frame that holds the sample flat at least in the area where the test is being performed. It is important that the sample is flat to determine the critical nominal load, RMS roughness Sq, total light transmittance, and goniospectrophotometry.

[0126] Average vertical orientation and local orientation index :

[0127] The method described herein describes how to measure the normal orientation of effect structures disposed within a material layer and the average normal orientation and LOI of the effect structures in a defined area of ​​a specific sample. To help better understand the method, a brief overview is set forth herein, followed by specific examples.

[0128] Before determining the average normal orientation of any group of effect structures or the LOI of any portion of the article, it is important to identify the specific area of ​​the article to be measured and the effect structures within the measurement area to be analyzed. Therefore, a person with 20 / 20 vision (or equivalent vision resulting from correction through glasses, contact lenses, or surgery) visually inspects the article 100, such as the bottle 180 shown in FIG. 15 , to locate a location on the wall sample from the wall 150 of the bottle 180. The selected location should be located so as not to completely overlap the neck 103, first shoulder 101, second shoulder 102, or base 106 of the bottle 180, and, if possible, not to overlap at all with any such portion or other irregularities in the outer surface 133 of the bottle 180. The sample portion 500 should be generally rectangular in shape. The sample portion 500 should be carefully removed from the bottle 180 so that it is not deformed or damaged and so that it can be further cut into specific sample sizes, such as the sample 505 shown in FIG. 16 , for analysis.

[0129] Once the sample 505 is obtained, it is scanned with a computed tomography (CT) system (optionally equipped with a microscope) at sufficient resolution to characterize the shape of the effect structure 300 therein. The CT x-ray energy and contrast mode are set to optimize the relationship between the signal due to the effect structure 300 and the signal from the material (e.g., plastic or polymer material) comprising the wall 150 of the article 100. Because CT data may contain "noise" or "artifacts," and because the sample 505 may contain secondary pigmentation or additives based on isotropic particles (e.g., traditional pigments and / or reheat additives), it is first important to characterize the general shape parameters of the effect structure 300 in order to be able to identify the effect structure 300. The shape parameters of the effect structure 300 can be obtained from the CT data, but the parameters can be supplemented or obtained from the manufacturer's specifications or other imaging systems and methods.

[0130] Once the shape parameters of effect structure 300 are known, the orientation of effect structure 300 within sample 505 can be determined. The orientation information can be obtained from a CT scan of sample 505. The CT scan can be the same scan used to characterize the shape of effect structure 300 or a separate scan used only to determine the orientation of effect structure 300. Starting with sample 505, a measurement region 510 is identified that extends across a boundary 515 of visual effect 360 and a portion of sample 505 that does not include visual effect 360. The CT scan data of the sample is segmented into 3D voxel patches using an intensity threshold, which are considered candidates for effect structure 300. The voxel patches are then refined using the previously determined shape parameters, such as to separate voxel patches representing effect structure 360 ​​from voxel patches caused by noise, artifacts, etc. The effect structure normal vector ESNV (as shown in FIG. 17 ) is calculated for each effect structure 360 ​​and compared to the outer surface normal vector OSNV of the outer surface 133 of the article 100 in a plane perpendicular to the boundary 515 of the visual effect 360 (or perpendicular to the tangent to the boundary at the center of the boundary 515 in the sample). If the angle between the ESNV and the OSNV is obtuse, the direction of the ESNV should be reversed so that the measured angle is acute. The OSNV at the point on the article surface should be extended toward the effect structure 300 until it intersects the effect structure 300 with the ESNV. The acute angle between the ESNV and the OSNV at that point is recorded.

[0131] Averaging the acute angles between ESNVs and OSNVs within this square area provides the average normal orientation of the effector structure at the analyzed location.

[0132] Critical nominal load (N) and scratch depth at the damaged area

[0133] If the sample readily delaminated when removed from the bottle, the sample was given a score of 0 N for the "critical nominal load." For samples that remained intact, they were subjected to damage caused by scratching according to the scratch test procedure (ASTM D7027-13 / ISO 19252:08) using a Scratch 5 from Surface Machine Systems, LLC with the following settings: 1 mm diameter spherical tip, initial load: 1 N, end load: 125 N, scratch rate: 10 mm / s, and scratch length 100 mm. For samples less than 100 mm, the scratch length can be reduced while keeping the initial and end loads the same. This provides an estimate of the critical nominal load. Using this estimate, additional samples can be run within a narrower load range to more accurately determine the critical nominal load.

[0134] Damage caused by scratches was performed on both sides of the sample corresponding to the inner and outer surfaces of the bottle. The sample was sealed by using a foam type double-sided tape (such as 3M) on the underside of the sample. It is critical to adhere the sample to the sample holder using permanent mounting tape (polyurethane double-sided high-density foam tape with acrylic adhesive, approximately 62 mils or 1.6 mm in total thickness, UPC# 021200013393). All samples were cleaned with compressed air prior to scratch testing.

[0135] After completing the scratch test, the damage point is visually determined to be the distance on the scratch length at which visible delamination begins to occur. Delamination introduces air gaps between layers that are visible to the naked eye or visible to a person skilled in the art with the aid of a stereomicroscope. This is verified based on three minimum scratches (defined as the cuts in the upper bottle) with a standard deviation of 10% or less on each side of the sample. The side with the lower critical nominal load is recorded as the result of the method. At the scratch position at the point where delamination begins to occur, the scratch depth at the damaged area is measured according to ASTM D7027. The critical nominal load (N) is defined as the nominal load recorded at the position determined to be the damage point. A laser scanning confocal microscope (KEYENCE VK-9700K) and VK-X200 analyzer software are used to analyze the damage caused by the scratches, including the damage point, scratch width and scratch depth.

[0136] Gloss 20° method

[0137] Gloss 20° is measured at 20° using a gloss meter, such as a Micro Tri Gloss Meter (BYK-Gardner GmbH), according to ASTM D2457-13. Each point is measured three times, and the average is calculated to determine Gloss 20°. All gloss measurements are made against a black background, referred to as "base black." Base black is the black area on an X-Rite Gray Balance card (45as45L*a*b*21.077 0.15-0.29). The measurements provided by the Micro Tri Gloss Meter have units "GU," which stands for "Gloss Units."

[0138] The minimum measurement area for measuring gloss 20° using a micro tri-angle gloss meter is 10mm×10mm.

[0139] Goniospectrophotometry

[0140] ΔE * Mathematically it is expressed by the following formula:

[0141] ΔE*=[(L* X -L* Y ) 2 +(a* X -a* Y ) 2 +(b* X -b* Y )2 ] 1 / 2

[0142] “X” represents the first measurement point (eg, Color45as45), and “Y” represents the second measurement point (eg, Color45as-15).

[0143] The reflectance color characteristics of L*, a*, b*, C*, and h° are measured using a multi-angle spectrophotometer (such as the MA-T12 or MA98 from X-Rite Incorporated) according to ASTM E 308, ASTM E 1164, ASTM E 2194, and ISO 7724. The sample is placed on a white background, which is referred to as "base white." "Base white" is the white area on the X-Rite Gray Balance Card (45as45 L*a*b*96.2-0.8 3.16).

[0144] The samples were measured using CIE standard illuminant D65 / 10°. The measurement nomenclature system used herein is written where the first angle provided is the illumination angle defined from the surface normal and the second angle is the retroreflective detection angle. Figure 3 Measure the area on the outer panel wall 3 times and record the average reading.

[0145] When colors are expressed in CIELAB (L*a*b*), L* defines lightness, a* represents the red / green value (+a=red, -a=green), b* represents the yellow / blue value (+b=yellow, -b=blue), C* defines chroma, and h° defines the hue angle. Chroma describes the vividness or dullness of a color, where + is brighter and - is duller. Chroma is also known as saturation. Brightness is the difference in lightness / darkness values, where + is "brighter" and - is "darker." L* represents the darkest black at L*=0 and the brightest white at L*=100. Hue is the property of a color that makes it recognizable as red, green, etc., and depends on its dominant wavelength and is independent of intensity or brightness. ΔL* is the difference between the maximum and minimum L* at the following six angles: Color45as-15, Color45as15, Color45as25, Color45as45, Color45as75, and Color45as110.

