Article with visual effects

Abstract

The article (100) has a body (12) portion that includes one or more walls (150, 270, 30) that surround an interior space (36). The one or more walls (150, 270, 30) have an inner surface (132, 32, 35), an outer surface (133, 33), a wall (150, 30) thickness (T1, T2, T3), a transparent portion, and one or more aesthetic regions (137, 1) having an elongated void between the outer surface (133, 33) and the inner surface (132, 32, 35) disposed within the outermost 70% of the wall (150, 30), and the one or more aesthetic regions (137, 1) are disposed in a predetermined pattern (154, 54).

Description

Technical Field

[0001] This invention relates to articles with unique visual effects, preforms for blow-molded articles, and methods for producing such articles and preforms. Background Technology

[0002] Articles made from thermoplastic materials are popular across various industries, including containers for consumer goods, food, and beverages. Blow-molded packaging, such as bottles, is a popular type of thermoplastic container. Blow-molded packaging is made by first forming a preform, which is then typically expanded in a mold under high pressure with air or another gas to form the resulting article. For some articles, injection blow molding or injection stretch blow molding is used, in which the preform is softened and / or stretched in the mold before expanding into the final article.

[0003] While blow molding has been found to be an efficient and effective process for manufacturing articles such as containers, the requirements of this process can make it difficult to provide articles with certain aesthetic and / or tactile qualities or characteristics. Typical preform manufacturing and blow molding processes often limit the available choices for the aesthetic appearance of the article's outer surface due to the steps required to manufacture preforms, the high cost of molds used in the blow molding process, and the processing requirements for blow molding preforms into the final article.

[0004] Therefore, it is desirable to improve the aesthetic features of blow-molded articles. Furthermore, it is desirable to provide blow-molded articles with visual effects such as color, translucency, or opacity, and / or dimensional visual effects such as depth or size (e.g., 3D) or texture appearance. It is also desirable that such blow-molded articles do not require the use of additives that could contaminate the recycled flow of the article. It is also desirable that such blow-molded articles maintain a generally smooth outer surface on the article.

[0005] The invention disclosed herein may provide any one or more of the described or other features and / or beneficial effects, and such features and / or beneficial effects may be provided individually or in any desired combination. Summary of the Invention

[0006] A blow-molded article is provided. The blow-molded article has a body portion including one or more walls surrounding an interior space. The one or more walls have an inner surface, an outer surface, a wall thickness, a transparent portion, and one or more aesthetic regions, the one or more aesthetic regions having an elongated gap between the outer surface and the inner surface disposed within the outermost 70% of the wall, and the one or more aesthetic regions being arranged in a predetermined pattern.

[0007] Also provided is a preform for blow molding articles. The preform is formed of a thermoplastic material and has a body having one or more walls extending from an opening to a base. The one or more walls have an inner surface, an outer surface, a wall thickness, a transparent portion, and one or more foamed regions disposed between the outer surface and the inner surface within the outermost 70% of the wall, the one or more foamed regions being arranged in a predetermined pattern.

[0008] A method for forming a blow-molded article from a preform is also provided. The method includes: a) providing a preform of thermoplastic material having a body having one or more walls and openings, the walls having inner and outer surfaces; b) foaming at least a portion of the walls of the preform to form one or more foamed regions within the outermost 70% of the walls; and c) stretching the preform to form a blow-molded article having article walls having one or more aesthetic regions with elongated voids, the one or more aesthetic regions being arranged in a predetermined pattern within the outermost 70% of the article walls. Attached Figure Description

[0009] Figure 1A It is a plan view of the preform.

[0010] Figure 1B It is a plan view of a multi-layer preform.

[0011] Figure 2A Is along such Figure 1A The cross-sectional view of the preform taken from section 2A-2A is shown.

[0012] Figure 2B Is along such Figure 1B The cross-sectional view of the multi-layer preform shown in section 2B-2B.

[0013] Figure 3 This is a plan view of a preform being produced using laser foaming.

[0014] Figure 3A Is Figure 3 The cross-sectional view of the preform taken along the cross section line 3A-3A after the preform has been foamed.

[0015] Figure 3B Is Figure 3 The cross-sectional view of the preform taken along the cross section line 3A-3A after the preform has been foamed.

[0016] Figure 4 This is a plan view of a multi-layer preform being produced using laser foaming.

[0017] Figure 4A Is Figure 4The cross-sectional view of the preform taken along the cross section line 4A-4A after the preform has been foamed.

[0018] Figure 5 It is a plan view of the product.

[0019] Figure 5A It was cut along the cross section line 5A-5A. Figure 5 A cross-sectional view of the product.

[0020] Figure 5B It was cut along the cross section line 5A-5A. Figure 5 A cross-sectional view of the product.

[0021] Figure 5C It is a plan view of the product.

[0022] Figure 5D It is a plan view of the product.

[0023] Figure 6 It is a plan view of the product.

[0024] Figure 6A It was cut along the cross section line 6A-6A. Figure 6 A cross-sectional view of the product.

[0025] Figure 6B It was cut along the cross section line 6A-6A. Figure 6 A cross-sectional view of the product.

[0026] Figure 7A It is a uCT scan image of the cross section of the preform.

[0027] Figure 7B It is a SEM image of the cross-section of the product.

[0028] Figure 8A It is a uCT scan image of a cross-sectional view of the preform.

[0029] Figure 8B It is based on the invention Figure 7A SEM images of blow-molded products from preformed parts.

[0030] Figure 9 It is a plan view of the preform in the injection molding mold.

[0031] Figure 10 This is a plan view of a preform being produced using laser foaming.

[0032] Figure 11 This is a plan view of the preform in the blow molding mold. Detailed Implementation

[0033] Blow-molded articles are popular containers for consumer products, and the recyclability of such articles is increasingly important. It may be desirable to provide such blow-molded articles with one or more aesthetic features (e.g., aesthetic features that appear to have some color or are translucent or opaque) or visual effects. Such features may be desired in single-layer or multi-layer articles, and the outer surface of the article may be smooth or textured. Aesthetic features can be imparted to blow-molded articles and to the preforms forming the blow-molded articles in any of a variety of ways, including adding opacifiers, colorants, and / or pigments to the preforms and / or articles. However, these pigments may reduce the recyclability of the articles.

[0034] Alternatively, visual effects such as color, translucency or opacity, pearlescent sheen, gloss, and / or dimensional visual effects such as depth, size, or texture appearance can be achieved by creating light scattering effects within the article of manufacture, such as by introducing immiscible materials into the preform (and thus into the article of manufacture). Examples of such methods include introducing silicone and polymethyl methacrylate into a preform made of polyethylene terephthalate (PET). This method may also affect the recyclability of the article of manufacture.

[0035] The visual effect of light scattering can also be achieved by introducing gases, such as air, into the preform in the form of foam. Such methods involve introducing air into the injection mold during the molding of the preform and trapping the air within the preform as foam during cooling. A drawback of this method is that the foaming area of ​​the preform cannot be controlled, thus it cannot be used to form predetermined patterns. Furthermore, foaming across the entire thickness of the preform wall may reduce the barrier properties of the finished container.

[0036] This invention describes blow-molded articles, preforms, and methods for producing blow-molded articles from preforms, wherein the article has one or more aesthetic regions having elongated voids between an outer surface and an inner surface disposed within the outermost 70% of a wall. The one or more aesthetic regions are arranged in a predetermined pattern. This invention utilizes the foaming of a predetermined portion of a wall of the preform to form a pattern of foamed regions within the outermost 70% of the wall, resulting in blow-molded articles having aesthetic regions with elongated voids. Such blow-molded articles are aesthetically pleasing and recyclable.

