Conditioning hair care compositions in the form of dissolvable solid structures

Information

  • Patent Grant
  • 12029799
  • Patent Number
    12,029,799
  • Date Filed
    Wednesday, April 27, 2022
    2 years ago
  • Date Issued
    Tuesday, July 9, 2024
    5 months ago
Abstract
The Dissolvable Solid Structure as described herein can be in the form of a fibrous structure comprising: (a) a polymeric structurant; (b) a high melting point fatty compound such as a fatty amphiphile, and (c) a cationic surfactant. The polymeric structurant has a weight average molecular weight of from about 10,000 to about 6,000,000 g/mol, and the components of the fibrous material form a homogenous material when molten. When water is added to the dissolvable solid structure at a ratio of about 5:1 a lamellar structure is formed.
Description
FIELD OF THE INVENTION

The present invention relates to conditioning hair care compositions in the form of dissolvable solid structures. The dissolvable solid structures comprise a polymeric structurant, a fatty amphiphiles and a cationic surfactant.


BACKGROUND OF THE INVENTION

Many personal care and other consumer products in the market today are sold in liquid form. While widely used, liquid products often have tradeoffs in terms of packaging, storage, transportation, and convenience of use. Liquid consumer products typically are sold in bottles which add cost as well as packaging waste, much of which ends up in land-fills.


Hair Care products in the form of a dissolvable solid structures present an attractive form to consumers. Market executions of dissolvable solid structures may include, dissolvable films, compressed powders in a solid, fibrous structures, porous foams, soluble deformable solids, powders, etc. However, many of these executions have consumer negatives during in use experience. For example, these products typically do not provide sufficient wet and dry conditioning to the hair. Products such as bars or prills, do not hydrate fast enough in the shower to satisfy the consumer's desire to quickly apply to the hair without undue effort to dissolve the product.


A need therefore still exists for dissolvable solid structures which deliver the desired wet and dry conditioning to the hair, and to improve the dissolving properties of the solid product to facilitate improved consumer in use satisfaction. A need also exists for a dissolvable solid structure that is not in a lamellar state when dry, yet yields a lamellar state upon wetting.


SUMMARY OF THE INVENTION

A dissolvable solid structure comprising: a fibrous material comprising; from about 1 wt % to about 50 wt % of a polymeric structurant; from about 10 wt % to about 85 wt % of one or more high melting point fatty material having a carbon chain length C12-C22 or mixtures thereof, wherein the melting point is above 25 C; from about 1 wt % to about 60 wt % of a cationic surfactant; wherein the polymeric structurant has a weight average molecular weight of from about 10,000 to about 6,000,000 g/mol, and wherein the components of the fibrous material form a homogenous material when molten, and wherein a lamellar structure is formed upon addition of water to the dissolvable solid structure in the ratio of about 5:1.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a schematic representation of an example of a fibrous element, in this case a filament, according to the present invention;



FIG. 2 is a schematic representation of an example of a fibrous structure comprising a plurality of filaments according to the present invention;



FIG. 3 is a scanning electron microscope photograph of a cross-sectional view of an example of a fibrous structure according to the present invention;



FIG. 4 is a schematic representation of a cross-sectional view of another example of a fibrous structure according to the present invention;



FIG. 5 is a schematic representation of a cross-sectional view of another example of a fibrous structure according to the present invention;



FIG. 6 is a scanning electron microscope photograph of a cross-sectional view of another example of a fibrous structure according to the present invention;



FIG. 7 is a schematic representation of a cross-sectional view of another example of a fibrous structure according to the present invention;



FIG. 8 is a schematic representation of a cross-sectional view of another example of a fibrous structure according to the present invention;



FIG. 9 is a schematic representation of a cross-sectional view of another example of a fibrous structure according to the present invention;



FIG. 10 is a schematic representation of a cross-sectional view of another example of a fibrous structure according to the present invention;



FIG. 11 is a schematic representation of an example of a process for making an example of a fibrous structure according to the present invention;



FIG. 12 is a schematic representation of an example of a die with a magnified view used in the process of FIG. 11;



FIG. 13 is a schematic representation of an example of another process for making an example of a fibrous structure according to the present invention;



FIG. 14 is a schematic representation of another example of a process for making another example of a fibrous structure according to the present invention;



FIG. 15 is a schematic representation of another example of a process for making another example of a fibrous structure according to the present invention;



FIG. 16 is a representative image of an example of a patterned belt useful in the processes for making the fibrous structure according to the present invention.





DETAILED DESCRIPTION OF THE INVENTION
A. Definitions

As used herein, The Dissolvable Solid Structure may be referred to herein as “the Dissolvable Solid Structure”, “the Structure”, or “the Dissolvable Structure”.


As used herein, “dissolvable” means that the Dissolvable Solid Structure is completely soluble in water or it provides a uniform dispersion upon mixing in water according to the hand dissolution test. The Dissolvable Solid Structure has a hand dissolution value of from about 1 to about 30 strokes, alternatively from about 2 to about 25 strokes, alternatively from about 3 to about 20 strokes, and alternatively from about 4 to about 15 strokes, as measured by the Hand Dissolution Method.


As used herein, “flexible” means a Dissolvable Solid Structure meets the distance to maximum force values discussed herein.


“Fibrous structure” as used herein means a structure that comprises one or more fibrous elements and optionally, one or more particles. The fibrous structure as described herein can mean an association of fibrous elements and optionally, particles that together form a structure, such as a unitary structure, capable of performing a function. For example, as shown in FIG. 1, a fibrous element, such as a filament 10 made from a fibrous element-forming composition such that one or more additives 12, for example one or more active agents, may be present in the filament rather than on the filament, such as a coating composition comprising one or more active agents, which may be the same or different from the active agents in the fibrous elements and/or particles.


As shown in FIG. 2, an example of an dissolvable solid structure 20 of the present invention, for example a multi-ply fibrous structure according to the present invention may comprise two or more different fibrous structure layers or plies 22, 24 (in the z-direction of the dissolvable solid structure 20 of filaments 10 of the present invention that form the fibrous structures of the dissolvable solid structure 20. The filaments 10 in layer 22 may be the same as or different from the filaments 10 in layer 24. Each layer or ply 22, 24 may comprise a plurality of identical or substantially identical or different filaments. For example, filaments that may release their active agents at a faster rate than others within the dissolvable solid structure 20 and/or one or more fibrous structure layers or plies 22, 24 of the dissolvable solid structure 20 may be positioned as an external surface of the dissolvable solid structure 20. The layers or plies 22 and 24 may be associated with each other by mechanical entanglement at their interface between the two layers or plies and/or by thermal or adhesive bonding and/or by depositing one of the layers or plies onto the other existing layer or ply, for example spinning the fibrous elements of layer or ply 22 onto the surface of the layer or ply 24.


As shown in FIG. 3, another example of an dissolvable solid structure 20, for example a fibrous structure according to the present invention comprises a first fibrous structure layer or ply 22 comprising a plurality of fibrous elements, for example filaments 10, a second fibrous structure layer 24 comprising a plurality of fibrous elements, for example filaments 10, and a plurality of particles or a particle layer 26 positioned between the first and second fibrous structure layers 22 and 24. A similar fibrous structure can be formed by depositing a plurality of particles on a surface of a first ply of fibrous structure comprising a plurality of fibrous elements and then associating a second ply of fibrous structure comprising a plurality of fibrous elements such that the particles or a particle layer are positioned between the first and second fibrous structure plies.