[0146] Haze and Reflectance Methods : Haze anisotropy, peak specular reflectance (GU), and reflective softness (FW at 3 / 5 height of specular profile)

[0147] The haze reported herein is also referred to as reflectance haze and is measured according to ASTM E430 using a haze meter / goniophotometer such as a Rhopoint IQ (20° / 60° / 85° gloss meter, DOI meter, haze meter, goniophotometer, Rhopoint Instruments Ltd.).

[0148] Reflection haze = 100 × (∑ pixels from 17° to 19° (sample) + ∑ pixels from 21° to 23° (sample)) / specular gloss (standard sample)

[0149] Haze anisotropy is the ratio of the haze measured on a bottle sample when oriented parallel to the bottle height (ie, reflected haze) to the haze measured when the sample is rotated 90°.

[0150] Peak specular reflectance is measured at 20°, with the diode array covering + / - 7.25° from the specular angle in 0.028° steps. Reflective softness is measured from the specular profile (+ / - 5.6° gloss units from the specular angle) as the full width (FW) at 3 / 5 of the peak height of the specular profile peak.

[0151] Local wall thickness

[0152] Using a 1 / 8" diameter target ball, use an Olympus Magna- The wall thickness at a specific location is measured using an 8600. Three measurements are taken at each location and their average is calculated to determine the local wall thickness.

[0153] The average local wall thickness is determined by determining the local wall thickness as described above over the entire length of the article or panel and then averaging the thickness near the shoulder and near the base.

[0154] Total light transmittance

[0155] Total light transmittance is measured using a benchtop sphere spectrophotometer such as the Ci7800 (X-Rite) using D65 illumination. Total light transmittance is measured according to ASTM D1003. Opacity % can be calculated by dividing 100 by total light transmittance %. Measure an area on the outer panel wall three times and record the average reading.

[0156] Root mean square roughness Sq measurement method

[0157] The root mean square roughness Sq is measured using a 3D laser scanning confocal microscope (such as the Keyence VK-X200 series microscope purchased from KEYENCE CORPORATION of the United States), which includes a VK-X200K controller and a VK-X210 measuring unit. The instrument manufacturer's software VK Viewer version 2.4.1.0 is used for data collection, and the manufacturer's software Multifile Analyzer version 1.1.14.62 and VK Analyzer version 3.4.0.1 are used for data analysis. The manufacturer's image stitching software VK Image Stitching version 2.1.0.0 is used. The manufacturer's analysis software complies with ISO 25178. The light source used is a semiconductor laser with a wavelength of 408 nm and a power of about 0.95 mW.

[0158] The sample to be analyzed is obtained by cutting a piece of the article, including the area to be analyzed, into a size suitable for proper analysis under the microscope. If the sample is not flat but flexible, it can be held down on the microscope stage with tape or other means. If, due to the sample's shape, flexibility, or other characteristics, the measurement results are more accurate when the sample is not flattened, a correction can be used, as explained below.

[0159] Measurement data from the samples were obtained using a 50X objective lens suitable for non-contact profilometry, such as a 50X Nikon CF IC Epi Plan DI interferometry objective lens with a numerical aperture of 0.95. Data were collected using the "Expert Mode" of the acquisition software, with the following parameters set as described herein: 1) the height scan range was set to cover the sample's height range (this can vary from sample to sample depending on the surface topography of each sample); 2) the Z-direction step size was set to 0.10 microns; 3) the actual peak detection mode was set to "on"; and 4) the laser intensity and detector gain were optimized for each sample using the automatic gain feature of the instrument control software. For each sample, a 3×3 image array was collected and stitched together, resulting in a field of view of 790×575 μm (width×height); the lateral resolution was 0.56 μm / pixel.

[0160] Prior to analysis, the data was corrected using the manufacturer's Multifile Analyzer software as follows: 1) 3x3 median smoothing, in which the center pixel of a 3x3 pixel array was replaced by the median of the array; 2) noise removal using weak height cutting (following the built-in algorithm in the analysis software), and 3) shape correction using waveform removal (0.5mm cutoff). The reference plane was specified using the set area method and selecting the same area as that used for form removal. Areas including foreign matter, artifacts of the sample collection process, or any other obvious anomalies should be excluded from the analysis, and alternative samples should be used for any samples that could not be accurately measured. The resulting value is the root mean square roughness Sq of the measured portion of the sample.

[0161] Layer thickness and plate size

[0162] Micro-CT scanning method

[0163] The bottle samples to be tested were imaged as a single data set with continuous voxels using a micro-CT X-ray scanner capable of scanning samples having dimensions of at least approximately 1 mm x 1 mm x 4 mm. An isotropic spatial resolution of at least 1.8 μm was required in the data set collected by the micro-CT scan. An example of a suitable instrument is a SCANCO Systems model μ50 micro-CT scanner (Scanco Medical AG, Brüttisellen, Switzerland), which was operated with the following settings: 55 kVp energy level at 72 μA; 3600 projections; 10 mm field of view; 1000 ms integration time; 10 averages; and a voxel size of 1.8 μm. For higher resolution, suitable instruments include the X-ray tomography microscopy capability at the TOMCAT beamline of the Swiss Light Source (SLS) at the Paul Scherrer Institute (PSI) in Switzerland, equipped with a high-quality microscope (Optique Peter (Lentilly, France)) with a 40× objective coupled to a PCO.edge 5.5sCMOS camera (PCO (Kelheim, Germany), a 20 μm thick LuAG:Ce scintillating screen, and a resulting isotropic voxel size of approximately 0.163 μm. The beam energy was set to 15 keV with an exposure time of 250 ms, and approximately 1501 projections were acquired for each scan.

[0164] The test samples to be analyzed are prepared as follows: a rectangular piece of plastic is cut from the wall, preferably the label panel area, with an Exacto knife, and then the sample is further trimmed to a width of approximately 1-5 mm using a fine-toothed Exacto saw, being careful to avoid causing cracks. The sample is positioned vertically using materials such as mounting the foam material inside a plastic cylindrical scanning tube or by attaching the sample to a brass pin (3.15 mm diameter) using double-sided sticky tape and / or clear nail paint. The image acquisition settings of the instrument are selected so that the image intensity contrast is sensitive enough to provide a clear and reproducible distinction of the sample structure from the air and surrounding mounting foam. Image acquisition settings that cannot achieve this contrast distinction or the required spatial resolution are not suitable for this method. Scans of the plastic sample are captured so that a similar volume of each sample with its thickness is included in the data set.

[0165] Software for performing data set reconstruction to generate 3D renderings is supplied by the scanner manufacturer. Suitable software for subsequent image processing steps and quantitative image analysis includes programs such as Avizo Fire 9.2 (Visualization Sciences Group / FEI Company (Burlington, Massachusetts, USA) and software with corresponding Image Processing Toolbox Version 9.1 (The Mathworks Inc. Natick, Massachusetts, USA). MicroCT data collected using 16-bit grayscale intensity depth were converted to 8-bit grayscale intensity depth, taking care to ensure that the resulting 8-bit dataset maintained the maximum dynamic range and the minimum number of saturated voxels feasible, while excluding extreme outliers.

[0166] Aligning the sample surface so that it is parallel to the YZ plane of the global axis system is achieved by one of the following means, including using a fixture for micro-CT of properly aligned materials, or by using software such as Avizo to visually align the surface and resample the dataset using interpolation.

