WO2025077840A1

WO2025077840A1 - Squeezable fiber-based bottle with a personal care composition

Info

Publication number: WO2025077840A1
Application number: PCT/CN2024/124207
Authority: WO
Inventors: Stefano Bartolucci; Emily Charlotte Boswell; Patti Jean Kellett; Cyril Michel DROUET; Michael Vincent Schlasinger; Robert Paul Cassoni; Jun You; Amber Nichole BARRON; Jennifer FLOHR; Geoffrey Allen King; Jodi Lee Brown; Valerie Wong; Jessa Leigh Meyers; Robert Michael Pettifer
Original assignee: The Procter & Gamble Company
Priority date: 2023-10-11
Filing date: 2024-10-11
Publication date: 2025-04-17
Also published as: WO2025076736A1

Abstract

A squeezable fiber-based bottle in combination with a liquid personal care composition comprising a pulp molded base and pulp side walls wherein the liquid personal care composition comprises from about 14% to about 50% water; from about 20% to about 70% of a humectant; wherein there is a Water Activity (Aw) of about 0.40 to about 0.90. The pulp molded base includes a liquid containing surface having an aperture for dispensing viscous liquid and a base perimeter having a perimeter surface with an upper edge and a lower edge. A base barrier is disposed on the liquid containing surface and the upper edge of the base perimeter. The fiber-based side wall has an upper edge, a lower edge, an inner surface, and an outer surface. The inner surface includes a fiber-based side wall barrier layer. The lower edge of the fiber-based side wall is attached to the pulp molded base forming an impermeable seal. The impermeable seal is formed about the entire perimeter surface of the pulp molded base near the perimeter surface upper edge but not the perimeter surface lower edge. The aperture for dispensing viscous fluid includes a separable slit valve disposed opposite the liquid containing surface. The separable slit valve is formed of plastic or other resin material.

Description

SQUEEZABLE FIBER-BASED BOTTLE WITH A PERSONAL CARE COMPOSITION

FIELD OF THE INVENTION

A squeezable fiber-based bottle in combination with a personal care composition with low water activity and low water content, for storing and on-demand dispensing viscous liquid product in wet environments. In the present invention, the squeezable fiber-based bottle may be recyclable.

BACKGROUND OF THE INVENTION

Since the era of industrialization, plastic products have been widely used in daily life. By virtue of quite low production costs and their versatility, plastic packaging materials have a higher rate of increase in the world market compared with other packaging materials. However, most of the plastics that we have on the market are made of virgin crude oil which is not a renewable source. Despite continuous improvement in the waste management infrastructure, plastic packing sometimes doesn’t get recycled after use and as a result, leak into the environment where it can be very persistent. Plastic pollution is causing both increased scrutiny by society in the use of plastics as well as an emergence of new environmental regulations limiting the use of plastics in packaging especially for applications with a short-life span.

Packaging made from natural cellulose fibers has become a point of increasing interest as part of a general movement towards inclusion of renewal and less persistent feedstock. Pulp packaging generally also has a very high rate of recyclability. Cellulosic articles are generally formed as film or multi-ply boards using paper making processes or as 3D formed objects using pulp molding methods. While pulp can provide excellent structural support and a good decoration surface, paper sheets or formed objects alone cannot be used to pack liquid products due to their poor oxygen and moisture barrier and poor liquid containment properties leading to integrity failures. Thus, a protective coating is generally applied on the inner side after the cellulosic article is manufactured to extend the shelf life of the packaged liquid products.

Liquid packaging boards (LPB) are generally laminated with polymers with heat seal properties such as PE in a structure that can include one or more barrier layers such as EVOH, vacuum metalized aluminum oxide, etc. or may be coated with thin layer applied using a dispersion technique such as spray, roll, dip, blade or curtain coating. However, such coatings bring trade-offs between barrier performance and package recyclability. Boards can be formed to make packages such as cartons, cans or paper tubes using high-speed manufacturing processes. Paper cartons or cans can be suitable to dispense liquids that can be poured but not viscous formulas such as those used in beauty and personal care. Current paper tubes including liquid boards require the use of a large amount of plastic due to the inclusion of plastic components needed to provide re-closability and dispensing control. Also, the hygroscopicity nature of pulp presents additional challenges for pulp packaging applications used in damp or wet environments such as in-shower or bathroom use. Liquid packaging boards typically contain relatively high amount of sizing agents such alkyl ketene dimers (AKD) to increase the hygroscopicity but suffers failures from in-plane edge wicking typically induced by liquid sorption into cut raw edges by capillary action. Such liquid sorption results in delamination and exposure of unsized fiber-fiber bonds and/or weakening of bonds between layers resulting in separation of multi-ply surfaces.

Packages such as bottles made from rigid pulp molding are not susceptible to edge wicking. Pulp molding also enables a larger shape and more material selection freedom compared to liquid packaging boards. To achieve the desired liquid containment, moisture and oxygen barrier properties, bottles can be coated by either a thin plastic liner e.g., made by blow or rotational molding or by spray coating. The pulp molded slurry may further include additives to modify the properties of the cellulosic material such as porosity, sizing, or wet strength. Like paper sheets, the inclusion of such liners, coating and additives come with compromises between either recyclability or barrier performances. Further, high fiber inclusion in functional appendices such as necks and closures present challenges due to high forming tolerances requirements and coating integrity reliability from multi-open/close cycles. Current pulp molded paper bottle manufacturing processes require plastic pumps for controlled and discreet dispensing of viscous formulas since the bottles are typically produced with large neck openings and rigid side panels.

Maximizing the inclusion of bio-based fibers in the package is desired to improve the bio-based renewable content and recovery in re-processing the fibers. Maximizing the inclusion of bio-based fibers in the package is also desired to form articles with mechanical properties that vary across regions of the article. For example, a bottle made from plastic can be formed having rigidity relative to top loading while further including a flexible panel that a user can squeeze to dispense product Increasing fiber inclusion is also desired to enable a product restitution above 95%and flatten the bottle at disposal, which is beneficial for sorting and circular economy. Fiber-based bottles are desired that both minimize plastic inclusion as well as provide unique design shapes, deliver a reasonable shelf life of at least 6 months to 2 years, in-shower survival, and recyclability. Squeezable pulp fiber-based bottles may be desired for use in wet environments, capable of maintaining integrity while containing liquid formulas, enabling on-demand dispensing, superior in-use ergonomics, exhibiting a reasonable shelf-life, and optimized for recycling and disposal.

Placing today’s liquid shampoo or other personal care formulas inside a squeezable fiber-based bottle limits the maximum level of fiber inclusion due to the need of using thick enough barrier and coating layers to maintain a reasonable liquid containment barrier and shelf life of upto 6 months to 2 years. The present invention identifies a way to include a liquid shampoo and other personal care products inside a squeezable fiber-based bottle maximizing fiber inclusion whilst maintaining a reasonable product shelf life.

SUMMARY OF THE INVENTION

The present invention is directed to a squeezable fiber-based bottle in combination with a liquid personal care composition comprising: a pulp molded base including a liquid containing surface having an aperture for dispensing viscous liquid, the pulp molded base having a base perimeter with a perimeter surface including an upper edge and a lower edge, a base barrier is disposed on the liquid containing surface and the upper edge of the base perimeter, and a fiber-based side wall having an upper edge, a lower edge, an outer surface and an inner surface, the inner surface including a fiber-based side wall barrier layer, wherein the lower edge of the fiber-based side wall is affixed about the entire perimeter surface of the pulp molded base near the perimeter surface upper edge but not the perimeter surface lower edge forming an impermeable seal, the pulp molded base perimeter surface lower edge is below the liquid containing surface allowing the squeezable fiber-based bottle to stand vertically a liquid personal care composition comprising from about 14%to about 50%water; from about 20%to about 70%of a humectant; wherein there is a Water Activity (Aw) of about 0.40 to about 0.90.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter which is regarded as forming the present invention, it is believed that illustrative embodiments of the present invention may be better understood from the following description taken in conjunction with the accompanying drawings, in which:

[Corrected under Rule 26, 27.12.2024]
FIG. 1a is a perspective view of a squeezable fiber-based bottle according to the present disclosure.

[Corrected under Rule 26, 27.12.2024]
FIG. 1b is a cross sectional view of the squeezable fiber-based bottle in FIG. 1a.

[Corrected under Rule 26, 27.12.2024]
FIG. 1c is a cross sectional view of a pulp molded base for the bottle in FIG. 1b.

FIG. 2a is an exploded view the bottom portion of the squeezable fiber-based bottle according to the present disclosure.

FIG. 2b is a perspective view of a separable slit valve according to the present disclosure.

FIG. 3a is a cross sectional view of the pulp molded base prior to assembly of the pulp molded base barrier layer.

FIG. 3b is a cross sectional view of the pulp molded base in FIG. 3a post assembly of the pulp molded base barrier layer.

FIG. 3c is a cross sectional view of the pulp molded base showing final assembly of the pulp molded base barrier layer.

FIG. 4a is a perspective view of squeezable fiber-based bottle having a cylindrical tubular structure having an open end opposite the pulp molded base according to the present disclosure.

FIG. 4b is a perspective view of the squeezable fiber-based bottle of FIG. 4a having a closed end opposite the pulp molded base according to the present disclosure.

FIG. 4c is a bottom view of the squeezable fiber-based bottle shown in FIG. 4a and 4b according to the present disclosure.

FIG. 4d is a side view of the squeezable fiber-based bottle shown in FIG 4b according to the present disclosure.

FIG. 5a is a cross section view of a lower portion of a squeezable bottle according to the present disclosure.

FIG. 5b is a cross section view of a lower portion of a squeezable bottle showing a barrier layer on both the inner and outer surface of the side wall according to the present disclosure.

FIG. 5c is a cross section view of a lower portion of a squeezable bottle showing a barrier layer on the liquid containing surface and the bottom surface of the pulp molded base according to the present disclosure.

FIG. 6a shows a perspective view of the upper edge of the side wall of the squeezable fiber-based bottle have an edge seal formed by a single folded edge protection according to the present disclosure.

FIG. 6b shows a perspective view of the upper edge of the side wall of the squeezable fiber-based bottle have an edge seal formed by a double folded edge protection according to the present disclosure.

FIG. 6c shows a perspective view of the upper edge of the side wall of the squeezable fiber-based bottle have an edge seal formed by a saddle folded edge protection according to the present disclosure.

FIG. 6d shows a perspective view of the upper edge of the side wall of the squeezable fiber-based bottle have an edge seal formed by a triple folded edge protection according to the present disclosure.

FIG. 7a is a perspective view of a squeezable fiber-based bottle having an open end opposite the pulp molded base according to the present disclosure.

FIG. 7b is a cross sectional view of squeezable fiber-based bottle having a cylindrical tubular structure having an open end opposite the pulp molded base according to the present disclosure.

FIG. 7c is a perspective view of squeezable fiber-based bottle shown in FIG. 7b having a closed end opposite the pulp molded base according to the present disclosure.

FIG. 7d is plane view of a blank used to form the side panel of the squeezable bottle shown in FIG. 7a-c according to the present disclosure.

FIG. 7e is a cross section view of the side panel of the squeezable bottle shown in FIG. 7a-c according to the present disclosure.

FIG. 8a is a perspective view of a squeezable fiber-based bottle having molded side panel according to the present disclosure.

FIG. 8b is a cross section view of a squeezable fiber-based bottle shown in FIG. 8a according to the present disclosure.

FIG. 8c is a perspective view of the cross-section shown FIG. 8b according to the present disclosure.

FIG. 9a is a perspective view of a squeezable fiber-based bottle according to the present disclosure.

FIG. 9b is a cross-sectional view of the pulp molded bottle shown in FIG. 9a according to the present disclosure.

FIG. 10a is a perspective view of a squeezable fiber-based bottle having an open end opposite the pulp molded base according to the present disclosure.

FIG. 10b is a cross-sectional view of the squeezable fiber-based bottle shown in FIG. 10a according to the present disclosure.

FIG. 10c is a perspective view of a squeezable fiber-based bottle shown in FIGs. 10a-b having closed, sealed end opposite the pulp molded base according to the present disclosure.

FIG. 10d is a cross-sectional view of a squeezable fiber-based bottle shown in FIG. 10c having closed, sealed end opposite the pulp molded base according to the present disclosure.

FIG. 11a is a cross-sectional view of a pulp molded base according to the present disclosure.

FIG. 11b is a bottom view of a pulp molded base according to the present disclosure.

FIG. 12 is an exploded perspective view of a pulp molded base according to the present disclosure.

FIG. 13 is a cross section view of a lower portion of a squeezable bottle according to the present disclosure.

FIG. 14 is a cross section view of a lower portion of a squeezable bottle according to the present disclosure.

FIG. 15 is a cross section view of a lower portion of a squeezable bottle according to the present disclosure.

FIG. 16 is a graph demonstrating the average weight change (gm/sqm/day) for a fiber-based bottle with a liquid personal cleansing composition of the present invention vs. a fiber-based bottle with water.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to the following detailed description of illustrative and preferred embodiments. It is to be understood that the scope of the claims is not limited to the specific components, methods, conditions, devices, or parameters described herein, and that the terminology used herein is not intended to be limiting of the claimed invention. Also, as used in the specification, including the appended claims, the singular forms “a, ” “an, ” and “the” include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. When a range of values is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent basis “about, ” it will be understood that the particular values form another embodiment. All ranges are inclusive and combinable.

An objective of this invention is to provide a squeezable fiber-based bottle for a liquid composition including 85%+ fiber content, repulpable, enabling 95%+ product evacuation, able to be flattened when disposed, dispensing control via self-sealing valve, and survive distribution, storage and use in a wet environment.

Another objective of this invention is to provide a squeezable bottle with a collapsible pulp side wall, molded as one component.

Another is to provide a squeezable bottle with collapsible molded pulp side wall that can be filled from the top and sealed similar to a cosmetic tube.

Another is to provide a squeezable pulp molded bottle formed in one piece.

Another objective of this invention is to provide a removable valve that can be separated from the bottle by consumers prior to disposal.

As used herein, "Pulp" is defined as a fibrous material produced by mechanically or chemically separating fibers from sustainable sources and then suspended in a fluid.

As used herein, “Fiber” is defined as a natural substance of wood or vegetable origin that is significantly longer than it is wide.

All percentages and ratios used herein are by weight of the total composition, unless otherwise designated. All measurements are understood to be made at ambient conditions, where “ambient conditions” means conditions at about 25 ℃, under about one atmosphere of pressure, and at about 50%relative humidity, unless otherwise designated. All numeric ranges are inclusive of narrower ranges; delineated upper and lower range limits are combinable to create further ranges not explicitly delineated.

The compositions of the present invention can comprise, consist essentially of, or consist of, the essential components as well as optional ingredients described herein. As used herein, “consisting essentially of” means that the composition or component may include additional ingredients, but only if the additional ingredients do not materially alter the basic and novel characteristics of the claimed compositions or methods.

“Apply” or “application, ” as used in reference to a composition, means to apply or spread the compositions of the present invention onto keratinous tissue such as the hair.

“Dermatologically acceptable” means that the compositions or components described are suitable for use in contact with human skin tissue without undue toxicity, incompatibility, instability, allergic response, and the like.

“Safe and effective amount” means an amount of a compound or composition sufficient to significantly induce a positive benefit.

The term "preservation" in the context of the present invention refers to the prevention or retardation of product deterioration due to microorganisms present in the product or composition. A "preservative agent" or "preservative" in the context of the present invention is a substance that prevents or retards the growth of microorganisms in a product or composition.

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.

As used herein, the term "fluid" includes liquids and gels.

As used herein, "comprising" means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms "consisting of" and "consisting essentially of" .

As used herein, "mixtures" is meant to include a simple combination of materials and any compounds that may result from their combination.

As used herein, “molecular weight” or “Molecular weight” refers to the weight average molecular weight unless otherwise stated. Molecular weight is measured using industry standard method, gel permeation chromatography ( “GPC” ) .

Where amount ranges are given, these are to be understood as being the total amount of said ingredient in the composition, or where more than one species fall within the scope of the ingredient definition, the total amount of all ingredients fitting that definition, in the composition.

For example, if the composition comprises from 1%to 5%fatty alcohol, then a composition comprising 2%stearyl alcohol and 1%cetyl alcohol and no other fatty alcohol, would fall within this scope.