[0037] As used herein, “article of manufacture” refers to a single object intended for consumer use, such as a container suitable for holding materials or compositions. Articles of manufacture can be containers, non-limiting examples of which include bottles, caps, tubes, cylinders, jars, cups, etc., and can be blow-molded. The compositions contained in such containers can be any of a variety of compositions, including but not limited to detergents (e.g., laundry detergents, fabric softeners, dishwashing liquids, skin and hair care products), beverages, powders, paper products (e.g., tissues, wipes), beauty care compositions (e.g., cosmetics, lotions), pharmaceutical products, oral care products (e.g., toothpaste, mouthwash), etc. Containers can be used for storing, transporting, and / or dispensing the materials and / or compositions contained therein.

[0038] "Blow molding" refers to a manufacturing process that forms articles containing hollow cavities. Generally, there are three main types of blow molding: extrusion blow molding (EBM), injection blow molding (IBM), and injection stretch blow molding (ISBM). The blow-molded articles of this invention can be produced via EBM, IBM, or ISBM, or any other known or developed blow molding method, all of which are simply referred to herein as blow molding. A blow molding process typically begins with the formation of a precursor structure or "preform" that eventually expands into the final article. As used herein, the preform can be of any shape or configuration, but is typically a general shape of a tube having at least one open end or two open ends. Examples of preforms include, but are not limited to, preforms (often given the name "preform structure for extrusion blow molding"), preforms, and other precursor structures for different blow molding techniques. As used herein, preforms can be formed by extrusion, injection, compression molding, 3D printing, and other known or developed methods. Injection molding of preforms can be a simple injection molding of a single material, a co-injection of two or more materials in a single step, and / or an overlay injection molding process performed in two or more steps. The injection steps can be tightly integrated into the blow molding step, such as in IBM, 1-step ISBM, or 1.5-step ISBM, or can be separated from the blow molding step in a secondary operation such as 2-step ISBM. During blow molding, the preform or other precursor structure is typically clamped into a mold, and fluid (usually compressed air) is introduced into the preform through an opening to inflate it to the shape of the mold. Sometimes the preform is mechanically stretched before or simultaneously with the introduction of fluid (a process known as "stretch blow molding"). Additionally, the preform may be heated or cooled before or after the introduction of fluid. The pressure generated by the fluid pushes the thermoplastic out to conform to or partially conform to the shape of the mold containing it. Once the plastic has cooled and hardened, the mold is opened and the formed article is removed.

[0039] As used herein, "blow-molded article" refers to an article formed by blow molding. Such articles have unique physical and structural properties well known to those skilled in the art and are not limited to any particular blow molding method or technique used to make the article.

[0040] In the context of this invention, the term "layer" means the thickness of a material that is generally continuous and generally homogeneous in its chemical composition. However, it is contemplated that any particular layer may have discontinuous portions and / or non-uniform material or regions in certain configurations, including but not limited to pigments, effect pigments, dyes, absorbent additives, and other materials within the layer.

[0041] As used herein, the term "opaque" means that the measured material, layer, article, or part of an article has 0% total light transmittance. Total light transmittance is measured according to ASTM D1003.

[0042] As used herein, the term “translucent” means that the measured material, layer, article, or part of an article has a total light transmittance greater than 0% and less than or equal to 90%.

[0043] As used herein, the term "transparent" means that the measured material, layer, article, or part of an article has a total light transmittance of 90% or higher.

[0044] Preform : An exemplary preform 10 is shown in Figure 1A and Figure 1B The preform 10 has a body 12 and at least one open end 16 with an opening 34. The preform 10 may also include a neck 14 and a closed end 18 disposed opposite the open end 16. The neck 14 of the preform 10 may include one or more features, such as a backflow feature or an attachment feature, such as a thread 20, or other structures that can be used to engage with a cap or other closure in the resulting article. The neck 14 may also include a transfer ring 22 or other structures that may facilitate the manufacturing process.

[0045] The preform 10 can be used in a blow molding process to provide a preliminary structure that can be transformed into a final article, such as a blow-molded article or bottle, by introducing pressurized fluid into the open end 16 of the preform 10 when it is set in the mold in the shape of a final article (or intermediate article). Typically, before the introduction of pressurized fluid, the preform 10 can be heated or otherwise mechanically or chemically manipulated to soften the material of the preform 10, thereby allowing the preform 10 to expand into the shape of the mold without crumbling or breaking. Further details relating to an exemplary blow molding process according to the invention are described below.

[0046] Typically, the preform 10 is formed separately from the blow molding step. The preform 10 can be formed by any suitable method, including but not limited to molding, extrusion, 3D printing, or other known or developed methods. The preform 10 can be formed from a single material or may comprise layers or regions of different materials. Figure 2A It was cut along section line 2A-2A. Figure 1A The figure shows a cross-section of the preform 10. As shown, the preform 10 includes one or more preform walls 30, a closed end 18, and an internal space 36. The preform wall 30 has an inner surface 32 adjacent to the internal space 36 and an outer surface 33 forming the exterior of the preform 10. The thickness of the preform wall 30 is typically, but not necessarily, between about 1.0 mm and about 6 mm.

[0047] Figure 2B Showing the section taken along section line 2B-2B Figure 1B The cross-section of the multilayer preform 10 shown is illustrated, wherein the preform wall 30 is shown to have three layers: an outer layer 40, an intermediate layer 42 adjacent to the outer layer 40 but extending inward from the outer layer 40, and an inner layer 44. Although three layers are shown, any number of layers can be used, including a single layer, two or more layers, three or more layers, or any other number of layers. Furthermore, although in Figure 2B These layers are shown as extending through the entire length of the preform 10, but any one or more layers may extend only partially through the preform 10.

[0048] The outer layer 40, the intermediate layer 42, and the inner layer 44 may each have thicknesses T1, T2, and T3. The thicknesses T1, T2, and T3 of each of the outer layer 40, intermediate layer 42, and inner layer 44 may be the same as or different from one or more of the other thicknesses. Furthermore, the thickness of any given layer may vary throughout the preform 10. For example, the thickness of any layer may vary randomly, may vary according to a predetermined pattern, may vary along the length of the preform 10, and / or may vary around the circumference of the wall 30 of the preform 10. The layers may be made of the same or different materials. They may also be the same or different colors, or have the same or different light transmittance. For example, the outer layer 40 may be transparent, and the inner layer 44 or the intermediate layer 42 may be colored or translucent or opaque, but any other combination of layers with the same or different light transmittance is conceivable. By including layers with different colors and / or different light transmittances, the article formed from the preform 10 may have interesting and / or unique aesthetic properties. In some cases, the preform may contain only recyclable components. In other cases, the preform may be free of pigments or additives, or may contain only recyclable additives or pigments.

[0049] The preform 10 or article according to the invention may be formed from a single thermoplastic material or resin, or from two or more materials that differ from each other in one or more respects. In the case where the preform 10 has different layers, the material constituting each of these layers may be the same as or different from any of the other layers. For example, the preform 10 or article may include one or more layers of thermoplastic resin selected from the group consisting of: polyethylene terephthalate (PET), ethylene glycol-modified polyethylene terephthalate (PETG), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene naphthalate (PEN), polycyclohexanediol terephthalate (PCT), glycol-modified PCT copolymer (PCTG), copolyester of cyclohexanediol and terephthalic acid (PCTA), polybutylene terephthalate (PBCT), acrylonitrile-styrene (AS), styrene-butadiene copolymer (SBC), or polyolefins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLPDE), high-density polyethylene (HDPE), polypropylene (PP), and combinations thereof.