As shown in FIG. 4, another example of an dissolvable solid structure 20, for example a fibrous structure of the present invention comprises a first fibrous structure layer 22 comprising a plurality of fibrous elements, for example filaments 10, wherein the first fibrous structure layer 22 comprises one or more pockets 28 (also referred to as recesses, unfilled domes, or deflected zones), which may be in an irregular pattern or a non-random, repeating pattern. One or more of the pockets 28 may contain one or more particles 26. The dissolvable solid structure 20 in this example further comprises a second fibrous structure layer 24 that is associated with the first fibrous structure layer 22 such that the particles 26 are entrapped in the pockets 28. Like above, a similar dissolvable solid structure can be formed by depositing a plurality of particles in pockets of a first ply of fibrous structure comprising a plurality of fibrous elements and then associating a second ply of fibrous structure comprising a plurality of fibrous elements such that the particles are entrapped within the pockets of the first ply. In one example, the pockets may be separated from the fibrous structure to produce discrete pockets.


As shown in FIG. 5, another example of an dissolvable solid structure 20, for example a multi-ply fibrous structure of the present invention comprises a first ply 30 of a fibrous structure according to FIG. 4 above and a second ply 32 of fibrous structure associated with the first ply 30, wherein the second ply 32 comprises a plurality of fibrous elements, for example filaments 10, and a plurality of particles 26 dispersed, in this case randomly, in the x, y, and z axes, throughout the dissolvable solid structure 20.


As shown in FIG. 6, another example of an dissolvable solid structure 20, for example a fibrous structure of the present invention comprises a plurality of fibrous elements, for example filaments 10, such as active agent-containing filaments, and a plurality of particles 26, for example active agent-containing particles, dispersed, in this case randomly, in the x, y, and z axes, throughout the fibrous structure of the dissolvable solid structure 20.


As shown in FIG. 7, another example of an dissolvable solid structure 20, for example a fibrous structure of the present invention comprises a first fibrous structure layer 22 comprising a plurality of fibrous elements, for example filaments 10, and a second fibrous structure layer 24 comprising a plurality of fibrous elements, for example filaments 10, for example active agent-containing filaments, and a plurality of particles 26, for example active agent-containing particles, dispersed, in this case randomly, in the x, y, and z axes, throughout the second fibrous structure layer 24. Alternatively, in another embodiment, the plurality of particles 26, for example active agent-containing particles, may be dispersed in an irregular pattern or a non-random, repeating pattern within the second fibrous structure layer 24. Like above, a similar dissolvable solid structure comprising two plies of fibrous structure comprising a first fibrous structure ply 22 comprising a plurality of fibrous elements, for example filaments 10, and a second fibrous structure ply 24 comprising a plurality of fibrous elements, for example filaments 10, for example active agent-containing filaments, and a plurality of particles 26, for example active agent-containing particles, dispersed, in this case randomly, in the x, y, and z axes, throughout the second fibrous structure ply 24. Alternatively, in another embodiment, the plurality of particles 26, for example active agent-containing particles, may be dispersed in an irregular pattern or a non-random, repeating pattern within the second fibrous structure ply 24.



FIG. 8 shows another example of an dissolvable solid structure 20, for example a multi-ply fibrous structure of the present invention comprising a first ply 30 of a fibrous structure as shown in FIG. 7 comprising a first fibrous structure layer 22 comprising a plurality of fibrous elements, for example filaments 10, and a second fibrous structure layer 24 comprising a plurality of fibrous elements, for example filaments 10, for example active agent-containing filaments, and a plurality of particles 26, for example active agent-containing particles, dispersed, in this case randomly, in the x, y, and z axes, throughout the second fibrous structure layer 24, a second ply 32 of a fibrous structure associated with the first ply 30, wherein the second ply 32 comprises a first fibrous structure layer 22 comprising a plurality of fibrous elements, for example filaments 10, and a second layer 24 comprising a plurality of fibrous elements, for example filaments 10, for example active agent-containing filaments, and a plurality of particles 26, for example active agent-containing particles, dispersed, in this case randomly, in the x, y, and z axes, throughout the second fibrous structure layer 24, and a third ply 34 of a fibrous structure associated with the second ply 32, wherein the third ply 34 comprises a first fibrous structure layer 22 comprising a plurality of fibrous elements, for example filaments 10, and a second fibrous structure layer 24 comprising a plurality of fibrous elements, for example filaments 10, for example active agent-containing filaments, and a plurality of particles 26, for example active agent-containing particles, dispersed, in this case randomly, in the x, y, and z axes, throughout the second fibrous structure layer 24.


As shown in FIG. 9, another example of an dissolvable solid structure 20, for example a multi-ply fibrous structure of the present invention comprises a first ply 30 of a fibrous structure comprising a plurality of fibrous elements, for example filaments 10, a second ply 32 of a fibrous structure associated with the first ply 30, wherein the second ply 32 comprises a plurality of fibrous elements, for example filaments 10, and a third ply 34 of a fibrous structure associated with the second ply 32, wherein the third ply 34 comprises a plurality of fibrous elements, for example filaments 10. In one embodiment of FIG. 9, each ply's filaments 10 may comprise active agent-containing filaments.



FIG. 10 shows another example of an dissolvable solid structure 20 multi-ply fibrous structure 20 of the present invention comprising a first ply 30 of a fibrous structure comprising a plurality of fibrous elements, for example filaments 10, a second ply 32 of fibrous structure comprising a plurality of fibrous elements, for example filaments 10, a third ply 34 of a fibrous structure comprising a plurality of fibrous elements, for example filaments 10, a fourth ply 36 of fibrous structure comprising a plurality of fibrous elements, for example filaments 10, and a fifth ply 38 of a fibrous structure comprising a plurality of fibrous elements, for example filaments 10. In this example, the dissolvable solid structure 20 further comprises one or more particles or particle layers 26 positioned between at least two adjacent fibrous structure plies, for example plies 30 and 32 or plies 32 and 34 or plies 34 and 36 or plies 36 and 38. The plies 30, 32, 34, 36, and 38 are associated with one or more other plies to form a unitary structure and to minimize particles 26, if any are present within the dissolvable solid structure 20, from becoming disassociated from the dissolvable solid structure 20. In another embodiment, the one or more particles or particle layers 26 positioned between at least two adjacent fibrous structure plies are present in an irregular pattern, a non-random, repeating pattern, or only in select zones between the plies.


The fibrous structures of the present invention may be homogeneous or may be layered. If layered, the fibrous structures may comprise at least two and/or at least three and/or at least four and/or at least five layers, for example one or more fibrous element layers, one or more particle layers and/or one or more fibrous element/particle mixture layers. A layer may comprise a particle layer within the fibrous structure or between fibrous element layers within a fibrous structure. A layer comprising fibrous elements may sometimes be referred to as a ply. A ply may be a fibrous structure which may be homogeneous or layered as described herein.


The single-ply fibrous structure or a multi-ply fibrous structure comprising one or more fibrous structure plies as described herein may exhibit a basis weight of less than 5000 g/m2 as measured according to the Basis Weight Test Method described herein. For example, the single- or multi-ply fibrous structure according to the present invention may exhibit a basis weight of greater than 10 g/m2 to about 5000 g/m2 and/or greater than 10 g/m2 to about 3000 g/m2 and/or greater than 10 g/m2 to about 2000 g/m2 and/or greater than 10 g/m2 to about 1000 g/m2 and/or greater than 20 g/m2 to about 800 g/m2 and/or greater than 30 g/m2 to about 600 g/m2 and/or greater than 50 g/m2 to about 500 g/m2 and/or greater than 300 g/m2 to about 3000 g/m2 and/or greater than 500 g/m2 to about 2000 g/m2 as measured according to the Basis Weight Test Method.


In one example, the fibrous structure of the present invention is a “unitary fibrous structure.”


“Unitary fibrous structure” as used herein is an arrangement comprising a plurality of two or more and/or three or more fibrous elements that are inter-entangled or otherwise associated with one another to form a fibrous structure and/or fibrous structure plies. A unitary fibrous structure of the present invention may be one or more plies within a multi-ply fibrous structure. In one example, a unitary fibrous structure of the present invention may comprise three or more different fibrous elements. In another example, a unitary fibrous structure of the present invention may comprise two or more different fibrous elements.


