Blow molded article with visual effect
阅读说明：本技术 具有视觉效果的吹塑制品 (Blow molded article with visual effect ) 是由 M·L·埃杰顿 M·A·玛玛克 A·S·埃尔哈特 B·S·纽法斯 A·J·霍顿 于 2020-04-10 设计创作，主要内容包括：本发明公开了一种吹塑单层制品。该制品具有由壁(30,31,3)限定的中空主体(250,25)。该壁(30,31,3)具有包含第一组合物的一个或多个区域和由第二组合物形成的一个或多个区域。(A blow molded single layer article is disclosed. The article has a hollow body (250,25) defined by walls (30,31, 3). The wall (30,31,3) has one or more regions comprising a first composition and one or more regions formed from a second composition.)
1. A blow molded single layer article comprising:
a. a hollow body defined by a wall comprising an inner surface and an outer surface, the wall formed by at least one pulsed layer comprising:
i. one or more first regions comprising a first composition, wherein the first regions extend from the inner surface to the outer surface;
one or more second regions comprising a second composition, wherein the second regions extend from the inner surface to the outer surface, and wherein the second regions comprise an axial color gradient;
wherein the one or more first regions and the one or more second regions form an irregular pattern on the surface of the article.
2. The blow molded article of claim 1, wherein the pulse layer comprises a plurality of first regions and a plurality of second regions.
3. The blow molded article of claims 1-2, wherein the wall comprises at least three layers, and wherein the pulse layer is a core layer.
4. A blow molded article according to claims 1-2 wherein said wall is comprised of said pulse layer.
5. The blow molded article of claims 1-2, wherein said wall comprises at least three layers, and wherein said pulse layer comprises an outer wall surface.
6. The blow molded article according to any of the preceding claims, wherein said first region and said second region are interpenetrating.
7. The blow molded article of any of the preceding claims, wherein the first composition and the second composition comprise polyethylene terephthalate.
8. The blow molded article according to any of the preceding claims, wherein said first composition and said second composition are different colors.
9. The blow molded article of any of the preceding claims, wherein the second composition comprises an effect pigment.
10. A blow molded article according to any of the preceding claims wherein said first composition comprises less than 1%, preferably less than 0.5%, and more preferably less than 0.1% effect pigments.
11. A blow molded article according to any of the preceding claims wherein the location of said one or more first regions has a surface roughness of less than 8 μ in (0.2032 μ ι η), more preferably less than 5 μ in (0.127 μ ι η), and even more preferably less than 3 μ in (0.0762 μ ι η) as measured by the surface roughness measurement method described herein.
12. The blow molded article according to any of the preceding claims, wherein at least a portion of said article is transparent.
13. The blow molded article of any of the preceding claims, wherein at least a portion of the article is opaque.
14. The blow molded monolayer article according to any of the preceding claims, wherein the article is a bottle.
15. The blow molded monolayer article according to any preceding claim, wherein the article has a critical nominal load of greater than or equal to 50N, preferably greater than or equal to 70N, and most preferably greater than or equal to 90N, as measured by the critical nominal load test method described herein.
Technical Field
The present invention relates to blow molded articles having a non-uniform visual effect including, but not limited to, banding, rippling, or streaking. The invention also relates to preforms for making such articles and methods for making these preforms and articles.
Background
Consumers desire to purchase articles, particularly hair and beauty products in blow-molded containers, that attract their attention due to their unique and/or premium appearance on store shelves and/or web pages/applications.
In order to make an article that embodies luxury and quality attractive, it may be desirable for the article to have a unique irregular pattern.
One way to create a unique pattern is to apply (e.g., by painting or printing) the pattern to the blow-molded article. However, this approach adds complexity and cost to the manufacture of articles, and is generally not sustainable in the mass production of blow molded articles. In addition, containers prepared by this method are generally less durable because the paint/printing may be scraped off during filling, shipping, and use.
The unique pattern may be achieved by Extrusion Blow Molding (EBM). EMBs are typically used with polypropylene (PP) and High Density Polyethylene (HDPE) and cannot be used with polyethylene terephthalate (PET). Articles formed via EMB are generally lighter and hazy.
Accordingly, there remains a need for blow molded PET bottles having irregular patterns, as well as preforms and methods for making such articles.
Disclosure of Invention
A blow molded single layer article comprising: (a) a hollow body defined by a wall including an inner surface and an outer surface, the wall formed from a layer comprising: (i) one or more first regions comprising a first composition, wherein the first regions extend from the inner surface to the outer surface; (ii) one or more second regions comprising a second composition, wherein the second regions extend from the inner surface to the outer surface, and wherein the second regions comprise an axial color gradient; wherein the one or more first regions and the one or more second regions form an irregular pattern on the surface of the article.
Drawings
The patent or patent application document contains at least one photograph which is drawn in color. Copies of this patent or patent application publication with one or more color photographs will be provided by the office upon request and payment of the necessary fee.
While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, it is believed that the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings, wherein:
FIG. 1 schematically represents a monolayer bottle, showing an enlarged schematic cross-section thereof;
FIG. 2 is a photograph of a single layer bottle having an irregular corrugated pattern;
FIG. 3 is a photograph of a preform having an irregular pattern; and is
FIG. 4A schematically represents a multilayer preform;
FIG. 4B schematically shows an enlarged cross-section of a wall of the multi-layer preform of FIG. 4A;
FIG. 4C schematically illustrates a blow-molded multilayer bottle, showing an enlarged schematic cross-section thereof;
FIG. 5A shows a schematic view of a cross section of an enlarged portion of a preform;
fig. 5B shows a schematic view of a cross section of an enlarged portion of the preform.
Detailed Description
While the specification concludes with claims particularly pointing out and distinctly claiming the present invention, it is believed that the present disclosure will be better understood from the following description.