[0167] Layer thickness was measured via micro-CT with image analysis, where the effect pigment layer was defined as containing 95% pigment. This analysis was performed on a processed micro-CT dataset containing a square section of material approximately 1.5 mm x 1.5 mm. The dataset spanned from boundary to boundary in the YZ direction. It fully intersected the minimum Y boundary, maximum Y boundary, minimum Z boundary, and maximum Z boundary. A small non-material buffer region existed between the minimum X boundary and the maximum X boundary. This region consisted of air or filler material.

[0168] Layer thickness method

[0169] The material threshold is determined by performing the Otsu method on all samples of interest and averaging the results. The material threshold should identify the bottle material while minimizing noise and filler material. The material threshold is applied to the aligned and trimmed data set. For each Y,Z value of the material data set, a line of voxel values ​​parallel to the x-axis is collected. A typical line will consist of a large continuous strip that is a bottle. Smaller strips may also be present due to filler material used to hold the sample in place or due to noise. The positions of the start and end voxels of the largest strip of each line are recorded. These positions are averaged together to obtain the edge of the material. The edge of the material can experience micro-CT diffraction artifacts caused by the sudden change in density from air to polymer. These streaking effects can cause the edge voxel values ​​to be high enough to be misclassified as pigment. To eliminate this effect, the material boundary determined by the average start and end positions is moved inward by 10 voxels.

[0170] In the case of establishing the material boundary, each sample is processed again by the Ostu method to determine the threshold value of the pigment. The pigment in the material is segmented using the average value of all sample thresholds. Each data set is thresholded to generate a pigment data set using the pigment threshold. The pigment voxels outside the material boundary are set to zero to remove any noise and streak effects.

[0171] Count the number of pigment voxels on each YZ slice within the material. Add the sum across the slices. Based on these sums, the boundary YZ slices are defined as those that enclose 95% of the pigment material. Record the layer thickness as the distance from the material boundary to the 95% pigment boundary.

[0172] Flake Sizing Method

[0173] The analysis is performed on a dataset of reconstructed voxels containing a square portion of the bottle material. A threshold is determined that separates the pigment flakes from the bottle material. A connected component function such as The bwconncomp function, available in Count, counts flakes in a sample. Flakes can be warped or damaged by the bottle-forming process. Flakes are ignored if they are too small to be accurately measured, contain holes, or are warped (non-planar as described below). The thickness and width of individual flakes are measured as described below.

[0174] First, the XYZ voxel position of the sheet is sent to the Principal component analysis of the PCA function is performed to determine the orientation of the flake. Using this information, the flake can be reoriented so that it lies nearly horizontally on the XY plane. Projecting the flake voxels onto the XY plane yields the outline of the flake. This can be used to find the largest circle in the projection, which then defines a trimming template that can be used to cut the flake into the shape of a disk. The Euclidean distance map generated from the top of the disk ( The bwdist function (with ) is used to measure the average thickness of the disk bottom. This distance measurement is independent of the orientation of the flake. If the flake is planar (no warping), the minimum Z distance from the XY plane should be nearly constant for each XY position, and the average height of the flake measured from the minimum Z value to the maximum Z value should be within 15% of the average thickness found earlier. Non-planar flakes are ignored.

[0175] The projection profile can be measured across its major axis width and its minor axis width using standard imaging methods, which are used to fit the The regionprops function gets the shape of the ellipse. This is a measure of the maximum width of the sheet and the minimum width of the sheet.

[0176] Adhesive layer thickness (interface layer thickness) :

[0177] Placing a unique additive, colorant, or resin within at least one of the layers allows Method A or Method B to map the composition over a distance perpendicular to the interface where the composition of the unique additive, colorant, or resin varies between a maximum concentration and a minimum concentration.

[0178] Method A: Energy Dispersive X-ray Spectroscopy (EDS) mapping of adjacent layers with unique elemental composition via resins (e.g., PET / nylon) or colorants / additives.

[0179] If the bottle sample (preparation of the bottle sample is described below) will contain equal to or greater than 2% by weight of colorants and / or additives, and the elemental composition of these colorants and / or additives can be appropriately mapped by EDS (e.g., elements above atomic number 3, excluding carbon or oxygen), then method A can be used. These colorants / additives can be molecular species or particles. If they are in particulate form, they should be well dispersed so that there are about 10 or more particles within a volume of 5 μm × 5 μm × 200 nm. Generally speaking, the largest dimension of the particles should be less than 500 nm.

[0180] Sample preparation :

[0181] Use a heated blade to extract a piece of the bottle label panel wall, measuring approximately 3 cm x 3 cm, at least 50 mm from the shoulder / neck or base area. The heated blade allows the bottle to be sliced ​​without applying a large amount of force that could cause premature delamination. This is achieved by melting, rather than cutting, the panel wall material. Remove the molten edge of this piece with scissors, and then use a new, sharp, single-edged razor blade to further cut the approximately 3 cm x 3 cm piece into several pieces measuring approximately 1 cm x 0.5 cm. Apply cutting force parallel to the layer / interface, rather than perpendicular to the interface, along the length of the piece to prevent staining across the interface.

[0182] The blocks, approximately 1 cm x 0.5 cm, were then edge-polished manually, resulting in a polished surface showing a cross-section of the bottle wall and layered structure. Initial polishing involved using SiC paper with decreasing grit sizes (400, 600, 800, and then 1200), using distilled water as a lubricant / coolant. The 1200 grit polished surface was then further polished using 0.3 μm Al₂O₃ polishing media, with distilled water used as a lubricant. The polished samples were then ultrasonically cleaned in a detergent + distilled water solution for 1 minute, followed by three additional rounds of ultrasonic cleaning in fresh distilled water to rinse the detergent from the samples. The final ultrasonic cleaning was performed in ethanol for 2 minutes. The polished and cleaned samples were mounted edge-up on an SEM stub with double-sided carbon tape and then coated with approximately 1020 nm of carbon, as deposited by a carbon evaporator such as a Leica EM ACE600 (Leica Microsystems).

[0183] Identification of the approximate interface by SEM :

[0184] Identification of the approximate interface between the A / C or C / B layers is necessary to allow the interface to be found in the dual beam FIB. To identify the approximate interface, a modern field emission SEM (such as FEI (Thermo Fisher Scientific)) was used. ) Apreo SEM equipped with a silicon drift EDS detector (SDD) (such as EDAX Octane Elect 30mm 2 SEM imaging and EDS mapping were performed using an SDD (EDAX Inc.). Preliminary EDS mapping at approximately 500 to 1000 times magnification was collected across the entire cross-sectional plane to confirm the presence of a layered structure by identifying the unique elements present in each layer. The accelerating voltage was set appropriately to ionize the most desirable electron shell of the element of interest, thereby generating an X-ray signal. USP <1181> (USP29-NF24) provides a useful reference for selecting the optimal operating conditions for collecting EDS signals.

[0185] The EDS map was used to show the approximate location of the interface between the layers, after which platinum fiducial markers were deposited via electron beam deposition using a gas injection system (GIS) to mark the location of the interface. Another EDS map with the Pt fiducial markers was collected to confirm their location relative to the interface.

[0186] Dual-beam FIB sample preparation :

[0187] Thin foil samples (100 nm-200 nm thick) are required to map interfaces with suitable high resolution. Using modern dual beam focused ion beams (such as FEI (Thermo Fisher Scientific) )Helios 600) is used to prepare the lamellae. The interface is positioned in the FIB with the help of platinum fiducial markers. A protective platinum cap is then deposited on the area of ​​interest at the interface in the FIB, measuring approximately 30μm × 2μm × 2μm. This is done to protect the material that will become the lamellae sample from unnecessary damage caused by the ion beam. The 30μm dimension is oriented perpendicular to the interface so that approximately 15μm covers one side of the interface and 15μm covers the other side. The material is then removed from each side of the platinum cap, leaving the capped area as a lamella, measuring approximately 30μm wide × 2μm thick × 10μm deep, where the interface is oriented parallel to the 10μm direction. The lamellae are then extracted with the help of an Omniprobe nanomanipulator (Oxford Instruments) and attached to a copper Omniprobe grid. The lamellae sample is then thinned using 30kV gallium ions until it is sufficiently thin (approximately 500nm-200nm). The freshly thinned wafer samples were then cleaned with 5 kV gallium ions to remove excessive damage caused by the 30 kV thinning process.