The amount of each particular ingredient or mixtures thereof described hereinafter can account for up to 100% (or 100%) of the total amount of the ingredient (s) in the personal care composition.

As used herein, “personal care compositions” includes products such as shampoos, shower gels, liquid hand cleansers, hair colorants, facial cleansers, and other surfactant-based liquid compositions

As used herein, the terms "include, " "includes, " and "including, " are meant to be non-limiting and are understood to mean "comprise, " "comprises, " and "comprising, " respectively.

All percentages, parts and ratios are based upon the total weight of the compositions 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 noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which 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.

FIG. 1 and FIG. 1a, an exemplary squeezable fiber-based bottle 10 is shown. The squeezable fiber-based bottle 10 includes a fiber-based side wall 12 having an upper edge 14, a lower edge 16, an inner surface 18 and an outer surface 19. The inner surface 18 of fiber-based side wall 12 includes a liquid containment material. The lower edge 16 is attached to a pulp molded base 20. The pulp molded base 20, shown in Fig. 1b, includes a liquid containing surface 28 with a base barrier 40 and an aperture 30 disposed at a center of the liquid containing surface 28 for dispensing viscous liquid contained in the squeezable fiber-based bottle 10.

FIG. 2a is an expanded view showing the lower edge 16 of the pulp molded side wall 12, the base barrier 40 and the pulp molded base 20 prior to assembly. As shown, the pulp molded base 20 includes a base perimeter having a perimeter surface 22 with an upper edge 24 and a lower edge 26 which is the same as the upper edge 24 and lower edge 26 of the pulp molded base 20.

The pulp molded base 20 can be formed using a wet pulp molding forming process. This process starts with making a slurry including fibers and additives dispersed in water. In the present text the terms fiber stock, pulp stock and slurry are used synonymously and are fully interchangeable with each other. As used herein “slurry” is a fiber suspension which can consist of 0.5-10%cellulosic fibers and the rest being water and additives. As explained in WO2018/020219, higher fiber contents affect the suspension's flow characteristics such that it becomes difficult to transport the suspension and to achieve an even coating on the mold. In the present invention, the concentration of fibrous material in the suspending liquid may be about 1 %. In the wet forming process, the slurry is deposited onto a screened mold to form a layer either by spray coating or, more commonly, by submerging the mold and subsequently applying a vacuum on the rear side of the screen mold. In a second step the slurry layer can be pressed on a tool comprising two mating tool parts, one of which can have a porous wall which contacts the pulp slurry layer and through which vacuum can be drawn to reduce water content. After this pressing step, the molded item is dried out in a heated mold or oven. After the heated mold or oven, the water content can still be about 10-20%. The item can then be subjected to a subsequent press operation applying heat to reduce the surface roughness and porosity and further reduce the water content which may be below 8%, may be below 5%may be below 1%. The wet molded part has substantially a uniform wall thickness. The average wall thickness of the wet molded part using this process can vary between 0.6 to 1.2 mm and may be from about 0.8 to 1.0 mm. Local variation of thickness and density in the part can be desired to improve assembly to other components or firmly support the part during the assembly process. There are several established techniques to achieve local variation of thickness and density in a wet pulp forming process. EP1081285 discloses the use of split molds with multiple hollow chambers wherein the suction pressure can be controlled independently: this allows varying the amount of pulp fiber deposition in different parts of the cavity to create thicker areas. EP1081285 also discloses the inclusion of areas in the mold where the pulp slurry can stagnate to increase the wall thickness. EP0656444 discloses the use of a mesh with varying aperture sizes to control the water flow rate through different areas of the mold: this variation in flow rate results in varying thicknesses of pulp deposition. EP0656444 also discloses a method wherein the size, spacing and/or disposition of the drainage holes is used to varying part thickness. WO2023104711 describes how local mechanical compression, ultrasonic treatment, and/or heating can be used to achieve local variation of thickness and/or density. After the pulp molding forming process, protruding edges can be trimmed as required.

Cellulose fibers can be wood or non-wood. Wood fibers can be softwood “long” fibers such as pine, spruce, fir and hemlock or hardwood “short” fibers such as birch, eucalyptus, aspen, acacia and oak. Generally, non-wood plant fibers can be grouped into softwood substitutes such as cotton staple and linters; flax, hemp and kenaf bast fibers; sisal; abaca; bamboo (longer fibers species) , and hardwood substitutes such as cereal straws, sugarcane, bagasse, bamboo (shorter fiber species) , reeds and grasses, esparto, kenaf (whole stalk or core fiber) , corn stalks, sorghum stalks etc. Generally, the fiber recipe is chosen to optimize dewatering and production cycle time, mechanical properties such as burst strength and surface finish (roughness, and porosity) . The fibers may include both short and long fibers depending on the desired properties of the final part. The fibers can be extracted using either a bleached or unbleached chemical process, or a mechanical process. The fibers can include recycled fibers.

The slurry can include additives for process control or functionality enhancement. Typical additives for process control include retention aids, anti-foaming agents, Ph-adjustment agents and slime control. Additives for functionality enhancements include (1) fillers such as inorganic mineral fillers; (2) sizing agents such as alkyl ketene dimer (AKD) , alkenyl succinic anhydride (ASA) , rosin or lignin; (3) additives for dry strength enhancement such as starch, amphoteric, cationic or anionic polyacrylamide resins, enzymes, modified polyamines; (4) additives for wet strength enhancement such as polyamidoamine (PAE) -or polyamine epichlorohydrin, epoxide or cationic glyoxylated resins or (5) micro fibrillated cellulose (MFC) or Cellulose Nano Crystals (CNC) additives. In case the barrier layers are applied by spray or dip coating, the present invention may include that the slurry includes some amount of inorganic mineral fillers to close the pores in the surface. In the present invention, the inorganic mineral filler particles may be selected from calcium carbonate as well as platy kaolin or any mixtures thereof.

In the present invention, the slurry can include from 0.5 to 2 %, may be about 1%AKD on a dry fiber basis to provide the slurry some waterproofing. In the present invention, an emulsion of Alkenyl succinic anhydride (ASA) or rosin may be used. The slurry can also include less than 0.5%PAE or Glyoxylated Polyacrylamide (GPAM) to provide wet strength to the final article. In the present invention, the slurry can include between 2 to 5%, may be between 3 to 4%of MFC on dry fiber basis to improve the surface smoothness for barrier application, stiffness, burst resistance and wet strength. Examples of commercially available MFC include Curran or Fiberlean. This addition is particularly advantageous to improve the barrier effectiveness of a spray or dip coating by decreasing the surface porosity to avoid coating penetration.

In the present invention, the pulp molded base 20 may be functionalized after molding by vapor phase deposition of an inorganic barrier layer. Functionalization here is to be understood as an alteration properties of a molded part such as increase hygroscopicity or wet strength, via surface, morphological, and chemical modifications of cellulose fibers. Suitable vapor-deposited inorganic coatings can be formed on pulp fibers from metal or oxides and related compounds. The inorganic barrier layer may be optically opaque, translucent or transparent, depending on the specific chemistry applied. Typically, a metal barrier layer such as aluminum would result in an opaque barrier, whereas a metal oxide barrier such as aluminum oxide or silicon dioxide would results in a transparent barrier. In the present invention, suitable inorganic coatings may be formed by vapor deposition of metals including but not limited to aluminum, magnesium, titanium, tin, indium, silicon, carbon, gold, silver, chromium, zinc, copper, cerium, hafnium, tantalum and diamond-like carbon. In the present invention, suitable inorganic coatings may be formed by vapor deposition of metal oxides, metal nitrides and related compounds. As used herein, metal oxides include aluminum oxides (e.g. Al₂O₃) , aluminum carbide, aluminum nitride, magnesium oxide, titanium oxides (such as titanium dioxide, titanium (3) oxide or titanium monoxide) , zinc oxide, tin oxide, yttrium oxide, or zirconium oxides (e.g. zirconium monoxide) , calcium oxide, boron oxide or metalloid oxides such as silicon oxides, silicon oxycarbides, and silicon nitrides. Silicon oxide or nitride-based coatings could also be one selected from the group consisting of SiOX (where x is an integer of 1-4) or SiOXNY (where each of x and y is an integer of 1-3) . The barrier layer may be a single component vapor deposition layer comprising at least one selected from the group above, or a dual component vapor deposition layer comprising at least one combination of two components selected from the group consisting of SiOx/Al203, SiO/ZnO, SiO/CaO, SiO/B2O3and CaO/Ca (OH) 2. As can be appreciated, metals and metal oxides can be vapor-deposited using a variety of processes. For example, a metal or metal oxide coating can be vapor-deposited using a chemical vapor deposition process or a physical vapor deposition process. Generally, most chemical vapor deposition processes can be suitable due to the stability of the metal, metal oxides and metal oxide precursors. In the present invention, a plasma-assisted chemical vapor deposition process may be used to form the vapor-deposited inorganic coating. In the present invention, an atomic layer chemical vapor deposition process may be used. In the present invention the inorganic barrier coating layer may have a thickness of 2-1,000 nm, may have a thickness of 10-200 nm, and may have a thickness of 20-100 nm. It has been found that this functionalization can significantly increase the wet strength, improve the bulk moisture barrier properties as well as increase the contact angle while preserving the recyclability. This effect is further enhanced when these deposition processes are used in a highly dense pulp matrix and especially in combination with a high refined pulp, MFC’s or CNC’s.

In the present invention, the pulp molded base 20 may be molded using a wet pulp mold forming process with fast dewatering and impulse drying as disclosed by Celwise in WO2020/016409 and US 2021/0269983, incorporated herein by reference. This process is found to produce parts with a higher degree of strength and hydrophobicity compared to parts formed by traditional wet forming. Without being bound by theory, it is hypothesized that this is due to both the fast dewatering enabling cellulose fibers to re-bond with each other quickly as well as high pressure/temperature process enhancing lignin polymerization.

In the present invention, the pulp molded base 20 may be molded using a dry molding approach. According to this process the cellulose fibers are transported and formed into the blank using air as a transport medium ( “airlay” ) . Then, the blank is subsequently formed in a press with temperatures above 100 ℃ and a pressure of at least 1 Mpa. According to this process, additives such as sizing agents can be sprayed or added to the cellulose fibers and/or cellulose blank in solid phase. An example of such process is disclosed by Pulpac in SE541995, SE1851373 and SE543410. Dry molding can be advantageous compared to traditional wet molding by reducing cycle time and energy consumption since there is no need for drying. Parts using this approach are found to be strong but also very flexible. It is hypothesized that this is due to low degree of inter-fiber hydrogen bonds. In the present invention, the pulp molded base can be realized using dry compression molding with a full metal isostatic mold as demonstrated by SACMI to allow a large variety of shapes including ability to mold parts with undercuts while achieving a good degree of dimensional control.

[Corrected under Rule 26, 27.12.2024]
As shown in Fig. 1c, the pulp molded base 20 includes a base barrier 40 disposed on the liquid containing surface 28 and a perimeter surface 22 near the upper edge 24 of the pulp molded base 20. The lower edge 16 of the fiber-based side wall 12 is attached to the pulp molded base 20 forming an impermeable seal 42. The impermeable seal 42 is formed about the entire perimeter surface 22 of the pulp molded base 20 near the perimeter surface upper edge 24 but not the perimeter surface lower edge 26. In the present invention the impermeable seal 42 may be formed by welding such as by exposing the area to hot air. However other means of creating an impermeable seal can be considered such as ultrasonics. In the present invention, the lower edge 16 of the fiber-based side wall 12 may be at least 1mm from the perimeter surface lower edge 26. The perimeter surface 22 of the pulp molded base 20 can include a ledge 25 to accommodate the lower edge 16 of the fiber-based side wall 12. The ledge 25 may be at least 1mm from the perimeter surface lower edge 26.

[Corrected under Rule 26, 27.12.2024]
As illustrated in Fig. 1c and Fig. 2a the aperture 30 for dispensing viscous fluid extends into a duct 32 disposed on the bottom surface 27 of the pulp molded base 20 which is the side opposite the liquid containing surface 28. The duct 32 includes a duct opening 34 and a flexible, resilient, slit-type valve 50 disposed on the duct opening 34. The slit valve 50 is configured to (1) permit fluid flow in response to a predetermined discharge pressure within the bottle when squeezed and (2) automatically close to shut off the flow when the pressure is reduced. Designs of such valves and of fitments using such valves are illustrated in the U.S. Pat. Nos. 5,271,732, 5,927,446, 5,942,712, 6,545,901 and 10,287,066. The slit valve can be selected based on the desired dispensing experience and product viscosity to adjust the seal pressure, cracking pressure as well as flow rate vs. pressure profile. In the present invention, the product viscosity can be between 3,000 to 30,000 cps 10 s^-1 may be between 5,000 to 20,000 cps 10s^-1. The slit valve 50 may be molded from a resilient flexible material and in a material inert to the fluid product being packed and dispensed. In the present invention, the slit valve 50 may be molded in liquid silicone rubber. Examples of commercially available silicone rubber grades are DC-99-525 and RBL-9525-54 sold by Dow Corning Corp. in the United States of America. The valve 50 can include other elastomers, such as a synthetic, thermosetting, or thermoplastic polymers or thermoplastic elastomers, including those based upon materials such as thermoplastic propylene, ethylene, and styrene, including their halogenated counterparts. The valve 50 can also be formed as a unitary structure from a film of material that is flexible, pliable, elastic, and resilient as disclosed in U.S. Pat. No. 10,287,066 and include linear low-density polyethylene (LLDPE) , low density polyethylene (LDPE) , LLDPE/LDPE blends, acetate, acetal, ultra-high-molecular-weight polyethylene (UHMW) , polyester, urethane, ethylene-vinyl acetate (EVA) , polypropylene, and high-density polyethylene. The separable slit valve 50 is releasably attached to the aperture 30 by snap fit or other means such as lightly gluing the slit valve 50 to the duct 32 so that it can simply be removed from the duct 32 by hand. The duct opening 34 can include a lip 36 to interface with the separable slit valve 50. The separable slit valve 50 is formed of plastic or other resin material. As shown in Fig. 2b, the separable slit valve 50 and can include a tab 52 or other feature to facilitate removal. The pulp molded base perimeter surface 22 lower edge 26 is below the liquid containing surface 28, the duct opening 34, and separable slit valve 50 allowing the squeezable fiber-based bottle 10 to stand vertically. The pulp molded base includes means to avoid dispensing through the valve during transportation or handling if pressure is accidentally exerted through the side wall. This can be a pulp molded closure that is dip coated, sprayed or vacuum laminated with a polymeric barrier (not shown) . In the present invention, the valve may be sealed with a removable lid using a metalized laminate attached to the pulp molded closure with a pressure sensitive adhesive (not shown) .

It has been found that the pulp molded base 20 according to the invention is surprisingly able to provide excellent protection to liquid formulas as well as integrity during use in a wet environment such as bathroom and in-shower while still having a fiber content larger than 80%and recyclable in the paper stream according to PTS-RH 021: 2012 Cat 2. The base barrier 40 disposed on the liquid containing surface 28 and perimeter surface 22 near the upper edge 24 of the pulp molded base 20 can be applied to the pulp molded base 20 by either spray, dip coating or may be as laminate by welding or gluing.

In the case of spray or dip-coating, the base barrier can include a primer, and one or more top-coat layers. The primer may be applied in the form of a polymer dispersion, may be an aqueous polymer dispersion. The primer can be a latex dispersion, polyvinyl alcohol dispersion, a polyhydroxyalkanoates (PHA) dispersion or a polyolefin dispersion. An example of polyolefin dispersion is commercialized by DOW. In the present invention, the primer may be a styrene acrylate, such as 4010 commercialized by BASF. Generally, the thickness of the barrier layer should be as thin as possible, but thick enough to form a barrier between pulp molded base as the topcoat. The average amount of the primer layer applied on the surface of the molded base may be less than 60 g /m², may be less than 40 g /m², may be -less than 20 g /m². The base barrier 40 can include one or more top-coat layers i.e., applied on top of the primer. Depending on the chemistry, the top-coat layers can be applied in the form of an aqueous dispersion immediately after the application of the primers before drying. The top-coat composition can comprise a polymer dispersion for producing a heat sealable coating layer. The polymer dispersion may be a hydrocarbon polymer dispersion, may be a synthetic hydrocarbon polymer dispersion such styrene acrylate latex. The top-coat layers can include also one or more additive agents to boost water barriers such as waxes, MFC’s or CNC’s. In the present invention, the top-coat layers may be styrene acrylate based, such as 4030 commercialized by BASF. The amount of each top-coat layer can be less than 30 g /m², may be in the range of 6 -26 g /m² , may be in the range of 12-18g/m². Generally, more than one top layer is applied to reduce the incidence of surface defects such as pin-holing, specs or cracks. After the application of the primer and top-coat layers, the part can be transferred to a heating unit such as a hot air-drying hood to remove moisture from the coating layer (s) as well as facilitate the film formation by melting or partially melting the polymers in the barrier layers. In the present invention, the drying temperature may be between 100 to 150 ℃, may be between 110 to 120 ℃. The average thickness of all barrier layers after spraying and drying can be between 10 to 100 microns.