As used herein, "article" refers to a single blow-molded hollow object for consumer use, such as a container suitable for holding a composition. Non-limiting examples may include bottles, cans, cups, lids, vials, tottles, and the like. The articles may be used for storage, packaging, transport/shipping, and/or for dispensing compositions in containers. Non-limiting volumes that can be contained within the container are about 10mL to about 1000mL, about 100mL to about 900mL, about 200mL to about 860mL, about 260mL to about 760mL, about 280mL to about 720mL, about 350mL to about 500 mL. Alternatively, the container may have a volume of at most 5L or at most 20L.
The composition contained in the article may be any of a variety of compositions, and includes detergents (such as laundry detergents or dishwashing detergents), fabric softeners, and fragrance enhancers (such asLaundry retention products), food products (including but not limited to liquid beverages and snack foods), paper products (e.g., facial tissues, wipes), beauty care compositions (e.g., cosmetics, lotions, shampoos, conditioners, hairsprays, deodorants, and antiperspirants, and personal cleansing products including washing, cleansing, rinsing, and/or peeling of the skin (including face, hands, scalp, and body), oral care compositions, and methods of making and using the samePhysical products (e.g., toothpaste, mouthwash, dental floss), medications (antipyretics, analgesics, vasoconstrictors, antihistamines, antitussives, supplements, antidiarrheals, proton pump inhibitors and other heartburn formulations, antiemetics, etc.), and the like. The composition may have a variety of forms, non-limiting examples of which may include a liquid, a gel, a powder, a bead, a solid stick, a bag (e.g., a bag) ) A sheet, a paste, a tablet, a capsule, an ointment, a filament, a fiber, and/or a sheet (including paper sheets such as toilet paper, facial tissue, and wipes).
The article may be a bottle for holding a product, for example a liquid product, such as a shampoo and/or a conditioner and/or a body wash.
As used herein, the term "blow molding" refers to a manufacturing process that forms a hollow plastic article containing a cavity suitable for containing a composition. Generally, there are three main types of blow molding: extrusion Blow Molding (EBM), Injection Blow Molding (IBM) and Injection Stretch Blow Molding (ISBM).
As used herein, the term "color" includes any color, such as white, black, red, orange, yellow, green, blue, violet, brown, and/or any other color, or variations thereof.
As used herein, the term "color gradient" refers to a colored region having a first region and a second region, wherein the colored region comprises any continuous function in L a b color space. The gradient may be a continuous function of any or all of the L, a and/or b values relative to the entire sample or the measured position along the sample.
As used herein, "effect pigment" means one of two broad classes of pigments, "metallic effect pigments" and "special effect pigments". Metallic effect pigments consist only of metallic particles. When having parallel alignment in their application systems, they produce a metal-like luster by reflecting light on the surface of the metal sheet. The incident light rays are totally reflected at the surface of the metal sheet without any transmissive part. Special effect pigments include all other platelet-shaped effect pigments which cannot be classified as "metallic effect pigments". These pigments are generally based on substrates with plate-like crystals (or particles), such as mica, (natural or synthetic) borosilicate glass, alumina flakes, silica flakes. These platelet particles are typically coated with an oxide, such as titanium dioxide, iron oxide, silica, or combinations thereof.
The particle size of the effect pigment in the 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 5 μm. The thickness of the effect pigments may be less than 5 μm, less than 3 μm, less than 1 μm, less than 800nm, less than 700nm, and/or less than 600 nm. The thickness of the effect pigment may be from about 25nm to about 5 μm, from about 100nm to about 900nm, from about 150nm to about 800nm, from about 200nm to about 700nm, from about 250nm to about 600nm, and/or from about 300nm to about 560 nm.
The effect pigment is prepared fromAndthe supplier of (a) sells as it is.
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. The preform is typically in the shape of a substantially "test tube".
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%.
As used herein, "transparent" means that the layer has a total light transmission of 50% or more and a reflection haze of less than 5 haze units. Total light transmission is measured according to ASTM D1003 and reflection haze is measured according to ASTM E430.
As used herein, the terms "comprising," "including," and "containing" are intended to be non-limiting and are understood to mean "having," "having," and "encompassing," respectively.
All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All such 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.
Unless otherwise specified, all components or compositions are on average with respect to the active portion of that component or composition, and do not include impurities, such as residual solvents or by-products, that may be present in commercially available sources of such components or compositions.
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 that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
In the case of the content ranges given, these are to be understood as the total amount of the stated ingredients in the composition, or in the case of more than one substance falling within the range defined by the ingredients, the total amount of all ingredients in the composition conforms to the stated definition.
Fig. 1 shows a hollow article 1, which in this example is a container, in particular a 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. In this example, the wall 3 is a single layer having a visual effect produced by alternating first regions 10 comprising a first composition and second regions 20 comprising a second composition. The second region 10 may be in one location, multiple locations, or, as in this example, multiple locations along the body of the article. In the single-layer structure, the first region may extend from the outer surface to the inner surface, and the second region may extend from the outer surface to the inner surface.
The alternating first and second regions may be created during the manufacture of the preform by using a stream of pulses when manufacturing the preform. The pulse flow is generated by a sudden, stepped or intermittent flow rate, resulting in a pressure change during injection of the preform. This may result in the second region not having a uniform color intensity, and the color may appear to taper at the top and/or bottom of the second region. When the preform is blown into a bottle, these color effects stretch and may resemble ribbons/corrugations, as seen in fig. 2.
The first and second compositions are mutually permeable between the first and second regions.
The first and second compositions may be the same thermoplastic resin, or they may be different thermoplastic resins. The first and second compositions may have different pigments and/or dyes. In one example, the first composition may be substantially free of pigments and/or dyes and the second composition may comprise pigments and/or dyes, or vice versa. The outer surface may have a variable gloss of 20 ° and/or surface roughness in the first region compared to the second region, or the gloss and surface roughness may be substantially the same.