“Article” as used herein refers to a consumer use unit, a consumer unit dose unit, a consumer use saleable unit, a single dose unit, or other use form comprising a unitary fibrous dissolvable solid structure and/or comprising one or more fibrous structures of the present invention.


“Fibrous element” as used herein means an elongated particulate having a length greatly exceeding its average diameter, i.e. a length to average diameter ratio of at least about 10. A fibrous element may be a filament or a fiber. In one example, the fibrous element is a single fibrous element rather than a yarn comprising a plurality of fibrous elements.


The fibrous elements of the present invention may be spun from a filament-forming compositions also referred to as fibrous element-forming compositions via suitable spinning process operations, such as meltblowing, spunbonding, electro-spinning, and/or rotary spinning.


The fibrous elements of the present invention may be monocomponent (single, unitary solid piece rather than two different parts, like a core/sheath bicomponent) and/or multicomponent. For example, the fibrous elements may comprise bicomponent fibers and/or filaments. The bicomponent fibers and/or filaments may be in any form, such as side-by-side, core and sheath, islands-in-the-sea and the like.


“Filament” as used herein means an elongated particulate as described above that exhibits a length of greater than or equal to 5.08 cm (2 in.) and/or greater than or equal to 7.62 cm (3 in.) and/or greater than or equal to 10.16 cm (4 in.) and/or greater than or equal to 15.24 cm (6 in.).


Filaments are typically considered continuous or substantially continuous in nature. Filaments are relatively longer than fibers. Non-limiting examples of filaments include meltblown and/or spunbond filaments. Non-limiting examples of polymers that can be spun into filaments include natural polymers, such as starch, starch derivatives, cellulose, such as rayon and/or lyocell, and cellulose derivatives, hemicellulose, hemicellulose derivatives, and synthetic polymers including, but not limited to polyvinyl alcohol and also thermoplastic polymer filaments, such as polyesters, nylons, polyolefins such as polypropylene filaments, polyethylene filaments, and biodegradable thermoplastic fibers such as polylactic acid filaments, polyhydroxyalkanoate filaments, polyesteramide filaments and polycaprolactone filaments.


“Fiber” as used herein means an elongated particulate as described above that exhibits a length of less than 5.08 cm (2 in.) and/or less than 3.81 cm (1.5 in.) and/or less than 2.54 cm (1 in.).


Fibers are typically considered discontinuous in nature. Non-limiting examples of fibers include staple fibers produced by spinning a filament or filament tow of the present invention and then cutting the filament or filament tow into segments of less than 5.08 cm (2 in.) thus producing fibers.


In one example, one or more fibers may be formed from a filament of the present invention, such as when the filaments are cut to shorter lengths (such as less than 5.08 cm in length). Thus, in one example, the present invention also includes a fiber made from a filament of the present invention, such as a fiber comprising one or more filament-forming materials and one or more additives, such as active agents. Therefore, references to filament and/or filaments of the present invention herein also include fibers made from such filament and/or filaments unless otherwise noted. Fibers are typically considered discontinuous in nature relative to filaments, which are considered continuous in nature.


“Filament-forming composition” and/or “fibrous element-forming composition” as used herein means a composition that is suitable for making a fibrous element of the present invention such as by meltblowing and/or spunbonding. The filament-forming composition comprises one or more filament-forming materials that exhibit properties that make them suitable for spinning into a fibrous element. In one example, the filament-forming material comprises a polymer. In addition to one or more filament-forming materials, the filament-forming composition may comprise one or more additives, for example one or more active agents. In addition, the filament-forming composition may comprise one or more polar solvents, such as water, into which one or more, for example all, of the filament-forming materials and/or one or more, for example all, of the active agents are dissolved and/or dispersed prior to spinning a fibrous element, such as a filament from the filament-forming composition.


In one example as shown in FIG. 1, a fibrous element, for example a filament 10 of the present invention made from a fibrous element-forming composition of the present invention is such that one or more additives 12, for example one or more active agents, may be present in the filament rather than on the filament, such as a coating composition comprising one or more active agents, which may be the same or different from the active agents in the fibrous elements and/or particles. The total level of fibrous element-forming materials and total level of active agents present in the fibrous element-forming composition may be any suitable amount so long as the fibrous elements of the present invention are produced therefrom.


In one example, one or more additives, such as active agents, may be present in the fibrous element and one or more additional additives, such as active agents, may be present on a surface of the fibrous element. In another example, a fibrous element of the present invention may comprise one or more additives, such as active agents, that are present in the fibrous element when originally made, but then bloom to a surface of the fibrous element prior to and/or when exposed to conditions of intended use of the fibrous element.


“Filament-forming material” and/or “fibrous element-forming material” as used herein means a material, such as a polymer or monomers capable of producing a polymer that exhibits properties suitable for making a fibrous element. In one example, the filament-forming material comprises one or more substituted polymers such as an anionic, cationic, zwitterionic, and/or nonionic polymer. In another example, the polymer may comprise a hydroxyl polymer, such as a polyvinyl alcohol (“PVOH”), polyvinylpyrrolidone (“PVP”), polydimethyl acrylamide, a partially hydrolyzed polyvinyl acetate and/or a polysaccharide, such as starch and/or a starch derivative, such as an ethoxylated starch and/or acid-thinned starch, carboxymethylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose. In yet another example, the filament-forming material is a polar solvent-soluble material.


As used herein, “porous” means that the Dissolvable Solid Structure has spaces, voids or interstices, (generally referred to herein as “pores”) provided by the microscopic complex three-dimensional configuration, that provide channels, paths or passages through which a liquid can flow.


As used herein, “porosity” and “percent porosity” are used interchangeably and each refers to a measure of void volume of the Dissolvable Solid Structure and is calculated as

[1−([basis weight of Dissolvable Solid Structure]/[thickness of Dissolvable Solid Structure X density of the bulk, dried material])]×100%

with the units adjusted so they cancel and multiplied by 100% to provide percent porosity.


The Dissolvable Solid Structure may be referred to herein as “the Dissolvable Solid Structure” or “the Dissolvable Structure”.


As used herein, “vinyl pyrrolidone copolymer” (and “copolymer” when used in reference thereto) refers to a polymer of the following structure (I): (I)




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In structure (I), n is an integer such that the polymeric structurant has the degree of polymerization such that it possesses characteristics described herein. For purposes of clarity, the use of the term “copolymer” is intended to convey that the vinyl pyrrolidone monomer can be copolymerized with other non-limiting monomers such as vinyl acetate, alkylated vinyl pyrrolidone, vinyl caprolactam, vinyl valerolactam, vinyl imidazole, acrylic acid, methacrylate, acrylamide, methacrylamide, dimethacrylamide, alkylaminomethacrylate, and alkylaminomethacrylamide monomers.


The term “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”).


As used herein, the articles including “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.


As used herein, the terms “include,” “includes,” and “including,” are meant to be non-limiting.


The methods disclosed in the Test Methods Section of the present application should be used to determine the respective values of the parameters of Applicants' inventions, including those discussed in the Dissolvable Structures—Physical Characteristics section below.


All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated. 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.


B. Dissolvable Solid Structure

Hair Care products in the form of a dissolvable solid structure present an attractive form to consumers. A typical use of these products includes a consumer holding the product in her hand, adding water to create a solution or dispersion and applying to the hair. In many cases, the products can take a long time to dissolve making it a less enjoyable experience for the consumer. Therefore, a need exists to have dissolvable solids that exhibit more rapid dissolution. Additionally, it is desirable to have a dissolvable solid structure that forms a lamellar structure upon addition of water to the dissolvable solid structure in the ratio of about 5:1.


Dissolvable Structures—Compositional

The Dissolvable Solid Structure as described herein can be in the form of a fibrous structure comprising: (a) from about 1 wt % to about 50 wt % polymeric structurant; (b) from about 10 wt % to about 85 wt % of a high melting point fatty compound such as a fatty amphiphile, and (c) from about 1 wt % to about 60 wt % of a cationic surfactant. When water is added to the dissolvable solid structure at a ratio of about 5:1 a lamellar structure is formed.