In the present invention, the base barrier 40 may be formed by means of a powder polymeric coating to reduce the emission of volatile organic compounds (VOC) and coating waste. In the present invention, the powder may comprise a thermoplastic polymer selected from polyolefins, e.g. polyethylene or polypropylene and copolymers thereof. The polymeric powder may also comprise water soluble synthetic polymers, such as polyvinyl alcohol, polyhydroxyalkanoates (PHA) or polysaccharides, such as cellulose. The powder particles typically have an average size in the range of 1 to 200 pm, e.g. from 5 to 100 pm, e.g. from 10 to 50 pm. This coating can be applied by a spray device and then cured/melted to form a continuous film on the surface e.g. according to the process described in WO2022207507, incorporated herein by reference. The average thickness of the film applied in this system may range from 10 to 100 microns.

In the present invention, the base barrier 40 may be a layer applied by hot vacuum thermoforming as depicted in Figs. 3a, 3b, and 3c. The barrier layer may be made by PE laminate of a thickness from 30 to 150 microns, may be between 60 to 90 microns before application depending on the average final thickness targeted. In the present invention, the laminate may include a P1B/LLDPE outer seal layer, a Nucleated HDPE 90/10 167/640i LDPE core layer and a 90%LLDPE/10%LDPE inner seal layer. The outer P1B/LLDPE seal layer can have a thickness range is 5-15 μm, and may have a mixing ratio of 15%P1B/85LLDPE to 25%P1B/75%LLDPE. The Nucleated HDPE 90/10 Surpass 167/640i LDPE core layer can have a thickness range of 30-200 μm. The inner LLDPE/LDPE seal layer can have a thickness range of 5-20 μm, and may have a mixing ratio of 95%LLDPE/5%LDPE to 85%LLDPE/15%LDPE. In the present invention, the multilayer barrier may have a total thickness of 90 μm multilayer including a top layer of 5 μm 15%P1B/85%LLDPE, a core layer of 70 μm Nucleated HDPE 90/10 Surpass 167/640i LDPE, and an inner layer of 15μm 90%LLDPE/10%LDPE. The barrier layer can be a biodegradable thermoplastic materials selected from the group consisting of aliphatic and/or aromatic polyesters or thermoplastic starches. An example of biodegradable laminate to use a liner includes a binary blend of PLA and PBAT marketed by BASF under the tradename The structure of the film lamination can be optimized and configured based on the performance requirements between barrier properties after application, bonding with pulp surfaces, and recyclability pulp percentage among others.

Fig. 3a shows the base barrier layer 40 comprising a laminate and pulp molded base 20 prior to thermoforming. Before the application, the barrier layer 40 is heated to the forming temperature by adhering to a heating plate by a pressure applied by vacuum. The pulp molded base 20 seats on a mandrel. Once the targeted temperature is achieved, the vacuum on the top plate is released and the barrier layer 40 is draped down by means of vacuum applied on the mandrel side. The bottom mandrel can also be heated to facilitate the adhesion of the laminate to the pulp molded base 20. Fig. 3b shows post lamination illustrating the base barrier layer 40, covering the liquid containing surface 28 including the duct opening 34 and pulp molded base perimeter surface 22. While the base barrier layer 40 is shown in Figure 3b having a uniform wall thickness, in practice a thickness gradient is developed depending on the amount of film stretching during the application process. It has been found that applying localized heat to the film i.e., by means of systems such as can help obtain a more uniform wall thickness and prevent the insurgence of pin holing. The average thickness of the base barrier layer 40 after application, may be below 90 microns, may be below 75 microns, may be below 50 microns and may be below 20 microns depending on the barrier properties desired. Figure 3c shows the pulp molded base 20 post thermoforming with the duct opening 34 cut out in the duct 32.

Figures 4a through 4d show a construction of exemplary squeezable fiber-based bottle 110 with a cylindrical tubular structural component. According to the present invention, the fiber-based side wall 112 may include a cardboard. The cardboard is often made of a multi-layer structure consisting of a multi-ply baseboard and one or more functional layers. As shown in Figure 4a, the functional layer 113 can be either on the inside layer 118 and/or the outer side 119. Examples of commercially available cardboards are Natura from Stora Enso or Liquid LC by Billerud. The inner coating may be an LDPE laminate to ensure both good weldability and in contact survival with product. In the present invention, the inner coating may be a polymeric water dispersion on the or Cupforma board from Stora Enso. Dispersions such as BASF or Down can be used. The water dispersions can be applied by a variety of techniques such as dip, rod, doctor blade, knife, gravure, reverse roll, air knife, and forward roll or spray followed by a drying step. The substrate of the liquid carton board may contain lignocellulosic fibers obtained by any conventional pulping process, including bleached or unbleached chemical, mechanical, chemi-mechanical pulping processes. The carton board can be made from more than one ply, typically 3 plies, and is usually in the form of a fibrous web. In the present invention, the carton board may have a grammage from 170 -350 gsm, may have a grammage from about 250-280 gsm. An example of carton boards using water-based dispersion coatings are Natura Aqua+ commercialized by Stora Enso and commercialized by Kotkamills. Additional layers can be employed such as an aluminum foil, one or more HDPE layers, thin layers created by vapor phase deposition of an inorganic material or a water dispersible nanocomposite layer that forms nanoplatelets during drying. In the present invention, the cylindrical tubular structural component may have a fiber percentage of total weight above 85%, may have a fiber percentage of total weight above 90%, and may have a fiber percentage of total weight above 95%.

The manufacture of a squeezable fiber-based bottle 110 comprising a cylindrical tubular structures using fiber-based side wall 112 is described in WO2022185176, WO2022229810, EP2007567, EP284389 and EP2630052, incorporated herein by reference. Based on the process described, the multi-layer sheet is assembled end to end into a tubular cylindrical structure and may be with the addition of reinforcement strips in the assembly position, and then cut into a discreet length. Subsequently, the pulp molded base 120 is placed into a mandrel and the impermeable seal 142 can be subjected to heating or a glue may be applied. In a further subsequent step, the inner surface 118 of the tubular body is pressed against the impermeable seal 142 to carry out the assembly.

Figure 5a shows an example of a pulp molded base 120 assembled to the cylindrical tubular structure according to such process where the side wall 112 is a single side coated side wall. In this configuration the valve 150 can be assembled on a corresponding seat on the liquid containing surface 128 of the pulp molded base 120. The valve 150 can be kept in place by heat stacking a fully lined pulp roundel 151 against the lined base. The liner coating the pulp roundel can be LDPE applied by vacuum forming or one of heat sealable polymeric water dispersion applied by either spray or dip coating. In the present invention, a glue compatible with the liquid can be used for the assembly. This configuration has the advantage of creating a natural resistance against the valve 150 being displaced due to the inner liquid pressure during dispensing. The sealing force of the roundel against the lined base can still be configured to ensure that the user can easily access and extract the valve 150 by crushing the container prior to disposal.

In the present invention, Figure 5b shows where the side wall 112 is a double coated side wall wherein the side wall 112 includes inside and outside layers 113 of coating. And Figure 5c shows the present invention which may have a pulp barrier layer 113 fully encapsulating the pulp molded base 120 e.g., by dip coating of a polymeric water dispersion.

The impermeable seal 142 connecting the fiber-based side wall 112 of the tubular structure and the pulp molded base 120 as well as the fiber-based side wall 112 upper seal area 129 can include means to protect from edge water wicking to avoid catastrophic integrity failures or unwanted deformation. Edge wicking is particularly problematic in the areas where a liquid carton board edge is cut ( “raw edge” ) and exposed to water such as when the bottle is used in shower. Edge wicking of boards has been amply studied e.g., Harju 2018 iiquid penetration in food service boards, Master Science thesis. Several methods may provide an edge protection such as spraying of a sizing or other hydrophobic agent, skiving, hemming, or covering the cut edge with an adhesive plastic strip. Edge protection methods for the upper seal 129 could employ spray, dip coating, adding an PE-PET-PE strip or folding as shown in Figures 6a-6d discussed below.

Figures 7a and 7b show a construction of exemplary squeezable fiber-based bottle 210 with a conical tubular structure. In this example the fiber-based side wall 212 can be formed cutting a blank as shown in Figure 7d from a reel of a liquid carton board. The fiber-based side wall 212 is then folded on the edges and welded as illustrated on Figure 7e. Typical welding technique can include hot air, ultrasonic or gluing. The cone can then include a polymeric strip 223 welded in the vertical seal 221 to protect the raw edges from edge wicking. The fiber-based side wall 212 of the tubular cone can be welded to the pulp molded base 220 to create a squeezable bottle 210 comprising a tube 213 as illustrated in Figure 7c. Subsequently the tube 213 can be filled and sealed as shown in Figure 7c. In the present invention, edge protection methods for the impermeable seal 242 between the pulp molded base 120 perimeter surface upper edge 224 and the fiber-based side wall lower edge 216 may be applied. The upper seal 129 between the pulp side wall 112 upper edge 114 first side 115 and second side 117 can also be formed. Examples of means of sealing the first side 115 and second side 117 of the fiber-based side wall 112 upper edge 114 are depicted in Figs. 6a-6d, where Fig. 6a depicts a single fold; Fig. 6b depicts a double fold; Fig, 6c depicts a saddle fold; and Fig. 6d depicts a triple fold.

Figures 8a -8c show a construction of exemplary squeezable fiber-based bottle 310 with a pulp molded side wall 312. The pulp side wall 312 can be formed by one or more components molded according to the wet molding processes and liquid containment barrier application processes described herein. In the present invention, the fiber-based bottle side wall 312 may be formed in one piece made by wet molding. The pulp side wall 312 can have an average wall thickness between 0.6 to 1.2 mm, may be between 0.8 to 1.0 mm. In the present invention, may have reduction of wall thickness localized in squeezing panel, may be from 0.6 to 0.8 mm. The wet molding of the pulp side wall 312 can follow the same process described for the pulp molded base, previously described. In the present invention, the process may include methods for fast dewatering and induction heating to reduce the cycle time. The starting slurry used to make the pulp molded side wall 312 can consist of 1-10%cellulosic fibers, may be about 1%, and the rest being water and additives. Cellulose fibers can be wood or non-wood. As previously described for the pulp molded base, the fiber recipe can be optimized for dewatering and production cycle time, mechanical properties such as burst strength and surface finish (roughness, and porosity) . The mechanical properties of the pulp side wall are particularly important to optimize the dispensing function. The pulp side wall 312 can be optimized to buckle when the user exerts a squeezing force producing a reduction of volume of the bottle inner chamber. In the present invention, the pulp side wall 312 wall may have low enough elastic modulus and geometrical stiffness to enable deformation but high enough to enable some bounce back for the first uses. As the content gets depleted, such as less than 50%total content has been dispensed or may be less than 30%, and the bottle wall may collapse to deform permanently to reduce the dispensing effort. The cellulose fibers can be of different types to balance these requirements.

In the present invention, the cellulose fibers forming the pulp molded side walls 312 may include softwood, bamboo, and bagasse. The length-weighted average fiber length, the arithmetic average fiber length (ISO 0.2-7.0 mm) and the arithmetic average fiber width according to TAPPI T271 can be determined using a Fiber Image Analyzer such as the Valmet FS5. Softwood fibers can have a length-weighted average fiber length of about 2.25 mm, an arithmetic average fiber length (ISO 0.2-7.0 mm) of about 1.4 mm and an arithmetic average fiber width of about 30 μm. Bamboo fibers can have a length-weighted average fiber length of about 15 mm, an arithmetic average fiber length (ISO 0.2-7.0 mm) of about 1.0 mm and an arithmetic average fiber width of about 15 μm. Bagasse fibers can have a length-weighted average fiber length of about 1.0 mm, an arithmetic average fiber length (ISO 0.2-7.0 mm) of about 0, 6 mm and an arithmetic average fiber width of about 22 μm. In the present invention, the fiber count may include between 50 to 60%bamboo, 40 to 50%bagasse and from 0 to 10%softwood.

The slurry of cellulosic fibers can also include additives for process control and/or functionality enhancement. Typical additives for process control include retention aids, anti-foaming agents, Ph-adjustment agents, and slime control. Additives for functionality enhancements include (1) fillers such as inorganic mineral fillers such as calcium carbonate and platy kaolin; (2) sizing agents such as alkyl ketene dimer (AKD) , alkenyl succinic anhydride (ASA) , rosin or lignin; (3) additives for dry strength enhancement such as starch, amphoteric, cationic or anionic polyacrylamide resins, enzymes, modified polyamines; (4) additives for wet strength enhancement such as polyamidoamine (PAE) -or polyamine epichlorohydrin, epoxide or cationic glyoxylated resins or (5) micro fibrillated cellulose (MFC) or Cellulose Nano Crystals (CNC) additions. Fiber chemical treatments, such as using deep eutectic solvents (DES) , can enhance fiber swelling and bonding potential.

In the present invention, the slurry may include from 0.5 to 2 %, may be about 1%AKD on a dry fiber basis to provide the slurry some excellent waterproofing. The slurry can include also between 0.1 to 0.5%PAE to provide to the final article some excellent wet strength. In the present invention the slurry may include between 2 to 5%, may include between 3 to 4%of MFC on dry fiber basis to improve the surface smoothness for barrier application, stiffness, burst resistance and wet strength. Examples of commercially available MFC include or This addition is particularly advantageous to improve the barrier effectiveness of a spray or dip coating by decreasing the surface porosity to avoid coating penetration. This addition is also particularly advantageous to increase the part resistance to mechanical stresses caused by the bottle squeeze pressure. In the present invention, the pulp part may be functionalized after molding by a vapor phase deposition of an inorganic barrier layer as previously described.

A pulp side wall barrier layer 313 is disposed on the liquid containing surface of the pulp side wall inner surface 318. The pulp side wall barrier can be applied to the pulp molded side wall 312 by either spray or dip coating. The pulp side wall barrier 313 can include a primer, and one or more top-coat layers. The primer may be applied in the form of a polymer dispersion, may be an aqueous polymer dispersion. The primer can be a latex dispersion, polyvinyl alcohol dispersion, a polyhydroxyalkanoates (PHA) dispersion or a polyolefin dispersion. An example of polyolefin dispersion is commercialized by DOW. In the present invention, the primer may be a styrene acrylate, such as 4010 commercialized by BASF. Generally, the thickness of the barrier layer should be as thin as possible, but thick enough to form a barrier on the pulp side wall inner surface as a top-coat. The average amount of the primer layer applied on the inner surface may be less than 20 g /m², may be 3 -10 g /m², may be 4 -9 g /m². The pulp side wall barrier can include one or more top-coat layers i.e., applied on top of the primer. Depending on the chemistry, the top-coat layers can be applied in the form of an aqueous dispersion immediately after the application of the primers before drying. The top-coat composition can comprise a polymer dispersion for producing a heat sealable coating layer. The polymer dispersion may be a hydrocarbon polymer dispersion, may be a synthetic hydrocarbon polymer dispersion such styrene acrylate latex. The top-coat layers can include also one or more additives agents to boost water barriers such as waxes, MFC’s or CNC’s. In the present invention, the top-coat layers may be styrene acrylate based, such as 4030 commercialized by BASF. The amount of each top-coat layer can be less than 30 g /m², may be in the range of 5 -12 g /m², may be in the range of 6 -9 g /m². Generally, more than one top layer is applied to reduce the incidence of surface defects such as pin-holing, specs or cracks. After the application of the primer and top-coat layers, the squeezable fiber-based bottle can be transferred to a heating unit such as a hot air-drying hood to both remove moisture from the coating layer (s) as well as facilitate the film formation by melting or partially melting the polymers in the barrier layers. In the present invention, the drying temperature may be between 100 to 150 ℃, may be between 110 to 120 ℃. The average thickness of all barrier layers after spraying and drying can be between 10 to 100 microns.