The article may have a smooth surface that will produce a glossy effect. In the first region and/or the second region, the outer surface may have a position with a 20 ° gloss of greater than or equal to 65GU, greater than or equal to 68GU, greater than or equal to 70GU, greater than or equal to 71GU, greater than or equal to 73GU, greater than or equal to 75GU, greater than or equal to 80GU, greater than or equal to 85GU, greater than or equal to 90GU, and/or greater than or equal to 100 GU. The glossy region may have a position with a gloss 20 ° of from about 65GU to about 150GU, from about 68GU to about 125GU, from about 69GU to about 100GU, from about 70GU to about 95GU, and/or from 75GU to about 89 GU. The gloss 20 ° may be substantially the same throughout the bottle. The gloss 20 ° may vary by less than 20%, less than 15%, less than 10%, and/or less than 5% across the bottle.
The outer surface of the first region and/or the second region of the article may have one or more regions having a low surface roughness of less than 8 μ in (0.2032 μm), 5 μ in (0.127 μm), less than 3 μ in (0.0762 μm) and/or less than 2 μ in (0.0508 μm). The shiny region may have a location with a surface roughness of about 0.5 μ in (0.0127 μm) to about 4 μ in (0.1016 μm), about 0.75 μ in (0.01905 μm) to about 3.5 μ in (0.0889 μm), about 1 μ in (0.0254 μm) to about 3.25 μ in (0.08255 μm), about 1 μ in (0.0254 μm) to about 3 μ in (0.0762 μm), and/or about 1.25 μ in (0.03175 μm) to about 3 μ in (0.0762 μm).
The outer surface of the first region and/or the second region of the article may have one or more regions with a relatively high surface roughness of greater than 25 μ in (0.635 μm), greater than 28 μ in (0.7112 μm), greater than 30 μ in (0.762 μm), greater than 31 μ in (0.7874 μm) and/or greater than 32 μ in (0.8128 μm). The matte region may have a position with a surface roughness of about 20 μ in (0.508 μm) to about 42 μ in (1.0668 μm), about 25 μ in (0.635 μm) to about 40 μ in (1.016 μm), about 28 μ in (0.7112 μm) to about 38 μ in (0.9652 μm), and/or about 30 μ in (0.762 μm) to about 36 μ in (0.9144 μm). In these examples, the article may have a higher surface roughness than a lower surface roughness, but still feel smooth to the touch of a human. It may feel like a pearl surface or have a soft feel.
Fig. 2 is a photograph of a monolayer bottle prepared via the methods described herein. In fig. 2, the bottle is substantially transparent. It is filled with conditioning agent to show the ribbon/corrugations more clearly. In fig. 2, the first region is substantially transparent and comprises a colorless PET resin, and the second region is transparent and comprises a PET resin and a dye, in this example, a blue color. In this example, the second area is responsible for forming the horizontal pattern of ribbons/corrugations, since the first area is colourless. As seen in fig. 2, the intensity of the blue color in the second region varies across the ribbon pattern due to the manufacturing process, as described herein. In fig. 2, the ribbon is relatively thin, however, the width of the stripes may be adjusted, as seen in the preform of fig. 3. In some examples, at least 60% of the bottle may be transparent, alternatively at least 70%, alternatively at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%.
Fig. 3 is a photograph of a preform prepared via the process described herein. The figure shows the variation between preforms prepared via the same process. Due to the manufacturing process, each preform and subsequently each bottle may have a unique pattern. This uniqueness can contribute to a good appearance of the product and can be noticeable at the store shelf or at the web browser/application.
The preforms and bottles described herein may be single or multi-layered. In a multi-layer preform or bottle, one or more layers may be pulsed, which changes the thickness over the entire length of the article. For example, in fig. 4A-4C described below, the core is pulsed, and in fig. 5A described below, the outer layer is pulsed, and in fig. 5B, layer 2 ", which may be the inner layer, is pulsed. In some examples, pulsing one or more layers may change the opacity of the vial.
Fig. 4A shows a schematic view of the preform 50 and fig. 4B shows a schematic view of a cross-section of the wall. Preform 50 comprises a hollow body defined by a wall 31 having an inner surface 51 and an outer surface 61. In this example, the wall has two skin layers 101 comprising the first composition. Skin 101 may include an outer surface 61 and an inner surface 51. During manufacture, the second composition may be pulsed between the skin layers, creating a third layer 201 in all or some areas of the bottle. The core 201 may be located between the skins 101. The core 201 may be pulsed (i.e., may accelerate and decelerate and/or stop flow as it is formed) to create a visual effect. The visual effect may be non-uniform. The preform may be stretched during blow molding to form the final article, and a schematic of the final article is in fig. 4C.
Fig. 4C shows a schematic view of a hollow article 15, in this example a container, in particular a bottle. The hollow article 15 includes a hollow body 250 defined by a wall 30 having an inner surface 50 and an outer surface 60. As shown in the enlarged cross-section, the wall 30 has at least two layers 100 comprising a first composition and comprises in different areas an additional layer 200 comprising a second composition. In some examples, as schematically illustrated in fig. 4C, the second composition is located between layers of the first composition throughout the body of the article. In other examples, the second composition may be pulled and stretched during blow molding such that it occupies at least a portion of the exterior and/or interior surfaces.
Similar to fig. 1, there may be two regions in the core: a first region comprising a first composition or consisting essentially of a first composition and a second region comprising a second composition or consisting essentially of a second composition. The first and second compositions are mutually permeable between the first and second regions.
In the example of fig. 4C, the glossiness of 20 ° and the surface roughness may be uniform throughout the body.
Fig. 5A shows a schematic view of a cross section of an enlarged portion of a preform. The wall 30' may have five layers: including the innermost layers 5 ', 4', 3 ', 2' of the inner wall 51 'and the outermost layer 1'. Layer 1 'is pulsed and is only present on discrete areas of the outer wall 61' of the preform. The thickness of the outermost layer 1 'varies over the length of the preform, and in some cases substantially the layer 1' may form a circle around the circumference of the preform. Layers 1 ', 3 ' and 5 ' may be opaque and layers 4 ' and 2 ' may be transparent. In some examples, layers 1 ', 3 ', and 5 ' may include effect pigments and/or dyes. In some examples, layers 2 'and 4' may comprise a dye. I is
Fig. 5B shows a schematic view of a cross section of an enlarged portion of the preform. The wall 30 "may have six layers: including the innermost layers 6 ", 5", 4 ", 3", 2 "and 1" of the inner wall 51 ". Layers 2 "and 1" may form the outer wall 61 ". Layers 2 ", 4" and 6 "may include pigments, such as effect pigments, and optionally dyes. Layers 2 ", 4" and 6 "may be opaque. Layers 1 ", 3" and 5 "may be transparent and may optionally include a dye. In some examples, layers 1 ", 3", and 5 "may include effect pigments, and layers 2", 4 ", and 6" may be transparent. When preparing the preform, the flow of 2 "is pulsed, but instead of turning it on and off as in the example in fig. 5A, the flow rate of the flow is adjusted up or down. In some cases, the flow rate of the stream used to make layer 2 "may exceed that of stream 1".