Polymeric Structurant

To improve the fiber spinning of low viscosity material, such as molten fatty alcohols, fatty quaternary ammonium compounds, fatty acids, etc., a polymeric ingredient called a structurant is added. The structurant increases the shear and extensional viscosity of the fluid to enable fiber formation. The structurant can be included at a level of from about 1 wt % to about 50 wt %, alternatively from about 1 wt % to about 30 wt %, alternatively from about 1 wt % to about 10 wt %, alternatively from about 2 wt % to about 6 wt %, and alternatively from about 3 wt % to about 5 wt % of the composition. The structurant has a weight average molecular weight of from about 10,000 to about 6,000,000 g/mol. The weight average molecular weight is computed by summing the average molecular weights of each polymer raw material multiplied by their respective relative weight percentages by weight of the total weight of polymers present within the Dissolvable Solid Structure. However, a balance is often struck between concentration and molecular weight, such that when a lower molecular weight species is used, it requires a higher level to result in optimal fiber spinning. Likewise, when a higher molecular species is used, lower levels can be used to achieve optimal fiber spinning. The structurant having a weight average molecular weight of from about 3,000,000 g/mol to about 5,000,000 g/mol in included at a level of from about 3 wt % to about 6 wt %. Alternatively, a structurant having a weight average molecular weight of from about 50,000 g/mol to about 100,000 g/mol can be included at a level of from about 30 wt % to about 50 wt %. The structurant is soluble in an oily mixture to enable viscosity build for fiber spinning. In addition, the structurant should also be soluble in water to promote removal and to prevent buildup. Suitable structurants include, but are not limited to, polyvinylpyrrolidone, polydimethylacrylamides, and combinations thereof. These polymers are oil (fatty alcohol, fatty acid, fatty quaternary ammonium compounds) soluble, water soluble, and capable of being produced at high weight average molecular weights. For example, suitable polymers for use are PVP K120 from Ashland Inc., having a weight average molecular weight of about 3,500,000 g/mol is soluble in the oil and water and enables fibers to be formed and collected onto a belt. Additional suitable polymers include copolymers of polyvinylpyrrolidone, such as Ganex® or PVP/VA (weight average molecular weight of about 50,000 g/mol) copolymers from Ashland Inc., also performed as suitable structurants but a higher level was utilized to be effective due to their lower weight average molecular weight. In addition, copolymers of polydimethylacrylamide also function as a suitable structurant. Hydroxyl propyl cellulose can also function as a suitable structurant.


Dispersing Agents

When preparing dissolvable solid structure, it has been found that the addition of a dispersing agent greatly increases the wetting, hydration, and dispersion of the conditioner materials. The dispersing agent can be included at a level of from about 1 wt % to about 30 wt % of the composition, alternatively from about 5 wt % to about 15 wt %, and alternatively from about 5 wt % to about 10 wt %. A surfactant from the nonionic class of alkyl glucamides can improve the wetting and hydration when added to the solid conditioner formula. The alkyl glucamide surfactant contains a hydrophobic tail of about 8-18 carbons and a nonionic head group of glucamide. For glucamide, the presence of the amide and hydroxyl groups may provide sufficient polarity that balances the hydrophobic carbon tail in such a way to permit the surfactant's solubility in the conditioner oils and also imparts a rapid dispersion of the conditioner ingredients upon exposure to water. Other similar dispersing agents include, but are not limited to, reverse alkyl glucamides, cocoamiodpropyl betaines, alkyl glucoside, Triethanol amine, cocamide MEAs and mixtures thereof.


Cationic Surfactant

The dissolvable solid structure can comprise a cationic surfactant can be included at a level of from about 1 wt % to about 60 wt %, alternatively from about 10 wt % to about 50 wt %, alternatively from about 20 wt % to about 40 wt % of the composition.


Cationic surfactant useful herein can be one cationic surfactant or a mixture of two or more cationic surfactants. The cationic surfactant can be selected from the group consisting of, but not limited to: a mono-long alkyl quaternized ammonium salt; a combination of a mono-long alkyl quaternized ammonium salt and a di-long alkyl quaternized ammonium salt; a mono-long alkyl amine; a combination of a mono-long alkyl amine and a di-long alkyl quaternized ammonium salt; and a combination of a mono-long alkyl amine and a mono-long alkyl quaternized ammonium salt, a tertiary amine and combinations thereof.


Mono-Long Alkyl Amine

Mono-long alkyl amine useful herein are those having one long alkyl chain of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 alkyl group. Mono-long alkyl amines useful herein also include mono-long alkyl amidoamines Primary, secondary, and tertiary fatty amines are useful.


Suitable for use in the dissolvable solid structure are tertiary amido amines having an alkyl group of from about 12 to about 22 carbons. Exemplary tertiary amido amines include: stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine, stearamidoethyldimethylamine, palmitamidopropyldimethylamine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethyl amine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachidamidopropyldimethylamine, arachidamidopropyldiethylamine, arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, diethylaminoethylstearamide. Useful amines in the present invention are disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al.


These amines can be used in combination with acids such as custom character-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, custom character-glutamic hydrochloride, maleic acid, and mixtures thereof; alternatively custom character-glutamic acid, lactic acid, citric acid, at a molar ratio of the amine to the acid of from about 1:0.3 to about 1:2, alternatively from about 1:0.4 to about 1:1.


Mono-Long Alkyl Quaternized Ammonium Salt

The mono-long alkyl quaternized ammonium salts useful herein are those having one long alkyl chain which has from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively a C18-22 alkyl group. The remaining groups attached to nitrogen are independently selected from an alkyl group of from 1 to about 4 carbon atoms or an alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 4 carbon atoms.


Mono-long alkyl quaternized ammonium salts useful herein are those having the formula (I):




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wherein one of R75, R76, R77 and R78 is selected from an alkyl group of from 12 to 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 30 carbon atoms; the remainder of R75, R76, R77 and R78 are independently selected from an alkyl group of from 1 to about 4 carbon atoms or an alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 4 carbon atoms; and Xis a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, and alkyl sulfonate radicals. The alkyl groups can contain, in addition to carbon and hydrogen atoms, ether and/or ester linkages, and other groups such as amino groups. The longer chain alkyl groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated. One of R75, R76, R77 and R78 can be selected from an alkyl group of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 carbon atoms, alternatively 22 carbon atoms; the remainder of R75, R76, R77 and R78 can be independently selected from CH3, C2H5, C2H4OH, and mixtures thereof; and X can be selected from the group consisting of Cl, Br, CH3OSO3, C2H5OSO3, and mixtures thereof. Nonlimiting examples of such mono-long alkyl quaternized ammonium salt cationic surfactants include: behenyl trimethyl ammonium salt; stearyl trimethyl ammonium salt; cetyl trimethyl ammonium salt; and hydrogenated tallow alkyl trimethyl ammonium salt.


Di-Long Alkyl Quaternized Ammonium Salts

When used, di-long alkyl quaternized ammonium salts can be combined with a mono-long alkyl quaternized ammonium salt and/or mono-long alkyl amine salt, at the weight ratio of from 1:1 to 1:5, alternatively from 1:1.2 to 1:5, alternatively from 1:1.5 to 1:4, in view of stability in rheology and conditioning benefits.