[0188] STEM Data Collection :

[0189] A modern field emission TEM such as the FEI Tecnai TF-20 (Thermo ) to collect Scanning Transmission Electron Microscopy (STEM) Energy Dispersive X-ray Spectroscopy (EDS) data using a modern field emission TEM equipped with a modern silicon drift EDS detector (SDD) such as the EDAX Apollo XLT2 30 mm 2 SDD detector (EDAX Inc.) with collection and analysis software such as Apex TM (EDAX Inc.). The interface region within the foil produced as described above was mapped using EDS to reveal the presence and location of elemental components in the two polymer layers. The EDS map was approximately 20 μm x 10 μm in size, with the interface perpendicular to the 20 μm direction ("Y" direction) and parallel to the 10 μm direction ("X" direction). The "Y" and "X" directions were perpendicular or nearly perpendicular to each other.

[0190] Maps were collected using an accelerating voltage between 200 kV and 300 kV and a beam current equal to or between 100 pA and 1 nA to achieve an SDD count rate of at least 3,000 counts per second. Map resolution was at least 256 × 160 pixels with a dwell time of approximately 200 μs per pixel. Approximately 200 frames were collected for a total mapping time of approximately 30 minutes. Elements of interest were selected, and a standardless automated ZAF analysis method (such as P / B-ZAF fundamental parameter analysis) was selected to achieve quantitative mapping.

[0191] Data processing :

[0192] The EDS plot data can be displayed as a color-coded image with a unique color corresponding to each element. The intensity of the color is proportional to the concentration of the elemental species. The EDS plot data is processed to display a line profile of normalized atomic % by summing the X-ray counts occurring in the "Y" direction (parallel to the interface) for each element, and the summed intensity is plotted as a function of distance across the interface in the "X" direction (perpendicular to the interface). The distance between the maximum normalized atomic % and the minimum normalized atomic % of at least one element, both with a slope of about zero in the range of about 2 microns to 4 microns, is defined as the interface layer thickness.

[0193] Method B: Confocal Raman spectroscopy mapping of adjacent layers with unique spectral characteristics via resins (e.g., PET / COC) or colorants / additives.

[0194] 2D chemical maps or line scans were collected across the layer interfaces using a confocal Raman microscope (Witec A300R confocal Raman spectrometer) equipped with a continuous laser beam, a motorized xy sample scanning stage, a video CCD camera, an LED white light source, diode-pumped laser excitation from 488 nm to 785 nm, and a 50x to 100x (Zeiss EC Epiplan-Neofluar, NA = 0.8 or better) microscope objective.

[0195] The samples were prepared in a similar manner as described in the Method A - Sample Preparation section, but the samples were uncoated.

[0196] The sample is mounted on a glass microscope slide with the edge facing up. A white light source is used to locate the region of interest near the layer interface with the aid of a video CCD camera. In the region of interest, a 2D chemical mapping map via spectral acquisition is obtained by focusing the laser beam at or below the surface and scanning across the entire layer interface in the XY direction with a step size of 1 μm or less, with an integration time of less than 1 s at each step size. The integration time should be adjusted to prevent detector saturation. Use suitable software (such as WITEC TM Project Five (version 5.0) software) was used to generate Raman images using spectral features unique to each polymer layer (such as peak intensity, integrated area, peak width, and / or fluorescence). Prior to image generation, the complete Raman spectral data at each pixel in the data set was corrected for cosmic rays and baselines. To determine intermixing between polymer layers, a cross-sectional analysis was performed in which the spectral features used to generate the chemical mapping were traced along lines drawn across the interface, which included at least 10 microns within the region covering the polymer layer of interest. The defined spectral features were plotted against distance (in microns). The interlayer mixing distance (i.e., the bonding layer) was defined as the distance between the maximum and minimum values ​​of the spectral features.

[0197] Example

[0198] Figure 5A is a photo of a three-layer bottle made via ISBM. The bottle has PCR pellets made from green mechanical recycling (purchased from Plastics), and a core layer made of virgin PET (DAK, Indiana, USA ) and chemically recycled PET (C181, purchased from Indorama, Bangkok, Thailand ) made of chemically recycled PET, which has essentially the same properties as virgin PET. The bottle is made via ISBM. Figure 1 Like the bottle 112 of FIG. 1 , the bottle is swamp water green and is not attractive to consumers.

[0199] Figure 5B This is a photo of a three-layer bottle made by ISBM. Figure 5A Like the bottle in Figure 5B The bottles in the bottle have The core is made of green mechanically recycled PCR pellets from Plastics. The core contains recycled PCR (C181, purchased from Indorama, Bangkok, Thailand ) and contains 5% opaque black pigment. The top layer contains virgin PET, chemically recycled PET and 4% effect pigment ( Colormotion Blue Topaz 9G680D special effect pigment, available from BASF). Figure 5B Contains Figure 5A The same plastic, but pigments in the core and effect pigments in the surface layer create a bottle with an ultra-premium aesthetic appearance.

[0200] Figure 5C This is a photo of a three-layer bottle made by ISBM. Figure 5B Like the bottle in Figure 5C The bottles in the PET bottle have a core containing PET and carbon black pigment, and the PET bottle has a core containing PET and 4% effect pigment ( Colormotion Blue Topaz9G680D special effect pigment, available from BASF) on the surface. Figure 5B The bottle is different in that Figure 5C The bottles in the range are made with virgin PET in the core and skin, rather than a core made from mechanically recycled PET. Figure 5B and Figure 5C The bottles in the box all have rich perspective chromatic optical response.

[0201] Measuring angle-dependent color for comparison Figure 2 B's three-layer bottle with recycled PET core Figure 2 Table 1 shows the three-layer bottle with a native core of C. Figure 5B bottles and Figure 5C As shown in Table 1, both a* and b* change with viewing angle. For bottles with recycled PET core ( Figure 5B ) and bottles with virgin PET cores ( Figure 5C ), a* and b* are approximately the same at all viewing angles. The observer will not be able to visually detect these differences.

[0202] Table 1

[0203]

[0204] Table 2 shows Figure 5B Three-layer bottles with mechanically recycled PET core and Figure 5CTable 2 shows how both C* and L* change with viewing angle for a three-layer bottle with a virgin PET core. Table 2 shows how both C* and L* change with viewing angle. C* is roughly the same across each of the six viewing angles, indicating that when viewed by a person with normal visual acuity, the bottle with a recycled PET core and the bottle with virgin PET will appear to have the same intense color effect. For both bottles, L* is maximum at the angle Color45as-15. For the bottle with the recycled core ( Figure 5B ), the maximum ΔL* across six viewing angles was 70.6, while for the bottle with native core ( Figure 5C ), with a ΔL* of 71.6. This indicates that the brightness varies significantly across all viewing angles for both bottles, and that an observer would not be able to visually detect these differences.

[0205] Table 2

[0206]

[0207] Table 3 shows the performance of three-layer bottles with recycled PET core ( Figure 5B ) and the color shift values ​​(ΔE) of Color45as-15 vs. Color45as45 for three-layer bottles with virgin PET cores. * ). Table 3 demonstrates that both bottles exhibit significant color shift, and that an observer would not be able to visually detect the difference.