[0050] Recyclable thermoplastic materials may also be used, such as post-consumer recycled (“PCR”) materials, post-industrial recycled (“PIR”) materials, and re-milled materials, such as polyethylene terephthalate (PCRPET), high-density polyethylene (PCRHDPE), low-density polyethylene (PCRLDPE), polyethylene terephthalate (PIRPET), high-density polyethylene (PIRHDPE), low-density polyethylene (PIRLDPE), etc. Thermoplastic materials may include combinations of monomers derived from renewable resources and monomers derived from non-renewable (e.g., petroleum) resources. For example, a thermoplastic resin may comprise a polymer made entirely of bio-derived monomers, or a polymer made partly of bio-derived monomers and partly of petroleum-derived monomers.

[0051] Thermoplastic resins can have a relatively narrow weight distribution, such as metallocene PE polymerized using a metallocene catalyst. These materials can improve gloss, thus resulting in articles with further improved gloss in embodiments of metallocene thermoplastics. However, metallocene thermoplastics can be more expensive than commercial materials.

[0052] The preform 10 can be formed by any known or developed method. For example, the preform 10 can be formed by extrusion, injection, co-injection and / or overmolding, as well as less conventional techniques such as compression molding, 3D printing, etc. The preform 10 can be formed such that at least a portion of the preform wall 30 includes some texture, such as lines, dots, patterns and / or markings, or they can be formed as smooth. By the methods described herein and / or by 3D printing the preform, some limitations associated with texturing the preform 10 by means of a preform mold can be avoided.

[0053] like Figure 3A As shown, the preform 10 may have one or more foamed regions 37 formed by clusters of air bubbles within the preform wall 30. Such foamed regions 37 may be formed on or near the outer surface 33 and / or at a specific depth within the preform wall 30. One or more foamed regions 37 are disposed in the outermost 70% of the wall and may include or adjoin the outer surface. As described herein, "outermost" is defined as the region of the wall furthest from the inner surface of the wall. Therefore, the outermost 50% of the wall will be the 50% of the wall closest to the outer surface. Typically, the foamed regions 37 will be disposed in the outermost 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5% of the wall. The foamed regions 37 may be open to the outer surface or may be entirely within the wall 30.

[0054] The swarm of bubbles constituting one or more foamed regions 37 can form a gradient, wherein any characteristics of the bubble swarm may vary within the foamed region. For example, when the foamed region 37 includes an outer surface 33, the gradient may include more bubbles positioned closer to or at the outer surface 33 (e.g., a higher bubble density per unit area or volume). The gradient foamed region may include variations within the swarm of bubbles constituting one or more foamed regions 37, such as the distribution of bubbles through the walls of the preform, the number distribution of bubbles, the volume distribution of bubbles, bubble size and / or aspect ratio, etc. The gradient can take any desired shape. For example, the foamed region gradient may be a gradient of the number of bubbles within the foamed region following a Gaussian curve, wherein the foamed region 37 is wider at the outermost boundary and narrower at the innermost boundary. The foamed region may be configured such that there are more bubbles at the outermost boundary of the foamed region and fewer bubbles facing the inner surface, such as... Figure 3A As shown.

[0055] At least the portion of the preform from the centerline to the inner surface may be substantially free of any foamed areas. In other words, the innermost 50% of the preform wall may be substantially free of any foamed areas. Furthermore, the innermost 60%, 70%, 80%, 90%, 95%, or greater than 95% of the preform wall may be substantially free of any foamed areas. A predetermined foam pattern may include foamed areas of varying depths within the preform wall. While the disclosure herein generally discusses the formation of one or more foamed areas in the wall of the preform, one or more foamed areas 37 may also be formed, or alternatively, within the closed end 18 or neck 14 of the preform.

[0056] One or more foamed regions 37 may be formed within the preform after the preform has been formed. Examples of ways to form the foamed regions 37 within the walls 30 of the preform 10 after its formation include laser foaming as described herein. The foamed regions 37 may take any desired shape and may be in the form of a predetermined pattern, including lines, dots, curves, letters, numbers, logos, etc.

[0057] Figure 3 An exemplary embodiment of a preform 10 being foamed by a laser beam 50 passing through a laser 52 is shown, but any other suitable technique may be employed. The laser beam 50 modifies the material, forming the wall 30 of the preform 10, thereby creating one or more foamed regions 37 within the outermost 70% of the wall 30. One advantage of post-forming modification of the wall 30 of the preform 10 is that there are virtually no limitations (if any) on the specific, predetermined pattern 54 that can be selected for the foamed regions. Furthermore, post-forming foaming, such as laser foaming, can also allow different preforms 10 from the same mold to have different patterns of foamed regions 37, which can significantly reduce the cost of producing articles with different aesthetic features 112, thereby making the production of small batches or even custom-made articles economically feasible.

[0058] Figure 3A It is along Figure 3 The section line 3A-3A cuts out such as Figure 3 A cross-sectional view of foamed preforms such as preforms. Figure 3A The exemplary embodiment shown includes a predetermined pattern 54 comprising a plurality of foamed regions 37. The foamed regions 37 can be formed using a laser in a portion of a preform disposed on the inner side of the outer surface 33, in the outermost portion of the wall 30.

[0059] Figure 3B It is along Figure 3 Section line 3A-3A cut Figure 3A cross-sectional view of the foamed preform. The predetermined pattern 54 includes a first foamed region and a second foamed region, the first foamed region including the outer surface 33 of the preform, and the second foamed region within the wall of the preform excluding the outer surface.

[0060] Out of respect for Figures 3 to 3B For the purposes of the examples shown, the foamed region 37 can be considered as having been formed by laser foaming. However, these examples are not intended to limit the scope of the invention, and as stated above, the foamed region 37 can be formed by any foaming method.

[0061] like Figure 3B As shown, one or more foamed regions 37 may have a layer depth Dp and an initial depth Op. In the figure, the layer depth Dp represents the depth (or thickness) of the foamed region 37 in the preform wall 30 in a direction perpendicular to the outer surface 33 of the preform. In the case where the foamed region 37 includes the outer surface 33 of the preform (e.g.) Figure 3A As shown), the depth of the foamed region layer can be taken from the outer surface of the preform. In the case where the foamed region 37 includes the outer surface 33 of the preform (e.g.) Figure 3A As shown in the figure, the initial depth of the foaming area is zero.

[0062] The initial depth Op of one or more foamed regions 37 may be greater than zero, that is, one or more foamed regions 37 may be formed within the preform wall 30, and an unfoamed portion of the preform wall may exist outside the foamed regions. The initial depth of one or more foamed regions 37 is taken as the distance from the outer surface 33 of the preform to the foamed region 37 in a direction perpendicular to the surface of the preform.

[0063] It should be understood that the initial depth Op and / or layer depth Dp of one or more foamed regions 37 forming a predetermined pattern 54 in the preform may differ from the initial depth and / or layer depth of one or more foamed regions in the resulting article. When an article is formed from a preform by, for example, blow molding, the wall thickness decreases as the preform is stretched. Therefore, the initial depth and / or layer depth of one or more foamed regions 37 can be reduced in a similar manner.