Di-long alkyl quaternized ammonium salts useful herein are those having two long alkyl chains of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 carbon atoms. Such di-long alkyl quaternized ammonium salts useful herein are those having the formula (I):




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wherein two of R71, R72, R73 and R74 are selected from an aliphatic group of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 30 carbon atoms; the remainder of R71, R72, R73 and R74 are independently selected from an aliphatic group of from 1 to about 8 carbon atoms, alternatively from 1 to 3 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 8 carbon atoms; and Xis a salt-forming anion selected from the group consisting of halides such as chloride and bromide, C1-C4 alkyl sulfate such as methosulfate and ethosulfate, and mixtures thereof. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 16 carbons, or higher, can be saturated or unsaturated. Two of R71, R72, R73 and R74 can be selected from an alkyl group of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 carbon atoms; and the remainder of R71, R72, R73 and R74 are independently selected from CH3, C2H5, C2H4OH, CH2C6H5, and mixtures thereof.


Suitable di-long alkyl cationic surfactants include, for example, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and dicetyl dimethyl ammonium chloride.


High Melting Point Fatty Compound

The composition of the present invention comprises a high melting point fatty compound. The high melting point fatty compound can be included in the composition at a level of from about 10 wt % to about 85 wt %, alternatively from 20 wt % to 70 wt %, alternatively from about 50 wt % to about 70 wt %, alternatively from about 10 wt % to about 20 wt % of the composition. The fatty compound can be selected from the group consisting of, but not limited to, fatty amphiphiles, fatty alcohol, fatty acid, fatty amide, fatty ester and combinations thereof.


The high melting point fatty compound useful herein have a melting point of 25° C. or higher, alternatively 40° C. or higher, alternatively 45° C. or higher, alternatively 50° C. or higher, in view of stability of the emulsion especially the gel matrix. Such melting point is up to about 90° C., alternatively up to about 80° C., alternatively up to about 70° C., alternatively up to about 65° C., in view of easier manufacturing and easier emulsification. The high melting point fatty compound can be used as a single compound or as a blend or mixture of at least two high melting point fatty compounds. When used as such blend or mixture, the above melting point means the melting point of the blend or mixture.


The high melting point fatty compound useful herein is selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, fatty amides, and mixtures thereof. It is understood by the artisan that the compounds disclosed in this section of the specification can in some instances fall into more than one classification, e.g., some fatty alcohol derivatives can also be classified as fatty acid derivatives. However, a given classification is not intended to be a limitation on that particular compound, but is done so for convenience of classification and nomenclature. Further, it is understood by the artisan that, depending on the number and position of double bonds, and length and position of the branches, certain compounds having certain required carbon atoms may have a melting point of less than the above. Such compounds of low melting point are not intended to be included in this section. Nonlimiting examples of the high melting point compounds are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992.


Among a variety of high melting point fatty compounds, fatty alcohols can be used in the composition described herein. The fatty alcohols useful herein are those having from about 14 to about 30 carbon atoms, alternatively from about 16 to about 22 carbon atoms. These fatty alcohols are saturated and can be straight or branched chain alcohols.


Suitable fatty alcohols include, but are not limited to, cetyl alcohol (having a melting point of about 56° C.), stearyl alcohol (having a melting point of about 58-59° C.), behenyl alcohol (having a melting point of about 71° C.), and mixtures thereof. These compounds are known to have the above melting point. However, they often have lower melting points when supplied, since such supplied products are often mixtures of fatty alcohols having alkyl chain length distribution in which the main alkyl chain is cetyl, stearyl or behenyl group.


Generally, in the mixture, the weight ratio of cetyl alcohol to stearyl alcohol is from about 1:9 to 9:1, alternatively from about 1:4 to about 4:1, alternatively from about 1:2.3 to about 1.5:1.


When using higher level of total cationic surfactant and high melting point fatty compounds, the mixture has the weight ratio of cetyl alcohol to stearyl alcohol of from about 1:1 to about 4:1, alternatively from about 1:1 to about 2:1, alternatively from about 1.2:1 to about 2:1, in view of maintaining acceptable consumer usage. It may also provide more conditioning on damaged part of the hair.


C. Optional Ingredients

The Structure (dried) optionally comprises from about 1 wt % to about 25 wt % plasticizer, in one embodiment from about 3 wt % to about 20 wt % plasticizer, in one embodiment from about 5 wt % to about 15 wt % plasticizer.


When present in the Structures, non-limiting examples of suitable plasticizing agents include polyols, copolyols, polycarboxylic acids, polyesters and dimethicone copolyols.


Examples of useful polyols include, but are not limited to, glycerin, diglycerin, propylene glycol, ethylene glycol, butylene glycol, pentylene glycol, cyclohexane dimethanol, hexane diol, polyethylene glycol (200-600), sugar alcohols such as sorbitol, manitol, lactitol, isosorbide, glucamine, N-methylglucamine and other mono- and polyhydric low molecular weight alcohols (e.g., C2-C8 alcohols); mono di- and oligo-saccharides such as fructose, glucose, sucrose, maltose, lactose, and high fructose corn syrup solids and ascorbic acid.


Examples of polycarboxylic acids include, but are not limited to citric acid, maleic acid, succinic acid, polyacrylic acid, and polymaleic acid.


Examples of suitable polyesters include, but are not limited to, glycerol triacetate, acetylated-monoglyceride, diethyl phthalate, triethyl citrate, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate.


Examples of suitable dimethicone copolyols include, but are not limited to, PEG-12 dimethicone, PEG/PPG-18/18 dimethicone, and PPG-12 dimethicone.


Other suitable plasticizers include, but are not limited to, alkyl and allyl phthalates; napthalates; lactates (e.g., sodium, ammonium and potassium salts); sorbeth-30; urea; lactic acid; sodium pyrrolidone carboxylic acid (PCA); sodium hyraluronate or hyaluronic acid; soluble collagen; modified protein; monosodium L-glutamate; alpha & beta hydroxyl acids such as glycolic acid, lactic acid, citric acid, maleic acid and salicylic acid; glyceryl polymethacrylate; polymeric plasticizers such as polyquaterniums; proteins and amino acids such as glutamic acid, aspartic acid, and lysine; hydrogen starch hydrolysates; other low molecular weight esters (e.g., esters of C2-C10 alcohols and acids); and any other water soluble plasticizer known to one skilled in the art of the foods and plastics industries; and mixtures thereof.


EP 0283165 B1 discloses suitable plasticizers, including glycerol derivatives such as propoxylated glycerol.


The Structure may comprise other optional ingredients that are known for use or otherwise useful in compositions, provided that such optional materials are compatible with the selected essential materials described herein, or do not otherwise unduly impair product performance.


Such optional ingredients are most typically those materials approved for use in cosmetics and that are described in reference books such as the CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1992.


Emulsifiers suitable as an optional ingredient herein include mono- and di-glycerides, fatty alcohols, polyglycerol esters, propylene glycol esters, sorbitan esters and other emulsifiers known or otherwise commonly used to stabilized air interfaces, as for example those used during preparation of aerated foodstuffs such as cakes and other baked goods and confectionary products, or the stabilization of cosmetics such as hair mousses.


Further non-limiting examples of such optional ingredients include preservatives, perfumes or fragrances, coloring agents or dyes, conditioning agents, hair bleaching agents, thickeners, moisturizers, emollients, pharmaceutical actives, vitamins or nutrients, sunscreens, deodorants, sensates, plant extracts, nutrients, astringents, cosmetic particles, absorbent particles, adhesive particles, hair fixatives, fibers, reactive agents, skin lightening agents, skin tanning agents, anti-dandruff agents, perfumes, exfoliating agents, acids, bases, humectants, enzymes, suspending agents, pH modifiers, hair colorants, hair perming agents, pigment particles, anti-acne agents, anti-microbial agents, sunscreens, tanning agents, exfoliation particles, hair growth or restorer agents, insect repellents, shaving lotion agents, co-solvents or other additional solvents, and similar other materials. Further non-limiting examples of optional ingredients include encapsulated perfumes, such as by β-cyclodetrins, polymer microcapsules, starch encapsulated accords and combinations thereof.


Suitable conditioning agents include high melting point fatty compounds, silicone conditioning agents and cationic conditioning polymers. Suitable materials are discussed in US 2008/0019935, US 2008/0242584 and US 2006/0217288.