[0208] Table 3

[0209]

[0210] Examples 1 to 10 described in the following tables are blow molded bottles formed from thermoplastic resins containing mechanically recycled PET (mPET), chemically recycled PET (arPET), virgin PET, and combinations thereof, and additives such as one or more pigments and / or dyes. arPET is similar to virgin PET in that it has visual and structural properties similar to virgin PET. mPET can have fairly strong mechanical properties, however, its visual properties are generally different from virgin PET because mPET is generally not as colorful and visually impactful. The inventors have discovered that, as demonstrated in the following examples, bottles with unique or premium visual effects can be formed from thermoplastic resins containing a significant portion of mPET if the bottle is a multilayer bottle that also has pigments or dyes in the core and / or skin layers.

[0211] The following examples illustrate the high level of optical properties of low-grade materials. The visual appearance of these blow-molded bottles was also tested by L*a*b*, haze, and gloss 20°. The methods for measuring haze and gloss 20° are described herein.

[0212] For Tables 4 to 13 below, the ΔE values ​​are mathematically represented by the following formula:

[0213] ΔE*=[(L* X -L* Y ) 2 +(a* X -a* Y ) 2 +(b* X -b* Y ) 2 ] 1 / 2

[0214] The ΔΕ of each Example is compared to the first Example in each table (eg, Example 1 vs. Example 2, Example 1 vs. Example 3, and so on).

[0215] The CIE LAB scale is the color scale used. Measurements are made with a spectrophotometer (such as a Hunter color reflectometer or an X-Rite Ci64 spherical spectrophotometer). A complete technical description of the system can be found in the paper "Photoelectric Color Difference Meter" (Journal of the Optical Society of America, Vol. 48, pp. 985-995, 1958) by R.S. Hunter. A device specifically designed for measuring color with the Hunter scale is described in U.S. Patent 3,003,388, issued to Hunter et al. on October 10, 1961. Generally speaking, the Hunter color "L" scale value is a unit of light reflectance measurement, and the higher the value, the lighter the color, because lighter coloring materials reflect more light. Specifically, in the Hunter color system, the "L" scale contains 100 equally divided units. Absolute black is at the bottom of the scale (L=0), and absolute white is at the top of the scale (L=100). Thus, when measuring Hunter color values ​​for articles according to the present invention, the lower the "L" scale value, the darker the material. The articles herein may be any color, provided that the L Hunter values ​​defined herein are met. When color is defined according to this system, L* represents lightness (0 = black, 100 = white), a* and b* each independently represent a dichroic axis, a* representing the red / green axis (+a = red, -a = green), and b* representing the yellow / blue axis (+b = yellow, -b = blue). Use a white background to maintain a similar color behind the sample (the white portion of an X-Rite Grayscale Balance Chart (45as45L*a*b*96.2-0.8 3.16), or a Byko-Chart Opacity 2A or similar opacity chart manufactured by BYK (a member of the Altana Group)).

[0216] Table 4: Description of Examples 1 to 3

[0217]

[0218] Table 5: Color difference, haze and gloss 20° of Examples 1 to 3

[0219]

[0220] Both Examples 1 and 2 demonstrate that multi-layer blow molded bottles in which the majority of the thermoplastic resin is PCR plastic can have high quality optical properties, especially when pigments are incorporated into the skin and / or core layers.

[0221] In Example 2, all thermoplastic resins in the bottles were mPET PCR. From Indorama mPET PCR is a food grade mPET used in the surface layer. Its color is not good and is clearly different from virgin PET or arPET. However, Indorama The color of mPET is usually better than that of Evergreen used in cores. The green / mixed-color bale of mPET is more consistent. By using a multilayer structure and placing pigments in both the skin layers and the core, the inventors were able to overcome the yellowing discoloration and cloudiness that typically occurs when mPET is processed into preforms and then bottles due to oxidation. Table 5 shows that the optical properties of Examples 1 and 2 are similar, and consumers are unlikely to notice this small difference on store shelves.

[0222] The bottles in Example 1 and Example 3 had the same total concentration of resin and additives. However, the multilayer bottle in Example 1 (see Figure 6A ) appears dark red, while the single-layer bottle in Example 3 (see Figure 6C ) appears as a very dark, almost black color, which is largely due to the black pigment suspended throughout the monolayer. Examples 1 and 2 have high chroma (C*), while Example 3 has very low chroma. Figure 6A The preforms that can be blown into bottles are cut transversely and Figure 6B As shown in Figure 6B In the example, the preform wall has three different layers: two red skin layers and a black core. Figure 6C The preforms that can be blown into bottles are cut transversely and Figure 6D As shown in Figure 6D In Example 1, the walls of the preform have only one layer and appear black. It may be difficult to make thermoplastic bottles with different colors in a single-layer bottle from a green / mixed-color bale of PCR thermoplastic material, so a multi-layer bottle like in Example 1 may be preferred.

[0223] Compared to Example 3, Example 1 and Example 2 have slightly lower glossiness 20°. This is because the red iridescent pigment is more concentrated in the surface layer of Example 1 and Example 2 compared to Example 3. The red iridescent pigment has a relatively large particle size, and since the large particles are located near or at the surface, surface roughness may be introduced. Introducing surface roughness reduces glossiness while increasing reflective haze. Therefore, compared to the glossiness 20° values ​​of other Examples (e.g., Examples 4 to 5, 7, and 9 to 12), the glossiness 20° values ​​of Example 1 and Example 2 are lower. Figure 6A As shown, the bottle has an attractive, high-quality visual appearance. However, if the highest possible gloss is desired, it may not be desirable to include pigments having large particle sizes in the top layer.

[0224] Table 6: Description of Examples 4 to 6

[0225]

[0226]

[0227] Table 7: Color difference, haze and gloss 20° of Examples 4 to 6

[0228] Example L* a* b* ΔE Haze Gloss 20° 4 42.79 37.02 16.8 6.47 74.42 5 42.81 41.69 19.12 5.21 2.49 83.62 6 50.3 34.19 19.26 8.39 11.26 15.14

[0229] As with Example 2, all thermoplastic resins in the multi-layer bottle of Example 4 were mPET PCR. By using a multi-layer structure and placing pigments in the skin layers and core, the inventors were able to achieve similar optical properties in Example 4 compared to Example 5 (see Table 7). The color attributes (L*, a*, b*) of Examples 4 and 5 were similar, resulting in a low ΔE. The gloss and haze of both Examples 4 and 5 were acceptable to consumers; however, Example 5 had slightly higher gloss and slightly lower haze, which may be preferred by consumers from a purely aesthetic standpoint. However, on store shelves, consumers would find both bottles to have a striking, premium appearance.

[0230] The bottles in Example 5 and Example 6 have the same total concentration of resin and additives. However, the multilayer bottle in Example 5 (see Figure 6E ) appears as a dark red and shiny bottle, while the multilayer bottle in Example 3 (see Figure 6G ) Compared with Example 5, the bottle is darker red and has a significantly lower gloss. The ΔE of Example 6 is greater than that of Example 5. Figure 6E The preforms that can be blown into bottles are cut transversely and Figure 6F As shown in Figure 6F In the example, the preform wall has three distinct layers: two red skin layers and a green core. Figure 6G The preforms that can be blown into bottles are cut transversely and Figure 6H As shown in Figure 6H In the example, the wall of the preform has only one layer and appears red with some cloudy parts. Figure 6H The haze in the preform comes from the pearly white pigment in the monolayer and the green / mixed color bale PCR. It can be difficult to make a thermoplastic bottle with a dark and glossy premium appearance in a monolayer bottle from a green / mixed color bale of PCR thermoplastic material, so a multilayer bottle like that in Example 5 may be preferred.

[0231] Table 8: Description of Examples 7 to 8

[0232]

[0233] Table 9: Color difference, haze and gloss 20° of Examples 7 to 8

[0234]

[0235] Example 7 is a multi-layer bottle with a 47.5% PCR content. In Example 7, both the skin layer and the core comprise arPET PCR. Example 8 is a red, opaque, single-layer PET bottle currently on the market. Both Examples 7 and 8 exhibit good optical properties. It was found that Example 7, even with 47.5% PCR, exhibited excellent optical properties, including high gloss and a vibrant color, as indicated by a high chroma (C*).