[0064] It should also be understood that one or more foamed regions 37 in the preform may correspond to one or more foamed regions in the article. In other words, one or more images depicted by a predetermined pattern formed by one or more foamed regions in the preform may produce a similar depiction in the resulting article, wherein the overall outline and / or shape of the image is similar in the preform and the article, even if the size of the image changes due to stretching of the preform during article formation.

[0065] It should also be understood that the initial depth Op and / or layer depth Dp of one or more foamed regions in the preform and the article can be similar relative to the wall thickness of the preform and the article, respectively. In other words, the initial depth and layer depth of one or more foamed regions can be similar in the preform and in the article, taken as a portion of the total wall thickness of the preform and the article. For example, if a foamed region is formed within the wall of the preform and its initial depth is 10% of the total wall thickness of the preform, then the initial depth of the corresponding region within the wall of the article can also be 10% of the thickness of the article wall material.

[0066] Typically, the layer depth Dp of the foamed region 37 in the preform 10 is between about 0.001 mm and about 2 mm, but any suitable layer depth Dp can be used. Alternatively, the layer depth of the foamed region can be between about 0.01 mm and about 1.5 mm, or between about 0.1 mm and about 1 mm, or between about 0.025 mm and about 1 mm, or between about 0.1 mm and about 1 mm, or between 0.1 mm and about 0.4 mm. Typically, the initial depth Op of one or more foamed regions in the preform is between about 0 mm and 2 mm. Alternatively, the initial depth of the foamed region can be between about 0.01 mm and about 2 mm, or between about 0.1 mm and about 2 mm, or between about 0.5 mm and about 2 mm, or between about 0.5 mm and about 1.5 mm. It should be noted that the predetermined pattern may include multiple foamed regions, which may have the same or different layer depths and / or initial depths.

[0067] Alternatively, the layer depth of the foamed region can be expressed as a percentage of the total wall thickness of the preform to the portion of the preform in which the foamed region is located. For example, the layer depth of the foamed region can be from about 0.0025% to about 50% of the wall thickness of the preform, or from about 0.005% to about 30%, or from about 0.01% to about 30%, or from about 0.025% to about 10%, or from 0.1% to about 3% or less. Typically, the initial depth Op of one or more foamed regions in the preform is from about 0 to 50% of the wall thickness of the preform, or from about 0.0025% to about 20%, or from about 0.005% to about 10%, or from about 0.01% to about 10%, or from about 0.05% to about 5%.

[0068] Figure 4 The image shows a multilayer preform 10 being foamed by a laser beam 50 passing through a laser 52. The laser beam 50 alters the material, forming a wall 30 of the preform 10, thereby creating one or more foamed regions 37 within the preform wall 30 in the outermost 70% of the wall 30.

[0069] Figure 4A It is along Figure 4 Section line 4A-4A cut Figure 4A cross-sectional view of the foamed preform. Figure 4A Includes a predetermined pattern 54, which includes multiple foamed regions 37. The foamed regions 37 can be formed using a laser in a portion of a preform disposed on the inner side of the outer surface 33, in the outermost 70% of the wall 30 (such as in the outer layer 40 or the middle layer 42).

[0070] laser : One method of forming a predetermined pattern 54 of the foamed region 37 on the preform 10 is by foaming. Any suitable laser can be used to foam the preform 10. An example of a laser 52 that can be used to foam the preform 10 is a UV-type laser with a power ranging from 0.5 watts to 100 watts and a wavelength of 355 nanometers or between 200 and 400 nanometers. Such lasers are available from various suppliers, including the ULPN-355-10-1-3-M integrated laser marker from IPG Photonics in Marlborough, Massachusetts, USA. Other brands and types of lasers are also possible, and different power ranges and settings can be used. As needed, the laser 52 may include optics that can be used to change the energy density, spot size, and focal plane of the laser beam. By adjusting the focal plane of the laser optics, the initial depth can be positioned from near the surface of the preform to a subsurface depth accessible to the inner surface of the preform.

[0071] Products : Articles according to the invention can take many forms. One form, a blow-molded article such as a bottle, is discussed throughout the specification and shown in the accompanying drawings. However, it should be understood that other forms are contemplated, and the scope of the invention should not be considered limited to any particular form or type unless specifically stated in the language of the relevant claims.

[0072] Article 100 may be provided with unique and beneficial characteristics. These characteristics are the result of unique features related to the structure of article 100 itself, the characteristics of preform 10, and the method of manufacturing preform 10 and / or article 100. Figures 5 to 6 An example of a blow-molded article 100 according to the present invention is shown. As described above, the present invention can provide the article 100 with aesthetic features that are currently unattainable and / or unattainable with currently available mass production equipment and techniques.

[0073] For example, such as Figures 5A to 5B , Figures 6A to 6B As shown, article 100 typically has an inner surface 132 and an outer surface 133. Article 100 may include a plurality of aesthetic regions 137 disposed within the wall 150 of article 100. Furthermore, as... Figure 5 and Figure 6 As shown, the outer surface 133 or any other surface of article 100 may be printed with aesthetic features and / or markings 110, including but not limited to graphics, colors, words, numbers, symbols, etc. Examples of printing technologies include, but are not limited to, laser printing, inkjet printing, contact printing, screen printing, offset printing, transfer printing, labeling, and combinations thereof. Although the article includes the aesthetic features of the present invention and / or is decorated, the article may still retain its recyclable properties. Article 100 may include, for example, Figures 5 to 6 The label shown is 115.

[0074] The wall 150 of article 100 can be of any suitable thickness. For example, the wall thickness can be in the range of about 0.1 mm to about 3.0 mm, but other thicknesses may also be used depending on the specific process used and the desired end result.

[0075] Article 100 may have one or more layers of material constituting part or all of article 100. In multilayer article 100, such as Figure 6A and Figure 6B As shown, two or more layers may exist. Furthermore, the relative thicknesses of the layers (if any) may differ from one another and may vary throughout a particular layer. That is, each of these layers may have a different thickness than the other layers, or some or all of these layers may have approximately the same thickness. Typically, each layer is a value between 5% and 95%, 5% and 75%, 5% and 50%, or 5% and 40% of the total thickness of the article wall. And, as mentioned above, the thicknesses of different portions of wall 150 and / or layers may be different as needed, for example, as... Figure 6A and Figure 6B As shown, the outer layer 140 has a thickness of T1, the middle layer 142 has a thickness of T2, and the inner layer 144 has a thickness of T3.

[0076] One beneficial effect of this invention is that it enables the addition of aesthetic features to blow-molded articles, which is otherwise impossible. This is important because blow-molded articles produced by processes such as IBM and ISBM can be made of PET, which is often superior to other materials because it is more widely recyclable than other translucent and glossy thermoplastics. This invention enables the production of blow-molded articles, such as those produced by IBM and ISBM processes, with aesthetic features without the need for additives such as colorants, pigments, or immiscible materials that could reduce the recyclability of the article. Article 100 may have a smooth outer surface.