In the example of fig. 5A and 5B, the gloss 20 ° and surface roughness of the multilayer bottle may be similar to the single layer bottle described herein.
In some examples, such as a bottle that may be formed from the preform in fig. 5A and 5B, the body may be largely opaque. For example, at least 60% of the body may have an opacity greater than 70%, alternatively at least 70% of the body may have an opacity greater than 70%, alternatively at least 80% of the body may have an opacity greater than 70%, alternatively at least 90% of the body may have an opacity greater than 70%, and alternatively at least 95% of the body may have an opacity greater than 70%. Opacity is measured according to the opacity test method described below.
The average wall thickness of the monolayer and multilayer articles may be from about 200 μm to about 5mm, alternatively from about 250 μm to about 2.5mm, alternatively from about 300 μm to about 2mm, alternatively from about 350 μm to about 1.5mm, alternatively from about 375 μm to about 1.4mm, 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 less than 15%, alternatively less than 10%, and alternatively less than 10% over the entire volume.
The article may comprise more than 50 wt%, preferably more than 70 wt%, more preferably more than 80 wt%, even more preferably more than 90 wt% of a thermoplastic resin selected from the group consisting of: one of polyethylene terephthalate (PET), ethylene 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., Low Density Polyethylene (LDPE), linear low density polyethylene (LLPDE), High Density Polyethylene (HDPE), polypropylene (PP), polymethylpentene (LCP), Liquid Crystal Polymer (LCP), Cyclic Olefin Copolymer (COC)), and combinations thereof. Preferably, the thermoplastic resin is selected from the group consisting of PET, HDPE, LDPE, PP, PVC, PETG, PEN, PS, and combinations thereof. In one example, the thermoplastic resin may be PET.
Recycled thermoplastics may also be used, such as post-consumer recycled polyethylene terephthalate (PCRPET); recycled polyethylene terephthalate (rPET), including post-industrial recycled PET, chemically recycled PET, and PET derived from other sources; reground polyethylene terephthalate.
The thermoplastic materials described herein can be formed by using a combination of monomers derived from renewable resources and monomers derived from non-renewable (e.g., petroleum) resources. For example, the thermoplastic resin may comprise a polymer made entirely of bio-derived monomers, or a polymer made partially of bio-derived monomers and partially of petroleum-derived monomers.
The thermoplastic resins used herein may have a relatively narrow weight distribution, such as metallocene PE polymerized by using a metallocene catalyst. These materials may improve gloss, whereby in embodiments of the metallocene thermoplastic, the formed article has further improved gloss. However, metallocene thermoplastics can be more expensive than commercial materials. Thus, in an alternative embodiment, the article is substantially free of expensive metallocene thermoplastics.
Both the first composition and the second composition may comprise a thermoplastic resin. The thermoplastic resin in the first composition may be the same as or different from the thermoplastic resin in the second composition. In one example, both the first and second compositions may be made of PET, which may allow for better interpenetration of layers and/or regions at the interface due to their chemical compatibility and stronger walls. By "based on the same type of resin" it is meant that the skin and core layers 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 belong 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, PET resins and PP resins are not considered to be of the same type. The different polyesters are not considered to be of the same type.
The first and second compositions and/or layers in the multilayer structure may be formed from the same thermoplastic resin (e.g., PET) and may differ only with respect to the type of colorant. The colorant may include dyes, pigments (including effect pigments and/or colored pigments), and any other material commonly used to color thermoplastic resins.
The first and second compositions may comprise similar resins, such as the same grade of PET, a different grade of PET, or virgin/recycled PET (rpet). For cost reduction and sustainability reasons, it is desirable to use r-PET. The skin and core layers may also comprise different resins that may be alternated within the article, such as PET/cyclic olefin copolymer, PET/PEN or PET/LCP. The composition of the first stream or the second stream may also include additives to aid in the dispersion or processing of the material. The resin pair is selected to have optimal properties such as appearance, mechanics, and air and/or moisture barrier.
The first composition and/or the second composition may comprise effect pigments, resulting in regions of the article, or in some cases, the entire article, that may appear metallic, shiny, and/or pearlescent. The incorporation of effect pigments and/or opacifying pigments into large-scale blow-molded articles can be expensive because it is difficult to provide the pigment particle loading weight percentages needed to achieve the desired optical and/or effect in the case of high volume disposable packaging.
The article may include one or more sub-layers having various functions. For example, the article may have a barrier material sublayer or a recycled material sublayer. The sublayer may form the outer surface of the wall of the article, the inner surface of the wall of the article, or it may even out the wall, forming an additional layer. Such layered containers may be made from a multi-layer preform according to common techniques employed in the art of thermoplastic manufacturing.
The article may include additives in any of its layers (so long as the desired properties of the layer are maintained) in an amount typically 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, catalytic stabilizers, nucleating agents, and combinations thereof.
The first composition and/or the second composition may comprise opacifying pigments. Opacifying pigments may include opacifying agents, opacifying absorbing pigments, and combinations thereof.