[0236] Table 10: Description of Examples 9 to 10

[0237]

[0238] Table 11: Color difference, haze and gloss 20° of Examples 9 to 10

[0239]

[0240] The bottles in Example 9 and Example 10 had the same total concentration of resin and additives. However, the multilayer bottle in Example 9 (see Figure 6I ) appears as a dark cherry red and glossy bottle, while the multilayer bottle in Example 10 (see Figure 6K ) Compared with Example 5, the bottle is shown to have a duller, darker red color (which appears dark brown or almost black) and poor gloss. The chromaticity (C*) of Example 9 is much higher than that of Example 10. Figure 6I The preforms that can be blown into bottles are cut transversely and Figure 6J As shown in Figure 6J In the example, the preform wall has three distinct layers: two red skin layers and a dark core. Figure 6K The preforms that can be blown into bottles are cut transversely and Figure 6L As shown in Figure 6L In Example 9, the walls of the preforms have only one layer and appear dark brown or black. It may be difficult to make thermoplastic bottles with different colors in a single-layer bottle from a green / mixed-color bale of PCR thermoplastic material, so a multi-layer bottle like that in Example 9 may be preferred.

[0241] Table 12: Description of Examples 11 to 12

[0242]

[0243] Table 13: Color difference, haze and gloss 20° of Examples 11 to 12

[0244]

[0245] Examples 11 and 12 are multi-layer blow-molded bottles containing a significant amount of PCR plastic that exhibit excellent visual properties, even though Example 11 contains 100% PCR. Examples 11 and 12 demonstrate that by using a multi-layer structure and placing pigments in the skin layers and core, the inventors were able to overcome the yellowing discoloration and cloudiness that typically occurs when mPET is processed into preforms and then into bottles due to oxidation. Table 13 shows that the optical properties of Examples 11 and 12 are similar, and consumers are unlikely to notice this small difference on store shelves.

[0246] combination

[0247] A. A blow-molded multi-layer article comprising:

[0248] a. A hollow body defined by a wall comprising an inner surface and an outer surface, the wall being formed in at least one region from three or more layers comprising:

[0249] i. A first surface layer and a second surface layer comprising:

[0250] a first thermoplastic material; and

[0251] Effect pigments and / or pore formers;

[0252] wherein the first skin forms an outer surface of the wall in the region and the second skin forms an inner surface of the wall in the region;

[0253] ii. a core sandwiched between a first skin and a second skin, wherein the core comprises:

[0254] about 90% to about 99% recycled thermoplastic material comprising a second thermoplastic material and greater than 200 ppm of impurities;

[0255] Pigments and / or dyes;

[0256] The article comprises greater than 30% recycled thermoplastic material.

[0257] B. A blow-molded multi-layer product comprising:

[0258] a. A hollow body defined by a wall comprising an inner surface and an outer surface, the wall being formed in at least one region from three or more layers comprising:

[0259] i. A first surface layer and a second surface layer comprising:

[0260] thermoplastic materials; and

[0261] Effect pigments and / or pore formers;

[0262] wherein the first skin forms an outer surface of the wall in the region and the second skin forms an inner surface of the wall in the region;

[0263] ii. an opaque core sandwiched between a first skin and a second skin, wherein the core comprises:

[0264] about 90% to about 99% recycled thermoplastic material comprising a second thermoplastic material and having an L* value less than or equal to 80;

[0265] Pigments and / or dyes;

[0266] The first skin layer and the core slightly interpenetrate each other at an interface between the first skin layer and the core.

[0267] C. An array of articles, wherein each article comprises

[0268] a. A hollow body defined by a wall comprising an inner surface and an outer surface, the wall being formed in at least one region from three or more layers comprising:

[0269] i. A first surface layer and a second surface layer comprising:

[0270] thermoplastic materials; and

[0271] Effect pigments and / or pore formers;

[0272] wherein the first skin forms an outer surface of the wall in the region and the second skin forms an inner surface of the wall in the region;

[0273] ii. a core sandwiched between a first skin and a second skin, wherein the core comprises:

[0274] a mechanically recycled thermoplastic material comprising a second thermoplastic material;

[0275] Pigments and / or dyes;

[0276] wherein each article has the following parameters: ΔE*, ΔL*, and average C* at -15° to 45° using 45° illumination; and the ΔE* and ΔL* at -15° to 45° vary by less than 6 units across the array, as measured according to the goniospectrophotometric method described herein.

[0277] D. The blow molded multilayer article of paragraphs A to C, wherein the recycled thermoplastic material comprises mechanically recycled thermoplastic material.

[0278] E. The blow molded multilayer article of paragraphs A to D, wherein the first thermoplastic material and / or the second thermoplastic material comprises polyethylene terephthalate.

[0279] F. The blow-molded multilayer article of paragraphs A to E, wherein the skin layer comprises an effect pigment comprising particles, and the particles are oriented such that their faces are parallel to the outer surface.

[0280] G. The blow-molded multilayer article of paragraphs A to F, wherein the core and / or the article is opaque.

[0281] H. The blown multilayer article of paragraphs A to G, wherein the core comprises from about 0.1% to about 6%, preferably from about 0.3% to about 4%, preferably from about 0.5% to about 2%, of pigments and / or dyes by weight of the core.

[0282] I. The blow molded multilayer article of paragraphs A to H, wherein the recycled thermoplastic material comprises from about 0.01% to about 2%, preferably from about 0.05% to about 1%, preferably from about 0.1% to about 0.75% impurities, based on the weight of the thermoplastic material.

[0283] J. The blow molded multilayer article according to paragraphs A to I, wherein the recycled thermoplastic material contains greater than 200 ppm, preferably greater than 500 ppm, and more preferably greater than 1000 ppm of impurities.

[0284] K. The blow molded multilayer article of paragraphs A to J, wherein the recycled thermoplastic material contains less than 99.99%, less than 99.9%, less than 99%, less than 98.75% and / or less than 98.5% thermoplastic material.

[0285] L. The blow molded multilayer article of paragraphs A to K, wherein the skin layer comprises from about 0.1% to about 6%, preferably from about 0.3% to about 4%, and more preferably from about 0.5% to about 2%, of effect pigments and / or pore formers, by weight of the skin layer.

[0286] M. A blow-molded multilayer article according to paragraphs A to L, wherein the skin layer comprises from about 94% to about 99.9%, preferably from about 96% to about 99.7%, more preferably from about 98% to about 99.5%, by weight of the skin layer, of a thermoplastic material selected from the group consisting of virgin thermoplastic material, recycled thermoplastic material, and combinations thereof.

[0287] N. A blow molded multilayer article according to paragraphs A to M, wherein the article comprises more than 30%, more than 35%, more than 40%, more than 45%, more than 50%, more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, more than 95%, more than 90%, more than 95% recycled thermoplastic material by weight of the article.

[0288] O. The blown multi-layer article of paragraphs A to N, wherein at least 30%, preferably at least 50%, more preferably at least 70%, and most preferably at least 90% of the area of ​​the exterior surface of the article has a 20° gloss of greater than or equal to 65 GU, preferably greater than or equal to 68 GU, preferably greater than or equal to 70 GU, preferably greater than or equal to 71 GU, preferably greater than or equal to 73 GU, preferably greater than or equal to 75 GU, preferably greater than or equal to 80 GU, preferably greater than or equal to 85 GU, preferably greater than or equal to 90 GU, and preferably greater than or equal to 95 GU, as measured according to the 20° Gloss Method described herein.

[0289] P. A blow molded multilayer article according to paragraphs A to O, wherein a location on the outer surface of the article has a haze of ≤30, preferably ≤20, preferably ≤15, preferably ≤10, preferably ≤5, preferably ≤3 and preferably ≤2, as measured according to the Haze and Reflectance method described herein.