[0077] As described above, the articles of the present invention are generally made from preforms as described above. Figure 3AAs shown, the preform 10 may have one or more foamed regions 37, and thus the article 100 may include one or more aesthetic regions 137. When the preform is transformed into an article, for example by blowing or stretching, the bubbles forming the foamed regions in the preform are stretched and deformed, causing them to flatten out like pancakes, becoming elongated voids. Therefore, the aesthetic region 137 can be described as being formed by a group of elongated voids within the article wall 130, such as... Figure 5A and Figure 6A As shown. Such aesthetic regions 137 may be disposed on or near the outer surface 133 and / or within the article wall. One or more aesthetic regions 137 may be disposed within the outermost 70% of the wall and may include the outer surface. Typically, aesthetic regions 137 will be disposed within the outermost 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5% of the article wall. Aesthetic regions 137 may be open to the outer surface or may be completely within the article wall 130.

[0078] As described above, the preform can be foamed within the wall portion or within the closed end 18 or neck 14. The foamed area formed in the closed end 18 or neck 14 of the preform can create an aesthetic region 137 in the article, provided that the portion of the preform including the foamed area is stretched when the preform is transformed into an article.

[0079] The elongated void groups constituting one or more aesthetic regions 137 can form a gradient, wherein any characteristics of the elongated void groups may vary within the aesthetic regions 137. For example, when the aesthetic region 137 includes an outer surface 33, the gradient may include more elongated voids positioned closer to or at the outer surface 33 (e.g., a higher density of elongated voids per unit area or volume). The gradient may include variations within the elongated void groups constituting one or more aesthetic regions 137, such as the distribution of elongated voids through the walls of the preform, the number distribution of elongated voids, the volume distribution of elongated voids, the size and / or aspect ratio of elongated voids, etc. The gradient can take any desired shape. For example, the gradient may be a gradient of the number of elongated voids within the aesthetic region 137 following a Gaussian curve, wherein the aesthetic region 137 is wider at the outermost boundary and narrower at the innermost boundary. The aesthetic region 137 may be formed such that there are more elongated voids at the outermost boundary and fewer elongated voids at the boundary toward the inner surface, such as... Figures 5A to 5B and 6A to Figure 6B As shown. The aesthetic area can form a predetermined pattern. In addition, the aesthetic area can usually be contained in the outermost 70% of the article wall.

[0080] At least the portion of the article wall from the centerline to the inner surface may be substantially free of any aesthetic areas. In other words, the innermost 50% of the article wall may be substantially free of any aesthetic areas. Furthermore, 60%, 70%, 80%, 90%, 95%, or more than 95% of the innermost portion of the article wall may be substantially free of any aesthetic areas. A predetermined aesthetic pattern may include aesthetic areas of varying depths. One or more aesthetic areas may be located within the article wall, or within the closed end or neck of the article, provided that the preform is sufficiently stretched in those areas to form a pancake. One or more aesthetic areas in the article may form a predetermined pattern. The predetermined pattern may take any desired shape, including lines, dots, curves, letters, numbers, logos, etc.

[0081] Figure 5A It is along Figure 5 The cross-sectional view of the article 100, including the aesthetic region 137, is taken from section line 5A-5A. Figure 5A The exemplary embodiment shown includes an aesthetic region comprising the outer surface 133 of the article 100 and a gradient, wherein the density of bubbles per unit volume decreases toward the inner surface of the article wall.

[0082] Figure 5B This is a cross-sectional view of an alternative embodiment of article 100. Figure 5B The exemplary embodiment shown includes a predetermined pattern 154, which comprises multiple aesthetic areas. For example... Figure 5 As shown, the predetermined pattern 154 includes a first aesthetic region and a second aesthetic region. The first aesthetic region includes the outer surface 133 of the article and a gradient, wherein the density of elongated voids per unit volume decreases toward the inner surface 132 of the article, and the second aesthetic region is within the article wall (i.e., excluding the outer surface).

[0083] Figure 5C This is a cross-sectional view of a multilayer article according to the present invention. An exemplary embodiment shows a first aesthetic region formed in the outer layer 140 and a second aesthetic region formed in the intermediate layer 142.

[0084] like Figure 5B As shown, one or more aesthetic regions 1 disposed in the article 100 (e.g., article wall) may have a layer depth Da and an initial depth Oa. In the figure, the layer depth Da represents the depth (or thickness) of the aesthetic region 137 in the article wall 130 in a direction perpendicular to the outer surface 133 of the article. In the case where the aesthetic region 137 includes the outer surface 133 of the article (e.g.... Figure 5A As shown), the depth of the aesthetic region layer can be taken from the outer surface of the product. In the case where the aesthetic region 137 includes the outer surface 33 of the product (e.g.) Figure 5A As shown), the initial depth Da of the aesthetic region is zero.

[0085] The initial depth Oa of one or more aesthetic regions 137 in the article 100 may be greater than zero, that is, one or more aesthetic regions 137 may be disposed within the article wall 30, and a portion of the article wall outside the aesthetic region may exist that is substantially free of any elongated voids or aesthetic regions. The initial depth of one or more aesthetic regions 137 is taken as the distance from the outer surface 33 of the article to the aesthetic region 137 in a direction perpendicular to the article surface.

[0086] Typically, the layer depth Da of the aesthetic region 137 in article 100 is between 0.001 mm and 1.5 mm, but any suitable layer depth Da can be used. Alternatively, the layer depth of the aesthetic region can be about 0.01 mm to about 1.5 mm, or about 0.01 mm to about 1 mm, or about 0.025 mm to about 1 mm, or about 0.025 mm to about 0.5 mm, or 0.1 mm to about 0.4 mm. Typically, the initial depth Oa is between about 0 mm and 1.5 mm. Alternatively, the initial depth of the aesthetic region can be about 0.0 mm to about 1.0 mm, or about 0.001 mm to about 1 mm, or about 0.01 mm to about 1 mm, or about 0.01 mm to about 0.5 mm, or 0.1 mm to about 0.5 mm. It should be noted that when the aesthetic region is located within the outermost 50% of the wall between the inner and outer surfaces, the initial depth plus the layer depth cannot exceed half the thickness of the article's wall.

[0087] Alternatively, the layer depth of the aesthetic region can be expressed as a percentage of the total wall thickness of the article to the portion of the article in which the aesthetic region is located. For example, the layer depth of the aesthetic region can be from about 0.0025% to about 50% of the wall thickness of the article, or from about 0.005% to about 30%, or from about 0.01% to about 30%, or from about 0.025% to about 10%, or from 0.1% to about 3% or less. Typically, the initial depth Oa of one or more aesthetic regions in the article is from about 0% to 50% of the wall thickness of the article, or from about 0.0025% to about 20%, or from about 0.005% to about 10%, or from about 0.01% to about 10%, or from about 0.05% to about 5%.

[0088] Reducing the wall thickness portion including the aesthetic region (i.e., reducing Da as a percentage of wall thickness) helps the article maintain its barrier properties, even when including the aesthetic region. In other words, by limiting the degree to which the article wall contains voids (e.g., by limiting the degree of foaming of the preform wall in a similar manner), the substantially void-free portion of the article wall is increased, and the barrier properties of the wall are maintained to be nearly similar to those of an article derived from an unfoamed preform. This can be expressed in terms of the density of the wall material. Specifically, the density of the article wall portion constituting the aesthetic region is nearly similar to the density of the wall portion that is substantially free of elongated voids. For example, the density of the article wall portion constituting the aesthetic region may be about 0.5% smaller than that of the article wall portion that is substantially free of elongated voids. Alternatively, the density of the article wall portion constituting the aesthetic region may be about 1%, about 2%, or about 5% smaller than that of the article wall portion that is substantially free of elongated voids.