In the present invention, the pulp side wall 312 barrier layer 313 may be formed by means of a powder polymeric coating to reduce the emission of volatile organic compounds (VOC) and coating waste. In the present invention, the powder may comprise a thermoplastic polymer selected from polyolefins, e.g. polyethylene or polypropylene and copolymers thereof. The polymeric powder may also comprise water soluble synthetic polymers, such as polyvinyl alcohol or polysaccharides, such as cellulose. The powder particles typically have an average size in the range of 1 to 200 pm, e.g. from 5 to 100 pm, e.g. from 10 to 50 pm. This coating can be applied by a spray device and then cured/melted to form a continuous film on the surface e.g. according to the process described in WO2022207507, incorporated herein by reference. The average thickness of the barrier layer applied in this system may range from 10 to 100 microns.

Figure 8a shows the pulp molded side wall 312 assembled to the pulp molded base 320. The assembly can be done either by means of hot-air welding, ultrasonic or gluing and/or combination thereof. Figures 8b and 8c show section views of the assembled squeezable fiber-based bottle 310 with pulp molded side wall 312. It has been found that this bottle is surprisingly resistant to water splashing while being recyclable and able to deliver good liquid barriers. The bottle 310 is also squeezable with a good degree of bounce back from the first use. During shower use, the bottle 310 can become soft making it easier to squeeze, while maintaining its integrity. At the end of use, the bottle can be conveniently crushed. Crushing can result in the disassembly of the pulp molded base 320 from the side wall 312 to ease the separation of the valve 350 from the pulp molded base 320. The components can also be easily flattened by consumers to ease the disposal.

Figure 9 show another exemplary construction of a squeezable fiber-based bottle 410 with a pulp molded side wall 412. In the present invention, the side wall barrier layer 413 may be a layer applied by hot vacuum thermoforming as previously described and depicted in Figs. 3a, 3b, and 3c for the pulp molded base 20. The barrier layer 413 may be made by PE laminate of a thickness from 30 to 150 microns, may be between 60 to 90 microns before application depending on the average final thickness targeted. In the present invention, the laminate may include a P1B/LLDPE outer seal layer, a Nucleated HDPE 90/10 Surpass 167/640i LDPE core layer and a 90%LLDPE/10%LDPE inner seal layer. The outer P1B/LLDPE seal layer can have a thickness range is 5-15 μm, may have a mixing ratio of 15%P1B/85LLDPE to 25%P1B/75%LLDPE. The Nucleated HDPE 90/10 Surpass 167/640i LDPE core layer can have a thickness range of 30-200 μm. The inner LLDPE/LDPE seal layer can have a thickness range of 5-20 μm, may have a mixing ratio of 95%LLDPE/5%LDPE to 85%LLDPE/15%LDPE. In the present invention, the multilayer barrier may have a total thickness of 90 μm multilayer including a top layer of 5 μm 15%P1B/85%LLDPE, a core layer of 70 μm Nucleated HDPE 90/10 Surpass 167/640i LDPE, and an inner layer of 15μm 90%LLDPE/10%LDPE. The structure of the film lamination can be optimized and configured based on the performance requirements between barrier properties after application, bonding with pulp surfaces, and recyclability pulp percentage among others.

Before the application, the barrier layer 413 is heated to the forming temperature by adhering to a heating plate by a pressure applied by vacuum. The pulp molded side wall 412 seats on a mandrel. Once the targeted temperature is achieved, the vacuum on the top plate is released and the barrier layer is draped down by mean of vacuum applied on the mandrel side. The bottom mandrel can also be heated to facilitate the adhesion of the laminate to the pulp molded base 420. Fig. 9b shows post lamination illustrating side wall 412 covered entirely by the barrier layer 413. The film also covers the pulp side wall 412 lower edge 416 as well as a portion of the outer surface 419 to facilitate sealing with the pulp molded base 420. While the pulp molded base base barrier 440 is shown in Figure 9b with a uniform wall thickness, in practice a thickness gradient is developed depending on the amount of film stretching during the application process. It has been found that applying localized heat to the film i.e., by means of systems such as WATTTRON can help obtain a more uniform wall thickness and prevent the insurgence of pin holing. The average thickness of the side wall barrier 413 after application may be below 90 microns, may be below 75 microns, may be below 50 microns and ideally below 20 microns depending on the barrier properties desired.

The pulp molded base 420 can be manufactured by pulp molding. The inner surface coated using either spray or dip coating or applying a layer by vacuum thermoforming. Figure 9a shows the pulp molded side wall 412 assembled to the pulp molded base 420 to form a liquid hermetic seal. The assembly can be done either by means of hot-air welding, ultrasonic or gluing and/or combination thereof.

Figures 10a and 10b show another exemplary construction of a squeezable fiber-based bottle 510 with a pulp molded side wall 512. In the present invention, the side wall 512 may be molded with two open surfaces at the upper edge 514 and the lower edge 516. The side wall barrier layer 513 on the inner surface 518 can be coated or laminated. In the present invention, the barrier layer 513 coating may be heat sealable. The pulp molded base 520 can be manufactured by pulp molding. The base barrier layer 540 can be applied using either spray or dip coating or applying a layer by vacuum thermoforming. The pulp molded side wall 512 is assembled to the pulp molded base 520 to form a liquid hermetic seal. The assembly can be done either by means of hot-air welding, ultrasonic or gluing and/or combination thereof. Figures 10a and 10b shows the bottle 510 after assembly with the pulp molded base 520 in the transport configuration to the filling plant. The bottle 510 can be filled in this configuration with intended amount of product through the opening in the pulp side wall 512 upper edge 514. After filling, the pulp side upper edge first side 515 can be sealed to the pulp side wall upper edge second side 517 forming an upper seal 529 such as a tube or a pouch as shown in Figures 10c and 10d. The upper seal 529 can be formed by hot-air welding or hot-jaw or ultrasonic.

Figure 11a shows an exemplary construction of the lower portion of a squeezable fiber-based bottle 610 with a mechanism to ease the separation of valve 650 from the pulp molded base 620 by the consumer. The separation of the valve 650 from the pulp molded base 620 by consumers can be desired to reduce the non-fiber fraction in the paper recycling stream. According to this construction, the valve 650 can be sandwiched between the pulp molded base 620 and an additional molded cover 653 which is attached to the bottom surface 627 of the pulp molded base 620. As shown in Figure 11b, the molded cover 653 can have flaps 655 that can be easily grasped by a consumer. The assembly of the molded cover 653 to the pulp molded base 620 can be performed using a glue to form a light bond strong enough to avoid premature separation during bottle distribution and use but low enough to facilitate separation of the molded cover 653 by the consumer prior to disposal. Before disposal, the consumer grasps the flaps 655 and exerts a twist to detach the cover 653 from the pulp molded base 620 thereby removing the valve 650.

In the present invention, Figure 12 shows where a cover 753 may be disassembled from the pulp molded base 720 and valve 750 by a tab 752.

Figure 13 shows an exemplary construction of the squeezable fiber-based bottle 10 wherein the pulp molded base 120 can include a fiber-based cardboard or carton board. The cardboard can be made from more than one ply, typically 3 plies, and is usually in the form of a fibrous web. In the present invention, the carton board may have a grammage from 170 -430 gsm and may be from about 250 to 350 gsm. The functional layers can be on both the inner surface forming the liquid containment portion 128 and the outer surface 127. The most inner and most outer layers are may be low-density polyethylene (LDPE) layers to ensure good sealing and liquid tightness. The liquid carton board used can be products of the Finnish company Stora Enso marketed with trademarks Natura^TM 2PE Board or Natura^TM Barr. The present invention may have both the inner and outer coating be a polymeric water dispersion, such as BASF or Down The water dispersions can be applied by a variety of techniques such as dip, rod, doctor blade, knife, gravure, reverse roll, air knife, and forward roll or spray followed by a drying step. An example of carton boards using water-based dispersion coatings are Cupforma Natura Aqua+ commercialized by Stora Enso and ISLA commercialized by Kotkamills.

The pulp molded base 120 can be made starting from a blanket, heated and thermoformed to achieve a specific shape. The blanket can be folded, and edges pressed against to form an impermeable seal 243. This seal can be strengthened by mechanically applying a knurling pattern. The edge 216 of the molded base 120 can also have protection from moisture intake using skiving or any of the other solutions known in the art. This construction is particularly advantageous to leverage commercially available cardboards, while strengthening the base with additional thickness to achieve a reliable impermeable sealing 142 with the side wall 112 as well as the base stability. The pulp molded base 120 may have flat portions near the opening 30 to ensure reliable assembly of the pulp roundel 151 via ultrasonic or heat sealing. The aperture 30 may be sealed with a removable lid using a metalized laminate attached to the molded closure with a pressure sensitive adhesive (not shown) .

Figure 14 shows an exemplary construction of the squeezable fiber-based bottle 10 wherein a film is applied to the outer surface 127 and another to the inner surface 128 of the pulp molded base 120. Figure 14 is particularly advantageous to minimize the risk or leakage and pinholing while guaranteeing a strong bonding with the pulp roundel 151 by ultrasonics or heat sealing. The film applied to outer surface 127 ensures the possibility to achieve a strong seal 142 with the side wall 112 by hot air or heat sealing or ultrasonics. This film also assures protection for the pulp molded base 120 against moisture pick-up, thus keeping it stable and integral during bottle use in wet environments.

In the present invention, the first film can be applied to the outer surface 127 by hot vacuum thermoforming. Subsequently, the second film can be applied to the inner surface 128 by vacuum lamination. Then, both films can be welded in areas 801 and 803 to completely encapsulate the pulp molded base 120 and excess film removed in areas 802 and 804 by the use of a knife tool.

Figure 15 shows an exemplary construction of the squeezable fiber-base bottle 10 wherein a film is applied to the outer surface 127 and a coating is applied to the inner surface 128 to completely encapsulate the pulp molded base 120. This configuration may be used to maximize the total fiber content. In Figure15, the film is applied to the outer surface by hot vacuum thermoforming. Then, the excess film is trimmed in the areas 805 and 806 with the use of a knife tool. Then, a primer such as 4010 and one or more layers of topcoat such as 4030 commercialized by BASF can be applied on the inner surface 128. Then the pulp roundel 151 can be glued to the pulp molded base 120.

METHODS

1) Individual Layer Thickness

The thickness of the overall film /individual layers is measured by cutting a 20 μm thick cross-section of a film sample via sliding microtome (e.g. Leica SM2010 R) , placing it under an optical microscope in light transmission mode (e.g. Leica Diaplan) , and applying an imaging analysis software.

2) Caliper

The caliper, or thickness, of a single-layer test sample is measured under a static load by a micrometer, in accordance with compendial method ISO 534, with modifications noted herein. All measurements are performed in a laboratory maintained at 23 ℃ ± 2 ℃ and 50%± 2%relative humidity and test samples are conditioned in this environment for at least 2 hours prior to testing. Caliper is measured with a micrometer equipped with a pressure foot capable of exerting a steady pressure of 70 kPa ± 0.05 kPa onto the test sample. The micrometer is a dead-weight type instrument with readings accurate to 0.1 micron. A suitable instrument is the TMI Digital Micrometer Model 49-56, available from Testing Machines Inc., New Castle, DE, or equivalent. The pressure foot is a flat ground circular movable face with a diameter that is smaller than the test specimen and capable of exerting the required pressure. A suitable pressure foot has a diameter of 16.0 mm. The test sample is supported by a horizontal flat reference platform that is larger than and parallel to the surface of the pressure foot. The system is calibrated and operated per the manufacturer’s instructions. Measurements are made on single-layer test samples taken from rolls or sheets of the raw material, or test samples obtained from a finished package. When excising the test sample from a finished package, use care to not impart any contamination or distortion to the sample during the process. The excised sample should be free from residual adhesive and taken from an area of the package that is free from any seams or folds. The test sample is ideally 200 mm2 and must be larger than the pressure foot. To measure caliper, first zero the micrometer against the horizontal flat reference platform. Place the test sample on the platform with the test location centered below the pressure foot. Gently lower the pressure foot with a descent rate of 3.0 mm per second until the full pressure is exerted onto the test sample. Wait 5 seconds and then record the caliper of the test sample to the nearest 0.1 micron. In like fashion, repeat for a total of ten replicate test samples. Calculate the arithmetic mean for all caliper measurements and report the value as Caliper to the nearest 0.1 micron.

3) Basis Weight

The basis weight of a test sample is the mass (in grams) per unit area (in square meters) of a single layer of material and is measured in accordance with compendial method ISO 536. The mass of the test sample is cut to a known area, and the mass of the sample is determined using an analytical balance accurate to 0.0001 grams. All measurements are performed in a laboratory maintained at 23 ℃ ± 2 ℃ and 50%± 2%relative humidity and test samples are conditioned in this environment for at least 2 hours prior to testing. Measurements are made on test samples taken from rolls or sheets of the raw material, or test samples obtained from a finished package. When excising the test sample from a finished package, use care to not impart any contamination or distortion to the sample during the process. The excised sample should be free from residual adhesive and taken from an area of the package that is free from any seams or folds. The test sample must be as large as possible so that any inherent material variability is accounted for. For flat samples, measure the dimensions of the single layer test sample using a calibrated steel metal ruler traceable to NIST, or equivalent. For non-flat samples, the area can be calculated using 3D data. Calculate the Area of the test sample and record to the nearest 0.0001 square meter. Use an analytical balance to obtain the Mass of the test sample and record to the nearest 0.0001 gram. The weight of a coating can be obtained by subtracting the weight of the coated from the uncoated samples. Calculate Basis Weight by dividing Mass (in grams) by Area (in square meters) and record to the nearest 0.01 grams per square meter (gsm) . In like fashion, repeat for a total of ten replicate test samples. Calculate the arithmetic mean for Basis Weight and report to the nearest 0.01 grams/square meter.

4) Pinholing Test Method

This is a test method to detect and locate any pin hole equal or greater than 10μm on a coated surface. The part to test is placed on an absorbent surface with the coated side facing up. Then a dye penetrant solution according to ASTM F3039-23 is spread across the surface under test, and may an eye dropper or pipette and a small roller to apply pressure on the surface to ensure adequate contact. The dye penetrant solution should contact all areas exhibiting questionable surface anomalies taking care not to allow dye penetrant solution to flow over the edge of the sample. Wipe excess dye from sample using a clean absorbent pad and carefully lift the sample. The test is passed is there is no evidence of dye penetration or staining to the opposite side of coated surface.

5) Bottle Leakage Test Method

This is a test method to measure the ability of the container and closure system to prevent leakage when stored or transported.

A minimum of three representative empty bottles of the type being tested are preconditioned for at least 24 hours at 22±3℃, 60%±10 RH. Prepare a tap water solution at room temperature adding a dye such as Rhodamine or Toluidine to give a permanent indication where there is leakage. Fill the specimen at lab ambient temperature with the water/dye solution to expected fill capacity e.g., 150±1 ml, fitted with their respective closure (if applicable) and hermetically closed in the storage configuration. Dry (if needed) the finish and shoulder areas of the bottles with a (paper) towel so that no product remains on them. Place the specimen in a flat position on a tray capable of holding the liquid should a leak develop. Place some absorbent blotting paper beneath the specimen to detect leakage more easily. Then put the specimen in storage at 25±3℃, 60%±10 RH. No weight or other bottles must be placed on top of the specimen being tested. Alternative specimen orientations during the test can be considered such that suspected leak areas are covered with the liquid inside the container. Inspect for liquid leakage at 24 h, after 1 week and after 2 weeks. Note location (s) of any eventual leakage.

If there is leakage to the outside of the specimen, the package fails the test. If there is no leakage to the outside of the specimen the package passes the test.