Non-limiting examples of opacifiers may include titanium dioxide, calcium carbonate, silica, mica, clay, minerals, and combinations thereof. The opacifier may be any domain/particle with a suitably different refractive index than the thermoplastic material (e.g., PET, which may include poly (methyl methacrylate), silicone, Liquid Crystal Polymer (LCP), polymethylpentene (PMP), air, gas, etc.). In addition, opacifiers may have the appearance of being white due to scattering of light or black due to absorption of light, as well as their midtones, provided they prevent most of the light from being transmitted into the underlying layer. Non-limiting examples of black opacifying pigments include carbon black and organic black pigments such asBlack L 0086(BASF)。
The opaque absorbing pigments may include particles that provide color and opacity to the materials in which they are present. The opaque absorption pigment may be an inorganic or organic particulate material. All absorbing pigments can be opaque if their average particle size is large enough (typically greater than 100nm, alternatively greater than 500nm, alternatively greater than 1 micron, and alternatively greater than 5 microns). The absorption pigment may be an organic pigment and/or an inorganic pigment. Non-limiting examples of organic absorption pigments may include azo and diazo pigments such as azo and diazo lakes, Hansa, benzimidazolone, diarylide, pyrazolone, pigment yellow and red; polycyclic pigments such as phthalocyanines, quinacridones, perylenes, naphthones, dioxazines, anthraquinones, isoindolines, thioindigoids, diaryl or quinoline yellow pigments, nigrosine, and combinations thereof. 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 pigments, and combinations thereof. The organic pigment and the inorganic pigment may be used alone or in combination.
Further, the multilayer articles described herein may be less susceptible to delamination than other articles. Delamination is a common problem in the manufacture of blow-molded multilayer hollow articles, such as bottles and containers. Delamination may occur immediately or over time due to thermal or mechanical stresses caused by mechanical handling of the container. It usually appears as a bubble on the surface of the container (which is actually the separation of the two layers at the interface as viewed through the bubble), but may also be at the source of container damage. Without being bound by theory, it is believed that parallel flow co-injection results in the formation of a joint region between layers where the layers slightly interpenetrate due to prolonged contact of the materials of the layers while still in a molten or partially molten state. The bonded area creates good adhesion between the layers, thus making it more difficult to separate them.
The presence and thickness of the interface between the skin and the core (also referred to as the tie layer) and/or the presence of interpenetration between the first and second regions (in a single or multilayer article) can be determined by the tie layer thickness method described below. The thickness of the interface is the distance perpendicular to the interface at which the composition of the unique pigment, additive or resin varies between a maximum concentration and a minimum concentration.
The thickness of the interface (i.e., the tie layer or transition layer or interpenetration region) may be from about 500nm 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 tie layer thickness method described below.
The walls of the multilayer article can be formed by ISBM without an adhesive (or substantially without an adhesive).
It has also been found that the multilayer article according to the invention has an improved resistance to delamination not only with respect to articles obtained by blow moulding preforms made using fractional flow co-injection or over-injection, but even with respect to articles obtained from single layer preforms. In other words, the interface layer appears to further strengthen the article wall relative to a single layer implementation. Delamination resistance was evaluated by measuring the critical nominal load, as described below. A higher critical nominal load indicates a higher resistance to delamination.
The critical nominal load of the article, particularly the multilayer article, can be greater than or equal to 50N, greater than or equal to 60N, greater than or equal to 70N, greater than or equal to 80N, greater than or equal to 90N, greater than or equal to 95N, greater than or equal to 100N, greater than or equal to 104N, greater than or equal to 105N, greater than or equal to 110N, and/or greater than or equal to 120N. The critical nominal load of the article can be about 50N to about 170N, alternatively about 80N to about 160N, alternatively about 90N to about 155N, and alternatively about 100N to about 145N. The critical nominal load may be measured by the critical nominal load using the method described below.
Another aspect of the present invention relates to a hollow preform that can be blow molded to produce an article as described above. The preform may be made by parallel co-injection of two or more streams, and wherein one or more streams constitute the first composition and the remaining streams constitute the second and subsequent compositions.
It will be apparent to the skilled person that such a preform, once blown, will form an article having a first composition and a second composition, wherein regions of the preform will form corresponding regions of the article.
Monolayer articles can be prepared as follows. The system for injection molding single layer preforms can be set up in a typical industrial fashion with modifications to the typical single stream feed system. The second melt stream can be introduced into a retrofit existing nozzle system. The nozzle system may continue to have the ability to control the positioning of the pins. This control positioning can vary the flow of the two streams by screw and/or nozzle pin position control. The pin position may allow more or less material from either stream to flow through the nozzle. With this capability, the material properties of one of the streams may be adjusted to have a difference in flow characteristics, which may promote flow instability.
Another way to create flow instability in the same system as described above may be to adjust the processing conditions that can affect the flow of the stream. Injecting one of the materials at different temperatures, pressures or fill times can create the instability needed to obtain a visual appearance. Using a system similar to that described above, one skilled in the art may change the geometry on the nozzle sidewall, cavity, or modify the shape of the pins, which may create destructive flow through the nozzle. In essence, bulk flow of one stream may dominate bulk flow through the nozzle, while changes to the nozzle, chamber wall, or pin geometry may promote leakage of a secondary stream, which may generate a feed stream into the bulk stream, creating a visual effect.
The multilayer article can be prepared as follows. The system for co-injection molding of multilayer structures can be arranged in a similar manner to that used in the industry today. In a typical co-injection system, two materials may be introduced into a nozzle to create a layer of material that when properly executed produces an article when typically used in the beverage industry. In this process, it was found that creating instability in the flow of one of the two materials creates a visual appearance in the final article that is appealing to the consumer. To create instability, multiple modifications may be made to material properties or processing parameters. Material modifications including molecular weight, melt flow index and/or intrinsic viscosity will result in flow characteristics that are uniquely different from another stream. These flow differences create flow instabilities when introducing material into the nozzle cavity. As noted above, modifications to the internal geometry of the nozzle, chamber wall or pin geometry may also create flow instabilities.