[0089] Figure 7A , Figure 7B , Figure 8A and Figure 8B This is an analytical cross-sectional view of examples of preforms and articles such as bottles according to the present invention. Figure 7A This shows a cross-section of the wall of a preform that has been laser-foamed (similar to...). Figure 3A The image shows a cross-sectional line (3A-3A cut). This image is a 2D slice of a 3D dataset collected using uCT. Figure 7B Showing a cross-section of the wall of the article (similar to) Figure 5A (The cross section shown is cut along line 5A-5A), the article is made of a material similar to Figure 6A The preform shown is formed by ISBM. The image was taken using SEM. Aesthetic region 137 is formed by foaming a preform used to make article 100, and then stretching the foamed preform, such as by blow molding (e.g., by ISBM) to form a bottle.

[0090] Stretching bubbles formed in the foamed areas of a preform provides aesthetic features. That is, elongated voids in articles such as bottles are stretched relative to bubbles formed in the preform. Table 1 lists... Figure 5 and Figure 6 The table shows the average size of bubbles in the example preform and the stretched product. As can be seen from the data in Table 1, the bubbles formed in the preform are roughly spherical, with a length L (taken as the average longest distance between individual bubbles) similar to the average thickness T (taken at the midpoint of L as the shortest distance between individual bubbles orthogonal to the axis of L). It should be noted that uCT analysis was used to measure bubbles in the preform, while SEM analysis was used to measure elongated voids in the product, due to the different resolution capabilities of the two methods.

[0091] Table 1

[0092] As shown in Table 2, when a preform is blown into a final product, the bubbles flatten (i.e., their thickness decreases) and widen (i.e., their length increases) to create elongated voids. Therefore, the aspect ratio of the bubbles increases significantly. Typically, predetermined patterns formed in the preform are transferred and preserved in articles such as bottles, but the patterned bubbles now flatten, becoming elongated voids. These flattened bubbles provide aesthetic features within the article.

[0093] Specifically, the preform is foamed within the outermost 70% of the preform wall in a predetermined pattern and to a predetermined depth. The predetermined depth can be controlled so that only a portion of the total wall thickness of the preform is foamed, thereby foaming articles such as bottles. Only a small portion of the wall thickness of the preform and / or article is foamed to maximize the integrity of the bottle, such as its strength and / or barrier properties. The preform can be foamed such that the foamed area accounts for approximately 50% of the total wall thickness of the preform and / or article. Alternatively, the preform can be foamed such that the foamed area accounts for only approximately 40%, 30%, 20%, 10%, 5%, or less than 5% of the total wall thickness of the preform and / or article, such as approximately 3% or less than approximately 3%. The predetermined pattern may include areas foamed to one depth and areas foamed to different depths. Table 3 lists... Figures 7A to 7B and Figures 8A to 8B The examples shown illustrate the depth of the foamed area of ​​the preform and the aesthetic area of ​​the finished product.

[0094] Table 2

[0095] The depth of the foamed region formed in the preform can be controlled by controlling the laser energy applied to the preform (e.g., energy density, focal length of the laser optics, etc.) and the degree to which the preform absorbs this energy. Specifically, a higher laser energy density (i.e., energy per unit area) and / or a shorter focal length can form a deeper foamed region.

[0096] Individually, increasing the absorption of laser energy by the preform can create shallower foamed areas and a more aesthetically pleasing result. For example, combining absorbent additives designed to absorb the wavelength of laser energy can make the laser energy absorbed more effectively. For instance, additives such as benzotriazole and / or benzophenone can be used to improve the absorption efficiency of UV laser energy. Alternatively, additives such as carbon black, titanium nitride, antimony tin oxide (ATO), indium tin oxide (ITO), mica coated with ATO or ITO, cesium tungsten oxide, alkali tungsten oxide, tungsten suboxide, titanium suboxide, zinc aluminum oxide, metal nanoparticles, and composite metal oxides can be used to improve the absorption efficiency of IR and near-IR laser energy.

[0097] By absorbing energy more effectively, laser energy cannot penetrate deeply into the preform, and the foamed areas will form closer to the surface of the preform. The foaming rate can also be increased by heating the preform 10 before and / or during the foaming step.

[0098] A higher laser energy density (i.e., energy density) can be used to provide the foamed region 37, which can provide a deeper foamed region 37 and a deeper coloration, such as Figure 7A As shown. Figure 7A The foaming area shown is 37 times larger than the previous one. Figure 8A The foamed area 37 shown in the diagram further penetrates toward the inner surface 35 of the wall 150.

[0099] The foamed region 37 and / or aesthetic region 137 may be suspended from and / or connected to the outer surface of the preform and / or article, or may be contained within the material of the preform and / or article (e.g., wall, neck, or base) and not connected to the outer surface. The foamed region can be formed below the surface of the preform by subsurface foaming, which can be achieved by changing the focal length of the laser optics.

[0100] The predetermined pattern of article 100 feels smooth to the touch. The degree of smoothness of a particular surface can be represented by various different surface morphology measurements. Two measurements have been found particularly helpful in characterizing the surface morphology of preforms and articles according to the invention: maximum peak / pit height (Sz) and root mean square roughness (Sq), as described in the measurement methods section of this specification.

[0101] For example, it may be desirable to limit some or all of the maximum peak / pit height and / or root mean surface roughness across the outer surface 133 of the article to provide a surface desired for printing and / or labeling, or for other tactile, aesthetic, or functional reasons. For example, it may be desirable that the Sz of some or all of the outer surfaces of the article 133 be less than or equal to 750 micrometers, 500 micrometers, 250 micrometers, 200 micrometers, 150 micrometers, 100 micrometers, or 50 micrometers. In addition, or as an alternative, it may be desirable that the Sq of some or all of the aesthetic regions 137 be a specific value or lower. For example, it may be desirable that the Sq of some or all of the aesthetic regions 137 be less than or equal to 10 micrometers, 8 micrometers, 5 micrometers, or 2 micrometers. The inner surface 132 may also have certain topological properties due to the processes used to form predetermined features 105 (such as predetermined patterns 54). For example, the Sq of some or all of the aesthetic regions 137 of the inner surface 132 may be greater than or equal to about 2 micrometers, 5 micrometers, 8 micrometers or 10 micrometers, and the Sz of some or all of the inner surfaces of the article 132 may be greater than or equal to 50 micrometers, 100 micrometers, 150 micrometers, 200 micrometers, 250 micrometers, 500 micrometers or 750 micrometers.

[0102] The preform 10 and article 100 according to the invention may include layers and / or materials in the layers having various functions. For example, article 100 may have a barrier material layer or a recyclable material layer between an outer thermoplastic material layer and an inner thermoplastic material layer. Article 100 may include, for example, additives, typically in amounts from 0.0001%, 0.001%, or 0.01% to about 1%, 5%, or 9% by weight of the article. Non-limiting examples of functional materials include, but are not limited to, titanium dioxide, fillers, curing agents, antistatic agents, lubricants, UV stabilizers, antioxidants, anti-blocking agents, catalyst stabilizers, colorants, pigments, nucleating agents, laser-absorbing additives, and combinations thereof. It should be understood that although these additives are contemplated for use in the invention, they may reduce the recyclability of the article.