6) Water Vapor Transmission Rate (WVTR) Test Method

The water vapor transmission rate (WVTR) is defined as the mass of water vapor penetrating through the membrane per unit area, per unit time, and it is used as a parameter for measuring water barrier properties. The measurement is conduced according to the ASTM E96 Inverted Cup Water Method. For this test, impermeable cups such as the “vapometer” E96 cups from Thwing-Albert Instrument Co. are filled with 50g of water. The mouth of the cup is 3070 square millimeter in area. The cups are made of noncorroding material, impermeable to water or water vapor. The flat portion of the specimen under measurement is cut into circles slightly larger than the opening of the cup. At least three specimens should be tested representative of the materials and condition being tested. The test specimen is sandwiched between two gaskets and placed on the cup mouth flange assuring the correct orientation. The specimen is then secured to the cup by creating an impermeable seal by tightening an open screw lid. The cups are then weighted with a balance of a resolution of at least 0.01g. Place the cups on a flat tray making sure the water is in direct contact covering the specimen being tested. Then put the cups in storage at 25±3℃, 60%±10 RH. Note the cups should be placed in such a way that the air flow is not restricted over the exposed surface. The cups are then weighted daily for at least 7 days. The rate of weight change of a specimen is at steady state when that rate is essentially constant over a period that is a minimum of six consecutive weight measurements. Where a straight line adequately fits the plot of at least six properly spaced points (periodic weight changes matching or exceeding 20 %of the multiple of 100 times the scale sensitivity) , steady state is assumed. If the rate of weight is not at steady state, the storage period should be extended.

If the target part to characterize is not flat and/or the coating is not homogeneous e.g., made from spray or dip coating application, the water transmission rate is measured on a representative flat specimen made according to the same process with the same materials and characterized such that both average substrate and coating thicknesses are matching the ones from target part’s within +/-20%tolerance.

The barrier water vapor transmission rate (WVTR) after thermoforming process can be calculated based on water vapor permeability theory, and there are two critical information needed. The first one is the intrinsic barrier material properties of water vapor permeability coefficients changing with thickness, and the second one is the barrier thickness changing after thermoforming. In the study, the water vapor permeability coefficient relationship with thickness are achieved by data regression process using WVTR values using ASTM F1249 (AMETEK, MOCON) of different film sample thicknesses. For the thickness profiles after thermoforming, it can be attained by either physical measurement of film sample from thermoforming or virtual thermoforming model prediction. Once we have this critical information, the WVTR after the thermoforming process can be predicted according to Permeability theory. These WVTR predictions are confirmed using a modified ASTM E96 desiccant method with custom metal sample holders. The sample holders are designed to create a hermetic seal between the cavity containing the bentonite clay desiccant, the thermoformed barrier film, and the surrounding controlled atmosphere. Following the ASTM E96 method, samples are weighed at repeatedly over a specified duration; the resulting graph with time (days) and weight gain (grams) is fitted with a linear regression. The slope of the line is reported and normalized by the area of the thermoformed liner and reported as the WVTR.

7) Weight Loss Test Method

This method is used to determine the water weight loss through a container or individual components such as the vessel and cover. A minimum of three representative empty specimens of the type being tested are preconditioned for at least 24 hours at 23±2℃, 60%±10 RH.

Then the specimens are filled with specified amount of tap water or another specified personal care composition at lab ambient temperature to their filled capacity fitted with their respective closure/cover (if applicable) and hermetically closed in the storage configuration. Any different type of closure such as aluminum foil with paraffin should be noted. Dry (if needed) any outer surfaces with a (paper) towel so that no product remains on them.

For flat components, such as the lidding film, the measurement is conduced according to a variant of the ASTM E96 Inverted Cup Water Method. For this test, impermeable cups such as the “vapometer” E96 cups from Thwing-Albert Instrument Co. are filled with 50g of water or specified personal care composition. The mouth of the cup is 3070 square millimeter in area. The cups are made of noncorroding material, impermeable to water or water vapor. The flat portion of the specimen under measurement is cut into circles slightly larger than the opening of the cup. At least three specimens should be tested representative of the materials and condition being tested. The test specimen is sandwiched between two gaskets and placed on the cup mouth flange assuring the correct orientation. The specimen is then secured to the cup by creating an impermeable seal by tightening an open screw lid.

The weight of the filled covered vessel or cup is recorded with a balance of a resolution of at least 0.01g. Then specimens are placed in storage at 25±3℃, 60%±10 RH or another relevant testing condition. The specimen should be placed such that the water or the product under test is in direct contact with the specimen being tested. If ASTM E96 cups are used, the cups should be placed in such a way that the air flow is not restricted over the exposed surface. The weight is recorded daily for 2 weeks. The daily weight loss is calculated once the gradient is stabilized at “steady state” . The surface area of the container is calculated. The weight loss is calculated and reported averaging the daily weight loss per a square meter at 25℃, 60%RH or in the relevant tested condition. The test is not applicable if the weight loss doesn’t reach a steady state such as in case of a package failure leading to a leak.

8) Water resistance test method

This method simulates heavy use in a wet environment. Bottles are filled with filling volume Pantene PRO-V Repair &Protect shampoo or another specified personal care composition at the specified filled capacity e.g., 150±1g and then preconditioned for a minimum of 24 hours at 22±3℃, 60%±10 RH.

Then 5g±1 of content is dispensed from the bottle; the package is submerged in water for 8 minutes and subsequently dried for 10 minutes. This sequence represents a heavy use cycle. This test cycle is repeated for 19 times. A minimum of 3 bottles are tested.

Test requirements are met if no integrity or performance failure is observed in any of the bottles which renders the package not usable at the completion of all 20 heavy use cycles.

9) Bottle squeeze test method

This method is used to measure how much force is necessary to dispense a certain amount of product from a bottle. Bottles are filled with Pantene PRO-V Repair &Protect shampoo or another specified personal care composition at the specified filled capacity e.g., 150±1g and then preconditioned for a minimum of 24 hours at 22±3℃, 60%±10 RH. The bottles are fitted with their respective closure to ensure no leaks.

Each bottle is then placed in a compression tester using a fixture to simulate a squeezing event. An example of compression tester is Z010TN All-round by ZwickRoell GmbH &Co. KG. The load probe has a 3/4 inch stainless steel ball attached simulating a thumb pressing on the bottle panel. The bottle is placed horizontally relatively to the load column with the front panel facing up by fixing one bottle extremity at one end resting on two curved aluminum supports (simulating fingers) just about the opposite direction where the load is applied. The bottle is adjusted to ensure the load is applied in the center of the panel and in the middle between the neck (or the bottle base) and the other bottle extremity. Then the probe is lower to contact the bottle reaching a max preload of 0.5 N. A scale with a precision of ±0, 01 g with a collector plate is placed underneath the package to collect the product dispensed from the orifice during squeezing. The closure is opened making sure no product is leaking from the orifice before the squeeze test. Sometimes it is necessary to re-orient the bottle.

Then the load is applied to the filled bottle at 20 mm/sec until the 10mm displacement is reached. Then, the probe is returned to the start position and another 2 load cycles are performed. The total amount of product dispensed is weighted. A minimum of 3 bottles are tested in total.

Test requirements are met if both the average product collected from each dispensing event from all tested bottles is at least 1g and all bottles survive the test with no catastrophic failures compromising the bottle functions such as leaking.

10) Recyclability in pulp stream based on PTS-RH 021 CAT 2

The testing is carried out with a representative amount of at least 250g of oven-dry material of the packaging type under test as intended to be disposed by consumers. The first step is to isolate, dry remove and weight non-paper constituents which can be easily separated such as closures, etc. The test material is reduced to specimens of about 2 cm x 2 cm and the moisture content determined according to DIN EN ISO 287: 2009-09. About 50±1 g of the test material is then disintegrated in a procedure according to DIN EN ISO 5263-1: 2004-12. For this purpose, a total volume of 2,000ml of specimen is defibrated in a standard disintegrator without prior swelling at a consistency of 2.5%. The disintegration time is 20 minutes, the speed is 3000 rpm, and the temperature of the tap water 40℃. Then, the fiber suspension such obtained is homogenized according to ZM V/6/61. For this purpose, the specimen is transferred into a distributor, diluted with tap water to a form a diluted stock with a consistency of 0.5%and homogenized for about 5 minutes.

Then, the disintegratability is tested after the Zellcheming method ZM V/18/62. For this purpose, the total stock is screened for 5 minutes without any further chemical additive by means of a Brecht-Holl fractionator using a perforated plate with a hole diameter of 0.7 mm. The residue is washed into a 2 liters tank and dewater it through a filter inserted in a Büchner funnel. The filter is folded once and placed in an oven to dry at 105 ℃ up to weight constancy. Then, the reject is visually inspected and the weighted. To calculate the total reject content, the proportion of removed-dry non-pulp constituents is also included. The fiber yield can be derived from the difference between the (oven-dry, 100%) initial material and the total reject. Products are rated “recyclable” is the total reject does not exceed 20%; “recyclable, but worthy of product design improvement" if the total reject is between 20%to 50%; and “not reasonably usable in paper recycling” if the total reject is above 50%to the initial material input respectively.

For evaluating the undisturbed sheet formation criterion, the total stock is first screened in a procedure after the Zellcheming method ZM V/1.4/86. For this purpose, the total stock is fractionated for 2 minutes by means of a Haindl fractionator using a slot plate of 0.15mm. The passing fraction, which is hereinafter referred as to ‘accept’ is then collected. Then, the accept is used to form a sheet on a Rapid sheet former after DIN EN ISO 5269-2: 2005-03. Two handsheets of 1.8g are formed of about 60 gsm. The drying temperature is about 96 ℃. For the sheet adhesion test, a dried handsheet together with a couch carrier board and a cover sheet are sandwiched between two brass plates and placed in a drying oven where a full surface pressure of 1.18 kPa is applied for 2 minutes. Next, the specimens are placed in an exicator where they are allowed to cool down for 10 minutes, then they undergo the sheet adhesion test and the visual inspection for any optical inhomogeneities.

For the sheet adhesion test, the carrier board and the cover sheet are one by one slowly peeled off the handsheets. While doing so, the test operator checks for potential adhesion effects. Also, the surfaces of the handsheet, cover sheet and carrier board are inspected for any damage or adhesion of the handsheet. The product is considered "recyclable” is no adhesion effect is observed; “limitedly recyclable due to the tackiness in the prepared fiber stock” if some little adhesion effects are observed with slight damage; “not recyclable due to the tackiness in the prepared fiber stock” if adhesion effect with damage is observed.

Then the handsheets are inspected under transmitted light for the presence of any flaws, transparent and white spots, or dirt specks from inks, coating, paint, lamination, and adhesive particles. In addition, the sheets are evaluated for stain from any dark colorants. The product is considered “recyclable” if no or non-disturbing optical inhomogeneities are observed, “limitedly recyclable due to optical inhomogeneities in the prepared fiber stock” if disturbing optical inhomogeneities are observed and “not recyclable due to optical inhomogeneities in the prepared fiber stock” if unacceptable optical inhomogeneities are observed.

11) Flat crush test

In a flat crush test, the empty bottle is placed sideways on a plate. A vertical load of 45 N with a cylinder of 6 cm of diameter is applied on the bottle body. The test is passed if the bottle is permanently deformed in a substantially flat configuration.

Personal Care Composition

DETERSIVE SURFACTANT

The personal care composition may comprise greater than about 1%by weight of a surfactant system which provides cleaning performance to the composition or may comprise greater than 5%by weight of a surfactant system which enables solubilization of a scalp care active and provide a transparent appearance to the composition. In addition, the composition may have sufficient surfactant to enable micellar or polymeric thickening. The surfactant system comprises an anionic surfactant and/or a combination of anionic surfactants and/or a combination of anionic surfactants and co-surfactants selected from the group consisting of amphoteric, zwitterionic, nonionic and mixtures thereof. Various examples and descriptions of detersive surfactants are set forth in U.S. Patent No. 8,440,605; U.S. Patent Application Publication No. 2009/155383; and U.S. Patent Application Publication No. 2009/0221463, which are incorporated herein by reference in their entirety.

The personal care composition may comprise from about 10%to about 23%, from about 12%to about 21%, from about 10%to about 18%, by weight of one or more surfactants.

Anionic surfactants suitable for use in the compositions are the alkyl and alkyl ether sulfates. Other suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid reaction products. Still other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Other similar anionic surfactants are described in U.S. Patent Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated herein by reference in their entirety.

Exemplary anionic surfactants for use in the personal care composition include ammonium lauryl sulfate, ammonium laureth sulfate, ammonium C10-15 pareth sulfate, ammonium C10-15 alkyl sulfate, ammonium C11-15 alkyl sulfate, ammonium decyl sulfate, ammonium deceth sulfate, ammonium undecyl sulfate, ammonium undeceth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, sodium C10-15 pareth sulfate, sodium C10-15 alkyl sulfate, sodium C11-15 alkyl sulfate, sodium decyl sulfate, sodium deceth sulfate, sodium undecyl sulfate, sodium undeceth sulfate, potassium lauryl sulfate, potassium laureth sulfate, potassium C10-15 pareth sulfate, potassium C10-15 alkyl sulfate, potassium C11-15 alkyl sulfate, potassium decyl sulfate, potassium deceth sulfate, potassium undecyl sulfate, potassium undeceth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium cocoyl isethionate and combinations thereof. The anionic surfactant may be sodium lauryl sulfate or sodium laureth sulfate.

The composition of the present invention can also include anionic surfactants selected from the group consisting of:

a) R₁ O (CH₂CHR₃O) _y SO₃M;

b) CH₃ (CH₂) _z CHR₂ CH₂ O (CH₂ CHR₃O) _y SO₃M; and

c) mixtures thereof,

where R₁ represents CH₃ (CH₂) ₁₀ , R₂ represents H or a hydrocarbon radical comprising 1 to 4 carbon atoms such that the sum of the carbon atoms in z and R₂ is 8, R₃ is H or CH₃, y is 0 to 7, the average value of y is about 1 when y is not zero (0) , and M is a monovalent or divalent, positively-charged cation.

Suitable anionic alkyl sulfates and alkyl ether sulfate surfactants include, but are not limited to, those having branched alkyl chains which are synthesized from C8 to C18 branched alcohols which may be selected from the group consisting of: Guerbet alcohols, aldol condensation derived alcohols, oxo alcohols, F-T oxo alcohols and mixtures thereof. Non-limiting examples of the 2-alkyl branched alcohols include oxo alcohols such as 2-methyl-1-undecanol, 2-ethyl-1-decanol, 2-propyl-1-nonanol, 2-butyl 1-octanol, 2-methyl-1-dodecanol, 2-ethyl-1-undecanol, 2-propyl-1-decanol, 2-butyl-1-nonanol, 2-pentyl-1-octanol, 2-pentyl-1-heptanol, and those sold under the tradenames (Sasol) , (Sasol) , and (Shell) , and Guerbet and aldol condensation derived alcohols such as 2-ethyl-1-hexanol, 2-propyl-1-butanol, 2-butyl-1-octanol, 2-butyl-1-decanol, 2-pentyl-1-nonanol, 2-hexyl-1-octanol, 2-hexyl-1-decanol and those sold under the tradename (Sasol) or sold as alcohol ethoxylates and alkoxylates under the tradenames LUTENSOL (BASF) and LUTENSOL (BASF) .

The anionic alkyl sulfates and alkyl ether sulfates may also include those synthesized from C8 to C18 branched alcohols derived from butylene or propylene which are sold under the trade names EXXAL^TM (Exxon) and (Sasol) . This includes anionic surfactants of the subclass of sodium trideceth-n sulfates (STnS) , where n is between about 0.5 and about 3.5. Exemplary surfactants of this subclass are sodium trideceth-2 sulfate and sodium trideceth-3 sulfate. The composition of the present invention can also include sodium tridecyl sulfate.

The composition of the present invention can also include anionic alkyl and alkyl ether sulfosuccinates and/or dialkyl and dialkyl ether sulfosuccinates and mixtures thereof. The dialkyl and dialkyl ether sulfosuccinates may be a C6-15 linear or branched dialkyl or dialkyl ether sulfosuccinate. The alkyl moieties may be symmetrical (i.e., the same alkyl moieties) or asymmetrical (i.e., different alkyl moieties) . Nonlimiting examples include: disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, sodium bistridecyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dicyclohexyl sulfosuccinate, sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate, linear bis (tridecyl) sulfosuccinate and mixtures thereof.

The personal care composition may comprise a co-surfactant. The co-surfactant can be selected from the group consisting of amphoteric surfactant, zwitterionic surfactant, non-ionic surfactant and mixtures thereof. The co-surfactant can include, but is not limited to, lauramidopropyl betaine, cocoamidopropyl betaine, lauryl hydroxysultaine, sodium lauroamphoacetate, disodium cocoamphodiacetate, cocamide monoethanolamide and mixtures thereof.