Another method of creating a visual effect using the above method may be to modify processing conditions that may affect the flow characteristics of one of the streams. Temperature, pressure and fill time may also have an effect on the flow material. One skilled in the art may modify material properties or processing conditions that may allow one material to flow differently in the nozzle cavity. One skilled in the art can also modify the pin position to allow for different volumetric flow rates of one material. These different volumetric flows can be in the range of very small amounts that leak into another stream. The process may produce an article that may have regions of higher concentration than another stream, producing an effect that may resemble ribbons, waves, marble, or streaks. Another method of creating flow instability as described above may be to actuate the pin so that it moves continuously in the nozzle from an open position to a closed position. This may substantially affect the pressure in the system, thereby generating pressure and volume pulses that may be translated into flow disturbances. These disturbances will create flow irregularities or instabilities that will produce the visual appearance we desire.
The flow of the first composition and/or the second composition may be stopped (partially or completely) or interrupted in order to create a pattern that may include bands, ripples, and/or striations in the preform and subsequently the blow molded article during injection molding. When the system feeds molten material into a nozzle configuration, there may be a flow resistance that results in a positive pressure in the system. If the screw speed, ram speed, or nozzle position is changed, flow fluctuations can result, creating a visual effect. In one example, pulsing may be accomplished during injection molding injection and methods using pressure variation.
This variation in flow rate and/or pressure variation produces bands, waves or striations that appear as a pattern primarily horizontal to the longitudinal axis of the preform. The non-uniform pattern may be most visible on the final article when there is a high level of contrast between the first and second compositions.
One such way to achieve this pressure differential may be a very rapid forward movement and stopping of the pulsed material injection screw, so that the primary material is able to overcome the pressure and completely "fill" the preform with the first composition, without or substantially without the second composition. When the pulse injection screw is continued again, a multilayer structure (e.g., a three-layer structure) can be regenerated until the screw is stopped again. Depending on the number of ribbons, corrugations or striations required, the process may be repeated as the preform is produced. Opening and then fully closing the screw in rapid succession can produce a plurality of thin ribbons. A slower sequential opening followed by a complete closing of the screw can result in several or several thicker bands. In other examples, the screw may be opened slowly and/or closed slowly, creating a color gradient. In other examples, a combination of open and closed patterns may be made to produce a combination of patterns. It can be difficult to control this to tight manufacturing tolerances, which can result in each preform and subsequent article having a unique appearance.
The process for the single and/or multiple layers can be adjusted to control the screw feed rate from 0% to 100%. In one example, the screw feed rate of the second material is always greater than 0%. In some examples, the screw feed rate was slowly adjusted from 0% to 100% to create a wider region with a steep gradient, and in other examples, the screw feed rate was quickly adjusted from 0% to 100% to create a narrow band.
In some examples, the screw feed rate of the second composition alone may be adjusted, and in other examples, the screw feed rate of the first composition is adjusted based on the amount of pigment and/or pattern desired on the final article. Additional compositions may also be added to create more complex patterns and/or more colored bottles.
Another method for producing a single or multi-layer preform may be to combine the intermittent combination of a second composition with pin positioning in the nozzle. The method will utilize the coordinated timing between the cessation of the second composition and the forward movement of the valve nozzle stem to seal the passage of the secondary material into the nozzle, thereby completely stopping the flow of the pulsed material and also preventing the primary material from entering the pulsed material passage. This can produce greater clarity in the ribbon rather than in a cord where the pulse material is slowly tapered at the start/stop position.
Most typically, the second composition will be pulsed (e.g., on/off) due to machine configuration and setup. However, the first composition or both compositions may be pulsed and, in some cases, may provide a similar look/feel.
Varying the temperature of the at least two resins can result in flow instability when forming the preform, which can cause an irregular visual effect on the bottle, as temperature can affect the viscosity of the thermoplastic material. In one example, when forming the multilayer preform, the material for the core layer (stream I) may be injected at a lower temperature than the material for the skin layer (stream II). In another example, the compositions may all comprise the same thermoplastic material and be at about the same temperature.
Another process parameter that can be controlled during co-injection of preforms is the pressure of the resin stream measured along the manifold line supplying the injection nozzles. The one or more streams comprising the material for the skin layer (stream II) may be maintained in a range between about 25 bar and about 400 bar, and alternatively between about 150 bar and about 400 bar, while the lower temperature/higher viscosity stream of the core layer (stream I) may be maintained in a range between about 1000 bar and about 1600 bar, alternatively between about 1000 bar and 1400 bar.
Test method
When the article is a container or bottle, the critical nominal load, gloss 20 ° and surface roughness measurements are all made on a sample panel removed from the article. Samples having a length of 100mm and a width dimension of about 50mm were cut from the major part of the article wall and away from the shoulder/neck and base regions by at least 50 mm.
Shorter samples with a width to length ratio of 1:2 may be used when the article does not allow removal of such large samples, as described in further detail below. For containers and bottles, it is preferred to remove the sample from the label panel of the bottle at least 50mm away from the shoulder/neck or base region. Cutting is performed with a suitable razor blade or utility knife to remove the larger area, which is then further cut to size with a new single-edged razor blade.
The sample should be flat if possible, or flattened by using a frame that keeps the sample flat at least in the area where the test is performed. It is important that the sample is flat to determine the critical nominal load, gloss 20 ° and surface roughness.
Critical nominal load (N) and scratch depth at damaged area
If the sample is prone to delamination when removed from the bottle, a fraction of 0N is given to the sample for the "critical nominal load". For the samples that remained intact, they were subjected to Scratch-induced damage according to the Scratch test procedure (ASTM D7027-13/ISO19252:08) using Scratch 5, available from Surface Machine Systems, LLC, with the following settings: 1mm diameter spherical tip, initial load: 1N, end load: 125N, scratch rate: 10mm/s and a scratch length of 100 mm. For samples less than 100mm, 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 over a narrower load range to more accurately determine the critical nominal load.
Damage caused by scratches was performed on both sides of the sample corresponding to the inner and outer surfaces of the bottle. By using foam type double-sided adhesive tape (such as 3M) on the underside of the samplePermanent mounting tape) (acrylic adhesive containing polyurethane double-sided high density foam tape with a total thickness of about 62 mils or 1.6mm, UPC #021200013393) was critical to adhering the sample to the sample carrier. All samples were cleaned with compressed air prior to scratch testing.