[0103] Methods for manufacturing blow-molded products : As described above, the article 100 of the present invention can be manufactured by molding, including but not limited to EBM, IBM, or ISBM. In such methods, the article 100 is formed from a preform 10, such as the preform shown in FIG. 1. The preform 10 can be manufactured by any known method, including injection molding, 3D printing, or any other suitable method. Figure 9An example is shown of preform 10 being injected into preform mold 200 after the material constituting preform 10 has been injected into the preform mold cavity 215 of preform mold 200 and the preform 10 has been formed into the desired shape. The material constituting preform 10 is injected into the mold through orifice 210. After the material is cooled or otherwise modified so that the preform 10 can retain its shape, the preform 10 is removed from the mold 200. The preform 10 can be subjected to any number of post-molding techniques, including but not limited to chemical treatment, heating, cooling, light exposure, mechanical manipulation such as cutting, etching, scratching, bending, coating, etc. These techniques can help provide the preform 10 and / or the final article 100 formed from the preform 10 with desired properties.

[0104] According to the invention, after the preform 10 is removed from the mold 200, it may be provided with a predetermined pattern 54, such as a pattern including at least one foamed region 37. Figure 10 As shown, the preform 10 can be foamed by one or more lasers 52. The lasers 52 can guide one or more laser beams 50 to modify a portion of the preform wall 30, neck 14, or base. Material modification can form a foamed region 37 within the wall 30 of the preform 10. The foamed region 37 can extend to any portion of the outer surface 33 of the preform 10, and the foamed region 37 can include bubbles that are open or completely closed to the outer surface 33. The foamed region 37 does not extend beyond the outermost 70% of the wall 30. The modification process can be performed in one step or in multiple different steps. During foaming, the preform 10 can be rotated about its longitudinal axis L so that the foaming apparatus can foam around the circumference of the preform 10, or the foaming apparatus can rotate around the preform 10, or both can be rotated.

[0105] Once the desired number of foamed areas 37 are applied to the preform 10, the preform can be moved to the blow molding step to form the article 100, or it can be stored or otherwise treated to obtain different properties. Typically, just before the blow molding step, the preform 10 is heated or otherwise treated to soften it from a hardened state. This makes it easier to blow the preform 10 into the shape of the article 100. The preform 10 is typically heated by lamps, hot air, radiation, or convection, but other methods of heating the preform 10 can also be used. When the preform 10 is ready to be “blown” or expanded into the shape of the final article 100, it is placed in a blow mold, for example... Figure 11In the blow mold shown, blow mold 250 has a cavity 260 formed by walls 270. Cavity 260 is generally shaped like article 100. Walls 270 may be smooth or may have some texture. Preform 10 in blow mold 250 expands such that the walls, neck 14, and base 30 of preform 10 form the shape of cavity 260. The expanded preform may not fully contact the walls of the mold. Typically, preform 10 is expanded by forcing air or another fluid through the open end 16 of the preform into the opening 34 of the preform. If desired, a vacuum created in cavity 260 may aid in the expansion of preform 10. Once preform 10 has expanded to the shape of blow mold 250 and thus to the shape of the final article 100, article 100 can be cooled and blow mold 250 can be removed. Article 100 may undergo additional processing steps, including but not limited to inspection, defect removal, cleaning, filling, labeling, printing, and sealing.

[0106] The blow forming process can be configured such that some or all of the foamed regions 37 form the aesthetic region 137 of the article 100, and ensure that other physical / mechanical properties of the article are appropriate. For example, it may be helpful to: 1) minimize additional thermal crystallization on the outer surface, 2) optimize strain-induced crystallization, and 3) set the material in the mold to avoid concave or convex surfaces in the transition from a thick surface to a thin surface.

[0107] For example, the product can be a bottle with a surface texture or a bottle with a smooth outer surface. The smoothness of the outer surface can be controlled during the blow molding process. Such textured features can make the bottle more attractive and appealing to consumers. Additionally, since the product 100 can be provided with a smooth outer surface 133, it is easier to label and / or easier to apply printing to it. Furthermore, since this method provides a way to add a predetermined pattern 54 to the preform 10 (and the resulting product) after it leaves the preform mold 200, it significantly simplifies the process of manufacturing complex features on the product 100. Although the preform 10 comes from the same preform mold 200, this also makes it possible to change the functional, textured, and / or aesthetic features of the final product 100, and to change the overall aesthetic, textured, or functional features of the product 100 more quickly and efficiently, because a new preform mold 200 is not required if changes to the resulting product 100 are desired. Therefore, small production batches and even customized products become economically feasible.

[0108] Measurement methods

[0109] Wall thickness : The wall thickness is measured at two or more locations in the area of ​​the workpiece where the wall thickness is to be measured using a digital micrometer (Shinwa 79523 digital micrometer from Shinwa Ltd., Japan). The accuracy of the digital micrometer is + / - 0.003 mm.

[0110] Micro-CT methods

[0111] The specimens of the artifacts under test were imaged as a single dataset with continuous voxels using a micro-CT X-ray scanner capable of scanning samples approximately 4 mm × 4 mm × 3 mm in size. An isotropic spatial resolution of 1.6 µm was required in the dataset collected by the micro-CT scan. The micro-CT measurements were performed using a SCANCO Systems model µ50 micro-CT scanner (ScancoMedical AG (Brüttisellen, Switzerland)) with the following settings: energy level of 55 kVp at 72 µA; projection of 3600°; field of view of 7 mm; integration time of 700 ms; average value of 8; and voxel size of 1.6 μm.

[0112] Prepare the test samples to be analyzed as follows: Cut a rectangular plastic sheet from the wall using an Exacto knife, then carefully trim the sample to approximately 4 mm in width using a fine-toothed Exacto saw or fine surgical scissors, avoiding cracking. Position the sample horizontally with the mounting foam material and place it in a cylindrical plastic scanning tube, securing it within a micro-CT scanner. Select the instrument's image acquisition settings such that the image intensity contrast is sufficiently sensitive to provide a clear and reproducible distinction between the sample structure and the air and surrounding mounting foam. Image acquisition settings that cannot achieve this contrast distinction or require the desired spatial resolution are not suitable for this method. Capture scans of the plastic samples such that each sample of similar volume and thickness is included in the dataset.

[0113] Software was supplied by the scanning instrument manufacturer (Avizo Lite 1019.1, Burlington, Massachusetts, USA, VisualizationSciences Group / FEI Company) for reconstructing the dataset to generate 3D renderings. Representative 2D slices perpendicular to the surface were taken from the 3D data volume set near the center of the foamed region (in the preform) or aesthetic region 137 (in the article). Distances were measured using the line measurement tool available in Avizo. It should be noted that preform bubbles are primarily isotropic and spherical in shape, while blown bottle bubbles are significantly flattened due to stretching along both axial and circular directions. The bubble length or thickness in the foamed region (in the preform) is the edge-to-edge distance of a representative bubble. The maximum bubble depth in the foamed region (in the preform) or aesthetic region (in the article) should be represented as the deepest layer of bubbles at the representative distance from the surface edge to the slice. Due to stretching, bubbles in the article resemble the shape of pancakes or elongated voids and can be represented as layers in a 2D cross-sectional view. The measurement begins at the point furthest from the edge of the bottle and ends at a point perpendicular to the bottle's surface.