The personal care composition may further comprise from about 0.5%to about 8%, from about 1.0%to about 7%, from about 1.5%to about 6%, by weight of one or more amphoteric, zwitterionic, nonionic co-surfactants, or a mixture thereof.

Suitable amphoteric or zwitterionic surfactants for use in the personal care composition herein include those which are known for use in shampoo or other personal care cleansing. Non limiting examples of suitable zwitterionic or amphoteric surfactants are described in U.S. Patent Nos. 5,104,646 and 5,106,609, which are incorporated herein by reference in their entirety.

Amphoteric co-surfactants suitable for use in the composition include those surfactants described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Suitable amphoteric surfactant include, but are not limited to, thoseselected from the group consisting of: sodium cocaminopropionate, sodium cocaminodipropionate, sodium cocoamphoacetate, sodium cocoamphodiacetate, sodium cocoamphohydroxypropylsulfonate, sodium cocoamphopropionate, sodium cornamphopropionate, sodium lauraminopropionate, sodium lauroamphoacetate, sodium lauroamphodiacetate, sodium lauroamphohydroxypropylsulfonate, sodium lauroamphopropionate, sodium cornamphopropionate, sodium lauriminodipropionate, ammonium cocaminopropionate, ammonium cocaminodipropionate, ammonium cocoamphoacetate, ammonium cocoamphodiacetate, ammonium cocoamphohydroxypropylsulfonate, ammonium cocoamphopropionate, ammonium cornamphopropionate, ammonium lauraminopropionate, ammonium lauroamphoacetate, ammonium lauroamphodiacetate, ammonium lauroamphohydroxypropylsulfonate, ammonium lauroamphopropionate, ammonium cornamphopropionate, ammonium lauriminodipropionate, triethanolamine cocaminopropionate, triethanolamine cocaminodipropionate, triethanolamine cocoamphoacetate, triethanolamine cocoamphohydroxypropylsulfonate, triethanolamine cocoamphopropionate, triethanolamine cornamphopropionate, triethanolamine lauraminopropionate, triethanolamine lauroamphoacetate, triethanolamine lauroamphohydroxypropylsulfonate, triethanolamine lauroamphopropionate, triethanolamine cornamphopropionate, triethanolamine lauriminodipropionate, cocoamphodipropionic acid, disodium caproamphodiacetate, disodium caproamphoadipropionate, disodium capryloamphodiacetate, disodium capryloamphodipriopionate, disodium cocoamphocarboxyethylhydroxypropylsulfonate, disodium cocoamphodiacetate, disodium cocoamphodipropionate, disodium dicarboxyethylcocopropylenediamine, disodium laureth-5 carboxyamphodiacetate, disodium lauriminodipropionate, disodium lauroamphodiacetate, disodium lauroamphodipropionate, disodium oleoamphodipropionate, disodium PPG-2-isodecethyl-7 carboxyamphodiacetate, lauraminopropionic acid, lauroamphodipropionic acid, lauryl aminopropylglycine, lauryl diethylenediaminoglycine, and mixtures thereof

The composition may comprise a zwitterionic co-surfactant, wherein the zwitterionic surfactant is a derivative of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate. The zwitterionic surfactant can be selected from the group consisting of: cocamidoethyl betaine, cocamidopropylamine oxide, cocamidopropyl betaine, cocamidopropyl dimethylaminohydroxypropyl hydrolyzed collagen, cocamidopropyldimonium hydroxypropyl hydrolyzed collagen, cocamidopropyl hydroxysultaine, cocobetaineamido amphopropionate, coco-betaine, coco-hydroxysultaine, coco/oleamidopropyl betaine, coco-sultaine, lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, and mixtures thereof.

Suitable nonionic surfactants for use in the present invention include those described in McCutcheion’s Detergents and Emulsifiers, North American edition (1986) , Allured Publishing Corp., and McCutcheion’s Functional Materials, North American edition (1992) . Suitable nonionic surfactants for use in the personal care compositions of the present invention include, but are not limited to, polyoxyethylenated alkyl phenols, polyoxyethylenated alcohols, polyoxyethylenated polyoxypropylene glycols, glyceryl esters of alkanoic acids, polyglyceryl esters of alkanoic acids, propylene glycol esters of alkanoic acids, sorbitol esters of alkanoic acids, polyoxyethylenated sorbitor esters of alkanoic acids, polyoxyethylene glycol esters of alkanoic acids, polyoxyethylenated alkanoic acids, alkanolamides, N-alkylpyrrolidones, alkyl glycosides, alkyl polyglucosides, alkylamine oxides, and polyoxyethylenated silicones.

The co-surfactant can be a non-ionic surfactant selected from the alkanolamides group including: Cocamide, Cocamide Methyl MEA, Cocamide DEA, Cocamide MEA, Cocamide MIPA, Lauramide DEA, Lauramide MEA, Lauramide MIPA, Myristamide DEA, Myristamide MEA, PEG-20 Cocamide MEA, PEG-2 Cocamide, PEG-3 Cocamide, PEG-4 Cocamide, PEG-5 Cocamide, PEG-6 Cocamide, PEG-7 Cocamide, PEG-3 Lauramide, PEG-5 Lauramide, PEG-3 Oleamide, PPG-2 Cocamide, PPG-2 Hydroxyethyl Cocamide, PPG-2 Hydroxyethyl Isostearamide and mixtures thereof.

Representative polyoxyethylenated alcohols include alkyl chains ranging in the C9-C16 range and having from about 1 to about 110 alkoxy groups including, but not limited to, laureth-3, laureth-23, ceteth-10, steareth-10, steareth-100, beheneth-10, and commercially available from Shell Chemicals, Houston, Texas under the trade names and mixtures thereof.

Also available commercially are the polyoxyethylene fatty ethers available commercially under the trade name from Uniqema, Wilmington, Delaware, including, but not limited to, and mixtures thereof.

Suitable alkyl glycosides and alkyl polyglucosides can be represented by the formula (S) n-O-R wherein S is a sugar moiety such as glucose, fructose, mannose, galactose, and the like; n is an integer of from about 1 to about 1000, and R is a C8-C30 alkyl group. Examples of long chain alcohols from which the alkyl group can be derived include decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and the like. Examples of these surfactants include alkyl polyglucosides wherein S is a glucose moiety, R is a C8-20 alkyl group, and n is an integer of from about 1 to about 9. Commercially available examples of these surfactants include decyl polyglucoside and lauryl polyglucoside available under trade names 325 CS, 600 CS and 625 CS) from Cognis, Ambler, Pa. Also useful herein are sucrose ester surfactants such as sucrose cocoate and sucrose laurate and alkyl polyglucosides available under trade names Triton^TM BG-10 and Triton^TM CG-110 from The Dow Chemical Company, Houston, Tx.

Other nonionic surfactants suitable for use in the present invention are glyceryl esters and polyglyceryl esters, including but not limited to, glyceryl monoesters, glyceryl monoesters of C12-22 saturated, unsaturated and branched chain fatty acids such as glyceryl oleate, glyceryl monostearate, glyceryl monopalmitate, glyceryl monobehenate, and mixtures thereof, and polyglyceryl esters of C12-22 saturated, unsaturated and branched chain fatty acids, such as polyglyceryl-4 isostearate, polyglyceryl-3 oleate, polyglyceryl-2-sesquioleate, triglyceryl diisostearate, diglyceryl monooleate, tetraglyceryl monooleate, and mixtures thereof.

Also useful herein as nonionic surfactants are sorbitan esters. Sorbitan esters of C12-22 saturated, unsaturated, and branched chain fatty acids are useful herein. These sorbitan esters usually comprise mixtures of mono-, di-, tri-, etc. esters. Representative examples of suitable sorbitan esters include sorbitan monolaurate sorbitan monopalmitate sorbitan monostearate sorbitan tristearate sorbitan monooleate sorbitan trioleate and sorbitan isostearate.

Also suitable for use herein are alkoxylated derivatives of sorbitan esters including, but not limited to, polyoxyethylene (20) sorbitan monolaurate polyoxyethylene (20) sorbitan monopalmitate polyoxyethylene (20) sorbitan monostearate polyoxyethylene (20) sorbitan monooleate polyoxyethylene (4) sorbitan monolaurate polyoxyethylene (4) sorbitan monostearate polyoxyethylene (5) sorbitan monooleate and mixtures thereof, all available from Uniqema.

Also suitable for use herein are alkylphenol ethoxylates including, but not limited to, nonylphenol ethoxylates (Tergitol^TM NP-4, NP-6, NP-7, NP-8, NP-9, NP-10, NP-11, NP-12, NP-13, NP-15, NP-30, NP-40, NP-50, NP-55, NP-70 available from The Dow Chemical Company, Houston, Tx. ) and octylphenol ethoxylates (Triton^TM X-15, X-35, X-45, X-114, X-100, X-102, X-165, X-305, X-405, X-705 available from The Dow Chemical Company, Houston, TX) .

Also suitable for use herein are tertiary alkylamine oxides including lauramine oxide and cocamine oxide.

Non limiting examples of other anionic, zwitterionic, amphoteric, and non-ionic additional surfactants suitable for use in the personal care composition are described in McCutcheon’s, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and U.S. Patent Nos. 3,929,678, 2,658,072; 2,438,091; 2,528,378, which are incorporated herein by reference in their entirety.

Suitable surfactant combinations comprise an average weight %of alkyl branching of from about 0.5%to about 30%, from about 1%to about 25%, from about 2%to about 20%. The surfactant combination can have a cumulative average weight %of C8 to C12 alkyl chain lengths of from about 7.5%to about 25%, from about 10%to about 22.5%, from about 10%to about 20%. The surfactant combination can have an average C8-C12 /C13-C18 alkyl chain ratio from about 3 to about 200, from about 25 to about 175.5, from about 50 to about 150, from about 75 to about 125.

HUMECTANT

The present invention may comprise a humectant. Humectants have an affinity to hydrogen bonds of water molecules. Non-limiting examples of suitable humectants for use in the present invention may include the following: amino acids and derivatives thereof such as proline and arginine aspartate, 1, 3-butylene glycol, propylene glycol and water and codium tomentosum extract, collagen amino acids or peptides, creatinine, diglycerol, biosaccharide gum-1, glucamine salts, glucuronic acid salts, glutamic acid salts, polyethylene glycol ethers of glycerine (e.g. glycereth 20) , glycerine, glycerol monopropoxylate, glycogen, hexylene glycol, honey, and extracts or derivatives thereof, hydrogenated starch hydrolysates, hydrolyzed mucopolysaccharides, inositol, keratin amino acids, LAREX A-200 (available from Larex) , glycosaminoglycans, methoxy PEG 10, methyl gluceth-10 and-20 (both commercially available from Amerchol located in Edison, N. J. ) , methyl glucose, 3-methyl-1, 3-butanediol, N-acetyl glucosamine salts, polyethylene glycol and derivatives thereof (such as PEG 15 butanediol, PEG 4, PEG 5 pentaerythitol, PEG 6, PEG 8, PEG 9) , pentaerythitol, 1, 2 pentanediol, PPG-1 glyceryl ether, PPG-9, 2-pyrrolidone-5-carboxylic acid and its salts such as glyceryl pca, saccharide isomerate, SEACARE (available from Secma) , sericin, silk amino acids, sodium acetylhyaluronate, sodium hyaluronate, sodium poly-aspartate, sodium polyglutamate, sorbeth 20, sorbeth 6, sugar and sugar alcohols and derivatives thereof such as glucose, sucrose, fructose, mannose and polyglycerol sorbitol, trehalose, triglycerol, trimethyolpropane, tris (hydroxymethyl) amino methane salts, and yeast extract, and mixtures thereof, ionic salts such as sodium chloride and potassium chloride and mixtures thereof.

In the present invention, the humectants may be polyhydric alcohols selected from the group consisting of glycerin, diglycerin, glycerol, erythritol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, maltitol, mannose, inositol, triethyleneglycol, sodium pyrrolidone carboxylic acid (PCA) , zinc PCA and derivatives and mixtures thereof.

The composition contains a safe and effective amount of the humectant. In particular, it may contain from about 20%to about 70%; from about 20%to about 50%; from about 23%to about 45%; by weight of a humectant.

In the present invention, the composition may contain two or more different humectants, for example, the composition may contain glycerin and xylitol.

THICKENING POLYMERS

The personal care composition may comprise a thickening polymer to increase the viscosity of the composition. Suitable thickening polymers can be used. The personal care composition may comprise from about 0.05%to about 10%of a thickening polymer, from about 0.05%to about 5%of a thickening polymer, from about 0.05%to about 2.5%of a thickening polymer, and from about 0.05%%to about 2%of a thickening polymer. The thickening polymer modifier may be a polyacrylate, polyacrylamide thickeners. The thickening polymer may be an anionic thickening polymer.

The personal care composition may comprise thickening polymers that are homopolymers based on acrylic acid, methacrylic acid or other related derivatives, non-limiting examples include polyacrylate, polymethacrylate, polyethylacrylate, and polyacrylamide.

The thickening polymers may be alkali swellable and hydrophobically-modified alkali swellable acrylic copolymers or methacrylate copolymers, non-limiting examples include acrylic acid/acrylonitrogens copolymer, acrylates/steareth-20 itaconate copolymer, acrylates/ceteth-20 itaconate copolymer, Acrylates/Aminoacrylates/C10-30 Alkyl PEG-20 Itaconate Copolymer, acrylates/aminoacrylates copolymer, acrylates/steareth-20 methacrylate copolymer, acrylates/beheneth-25 methacrylate copolymer, acrylates/steareth-20 methacrylate crosspolymer, acrylates/beheneth-25 methacrylate/HEMA crosspolymer, acrylates/vinyl neodecanoate crosspolymer, acrylates/vinyl isodecanoate crosspolymer, Acrylates/Palmeth-25 Acrylate Copolymer, Acrylic Acid/Acrylamidomethyl Propane Sulfonic Acid Copolymer, and acrylates/C10-C30 alkyl acrylate crosspolymer.

The thickening polymers may be soluble crosslinked acrylic polymers, a non-limiting example includes carbomers.

The thickening polymers may be an associative polymeric thickeners, non-limiting examples include: hydrophobically modified, alkali swellable emulsions, non-limiting examples include hydrophobically modified polypolyacrylates; hydrophobically modified polyacrylic acids, and hydrophobically modified polyacrylamides; hydrophobically modified polyethers wherein these materials may have a hydrophobe that can be selected from cetyl, stearyl, oleayl, and combinations thereof.

The thickening polymers may be used in combination with polyvinylpyrrolidone, crosslinked polyvinylpyrrolidone and derivatives. The thickening polymers may be combined with polyvinyalcohol and derivatives. The thickening polymers may be combined with polyethyleneimine and derivatives.

The thickening polymers may be combined with alginic acid based materials, non-limiting examples include sodium alginate, and alginic acid propylene glycol esters.

The thickening polymers may be used in combination with polyurethane polymers, non-limiting examples include: hydrophobically modified alkoxylated urethane polymers, non-limiting examples include PEG-150/decyl alcohol/SMDI copolymer, PEG-150/stearyl alcohol/SMDI copolymer, polyurethane-39.

The thickening polymers may be combined with an associative polymeric thickeners, non-limiting examples include: hydrophobically modified cellulose derivatives; and a hydrophilic portion of repeating ethylene oxide groups with repeat units from about 10 to about 300, from about 30to about 200, from about 40 to about 150. Non-limiting examples of this class include PEG-120-methylglucose dioleate, PEG- (40 or 60) sorbitan tetraoleate, PEG-150 pentaerythrityl tetrastearate, PEG-55 propylene glycol oleate, PEG-150 distearate.

The thickening polymers may be combined with cellulose and derivatives, non-limiting examples include microcrystalline cellulose, carboxymethylcelluloses, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, methylcellulose, ethyl cellulose; nitro cellulose; cellulose sulfate; cellulose powder; hydrophobically modified celluloses.

The thickening polymers may be combined with a guar and guar derivatives, non-limiting examples include hydroxypropyl guar, and hydroxypropyl guar hydroxypropyl trimonium chloride.

The thickening polymers may be combined with polyethylene oxide; polypropylene oxide; and POE-PPO copolymers.