[0290] Q. A blown multilayer article according to paragraphs A to P, wherein a location on the exterior surface of the article has a haze anisotropy of <1, preferably ≤0.9, preferably ≤0.8, preferably ≤0.7 and more preferably ≤0.6, as measured according to the Haze and Reflection method described herein.

[0291] R. A blow molded multilayer article according to paragraphs A to Q, wherein there is an interface layer between the first skin layer and the core, and the interface layer has the following thickness measured according to the tie layer thickness method described herein: from about 500 nm to about 125 μm, preferably from about 1 μm to about 100 μm, preferably from about 3 μm to about 75 μm, preferably from about 6 μm to about 60 μm, preferably from about 10 μm to about 50 μm.

[0292] S. A blow molded multilayer article according to paragraphs A to R, wherein the article has a critical nominal load greater than 30 N, preferably greater than or equal to 50 N, more preferably greater than or equal to 60 N, and most preferably greater than or equal to 90 N, as measured by the critical nominal load test method described herein.

[0293] T. A blow molded multilayer article according to paragraphs A to S, wherein the core layer has an L* less than or equal to 80, preferably less than or equal to 70, preferably less than or equal to 60, preferably less than or equal to 50, preferably less than or equal to 40, preferably less than or equal to 30, preferably less than or equal to 20, preferably less than or equal to 10, alternatively less than or equal to 5, as measured according to the goniospectrophotometer method described herein.

[0294] U. The blow molded multilayer article of paragraphs A to T, wherein L* is from about 0 to about 80, preferably from about 0 to about 75, preferably from about 0 to about 65, preferably from about 0 to about 55, preferably from about 0 to about 50, preferably from about 0 to about 45, and / or from about 0 to about 40, as measured according to the goniospectrophotometric method described herein.

[0295] V. The blow molded multilayer article of paragraphs A to U, wherein the multilayer article has a ΔE*, ΔL*, and average C* at -15° to 45° using 45° illumination as measured according to the goniospectrophotometer method described herein that differs by about 6 units, preferably about 5 units, preferably about 4 units, preferably about 3 units, preferably about 2 units, and preferably about 1 unit compared to a multilayer structure comprising the same material except that the core comprises virgin thermoplastic material.

[0296] W. A blow molded multilayer article according to paragraphs A to U, wherein the article has a ΔE* at -15° to 45° using 45° illumination of greater than 20, preferably greater than 30, preferably greater than 40, preferably greater than 50, preferably greater than 60, preferably greater than 75, preferably greater than 80, preferably greater than 85, preferably greater than 90, preferably greater than 95, preferably greater than 100, and preferably greater than 105 according to the goniospectrophotometer method described herein.

[0297] X. The blown multilayer article of paragraphs A to U, wherein the article has a ΔE* at -15° to 45° using 45° illumination of from about 25 to about 150, from about 35 to about 145, from about 45 to about 140, from about 50 to about 135, from about 55 to about 130, from about 60 to about 130, from about 75 to about 130, from about 90 to about 125, from about 95 to about 130, from about 100 to about 125, and / or from about 105 to about 120 according to the goniospectrophotometer method described herein.

[0298] Y. The article of paragraphs A to X, wherein the article is a bottle.

[0299] Z. The article of paragraphs A to Y, wherein the first thermoplastic material and / or the second thermoplastic material is selected from the group consisting of polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene naphthalate (PEN), polycyclohexanedimethanol terephthalate (PCT), glycol-modified PCT copolymer (PCTG), copolyester of cyclohexanedimethanol and terephthalic acid (PCTA), polybutylene terephthalate (PBCT), acrylonitrile-styrene (AS), styrene-butadiene copolymer (SBC), low density polyethylene (LDPE), linear low density polyethylene (LLPDE), high density polyethylene (HDPE), polypropylene (PP), and combinations thereof.

[0300] AA. The article of paragraphs A to Z, wherein the first thermoplastic material and / or the second thermoplastic material is selected from the group consisting of PET, PP, HDPE, LDPE, and combinations thereof.

[0301] BB. The article of paragraphs A to AA, wherein the core comprises a pigment comprising an opacifying pigment comprising particles wherein the pigment has a particle size greater than 15 nm, preferably greater than 100 nm, preferably greater than 500 nm, and preferably greater than 1 micron.

[0302] CC. An article according to paragraphs A to BB, wherein the outer surface of the article includes a location having a root mean square roughness Sq. of less than 50 μin (1.27 μm), less than 45 μin (1.12 μm), less than 40 μin (1.016 μm), less than 35 μin (0.89 μm), and / or less than 32 μin (0.8128 μm), as measured according to the root mean square roughness Sq measurement method described herein.

[0303] DD. The article of paragraphs A to CC, wherein the outer surface of the multi-layer structure has a ΔE* at -15° to 45° using 45° illumination of preferably greater than 20, preferably greater than 30, greater than 40, preferably greater than 50, preferably greater than 60, preferably greater than 75, preferably greater than 80, preferably greater than 85, preferably greater than 90, preferably greater than 95, preferably greater than 100, and preferably greater than 105 according to the goniospectrophotometer method described herein.

[0304] EE. The article of paragraphs A to DD, wherein the outer surface of the multi-layer structure has a ΔE* at -15° to 45° using 45° illumination of from about 25 to about 150, preferably from about 35 to about 145, preferably from about 45 to about 140, preferably from about 50 to about 135, preferably from about 55 to about 130, preferably from about 60 to about 130, preferably from about 75 to about 130, preferably from about 90 to about 125, preferably from about 95 to about 130, preferably from about 100 to about 125, and preferably from about 105 to about 120 according to the goniospectrophotometer method described herein.

[0305] FF. An article according to paragraphs A to EE, wherein the first skin layer is 10% thicker, preferably 20% thicker, preferably 25% thicker, preferably 30% thicker, preferably 40% thicker, and preferably 50% thicker than the second skin layer, as measured according to the Layer Thickness Method described herein.

[0306] GG. The article of paragraphs A to FF, wherein the average panel wall thickness constitutes from about 30% to about 80% of the core, preferably from about 35% to about 75% of the core, preferably from about 40% to about 70% of the core, preferably from about 45% to about 65% of the core, preferably from about 50% to about 60% of the core, as measured according to the Layer Thickness method described herein.

[0307] HH. An array according to paragraph C, wherein the ΔE*, ΔL*, and average C* of each article at -15° to 45° using 45° illumination, as measured according to the goniospectrophotometric method described herein, varies across the array by less than 5 units, preferably less than 4 units, preferably less than 3 units, preferably less than 2 units, and preferably less than 1 unit.

[0308] II. An array according to paragraph C, wherein the ΔE*, ΔL*, and average C* of each article at -15° to 45° when using 45° illumination vary across the array by less than 5 units, preferably less than 10%, preferably less than 7%, preferably less than 5%, preferably less than 3%, preferably less than 2%, and preferably less than 1%.

[0309] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0310] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the presently disclosed or claimed inventions, or an admission that it, by itself or in combination with any one or more of the references, proposes, suggests, or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0311] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the invention. It is therefore intended that all such changes and modifications within the scope of the invention be encompassed in the appended claims.

Claims

1. A blow-molded multi-layer product comprising: a. A hollow body defined by a wall comprising an inner surface and an outer surface, wherein the wall is formed in at least one region from three or more layers comprising: i. A first surface layer and a second surface layer, each of the first surface layer and the second surface layer comprising: 94% to 99.9% by weight of the first skin layer or the second skin layer of a first thermoplastic material; wherein the first skin constitutes the outer surface of the wall in the region and the second skin constitutes the inner surface of the wall in the region; ii. a core sandwiched between the first skin and the second skin, wherein the core comprises: 90% to 99% recycled thermoplastic material by weight of the core, the recycled thermoplastic material comprising a second thermoplastic material, and greater than 200 ppm of impurities by weight of the core; 0.1% to 6% by weight of the core of pigments and / or dyes; wherein the first skin layer and the core interpenetrate each other at an interface layer between the first skin layer and the core; wherein the surface layer further comprises from 0.1% to 6% by weight of the surface layer of effect pigments and / or pore formers; wherein the article comprises greater than 30%, by weight of the article, of recycled thermoplastic material.