After the scratch test was completed, the point of damage was visually determined to be the distance over the length of the scratch at which delamination was seen to begin to occur. Delamination introduces air gaps between the layers that are visible to the naked eye or to those skilled in the art with the aid of stereomicroscopy. This was verified based on three minimum scratches (defined as 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 location at the point where delamination started to occur, the scratch depth at the damaged area was measured according to ASTM D7027. The critical nominal load (N) is defined as the nominal load recorded at the location determined to be the defect point. Damage caused by scratches, including damage point, scratch width and scratch depth, was analyzed using a laser scanning confocal microscope (KEYENCE VK-9700K) and VK-X200 analyzer software.
Gloss 20 ° process
Gloss 20 ℃ was measured with a gloss meter according to ASTM D2457/D523 at 20 ℃ micro-triangulation gloss meter (BYK-Gardner GmbH). Each point was measured three times and the average was calculated to determine the gloss 20 °. All gloss measurements were made on a black background, referred to as "base black". The base black is the black area in the X-Rite gray balance card (45as 45L a b 21.0770.15-0.29). The measurement provided by the micro-tri gloss meter has a unit "GU" representing a "gloss unit".
Local wall thickness
Using 1/8 "diameter target sphere, using Olympus8600 to measure the wall thickness at a specific location. Three measurements were taken at each location and their average was calculated to determine the local wall thickness.
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 calculating the average thereof. The thickness near the shoulder and near the base is excluded from the average local wall thickness.
Surface roughness measuring method
The Ra (arithmetic mean height) of the sample panels was analyzed using a portable surface roughness tester such as Surftest SJ-210(Mitutoyo usa) placed at equal heights of the bottles. Roughness is measured in μm.
Thickness of adhesive layer (thickness of interface layer)：
Placing the unique additive, colorant, or resin within at least one of the layers allows method a or method B to plot the composition over a distance normal to the interface at which the composition of the unique additive, colorant, or resin varies between a maximum concentration and a minimum concentration.
The method A comprises the following steps: an energy dispersive X-ray spectroscopy (EDS) mapping method is performed on adjacent layers having unique elemental compositions with the aid of resins (e.g., PET/nylon) or colorants/additives.
Method a may be used if a vial sample (preparation of vial sample is described below) will contain equal to or greater than 2 wt% of a colorant and/or additive whose elemental composition can be suitably mapped by EDS (e.g., elements above atomic number 3, excluding carbon or oxygen). These colorants/additives may be molecular substances or particles. If they are in the form of particles, they should be sufficiently dispersed so that about 10 or more particles are present in a volume of 5 μm × 5 μm × 200 nm. Generally, the maximum size of the particles should be less than 500 nm.
Sample preparation：
A heated blade was used to extract a piece of bottle label panel wall at least 50mm from the shoulder/neck or base region, measuring about 3cm x 3 cm. The heated blade can cut the bottle into slices without applying a large amount of force that can cause premature delamination. This is achieved by melting rather than cutting the face plate wall material. The melted edge of this block was removed with scissors and the block of about 3cm x 3cm was further cut into several blocks measuring about 1cm x 0.5cm using a new sharp single-edged razor blade. A cutting force is applied along the length of the block parallel to the layers/interface rather than perpendicular to the interface to prevent smearing across the interface.
The block of about 1cm by 0.5cm was then edge hand polished, resulting in a polished surface showing a cross section of the bottle wall and layered structure. The initial polishing included the use of SiC paper with gradually decreasing abrasive particle size (400, 600, 800, then 1200) while using distilled water as a lubricant/coolant. Then, 0.3 μm Al was used2O3The polishing medium further polishes 1200 the abrasive polished surface, with distilled water serving as a lubricant. The polished sample was then washed with detergent + evaporatedThe solution was ultrasonically cleaned for 1 minute in distilled water and then again ultrasonically cleaned for three more cycles in fresh distilled water to rinse the detergent from the sample. The final ultrasonic cleaning was performed in ethanol for 2 minutes. The polished and cleaned sample was mounted edge up on a SEM stub with double-sided carbon tape and then coated with approximately 1020nm carbon as deposited by a carbon evaporator such as Leica EM ACE600(Leica Microsystems).
Identifying rough interfaces by SEM：
It is necessary to identify the approximate interface between the a/C or C/B layers in order to allow the interface to be found in the dual beam FIB. To identify rough interfaces, by modern field emission SEMs (such as FEI (Thermo)) Apreo SEM equipped with a silicon drift EDS detector (SDD) (such as EDAX Octane electric 30 mm)2SDD (EDAX Inc.)) for SEM imaging and EDS rendering. A preliminary EDS plot of approximately 500 to 1000 times magnification is collected across the cross-sectional plane to confirm the presence of the layered structure by identifying the unique elements present in each layer. The accelerating voltage is set appropriately so as to ionize the optimal electron shells of the element of interest, thereby generating an X-ray signal. USP<1181>(USP29-NF24) provides a useful reference for selecting optimal operating conditions for collecting EDS signals.
EDS mapping is used to show the approximate location of the interface between layers, after which platinum fiducial marks are deposited via electron beam deposition using a Gas Injection System (GIS) to mark the location of the interface. Another EDS plot with Pt fiducial markers was collected to confirm their position relative to the interface.
Dual beam FIB sample preparation：
Thin foil samples (100nm-200nm thick) are required to map the interface with a reasonably high resolution. Using modern dual beam FIBs (such as FEI (Thermo)) Helios 600) to prepare flakes. Positioning an interface in the FIB by means of platinum reference marks. A protective platinum cap was then deposited on the region of interest at the interface in the FIB, measuring approximately 30 μm x2 μm. This is done to protect the material that will become the thin slice sample from unwanted damage caused by the ion beam. The 30 μm dimension is oriented perpendicular to the interface such that approximately 15 μm covers one side of the interface and 15 μm covers the other side. The material was then removed from each side of the platinum cap, leaving the capped areas as flakes measuring approximately 30 μm wide by 2 μm thick by 10 μm deep with the interfaces oriented parallel to the 10 μm direction. The sheet was then extracted by means of an Omniprobe nano-manipulator (Oxford Instruments) and attached to a copper Omniprobe grid. The flake sample was then thinned using 30kV gallium ions until it was sufficiently thin (about 500nm-200 nm). The freshly thinned, thin flake-like sample was then cleaned with 5kV gallium ions to remove excess damage caused by the 30kV thinning process.