The thickening polymers may be combined with polyalkylene glycols characterized by the general formula:

wherein R is hydrogen, methyl, or mixtures thereof, and further hydrogen, and n is an integer having an average from 2,000-180,000, or from 7,000-90,000, or from 7,000-45,000. Non-limiting examples of this class include PEG-7M, PEG-14M, PEG-23M, PEG-25M, PEG-45M, PEG-90M, or PEG-100M.

The thickening polymers may be combined with silicas, non-limiting examples include fumed silica, precipitated silica, and silicone-surface treated silica.

The thickening polymers may be combined with water-swellable clays, non-limiting examples include laponite, bentolite, montmorilonite, smectite, and hectonite.

The thickening polymers may be combined with gums, non-limiting examples include xanthan gum, guar gum, hydroxypropyl guar gum, Arabia gum, tragacanth, galactan, carob gum, karaya gum, and locust bean gum.

The thickening polymers may be combined with, dibenzylidene sorbitol, karaggenan, pectin, agar, quince seed (Cydonia oblonga Mill) , starch (from rice, corn, potato, wheat, etc) , starch-derivatives (e.g. carboxymethyl starch, methylhydroxypropyl starch) , algae extracts, dextran, succinoglucan, and pulleran,

Non-limiting examples of thickening polymers include acrylamide/ammonium acrylate copolymer (and) polyisobutene (and) polysorbate 20; acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate 80, ammonium acryloyldimethyltaurate/VP copolymer, Sodium Acrylate/Sodium Acryloyldimethyl Taurate Copolymer, acrylates copolymer, Acrylates Crosspolymer-4, Acrylates Crosspolymer-3, acrylates/beheneth-25 methacrylate copolymer, acrylates/C10-C30 alkyl acrylate crosspolymer, acrylates/steareth-20 itaconate copolymer, ammonium polyacrylate/Isohexadecane/PEG-40 castor oil; carbomer, sodium carbomer, crosslinked polyvinylpyrrolidone (PVP) , polyacrylamide/C13-14 isoparaffin/laureth-7, polyacrylate 13/polyisobutene/polysorbate 20, polyacrylate crosspolymer-6, polyamide-3, polyquaternium-37 (and) hydrogenated polydecene (and) trideceth-6, Acrylamide/Sodium Acryloyldimethyltaurate/Acrylic Acid Copolymer, sodium acrylate/acryloyldimethyltaurate/dimethylacrylamide, crosspolymer (and) isohexadecane (and) polysorbate 60, sodium polyacrylate. Exemplary commercially-available thickening polymers include ACULYN^TM 28, ACULYN^TM 33, ACULYN^TM 88, ACULYN^TM 22, ACULYN^TM Excel, Aqua SF-1, ETD 2020, Ultrez 20, Ultrez 21, Ultrez 10, Ultrez 30, 1342, Aqua SF-2 Polymer, Sepigel^TM 305, Simulgel^TM 600, Sepimax Zen, SMART 1000, TTA, SC-Plus, PLUS, AVC, Stabylen 30 and combinations thereof.

Scalp Care Actives

The present invention may comprise a scalp care active. The scalp care active includes soluble scalp care actives and scalp health agents.

a) Soluble Scalp Care Active

Soluble scalp care active and/or anti-dandruff agent may be one material or a mixture selected from the groups consisting of: azoles, such as climbazole, ketoconazole, itraconazole, econazole, and elubiol; hydroxy pyridones, such as octopirox (piroctone olamine) , ciclopirox, rilopirox, and MEA-Hydroxyoctyloxypyridinone; kerolytic agents, such as salicylic acid and other hydroxy acids; strobilurins such as azoxystrobin and metal chelators such as 1, 10-phenanthroline.

In the present invention, the azole anti-microbials may be an imidazole selected from the group consisting of: benzimidazole, benzothiazole, bifonazole, butaconazole nitrate, climbazole, clotrimazole, croconazole, eberconazole, econazole, elubiol, fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole, lanoconazole, metronidazole, miconazole, neticonazole, omoconazole, oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole, thiazole, and mixtures thereof, or the azole anti-microbials is a triazole selected from the group consisting of: terconazole, itraconazole, and mixtures thereof. The azole anti-microbial agent may be ketoconazole. Further, the sole anti-microbial agent may be ketoconazole.

The soluble anti-dandruff agent may be present in an amount from about 0.01%to 10%, from about 0.1%to about 9%, from about 0.25%to 8%, and from about 0.5%to 6%. The soluble antidandruff agent can be surfactant soluble and thus surfactant soluble antidandruff agents.

b) Scalp Health Agents

In the present invention, one or more scalp health agent may be added to provide scalp benefits and/or anti-fungal/anti-dandruff efficacy. This group of materials is varied and provides a wide range of benefits including moisturization, barrier improvement, anti-fungal, anti-microbial and anti-oxidant, anti-itch, and sensates, and additional anti-dandruff agents such as polyvalent metal salts of pyrithione, non-limiting examples include zinc pyrithione (ZPT) and copper pyrithione, sulfur, or selenium sulfide. Such scalp health agents include but are not limited to: vitamin E and F, salicylic acid, niacinamide, caffeine, panthenol, zinc oxide, zinc carbonate, basic zinc carbonate, glycols, glycolic acid, PCA, PEGs, erythritol, glycerin, triclosan, lactates, hyaluronates, allantoin and other ureas, betaines, sorbitol, glutamates, xylitols, menthol, menthyl lactate, vanillyl butyl ether, iso cyclomone, benzyl alcohol, a compound comprising the following structure:

R₁ is selected from H, alkyl, amino alkyl, alkoxy;

Q = H₂, O, -OR₁, -N (R₁) ₂, -OPO (OR₁) _x, -PO (OR₁) _x, -P (OR₁) _x where x = 1-2;

V = NR₁, O, -OPO (OR₁) _x, -PO (OR₁) _x, -P (OR₁) _x where x = 1-2;

W = H₂, O;

X, Y = independently selected from H, aryl, naphthyl for n=0;

X, Y = aliphatic CH₂ or aromatic CH for n ≥ 1 and Z is selected from aliphatic CH₂, aromatic

CH, or heteroatom;

A = lower alkoxy, lower alkylthio, aryl, subsitituted aryl or fused aryl; and

stereochemistry is variable at the positions marked*.

and natural extracts/oils including peppermint, spearmint, argan, jojoba and aloe.

The scalp care active may be in an encapsulated form in the present invention. In one aspect, the capsule may comprise: melamine, polyacrylamide, silicones, silica, polystyrene, polyurea, polyurethanes, polyacrylate based materials, polyacrylate esters-based materials, gelatin, styrene malic anhydride, polyamides, aromatic alcohols, polyvinyl alcohol, fatty alochols, polysaccharides, waxes, hydrogenated vegetable oils and other materials known to those skilled in the art. In one aspect, said polyurea may comprise cross-linked urea, such as urea crosslinked with formaldehyde, urea crosslinked with gluteraldehyde, and mixtures thereof. In one aspect, said polysaccharides may comprise gelatin, agar, alginate, chitosan, cellulose, glycogen, hyaluronic acid, dextran, xylan, inulin, pectin and mixtures thereof. In one aspect, said polysaccharide may be cross-linked. Suitable cross-linkers may comprise calcium chloride, calcium carbonate, isocyanates, glutaraldehyde and mixtures thereof. Typically, ant-dandruff or scalp care actives may be present in an encapsulated form at a concentration from 1%to 5%and even up to 50%weight based on total formula weight or more depending on the chemistry of both the material to be encapsulated and the encapsulate structure itself. In the present invention the composition may contain up to 90%encapsulates, may be up to 10%, may contain up to 5%, may be up to 1%.

In the present invention the personal care composition may be transparent or clear. The term "clear" or “transparent” as used herein, means that the compositions have a percent transparency (%T) of at least about 70%transmittance at 600 nm. The %T may be at 600 nm from about 70%to about 100%, from about 80%to about 100%, from about 90%to about 100%. In the present invention, the percent transparency (%T) may be at least about 80%transmittance at 600 nm; percent transparency (%T) may be at least about 90%transmittance at 600 nm.

In the present invention the personal care composition may be translucent or may be opague. The transparency of the composition is measured by Ultra-Violet/Visible ( “UV/VIS” ) spectrophotometry, which determines the absorption or transmission of UV/VIS light by a sample, using a Gretag Macbeth Colorimeter Color. A light wavelength of 600 nm has been shown to be adequate for characterizing the degree of clarity of cleansing compositions.

The personal care compositions of the present invention may have from about 14%to about 50%water; may have from about 35 %to about 50%water.

TEST METHODS FOR FORMULATION

WATER ACTIVITY

In the present invention, water activity is either measured in Aw (when on a scale of 0-1) or relative humidity -%RH when it is reported as a percentage RH%= aw*100. The water activity (Aw) of the personal care composition is the ratio between the vapor pressure of the personal care composition itself, when in an undisturbed balance with the surrounding air media, and the vapor pressure of distilled water under identical conditions.

WATER ACTIVITY DETERMINATION

In the present invention, equipment that may be used for Water Activity Determination may be: A) Hygrolab C-1 water activity meter, equipped with temperature and humidity probe (Available from Rotronic AG) and B) Shallow, disposable sample cup (Available from Rotronic AG) . In the present invention, the water activity of the test materials may be determined by using a temperature and humidity probe and a Hygrolab C-1 meter (available from Rotronic AG) A disposable sample cup (available from Rotronic AG) is filled with test material, lowered into the sample holder, and covered by the humidity and temperature probe. Using the meter’s AwE mode, the water activity of the equilibrated product will be displayed on the meter as water activity (Aw) . The following conversion factor can be used to switch between units: 1.000 Aw = 100%RH. Viscosity Method.

The present invention may have a Water Activity (Aw) of from about 0.40 to about 0.90; may have a Water Activity (AW) of from about 0.80 to about 0.87. The present invention may have a Water Activity (Aw) that is below from about 0.80.

VISCOSITY DETERMINATION

In the present invention, equipment and instrumentation that may be used for viscosity determination are: A) Disposable syringe (Available from VWR) ; Rheometer (Available from TA Instruments) and C) 40 mm parallel steel plates (Available from TA Instruments) . In the present invention, the viscosity of the shampoo test materials may be determined by using a Discovery DHR rheometer from TA instruments (New Castle, Delaware, USA) . Data collection, processing, and reporting are executed using TRIOS software, version 5.1.1.46572 (available from TA Instruments) . The instrument is configured using a 40mm diameter parallel steel plate, a gap size of 1000 μm, and a temperature of 25℃. The data is collected using a flow peak hold at a shear rate of 2.0 s^-1 with a duration of 180 seconds, and the reported viscosity is the value measured at 180 seconds. In the present invention, the personal care composition may have a viscosity of from about 5,000 cps to about 20,000 cps; from about 8,000 cps to about 14,000 cps; from about 7,000 cps to about 12,000 cps.

TABLE OF EXAMPLES : Squeezable Fiber-based bottle Package

TABLE 1

EXAMPLES

Table 1 include examples of squeezable bottles that could be used to store and dispense consumer products. All bottles of these examples have a net capacity of at least 150 ml. All bottles assessed are found no leaking and free of pinholes larger than 10 microns. The bottles are tested for fiber content, shower integrity according to the water resistance method, squeezability and re-pulpability according to the PTS-RH 021/97 cat 2 method. The side wall and the base of the bottles of these examples are also assessed for moisture vapor barrier performance.

Example 1 discloses a commercially available paper tube using a liquid carton board for the side wall, a welded polyethylene shoulder and a polypropylene cap with a living hinge. This execution is found to have a low fiber content as well as low fiber recovery in re-pulping below 50%.

Examples 2-6 cover different examples of the invention all (1) having fiber content above 85%, (2) passing the squeezing test, (3) having both side wall and base vapor transmission rate below 20 g/sqm/day at 25C 60%RH, (4) passing the water resistance test, as well as (5) fully passing with PTS-RH 021/97 cat 2 test with a fiber recovery of 80%or above. Additionally, all bottles can be flattened and crashed near empty to both access all contents with minimal product waste residual and ensure optimal disposal.

[Corrected under Rule 26, 27.12.2024]
Example 2 discloses a squeezable fiber-based bottle with a lined wet molded base and side wall including a single coated liquid carton board. The liquid carton board is a 270gsm pulp stock with a 30gsm LDPE coating. In this example the pulp molded base120 is molded from a slurry including 50%bamboo, 40%bagasse and 10%softwood fiber fraction. The slurry also includes 1%AKD added as a 10%emulsion. The pulp molded base 120 includes base barrier 140 composed of a laminate from NOVA including nucleated HDPE. The average thickness of the laminate before and after forming is 90 and 60 microns respectively. The pulp molded base 120 includes a small silicone valve 150 to promote dispensing. The valve is sandwiched between the pulp molded base 120 liquid containing surface 128 and as per the construction shown in Figure 1a. The valve 150 is sealed externally by means of a removable film sticker (not shown) to prevent accidental dispensing during distribution and storage.

In the present invention, Example 3 discloses the squeezable fiber-based bottle may have a spray coated wet molded base 120 and side wall 112 including a single coated liquid carton board. The pulp molded base barrier 140 is applied on the liquid containing surface 128 of the pulp molded base 120 and includes a primer and a topcoat applied by spraying. The valve 150 is the same of example 2.

Example 4 discloses a squeezable fiber-based bottle as shown in Figure 5b with wet molded lined base 120 and side wall 112 including a double coated liquid carton board. The liquid carton board is a high barrier double-side coated liquid carton board from Stora Enso commercialized as Natura Barr. The lined base, valve and valve assembly are the same as example 2.

Example 5 discloses a squeezable fiber-based bottle with a lined wet molded base and a coated wet molded side wall. The side wall is manufactured in one piece using a wet molding process using the same slurry disclosed in Example 2. The side wall is very flexible and deformable. The barrier system is applied on the inner surface of the side wall and includes a primer and a topcoat applied by spraying. The lined base, valve and valve assembly are the same as example 2.

Example 6 discloses a squeezable fiber-based bottle with a wet molded lined base and a wet molded coated side wall. The construction of this bottle is the same as Example 5 except the base assembly. In the present invention, the valve may be sandwiched between the pulp molded base and an additional molded cover as showed in Figures 11a and 11b.

Product Reformulation to Reduce Water Activity &Water Content

In the present invention, the reduction of the water activity and water content of the shampoo formulation is achieved by modifying a commercial marketed shampoo formulation, by removing any added water that does not come into the formula as part of another ingredient (e.g. surfactants typically come as part of a solution containing water) . Because there is a need of the shampoo to be liquid and to have a similar viscosity as commercial marketed shampoo (in order to allow good spread across the hair) , only flowable liquids and soluble solids are considered to replace the 29-41%added water in the cosmetic marketed shampoo. Because it is desired to not only reduce the water content, but also reduce the water activity (mobility) of the remaining water in the formula, ingredients that bind water (humectants) are selected. Replacing 29-41%water in the shampoo with a combination of both glycerol and sodium chloride results in a stable formula with both lower water content and activity. In addition, in comparison to water glycerol is known to provide a conditioned feel on hair.

Non-limiting Examples

The personal care compositions illustrated in the following examples are prepared by conventional formulation and mixing methods. All exemplified amounts are listed as weight percent on an active basis and exclude minor materials such as diluents, preservatives, color solutions, imagery ingredients, botanicals, and so forth, unless otherwise specified. All percentages are based on weight unless otherwise specified.

Formula Examples

Ex. A and Ex. B are traditional cosmetic formula examples with Higher water activity (Aw) included as control comparisons to Examples C -I which are reduced water activity (Aw) formulae examples of this invention.

Example descriptions:

A -Higher Aw Traditional shampoo

B -Higher Aw Traditional anti-dandruff shampoo

C -Lower Aw

D -Lower Aw

E -Lower Aw Anti-dandruff

F -Lower Aw Anti-dandruff

G -Lower Aw Alternate Humectant

H -Lower Aw Sulfate-free

I -Lower Aw Sulfate -free

Ingredients code:

Fiber-based bottle with Lower Aw Shampoo Stability Data

Lower water activity (Aw) shampoo Formula Ex. D is placed in fiber-based bottle Ex. 3 and measured for weight change over time using Method #7 Weight Loss Test Method discussed above (page 26) . The water only control leg represents a high water activity liquid such as high Aw shampoo formula Ex. A. There is considerably less weight change over time for the lower Aw shampoo in typical distribution and usage temperature and humidity conditions in a temperate countries (ICH zone 1) . FIG. 16 is a graph demonstrating that a high Aw formula has significant weight change in this fiber-based bottle as compared to the low Aw formula example that has less than 10%weight change at these same conditions.