Non-limiting examples of product type embodiments for use by the Structure include hand cleansing Structures, hair shampoo or other hair treatment Structures, body cleansing Structures, shaving preparation Structures, personal care Structures containing pharmaceutical or other skin care active, moisturizing Structures, sunscreen Structures, chronic skin benefit agent Structures (e.g., vitamin-containing Structures, alpha-hydroxy acid-containing Structures, etc.), deodorizing Structures, fragrance-containing Structures, and so forth.


For fibrous Structures, the Structure comprises a significant number of dissolvable fibers with an average diameter less than about 150 micron, alternatively less than about 100 micron, alternatively less than about 10 micron, and alternatively less than about 1 micron with a relative standard deviation of less than 100%, alternatively less than 80%, alternatively less than 60%, alternatively less than 50%, such as in the range of 1% to 50%, for example. As set forth herein, the significant number means at least 10% of all the dissolvable fibers, alternatively at least 25% of all the dissolvable fibers, alternatively at least 50% of all the dissolvable fibers, alternatively at least 75% of all the dissolvable fibers. The significant number may be at least 99% of all the dissolvable fibers. Alternatively, from about 50% to about 100% of all the dissolvable fibers may have an average diameter less than about 10 micron. The dissolvable fibers produced by the method of the present disclosure have a significant number of dissolvable fibers with an average diameter less than about 1 micron, or sub-micron fibers. In an embodiment, Dissolvable Solid Structure may have from about 25% to about 100% of all the dissolvable fibers with an average diameter less than about 1 micron, alternatively from about 35% to about 100% of all the dissolvable fibers with an average diameter less than about 1 micron, alternatively from about 50% to about 100% of all the dissolvable fibers with an average diameter less than about 1 micron, and alternatively from about 75% to about 100% of all the dissolvable fibers with an average diameter less than about 1 micron.


The percent porosity of the dissolvable solid Structure is at least about 25%, alternatively at embodiment at least about 50%, alternatively at least about 60%, alternatively at least about 70% and alternatively at least about 80%. The porosity of the dissolvable solid Structure is not more than about 99%, alternatively not more than about 98%, alternatively not more than about 95%, and alternatively not more than about 90%. Porosity of a Structure is determined according to the procedure set forth in the definition of “porosity” above.


A range of effective sizes of pores can be accommodated. The pore size distribution through the Structure cross-section may be symmetric or asymmetric.


The Structure can be flexible and have a distance to maximum force value of from about 6 mm to about 30 mm. The distance to maximum force value from about 7 mm to about 25 mm, alternatively from about 8 mm to about 20 mm, and alternatively from about 9 mm to about 15 mm.


The Structure can be characterized in one aspect by its Specific Surface Area. The Structure can have a Specific Surface Area of from about 0.03 m2/g to about 0.25 m2/g, alternatively from about 0.035 m2/g to about 0.22 m2/g, alternatively from about 0.04 m2/g to about 0.19 m2/g, and alternatively from about 0.045 m2/g to about 0.16 m2/g.


The Structure can be a flat, flexible Structure in the form of a pad, a strip, or tape and having a thickness of from about 0.5 mm to about 10 mm, alternatively from about 1 mm to about 9 mm, alternatively from about 2 mm to about 8 mm, and alternatively from about 3 mm to about 7 mm as measured by the below methodology. The Structure can be a sheet having a thickness from about 5 mm to about 6.5 mm. Alternatively two or more sheets are combined to form a Structure with a thickness of about 5 mm to about 10 mm.


The Structure can have a basis weight of from about 200 grams/m2 to about 2,000 grams/m2, alternatively from about 400 g/m2 to about 1,200 g/m2, alternatively from about 600 g/m2 to about 2,000 g/m2, and alternatively from about 700 g/m2 to about 1,500 g/m2.


The Structure can have a dry density of from about 0.08 g/cm3 to about 0.40 g/cm3, alternatively from about 0.08 g/cm3 to about 0.38 g/cm3, alternatively from about 0.10 g/cm3 to about 0.25 g/cm3, and alternatively from about 0.12 g/cm3 to about 0.20 g/cm3.


Methods of Manufacture—Fibrous Structures

The fibrous elements of the present invention may be made by any suitable process. A non-limiting example of a suitable process for making the fibrous elements is described below.


As shown in FIG. 13, a fibrous structure, for example a fibrous structure layer or ply 22 of the present invention may be made by spinning a filament-forming composition from a spinning die 42, as described in FIGS. 11 and 12, to form a plurality of fibrous elements, such as filaments 10, and then optionally, associating one or more particles 26 provided by a particle source 50, for example a sifter or an airlaid forming head. The particles 26 may be dispersed within the fibrous elements, for example filaments 10. The mixture of particles 26 and fibrous elements, for example filaments 10 may be collected on a collection belt 52, such as a patterned collection belt that imparts a texture, such as a three-dimensional texture to at least one surface of the fibrous structure layer or ply 22.



FIG. 14 illustrates an example of a method for making a dissolvable solid structure 20 according to FIG. 4. The method comprises the steps of forming a first fibrous structure layer 22 of a plurality of fibrous elements, for example filaments 10 such that pockets 28 are formed in a surface of the first fibrous structure layer 22. One or more particles 26 are deposited into the pockets 28 from a particle source 50. A second fibrous structure layer 24 comprising a plurality of fibrous elements, for example filaments 10 produced from a spinning die 42 are then formed on the surface of the first fibrous structure layer 22 such that the particles 26 are entrapped in the pockets 28.



FIG. 15 illustrates yet another example of a method for making a dissolvable solid structure 20 according to FIG. 3. The method comprises the steps of forming a first fibrous structure layer 22 of a plurality of fibrous elements, for example filaments 10. One or more particles 26 are deposited onto a surface of the first fibrous structure layer 22 from a particle source 50. A second fibrous structure layer 24 comprising a plurality of fibrous elements, for example filaments 10 produced from a spinning die 42 are then formed on top of the particles 26 such that the particles 26 are positioned between the first fibrous structure layer 22 and the second fibrous structure layer 24.


The dry embryonic fibrous elements, for example filaments may be collected on a molding member as described above. The construction of the molding member may provide areas that are air-permeable due to the inherent construction. The filaments that are used to construct the molding member will be non-permeable while the void areas between the filaments will be permeable. Additionally a pattern may be applied to the molding member to provide additional non-permeable areas which may be continuous, discontinuous, or semi-continuous in nature. A vacuum used at the point of lay down is used to help deflect fibers into the presented pattern. An example of one of these molding members is shown in FIG. 16.


In addition to the techniques described herein in forming regions within the fibrous structures having a different properties (e.g., average densities), other techniques can also be applied to provide suitable results. One such example includes embossing techniques to form such regions. Suitable embossing techniques are described in U.S. Patent Application Publication Nos. 2010/0297377, 2010/0295213, 2010/0295206, 2010/0028621, and 2006/0278355.


In a multi-ply dissolvable solid structure, one or more fibrous structure plies may be formed and/or deposited directly upon an existing ply of fibrous structure to form a multi-ply fibrous structure. The two or more existing fibrous structure plies may be combined, for example via thermal bonding, gluing, embossing, aperturing, rotary knife aperturing, die cutting, die punching, needle punching, knurling, pneumatic forming, hydraulic forming, laser cutting, tufting, and/or other mechanical combining process, with one or more other existing fibrous structure plies to form the multi-ply dissolvable solid structure described herein.


Pre-formed dissolvable fibrous web (comprised of dissolvable fibers and, optionally, agglomerate particles), having approximately ⅓ the total desired basis weight of the finished dissolvable solid structure, can be arranged in a face to face relationship with post-add minor ingredients disposed between layers, and laminated with a solid state formation process. The resulting laminate is cut into the finished dissolvable solid structure shape via die cutting.