2. The article of claim 1, wherein the first and second skin layers each comprise, by weight of the first or second skin layer, 96% to 99.7% of the first thermoplastic material.

3. The article of claim 1, wherein the first and second skin layers each comprise, by weight of the first or second skin layer, 98% to 99.5% of the first thermoplastic material.

4. The article of claim 1 , wherein the recycled thermoplastic material comprises more than 500 ppm of impurities based on the weight of the core.

5. The article of claim 1, wherein the recycled thermoplastic material comprises more than 1000 ppm of impurities based on the weight of the core.

6. The article of claim 1 wherein the core comprises: from 0.3% to 4% pigments and / or dyes, by weight of the core.

7. The article of claim 1 wherein the core comprises: from 0.5% to 2% pigments and / or dyes, by weight of the core.

8. The article of claim 1 , wherein the article comprises greater than 40% recycled thermoplastic material by weight of the article.

9. The article of claim 1 , wherein the article comprises greater than 50% recycled thermoplastic material by weight of the article.

10. The article of claim 1, wherein the article comprises greater than 60% recycled thermoplastic material by weight of the article.

11. The article of claim 1 , wherein the second thermoplastic material has an L* value of less than or equal to 80 as measured according to the goniospectrophotometer method described herein.

12. The article of claim 1, wherein the second thermoplastic material has an L* value of less than or equal to 60 as measured according to the goniospectrophotometer method described herein.

13. The article of claim 1, wherein the second thermoplastic material has an L* value of less than or equal to 40 as measured according to the goniospectrophotometer method described herein.

14. The article of claim 1, wherein the recycled thermoplastic material comprises a mechanically recycled thermoplastic material.

15. The article of claim 1, wherein the skin layer comprises from 0.3% to 4% effect pigments and / or pore formers, by weight of the skin layer.

16. The article of claim 1, wherein the skin layer comprises from 0.5% to 2% effect pigments and / or pore formers, by weight of the skin layer.

17. The article of claim 1, wherein the first skin layer and / or the second skin layer comprises a recycled thermoplastic material.

18. The article of claim 1, wherein the first thermoplastic material and the second thermoplastic material comprise mechanically recycled thermoplastic materials.

19. The article of claim 1, wherein all of the thermoplastic material in the article is mechanically recycled thermoplastic material.

20. The article of claim 1, wherein an interfacial layer is present between the first skin layer and the core, the interfacial layer having a thickness of 500 nm to 125 μm as measured according to the Bond Layer Thickness test method described herein.

21. The article of claim 1, wherein an interfacial layer is present between the first skin layer and the core, the interfacial layer having a thickness of 1 μm to 100 μm as measured according to the Tie Layer Thickness test method described herein.

22. The article of claim 1, wherein an interfacial layer is present between the first skin layer and the core, the interfacial layer having a thickness of 3 μm to 75 μm as measured according to the Tie Layer Thickness test method described herein.

23. The article of claim 1, wherein an interfacial layer is present between the first skin layer and the core, the interfacial layer having a thickness of 10 μm to 50 μm as measured according to the Tie Layer Thickness test method described herein.

24. The article of claim 1, wherein the first thermoplastic material and / or the second thermoplastic material is selected from the group consisting of polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene naphthalate (PEN), polycyclohexanedimethanol terephthalate (PCT), glycol-modified PCT copolymer (PCTG), copolyester of cyclohexanedimethanol and terephthalic acid, polybutylene terephthalate (PBT), acrylonitrile-styrene copolymer (ASC), styrene-butadiene copolymer (SBC), low-density polyethylene (LDPE), linear low-density polyethylene (LLPDE), high-density polyethylene (HDPE), polypropylene (PP), and combinations thereof.

25. The article of claim 24, wherein the first thermoplastic material and / or the second thermoplastic material is selected from the group consisting of polyethylene terephthalate, polypropylene, high density polyethylene, low density polyethylene, and combinations thereof.

26. The blow molded article of claim 1, wherein the first thermoplastic material and the second thermoplastic material are the same.

27. The blow molded article of claim 1, wherein the article has a Critical Nominal Load greater than 50 N as measured by the Critical Nominal Load test method described herein.

28. The blow molded article of claim 1, wherein the article has a Critical Nominal Load greater than or equal to 60 N as measured by the Critical Nominal Load test method described herein.

29. The blow molded article of claim 1, wherein the article has a Critical Nominal Load greater than or equal to 90 N as measured by the Critical Nominal Load test method described herein.

30. The blow molded article of claim 1, wherein the core layer comprises a pigment, and the pigment is an opacifying pigment having an average particle size greater than 15 nm.

31. The blow molded article of claim 1, wherein the core layer comprises a pigment, and the pigment is an opacifying pigment having an average particle size greater than 100 nm.

32. The blow molded article of claim 1, wherein the core layer comprises a pigment, and the pigment is an opacifying pigment having an average particle size greater than 500 nm.

33. The blow molded article of claim 1, wherein the article is a bottle.

34. The blow molded article of claim 25, wherein the ΔE* at -15° to 45° is from 25 to 150 using 45° illumination according to the goniospectrophotometer method described herein.

35. The blow molded article of claim 25, wherein the ΔE* at -15° to 45° is from 45 to 140 using 45° illumination according to the goniospectrophotometer method described herein.

36. The blow molded article of claim 25, wherein the ΔE* at -15° to 45° using 45° illumination is from 50 to 135 according to the goniospectrophotometer method described herein.

37. The blow molded article of claim 25, wherein the ΔE* at -15° to 45° is from 60 to 130 using 45° illumination according to the goniospectrophotometer method described herein.

38. The blow molded article of claim 25, wherein the ΔE* at -15° to 45° using 45° illumination is from 95 to 130 according to the goniospectrophotometer method described herein.

39. The blow molded article of claim 1 having a ΔE*, ΔL*, and average C* of -15° to 45° using 45° illumination, wherein the ΔE*, ΔL*, and average C* of -15° to 45° differ by 6 units as compared to a second multi-layer structure comprising: A skin layer having the same elements as the first skin layer and the second skin layer, and a core having the same elements as the core but comprising virgin thermoplastic material instead of the recycled thermoplastic material.

40. The blow molded article of claim 1 having a ΔE*, ΔL*, and average C* of -15° to 45° using 45° illumination, wherein the ΔE*, ΔL*, and average C* of -15° to 45° differ by 5 units as compared to a second multi-layer structure comprising: A skin layer having the same elements as the first skin layer and the second skin layer, and a core having the same elements as the core but comprising virgin thermoplastic material instead of the recycled thermoplastic material.

41. The blow molded article of claim 1 having a ΔE*, ΔL*, and average C* at -15° to 45° using 45° illumination, wherein the ΔE*, ΔL*, and average C* at -15° to 45° differ by 4 units as compared to a second multi-layer structure comprising: A skin layer having the same elements as the first skin layer and the second skin layer, and a core having the same elements as the core but comprising virgin thermoplastic material instead of the recycled thermoplastic material.

42. The blow molded article of claim 1 having a ΔE*, ΔL*, and average C* at -15° to 45° using 45° illumination, wherein the ΔE*, ΔL*, and average C* at -15° to 45° differ by 3 units as compared to a second multi-layer structure comprising: A skin layer having the same elements as the first skin layer and the second skin layer, and a core having the same elements as the core but comprising virgin thermoplastic material instead of the recycled thermoplastic material.

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