STEM data collection：
Modern field emission TEMs (such as FEI Tecnai TF-20 (Thermo)) Equipped with a modern silicon drift EDS detector (SDD), such as EDAX Apollo XLT230mm2SDD detectors (EDAX Inc.) with collection and analysis software (such as Apex)TM(EDAX Inc.)) collection Scanning Transmission Electron Microscope (STEM) energy dispersive X-ray spectroscopy (EDS) data. The interfacial region within the foil produced as described above was drawn with EDS to show the presence and location of elemental constituents in the two polymer layers. The EDS plot is about 20 μm by 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 are perpendicular or nearly perpendicular to each other.
The plots were collected by using an acceleration voltage between 200kV and 300kV and a beam current equal to or between 100pA and 1nA to achieve an SDD count rate of at least 3,000 counts per second. The map resolution is plotted at least 256 x 160 pixels with a dwell time of about 200 mus per pixel. About 200 frames were collected and the total mapping time was about 30 minutes. The elements of interest are selected and label-free automatic ZAF analysis methods (such as P/B-ZAF basic parameter analysis) are selected to achieve quantitative mapping.
Data processing：
The EDS rendering data may 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. EDS mapping data is processed by summing the X-ray counts that each element appears in the "Y" direction (parallel to the interface) to display a normalized atomic% line profile, and the summed intensity is plotted as a function of distance in the "X" direction (perpendicular to the interface) across the interface. The distance between the maximum normalized atomic% and the minimum normalized atomic% of the at least one element (both having a slope of about zero in the range of about 2-4 microns) is defined as the interfacial layer thickness.
The method B comprises the following steps: the adjacent layers with unique spectral characteristics are subjected to a confocal raman spectroscopy mapping method with the aid of a resin (e.g., PET/COC) or a colorant/additive.
A 2D chemical mapping or line scan is collected at the layer interface using a confocal raman microscope (Witec a300R confocal raman spectrometer) equipped with a continuous laser beam, an electrically powered x-y sample scanning stage, a video CCD camera, an LED white light source, diode pumped laser excitation at 488nm to 785nm, and a 50-fold to 100-fold (Zeiss EC Epiplan-neoflurar, NA ═ 0.8 or better) microscope objective.
Samples were prepared in a similar manner as described in method a-sample preparation section, but the samples were uncoated.
The sample was mounted edge up on a glass microscope slide. The region of interest near the layer interface is located by means of a video CCD camera using a white light source. In a region of interest, a 2D chemical map via spectral acquisition is acquired by focusing a laser beam at or below the surface and scanning across the layer interface in X-Y directions in steps of 1 μm or less, with an integration time at each step being less than 1 s. The integration time should be adjusted to prevent detector saturation. Using appropriate software (such as WItec)TMProject Five (version 5.0) software), useSpectral features unique to each polymer layer, such as peak intensity, integrated area, peak width, and/or fluorescence, generate a raman image. Prior to image generation, cosmic ray and baseline corrections were made to the complete raman spectral data at each pixel in the data set. To determine intermixing between the polymer layers, a cross-sectional analysis was performed in which the spectral features used to generate the chemical map were traced along lines drawn across the interface comprising at least 10 microns in the area covering the polymer layer of interest. The defined spectral features are plotted against distance (in microns). The interlayer mixing distance (i.e., the bond layer) is defined as the distance between the maximum and minimum of the spectral feature.
Opacity testing method
Opacity is measured on the cut-out portion of the bottle with a portable densitometer such as X-Rite 341C (X-Rite, Inc.) with a 3mm diameter hole. Measuring the absolute optical density (D), and then determining the absolute optical density by D ═ log10T is converted to transmission (T), with% opacity being 100-% T. The optical density (D) of 5.00 is 100% opaque, and 0.00 is 0% opaque. Each point was measured three times and the average was calculated to determine the% opacity.
Additional embodiments
1. A blow molded single layer article comprising:
a. a hollow body defined by a wall including an inner surface and an outer surface, the wall formed by a layer comprising:
i. one or more first regions comprising a first composition, wherein the first regions extend from the inner surface to the outer surface;
one or more second regions comprising a second composition, wherein the second regions extend from the inner surface to the outer surface, and wherein the second regions comprise an axial color gradient;
wherein the one or more first regions and the one or more second regions form an irregular pattern on the surface of the article.
2. The blow molded article of paragraph a, wherein the wall comprises a plurality of first regions and a plurality of second regions.
3. The blow molded article of paragraph B, wherein the first region and the second region are interpenetrating.
4. The blow molded article of paragraph a, wherein the first composition and the second composition comprise polyethylene terephthalate.
5. The blow molded article of paragraph D, wherein the first composition and the second composition are different colors.
6. The blow molded article of paragraph E, wherein the second composition comprises an effect pigment.
7. The blow molded article of paragraph F, wherein the first composition is substantially free of effect pigments.
8. The blow molded article of paragraph F, wherein the location of the one or more second regions has a surface roughness greater than 25 μ in.
9. The blow molded article of paragraph a, wherein the location of the one or more first regions has a surface roughness of less than 8 μ in.
10. The blow molded article of paragraph a, wherein at least a portion of the article is transparent.
11. The blow molded article of paragraph a, wherein at least a portion of the article is opaque.
12. The blow molded monolayer article of paragraph a, wherein the article is a bottle.
13. The blow molded, monolayer article of paragraph a, wherein the article has a critical nominal load of greater than 50N.
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 its benefits, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with any disclosure of the invention or the claims herein or that it alone, or in combination with any one or more of the references, teaches, 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.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.