Lamination and Formation of Apertures via Solid State Formation

The 3-layer web stack with minors disposed between layers can be passed together through a solid state formation process (see Rotary Knife Aperturing apparatus below), forming roughly conical apertures in the dissolvable solid structure and causing inter-layer fiber interactions which result in a mechanically lamination dissolvable solid structure. Lamination aids (e.g. web plasticizing agents, adhesive fluids, etc.) may be additionally used to aid in secure lamination of layers.


Rotary Knife Aperturing Apparatus

Suitable solid state description in disclosed in U.S. Pat. No. 8,679,391. Also, suitable dissolvable web aperturing description is disclosed in US 2016/0101026 A1.


The nip comprises (2) intermeshed 100 pitch toothed rolls The teeth on the toothed rolls have a pyramidal shape tip with six sides that taper from the base section of the tooth to a sharp point at the tip. The base section of the tooth has vertical leading and trailing edges and is joined to the pyramidal shape tip and the surface of the toothed roller. The teeth are oriented so the long direction runs in the MD.


The teeth are arranged in a staggered pattern, with a CD pitch P of 0.100 inch (2.5 mm) and a uniform tip to tip spacing in the MD of 0.223 inch (5.7 mm). The overall tooth height TH (including pyramidal and vertical base sections) is 0.270 inch (6.9 mm), the side wall angle on the long side of the tooth is 6.8 degrees and the side wall angle of the leading and trailing edges of the teeth in the pyramidal tip section is 25 degrees.


Opposing rollers are aligned such that the corresponding MD rows of each roller are in the same plane and such that the pins intermesh in a gear-like fashion with opposing pins passing near the center of the space between pins in the opposing roller MD row of pins. The degree of interference between the virtual cylinders described by the tips of the pins is described as the Depth of Engagement.


As web passes through the nip formed between the opposing rollers, the teeth from each roller engage with and penetrate the web to a depth determined largely by the depth of engagement between the rollers and the nominal thickness of the web.


E. The Optional Preparing of the Surface Resident Coating Comprising the Active Agent

The preparation of the surface resident coating comprising the active agent may include any suitable mechanical, chemical, or otherwise means to produce a composition comprising the active agent(s) including any optional materials as described herein, or a coating from a fluid.


Optionally, the surface resident coating may comprise a water releasable matrix complex comprising active agent(s). The water releasable matrix complexes can comprising active agent(s) are prepared by spray drying wherein the active agent(s) is dispersed or emulsified within an aqueous composition comprising the dissolved matrix material under high shear (with optional emulsifying agents) and spray dried into a fine powder. The optional emulsifying agents can include gum arabic, specially modified starches, or other tensides as taught in the spray drying art (See Flavor Encapsulation, edited by Sara J. Risch and Gary A. Reineccius, pages 9, 45-54 (1988), which is incorporated herein by reference). Other known methods of manufacturing the water releasable matrix complexes comprising active agent(s) may include but are not limited to, fluid bed agglomeration, extrusion, cooling/crystallization methods and the use of phase transfer catalysts to promote interfacial polymerization. Alternatively, the active agent(s) can be adsorbed or absorbed into or combined with a water releasable matrix material that has been previously produced via a variety of mechanical mixing means (spray drying, paddle mixers, grinding, milling etc.). The water releasable matrix material in either pellet or granular or other solid-based form (and comprising any minor impurities as supplied by the supplier including residual solvents and plasticizers) may be ground or milled into a fine powder in the presence of the active agent(s) via a variety of mechanical means, for instance in a grinder or hammer mill.


Where the Dissolvable Solid Structure has a particulate coating, the particle size is known to have a direct effect on the potential reactive surface area of the active agents and thereby has a substantial effect on how fast the active agent delivers the intended beneficial effect upon dilution with water. In this sense, the active agents with smaller particle sizes tend to give a faster and shorter lived effect, whereas the active agents with larger particle sizes tend to give a slower and longer lived effect. The surface resident coatings may have a particle size from about 1 μm to about 200 μm, alternatively from about 2 μm to about 100 μm, and alternatively from about 3 μm to about 50 μm.


It can be helpful to include inert fillers within the grinding process, for instance aluminum starch octenylsuccinate under the trade name DRY-FLO® PC and available from Akzo Nobel, at a level sufficient to improve the flow properties of the powder and to mitigate inter-particle sticking or agglomeration during powder production or handling. Other optional excipients or cosmetic actives, as described herein, can be incorporated during or after the powder preparation process, e.g., grinding, milling, blending, spray drying, etc. The resulting powder may also be blended with other inert powders, either of inert materials or other powder-active complexes, and including water absorbing powders as described herein.


The active agents may be surface coated with non-hygroscopic solvents, anhydrous oils, and/or waxes as defined herein. This may include the steps of: (i) coating the water sensitive powder with the non-hydroscopic solvents, anhydrous oils, and/or waxes; (ii) reduction of the particle size of the active agent particulates, prior to, during, or after a coating is applied, by known mechanical means to a predetermined size or selected distribution of sizes; and (iii) blending the resulting coated particulates with other optional ingredients in particulate form. Alternatively, the coating of the non-hydroscopic solvents, anhydrous oils and/or waxes may be simultaneously applied to the other optional ingredients, in addition to the active agents, of the surface resident coating composition and with subsequent particle size reduction as per the procedure described above.


Where the coating is applied to the Structure as a fluid (such as by as a spray, a gel, or a cream coating), the fluid can be prepared prior to application onto the Structure or the fluid ingredients can be separately applied onto the Structure such as by two or more spray feed steams spraying separate components of the fluid onto the Structure.


Post-add minor ingredients can be applied to the surface of one or more web layers in the dissolvable solid structure, typically an interior surface. Individual minor ingredients may be applied together to a single selected surface or to separate surfaces. Minor ingredients may be applied to interior or exterior surfaces. In the present examples, minors were applied to the same interior surface, namely to one side of the middle of three layers.


Post-add ingredients in the present examples include fragrance and amodimethicone, both fluid at room temperature. Additional minor ingredients could include alternative conditioning agents, co-surfactants, encapsulated fragrance vehicles, rheology modifiers, etc. Minor ingredients could include fluids, particulates, pastes, or combinations.


In the present examples, fragrance is applied by atomizing through a spray nozzle (example Nordson EFD spray nozzle) and directing the resulting droplets of perfume to the target web surface, essentially uniformly over the surface.


In the present examples, amodimethicone is applied by expressing the fluid through an extrusion nozzle (example ITW-Dynatec UFD hot melt glue nozzle), comprising a series of orifices, approximately 500 microns in diameter and spaced at 2.5 mm, resulting in stripes of fluid extending the length of the target web surface.


Alternate fluid dispensing technologies, application patterns, and characteristic dimensions are contemplated.


Methods of Use

The compositions described herein may be used for cleaning and/or treating hair, hair follicles, skin, teeth, and the oral cavity. The method for treating these consumer substrates may comprise the steps of: a) applying an effective amount of the Structure to the hand, b) wetting the Structure with water to dissolve the solid, c) applying the dissolved material to the target consumer substrate such as to clean or treat it, and d) rinsing the diluted treatment composition from the consumer substrate. These steps can be repeated as many times as desired to achieve the desired cleansing and or treatment benefit.


A method useful for providing a benefit to hair, hair follicles, skin, teeth, and/or the oral cavity, includes the step of applying a composition according to the first embodiment to these target consumer substrates in need of regulating.


Alternatively a useful method for regulating the condition of hair, hair follicles, skin, teeth, the oral cavity, includes the step of applying one or more compositions described herein to these target consumer substrates in need of regulation.


The amount of the composition applied, the frequency of application and the period of use will vary widely depending upon the purpose of application, the level of components of a given composition and the level of regulation desired. For example, when the composition is applied for whole body or hair treatment, effective amounts generally range from about 0.5 grams to about 10 grams, alternatively from about 1.0 grams to about 5 grams, and alternatively from about 1.5 grams to about 3 grams.