The low rate of weight change for lower Aw formula can be used to extend the usable shelf life of the product being marketed. In the present invention, it may be used to maximize the fiber content as showed in Table 2 below in Ex. 3 (bis) , wherein the total coating thickness is

40μm and the total stock fiber %is 98%. The formula of example D combined with wall stock Ex.3 (bis) resulted into a weight loss of less than 20 g/sqm/day at 25℃ 60%RH.

TABLE 2

Additional Examples/Combinations

A. A squeezable fiber-based bottle in combination with a liquid personal care composition comprising: a pulp molded base including a liquid containing surface having an aperture for dispensing viscous liquid, the pulp molded base having a base perimeter with a perimeter surface including an upper edge and a lower edge, a base barrier is disposed on the liquid containing surface and the upper edge of the base perimeter;

a fiber-based side wall having an upper edge, a lower edge, an outer surface and an inner surface, the inner surface including a fiber-based side wall barrier layer, wherein the lower edge of the fiber-based side wall is affixed about the entire perimeter surface of the pulp molded base near the perimeter surface upper edge but not the perimeter surface lower edge forming an impermeable seal, the pulp molded base perimeter surface lower edge is below the liquid containing surface allowing the squeezable fiber-based bottle to stand vertically; and

a liquid personal care composition comprising from about 14%to about 50%water; from about 20%to about 70%of a humectant; wherein there is a Water Activity (Aw) of about 0.40 to about 0.90.

B. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A, wherein the base barrier has a weight loss of less than 20 g/sqm/day at 25℃, 60%relative humidity.

C. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-B, wherein the fiber-based side wall barrier layer has a weight loss of less than 20 g/sqm/day at 25℃, 60%relative humidity.

D. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-C, wherein the base barrier comprises a polymeric liner.

E. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-D, wherein the base barrier is a water-based dispersion and comprises micro fibrillated cellulose (MFC) or Cellulose Nano Crystals (CNC) additives.

F. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-E, wherein the squeezable fiber-based bottle comprises a fiber content of at least 85%fibers.

G. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-F, wherein the fiber-based side wall is a pulp molding comprising a squeezable side panel.

H. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-G, wherein the aperture for dispensing viscous fluid includes a separable slit valve.

I. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-H, wherein the separable slit valve is attached to a cover, wherein the cover is lightly attached to the bottom surface of the pulp molded base wherein the cover can be twisted to release the slit valve from the aperture.

J. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-I, wherein the lower edge of the fiber-based side wall is affixed about the entire perimeter surface of the pulp molded base near the perimeter surface upper edge and separated from the perimeter surface lower edge by at least 1mm.

K. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-J, wherein the pulp molded side wall is an integral one-piece side wall.

L. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-K, wherein the one-piece side wall upper edge includes a first upper edge and a second upper edge wherein the first upper edge is attached to the second upper edge forming a seal.

M. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-L, wherein the outer surface of the pulp molded side wall includes score lines to encourage two-way fold for dispensing all viscous liquid.

N. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-M, wherein the fiber-based side wall barrier layer comprises a liner on the interior surface.

O. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-N, wherein the squeezable fiber-based bottle is crushable into a flat configuration providing at least 95%product evacuation.

P. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-O, wherein the squeezable fiber-based bottle maintains structural integrity and performance when used in a wet environment.

Q. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-P, wherein the fiber count comprises between 50%to 60%bamboo, 40%to 50%bagasse and from 0%to 10%softwood.

R. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-Q, wherein the fiber count comprises between 50%to 60%bamboo, 35%to 50%bagasse and up to 5%of micro-fibrillated or nano-fibrillated cellulose fibers.

S. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-R, wherein an inorganic barrier layer is applied by a vapor phase deposition after pulp molding.

T. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-S, wherein the viscous fluid has a viscosity from 5,000 to 20,000 cps 10^-1 seconds.

U. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-T, wherein the liquid personal care composition comprises from about 35 %to about 50%water.

V. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-U, wherein the humectant is from about 23%to about 45%.

W. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-V, wherein the humectant is selectant from the group consisting of glycerin, amino acids, proline, arginine aspartate 1, 3-butylene glycol, propylene glycol and water, codium tomentosum extract, collagen amino acids or peptides, creatinine, diglycerol, biosaccharide gum-1, glucamine salts, glucuronic acid salts, glutamic acid salts, polyethylene glycol ethers of glycerine, glycerine, glycerol monopropoxylate, glycogen, hexylene glycol, honey, hydrogenated starch hydrolysates, hydrolyzed mucopolysaccharides, inositol, keratin amino acids, glycosaminoglycans, methoxy PEG 10, methyl gluceth-10 and-20, methyl glucose, 3-methyl-1, 3-butanediol, N-acetyl glucosamine salts, polyethylene glycol, PEG 4, PEG 5 pentaerythitol, PEG 6, PEG 8, PEG 9, pentaerythitol, 1, 2 pentanediol, PPG-1 glyceryl ether, PPG-9, 2-pyrrolidone-5-carboxylic acid and salts, glyceryl pca, saccharide isomerate, sericin, silk amino acids, sodium acetylhyaluronate, sodium hyaluronate, sodium poly-aspartate, sodium polyglutamate, sorbeth 20, sorbeth 6, sugar and sugar alcohols, glucose, sucrose, fructose, mannose, polyglycerol sorbitol, trehalose, triglycerol, trimethyolpropane, tris (hydroxymethyl) amino methane salts, yeast extract, ionic salts, sodium chloride potassium chloride and mixtures thereof.

X. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-W, wherein the humectant is selected from the group consisting of glycerin, sodium chloride and mixtures thereof.

Y. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-X, wherein the Water Activity (Aw) is from about 0.80 to about 0.90.

Z. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-Y, wherein the Water Activity (Aw) is below from about 0.80.

AA. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-Z, wherein the liquid personal care composition comprises a surfactant.

BB. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-AA, wherein the surfactant is from about 10%to about 18%.

CC. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-BB, wherein the surfactant is selected from one or more anionic surfactants.

DD. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-CC, wherein the liquid personal care composition comprises an amphoteric co-surfactant.

EE. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-DD, wherein the amphoteric co-surfactant is selected from the group consisting of cocamidopropyl betaine, lauramidopropyl betaine and mixtures thereof.

FF. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-EE, wherein the liquid personal care composition comprises a thickener.

GG. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-FF, wherein the liquid care composition comprises a thickener selected from the group consisting of acrylic acid/acrylonitrogens copolymer, acrylates/steareth-20 itaconate copolymer, acrylates/ceteth-20 itaconate copolymer, Acrylates/Aminoacrylates/C10-30 Alkyl PEG-20 Itaconate Copolymer,acrylates/aminoacrylates copolymer, acrylates/steareth-20 methacrylate copolymer, acrylates/beheneth-25 methacrylate copolymer, acrylates/steareth-20 methacrylate crosspolymer, acrylates/beheneth-25 methacrylate/HEMA crosspolymer, acrylates/vinyl neodecanoate crosspolymer, acrylates/vinyl isodecanoate crosspolymer,Acrylates/Palmeth-25 Acrylate Copolymer, Acrylic Acid/Acrylamidomethyl Propane Sulfonic Acid Copolymer, and acrylates/C10-C30 alkyl acrylate crosspolymer and mixtures thereof.

HH. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-GG, wherein the thickener is selected from the group consisting of hydroxyethyl cellulose.

II. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-HH, wherein the liquid personal care composition comprises sodium chloride.

JJ. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-II, wherein the liquid personal care composition comprises a scalp health active.

KK. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-JJ, wherein the scalp health active is selected from the group consisting of piroctone olamine, zinc pyrithione, climbazole, sulfur and mixtures thereof.

LL. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-KK, wherein the personal care composition has a viscosity of from about 5,000 cps to about 20,000 cps.

MM. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-LL, wherein the personal care composition has a viscosity of from about 5,000 cps to about 20,000 cps.

NN. The squeezable fiber-based bottle in combination with a liquid personal care composition according to Paragraph A-MM, comprising a package wherein the liquid personal care composition gains water when packaged inside the package, wherein the liquid personal care composition gain of water enables the physical or chemical properties of a final formulation of the liquid personal care composition.

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

Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein 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 respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or 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.

Claims

A squeezable fiber-based bottle in combination with a liquid personal care composition comprising:

a pulp molded base including a liquid containing surface having an aperture for dispensing viscous liquid, the pulp molded base having a base perimeter with a perimeter surface including an upper edge and a lower edge, a base barrier is disposed on the liquid containing surface and the upper edge of the base perimeter;

a fiber-based side wall having an upper edge, a lower edge, an outer surface and an inner surface, the inner surface including a fiber-based side wall barrier layer, wherein the lower edge of the fiber-based side wall is affixed about the entire perimeter surface of the pulp molded base near the perimeter surface upper edge but not the perimeter surface lower edge forming an impermeable seal, the pulp molded base perimeter surface lower edge is below the liquid containing surface allowing the squeezable fiber-based bottle to stand vertically; and

a liquid personal care composition comprising from 14%to 50%water, preferably from 35 %to 50%water; from 20%to 70%of a humectant, preferably from 23%to 45%of a humectant, preferably wherein the humectant is selectant from the group consisting of glycerin, amino acids, proline, arginine aspartate 1, 3-butylene glycol, propylene glycol and water, codium tomentosum extract, collagen amino acids or peptides, creatinine, diglycerol, biosaccharide gum-1, glucamine salts, glucuronic acid salts, glutamic acid salts, polyethylene glycol ethers of glycerine, glycerine, glycerol monopropoxylate, glycogen, hexylene glycol, honey, hydrogenated starch hydrolysates, hydrolyzed mucopolysaccharides, inositol, keratin amino acids, glycosaminoglycans, methoxy PEG 10, methyl gluceth-10 and-20, methyl glucose, 3-methyl-1, 3-butanediol, N-acetyl glucosamine salts, polyethylene glycol, PEG 4, PEG 5 pentaerythitol, PEG 6, PEG 8, PEG 9, pentaerythitol, 1, 2 pentanediol, PPG-1 glyceryl ether, PPG-9, 2-pyrrolidone-5-carboxylic acid and salts, glyceryl pca, saccharide isomerate, sericin, silk amino acids, sodium acetylhyaluronate, sodium hyaluronate, sodium poly-aspartate, sodium polyglutamate, sorbeth 20, sorbeth 6, sugar and sugar alcohols, glucose, sucrose, fructose, mannose, polyglycerol sorbitol, trehalose, triglycerol, trimethyolpropane, tris (hydroxymethyl) amino methane salts, yeast extract, ionic salts, sodium chloride potassium chloride and mixtures thereof, preferably wherein the humectant is selected from the group consisting of glycerin, sodium chloride and mixtures thereof;wherein there is a Water Activity (Aw) of 0.40 to 0.90, preferably wherein the Water Activity (Aw) is from 0.80 to 0.90.
The squeezable fiber-based bottle according to any preceding claims, wherein the base barrier has a weight loss of less than 20 g/sqm/day at 25℃, 60%relative humidity.
The squeezable fiber-based bottle according to any preceding claims, wherein the fiber-based side wall barrier layer has a weight loss of less than 20 g/sqm/day at 25℃, 60%relative humidity.
The squeezable fiber-based bottle according to any preceding claims, wherein the base barrier comprises a polymeric liner.
The squeezable fiber-based bottle according to any preceding claims, wherein the base barrier is a water-based dispersion and comprises micro fibrillated cellulose (MFC) or Cellulose Nano Crystals (CNC) additives.
The squeezable fiber-based bottle according to any preceding claims, wherein the squeezable fiber-based bottle comprises a fiber content of at least 85%fibers.
The squeezable fiber-based bottle according to any preceding claims, wherein the fiber-based side wall is a pulp molding comprising a squeezable side panel.
The squeezable fiber-based bottle according to any preceding claims, wherein the aperture for dispensing viscous fluid includes a separable slit valve, preferably wherein the separable slit valve is attached to a cover, wherein the cover is lightly attached to the bottom surface of the pulp molded base wherein the cover can be twisted to release the slit valve from the aperture.
The squeezable fiber-based bottle according to any preceding claims, wherein the lower edge of the fiber-based side wall is affixed about the entire perimeter surface of the pulp molded base near the perimeter surface upper edge and separated from the perimeter surface lower edge by at least 1mm.
The squeezable fiber-based bottle according to any preceding claims, wherein the pulp molded side wall is an integral one-piece side wall, preferably wherein the one-piece side wall upper edge includes a first upper edge and a second upper edge wherein the first upper edge is attached to the second upper edge forming a seal.
The squeezable fiber-based bottle according to any preceding claims, wherein the outer surface of the pulp molded side wall includes score lines to encourage two-way fold for dispensing all viscous liquid.
The squeezable fiber-based bottle according to any preceding claims, wherein the fiber-based side wall barrier layer comprises a liner on the interior surface.
The squeezable fiber-based bottle according to any preceding claims, wherein the squeezable fiber-based bottle is crushable into a flat configuration providing at least 95%product evacuation.
The squeezable fiber-based bottle according to any preceding claims, wherein the squeezable fiber-based bottle maintains structural integrity and performance when used in a wet environment.
The squeezable fiber-based bottle according to any preceding claims, wherein the fiber count comprises between 50%to 60%bamboo, 40%to 50%bagasse and from 0%to 10%softwood.
The squeezable fiber-based bottle according to any preceding claims, wherein the fiber count comprises between 50%to 60%bamboo, 35%to 50%bagasse and up to 5%of micro-fibrillated or nano-fibrillated cellulose fibers.
The squeezable fiber-based bottle according to any preceding claims, wherein an inorganic barrier layer is applied by a vapor phase deposition after pulp molding.
The squeezable fiber-based bottle according to any preceding claims, wherein the viscous fluid has a viscosity from 5,000 to 20,000 cps 10^-1 seconds.
A squeezable fiber-based bottle according to Claim 1, wherein the Water Activity (Aw) is below from 0.80.
A squeezable fiber-based bottle according to any preceding claims, wherein the liquid personal care composition comprises a surfactant, preferably wherein the surfactant is from 10%to 18%, preferably wherein the surfactant is selected from one or more anionic surfactants.
A squeezable fiber-based bottle according to any preceding claims, wherein the liquid personal care composition comprises an amphoteric co-surfactant, preferably wherein the amphoteric co-surfactant is selected from the group consisting of cocamidopropyl betaine, lauramidopropyl betaine and mixtures thereof.
A squeezable fiber-based bottle according to any preceding claims, wherein the liquid personal care composition comprises a thickener, preferably wherein the thickener selected from the group consisting of acrylic acid/acrylonitrogens copolymer, acrylates/steareth-20 itaconate copolymer, acrylates/ceteth-20 itaconate copolymer, Acrylates/Aminoacrylates/C10-30 Alkyl PEG-20 Itaconate Copolymer, acrylates/aminoacrylates copolymer, acrylates/steareth-20 methacrylate copolymer, acrylates/beheneth-25 methacrylate copolymer, acrylates/steareth-20 methacrylate crosspolymer, acrylates/beheneth-25 methacrylate/HEMA crosspolymer, acrylates/vinyl neodecanoate crosspolymer, acrylates/vinyl isodecanoate crosspolymer, Acrylates/Palmeth-25 Acrylate Copolymer, Acrylic Acid/Acrylamidomethyl Propane Sulfonic Acid Copolymer, and acrylates/C10-C30 alkyl acrylate crosspolymer and mixtures thereof, preferably wherein the thickener is selected from the group consisting of hydroxyethyl cellulose.
A squeezable fiber-based bottle according to any preceding claims, wherein the liquid personal care composition comprises sodium chloride.
A squeezable fiber-based bottle according to any preceding claims, wherein the liquid personal care composition comprises a scalp health active, preferably wherein the scalp health active is selected from the group consisting of piroctone olamine, zinc pyrithione, climbazole, sulfur and mixtures thereof.
A squeezable fiber-based bottle according to any preceding claims, wherein the personal care composition has a viscosity of from 5,000 cps to 20,000 cps.
A squeezable fiber-based bottle in combination with a liquid personal care composition according to any preceding claims, comprising a package wherein the liquid personal care composition gains water when packaged inside the package, wherein the liquid personal care composition gain of water enables the physical or chemical properties of a final formulation of the liquid personal care composition.