[0114] SEM method

[0115] Use sharp scissors or a utility knife to remove the area from the blown piece, including the aesthetic area. Remove approximately 0.5 cm from the stretched portion of the piece. 2 Or larger specimens. Specimens include both the outer and inner wall surfaces, as well as the material in between, including the aesthetic area. A sharp razor blade is used, preferably a single-bladed PTFE-coated stainless steel GEM. ® A blade was used to further cut the specimen parallel to the height dimension of the bottle to create a cross-sectional observation plane. The specimen was then fixed to the cross-sectional SEM sample substrate using double-sided conductive tape and conductive silver pigment, and the newly exposed cross-sectional observation plane was installed for electron beam imaging. To mitigate charging issues in the SEM, a Gatan Alto Cryo-Prep device was used for observation, and the mounted specimen was coated with a very thin gold / palladium conductive coating. The specimen was imaged using a Hitachi S-4700 Field Emission SEM.

[0116] Images were captured at sufficient magnification to determine the size of the bubbles. The longest and shortest dimensions of 10 representative bubbles were measured using image measurement software such as Quartz PCI (Quartz Imaging Corporation, Vancouver, British Columbia, Canada). First, the longest dimension of the elongated void was measured and recorded as its length (L). The shortest dimension, orthogonal to the longest dimension, was then obtained at the midpoint of the longest dimension. This shortest dimension is called the thickness (T) of the elongated void.

[0117] Root mean square roughness (Sq) and maximum peak / pit height (Sz) : The root mean square roughness Sq and maximum peak / pit height Sz were measured using a 3D laser scanning confocal microscope, such as the Keyence VK-X200 series microscope (including the VK-X200K controller and VK-X210 measurement unit) purchased from Keyence Corporation, USA. VK Viewer version 2.4.1.0 software from the instrument manufacturer was used for data collection, and Multifile Analyzer version 1.1.14.62 and VK Analyzer version 3.4.0.1 software from the manufacturer were used for data analysis. If needed, VK Image Stitching version 2.1.0.0 image stitching software from the manufacturer could be used. The manufacturer's analysis software conforms to ISO 25178. The light source used was a semiconductor laser with a wavelength of 408 nm and a power of approximately 0.95 mW.

[0118] The sample to be analyzed is obtained by cutting a piece of the article from the area to be analyzed, the size of which is suitable for proper analysis under a microscope. To measure Sq and Sz of the foamed portion of the article, a sample including the foamed area should be obtained, and the analysis should be performed only above the foamed portion of the sample. Similarly, to measure Sq and Sz of the non-foamed portion of the article, a sample including the non-foamed area should be obtained, and the analysis should be performed only above the non-foamed portion of the sample. If the sample is not flat but flexible, it can be held downwards on the microscope stage using tape or other means. If, due to the shape, flexibility, or other characteristics of the sample, the measurement results would be more accurate when the sample is not flattened, a correction can be used, as explained below.

[0119] Measurement data from the samples were acquired using a 20X objective, such as a 20X Nikon CF IC EpiPlan DI interferometric objective with a numerical aperture of 0.40, suitable for non-contact profilometry. Data was acquired 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 height range of the samples (this may vary from sample to sample depending on the surface topography); 2) the Z-axis step size was set to 0.50 μm; 3) the actual peak detection mode was set to "On"; and 4) the laser intensity and detector gain for each sample were optimized using the automatic gain features of the instrument control software.

[0120] Surface texture parameters were obtained using software conforming to ISO-25178-2:2012, following the guidelines in the standard. For the example shown here, eight regions measuring 713 × 535 µm were obtained at a resolution of 0.70 µm / pixel; roughness parameters were calculated using the following conditions: 1) a Gaussian filter capable of end-effect correction; 2) a 2.5 µm S-shaped filter; 3) a second-order polynomial F-operation; and 4) a 1 mm L-shaped filter. The average values ​​are shown in the table. The S-shaped filter, L-shaped filter, and F-operation can be selected to correctly extract the data used for parameter calculation. For example, the F-operation can be used to remove sample patterns caused by bottle bending that may not be removable before imaging; the L-shaped filter can be used to remove ripples inherent in the bottle design.

[0121] Areas containing foreign impurities, traces of human intervention during sample collection, or any other obvious anomalies should be excluded from the analysis, and alternative samples should be used if any samples cannot be accurately measured. The resulting values ​​are the root mean square roughness Sq and the maximum peak / pit height Sz of the measured portion of the sample.

[0122] Table 3

[0123] Unless otherwise specified, all percentages are weight percentages based on the weight of the composition. Unless otherwise specifically stated, all ratios are weight ratios. All numerical ranges are narrower ranges including endpoints; the upper and lower limits of the described ranges are interchangeable to further form ranges not explicitly described. The number of significant digits does not limit the quantity indicated or the precision of the measurement. All measurements are understood to have been performed at approximately 25°C and ambient conditions, where “ambient conditions” means conditions at approximately one atmosphere and approximately 50% relative humidity.

[0124] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​cited. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0125] Unless expressly excluded or otherwise limited, every reference cited herein, including any cross-references or related patents or patent applications, and any patent application or patent claiming priority to or benefiting from it, is incorporated herein by reference in its entirety. Reference to any reference is not an endorsement of it as prior art to any disclosed or protected art herein, nor is it an endorsement of any such invention, either on its own or in combination with any one or more references. Furthermore, where any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in referenced documents, the meaning or definition given to that term in this invention shall prevail.

[0126] While specific embodiments of the invention have been shown and described, it will be apparent 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. Therefore, it is intended that all such changes and modifications falling within the scope of the invention be covered by the appended claims.

Claims

1. A blow-molded article, comprising: The main body includes one or more walls surrounding the interior space. The one or more walls have an inner surface, an outer surface, a wall thickness, a transparent portion, and one or more aesthetic regions. The one or more aesthetic regions include an elongated gap between the outer surface and the inner surface, located within the outermost 60% of the wall. The one or more aesthetic regions are configured in a predetermined pattern. The innermost 40% of the wall contains virtually no aesthetically pleasing area. The one or more aesthetic regions are defined by portions of the article that are substantially free of elongated gaps.

2. The article of claim 1, wherein, The aesthetic region has a layer depth and an initial depth. The layer depth is the thickness of the aesthetic region in a direction perpendicular to the outer surface. The initial depth is the distance from the outer surface to the aesthetic region as cut off in a direction perpendicular to the outer surface. The initial depth is greater than zero and there is an unfoamed portion of the wall outside the aesthetic region.

3. The article of claim 2, wherein, The layer depth starting from the outer surface is between 0.001 mm and 2 mm, and the initial depth starting from the outer surface is between 0.1 mm and 2 mm.

4. The article of claim 2 or 3, wherein, The layer depth is 0.0025% to 50% of the wall thickness, and the starting depth is 0.0025% to 20% of the wall thickness.

5. The article according to claim 1, wherein the article has a plurality of aesthetic regions, each aesthetic region being defined by an unfoamed region.

6. The article of claim 1, wherein the one or more aesthetic regions have more elongated gaps at the boundary closest to the outer surface and fewer elongated gaps at the boundary toward the inner surface.

7. The article of claim 1, wherein, The aspect ratio of the elongated void is greater than 2.

8. The article of claim 1, wherein, The one or more aesthetic regions are located between the outer surface and the inner surface within the outermost 40% of the wall.

9. A preform for blow molding an article, the preform being formed of a thermoplastic material, the preform comprising: The body has one or more walls extending from the opening to the base. One or more walls, the one or more walls having an inner surface, an outer surface, a wall thickness, a transparent portion, and one or more foamed areas, the one or more foamed areas being disposed between the outer surface and the inner surface within the outermost 60% of the wall, the one or more foamed areas being configured in a predetermined pattern. The innermost 40% of the wall contains virtually no foamed area. The one or more foamed areas are defined by unfoamed areas.

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