Product Types and Articles of Commerce

Non-limiting examples of products that utilize the dissolvable solid structures include hand cleansing substrates, teeth cleaning or treating substrates, oral cavity substrates, hair shampoo or other hair treatment substrates, body cleansing substrates, shaving preparation substrates, personal care substrates containing pharmaceutical or other skin care active, moisturizing substrates, sunscreen substrates, chronic skin benefit agent substrates (e.g., vitamin-containing substrates, alpha-hydroxy acid-containing substrates, etc.), deodorizing substrates, fragrance-containing substrates, and so forth.


Described herein is an article of commerce comprising one or more dissolvable solid structures described herein, and a communication directing a consumer to dissolve the Structure and apply the dissolved mixture to hair, hair follicles, skin, teeth, the oral cavity, to achieve a benefit to the target consumer substrate, a rapidly lathering foam, a rapidly rinsing foam, a clean rinsing foam, and combinations thereof. The communication may be printed material attached directly or indirectly to packaging that contains the dissolvable solid structure or on the dissolvable solid structure itself. Alternatively, the communication may be an electronic or a broadcast message that is associated with the article of manufacture. Alternatively, the communication may describe at least one possible use, capability, distinguishing feature and/or property of the article of manufacture.


Test Methods
Method of Visual Homogeneity of Molten Composition

In an appropriate container, the fatty amphiphile is heated to 90 C with agitation. If desired, the dispersing agent is then added under agitation and allowed to melt. The polymeric structurant is then added under agitation and allowed to melt. The cationic surfactant is then added to the molten mixture under agitation and allowed to melt. Final molten composition is allowed to dearate. Visual assessment of homogeneity is made as being either an optically clear, single phase composition or a uniform dispersion prior to fiber formation. Data is recorded as Yes or No.


Lamellar Structure Test Method

The Lamellar Structure Test Method makes use of small-angle x-ray scattering (SAXS) to determine if a lamellar structure is present in an dissolvable solid structure either in a conditioned, dry state or upon wetting after having been previously in a conditioned, dry state. Dissolvable solid structure are conditioned at a temperature of 23° C.±2.0° C. and a relative humidity of 40%±10% for a minimum of 12 hours prior to the test. Dissolvable solid structure conditioned as described herein are considered to be in a conditioned, dry state for the purposes of this invention. All instruments are calibrated according to manufacturer's specifications.


Dry Sample Preparation

To prepare a sample to be analyzed directly in the conditioned, dry state, a specimen of about 1.0 cm diameter disc is isolated from the center of a dissolvable solid structure and is loaded into a conventional SAXS solid sample holder with aperture diameter between 4 and 5 mm (Multiple specimen discs may be extracted from multiple dissolvable solid structures and stacked, if necessary, to ensure sufficient scattering cross-section.) The loaded sample holder is immediately placed in the appropriate instrument for data collection.


Wet Sample Preparation

Three samples are analyzed upon wetting from the dry, conditioned state. Specimens are extracted from dry, conditioned dissolvable solid structure and hydrated with water in order to achieve three separate preparations each possessing a different material-to-water mass ratio. The three different material-to-water mass ratios to be prepared are 1:5; 1:9; and 1:20. For each mass ratio, one or more specimens (as needed) 1 cm in diameter are extracted from the geometric centers of one or more dissolvable solid structure in the dry, conditioned state are hydrated with 23° C.±2.0° C. filtered deionized (DI) water in order to achieve the intended material-to-water mass ratio. Each of the three material/water mixtures (each corresponding to a different mass ratio) is stirred under low shear gently by hand at room temperature using a spatula until visibly homogenous. Each material/water mixture is then immediately loaded into a separate quartz capillary tube with outer diameter 2.0 mm in diameter and 0.01 mm wall thickness. The capillary tubes are immediately sealed with a sealant such as an epoxy resin to prevent the evaporation of water from the preparations. The sealant is permitted to dry for at least 2 hours and until dry at a temperature of 23° C.±2.0° C. prior to sample analysis. Each prepared wet sample is introduced into an appropriate SAXS instrument and data are collected.


Testing and Analysis

Samples are tested using SAXS in 2-dimension (2D) transmission mode over an angular range in of 0.3° to 3.0° 2θ, to observe the presence and spacing of any intensity bands in the x-ray scatter pattern. The test is conducted using a SAXS instrument (such as the NanoSTAR, Bruker AXS Inc., Madison, Wisconsin, U.S.A., or equivalent). Conditioned, dry samples are analyzed under ambient pressure. Sealed liquid samples are analyzed in the instrument under vacuum. All samples are analyzed at a temperature of 23° C.±2.0° C. The x-ray tube of the instrument is operated sufficient power to ensure that any scattering bands present are clearly detected. The beam diameter is 550±50 μm. One suitable set of operating conditions includes the following selections: NanoSTAR instrument; micro-focus Cu x-ray tube; 45 kV and 0.650 mA power; Vantec 2K 2-Dimensional area detector; collection time of 1200 seconds; and distance between the sample and detector of 112.050 cm. The raw 2-D SAXS scattering pattern is integrated azimuthally to determine intensity (I) as a function of the scattering vector (q), which are expressed throughout this method units of reciprocal angstroms (Å−1). The values for q are calculated by the SAXS instrument according to the following equation:






q
=



4

π

λ


sin

θ







    • where:

    • 2θ is the scattering angle; and

    • 2 is the wavelength used.





For each integrated SAXS analyzed, the value of q in A−1 corresponding to each intensity peak on the plot of I vs q is identified and recorded from smallest to largest. (One of skill in the art knows that a sharp peak in q near the origin corresponds to scatter off of the beam stop and is disregarded in this method.) The value of q corresponding to the first intensity peak (the lowest value of q) is referred to as q*.


For a sample analyzed directly in the dry, conditioned state, if an intensity peak is present at 2q*±0.002 Å−1, the sample is determined to exhibit a lamellar structure, and the characteristic d-spacing parameter is defined as 2π/q*. If no intensity peak if present at 2q*±0.002 Å−1, the sample analyzed directly in the dry, conditioned state is determined to not exhibit a lamellar structure.


For a sample analyzed upon wetting from the dry, conditioned state, if an intensity peak is present at 2q*±0.002 Å−1, the sample is determined to exhibit a lamellar structure, and the characteristic d-spacing parameter is defined as 2π/q*. If no intensity peak is present at 2q*±0.002 Å−1, the sample is determined to not exhibit a lamellar structure. If a lamellar structure is determined to be present in at least any one of the three material/water ratios prepared, then this material is determined to exhibit a lamellar structure upon wetting. If no intensity peak is present at 2q*±0.002 Å−1, in any of the three material/water ratios prepared, the material is determined to not exhibit a lamellar structure upon wetting.


Method for % Mass Loss Measured at 96 Hours

Place 500 g agglomerated particles in plastic bag with end open. Place plastic bag with Agglomerated Particle in beaker with open end up exposed to atmosphere. Allow to stand open for 96 hours. Weigh Agglomerated Particle. Calculate % loss.


Basis Weight Measurement

In general, basis weight of a material or article (including the dissolvable solid structure) is measured by first cutting the sample to a known area, using a die cutter or equivalent, then measuring & recording the weight of the sample on a top-loading balance with a minimum resolution of 0.01 g, then finally by calculating the basis weight as follows:

Basis Weight (g/m2)=weight of basis weight pad (g)







Basis


Weight



(

g

m
2


)


=


Weight


of


pad



(
g
)

×
10
,
000




c


m
2



m
2




area


of


pad



(

cm
2

)







Suitable pad sample sizes for basis weight determination are >10 cm2 and should be cut with a precision die cutter having the desired geometry. If the dissolvable solid structure to be measured is smaller than 10 cm2, a smaller sampling area can be sued for basis weight determination with the appropriate changes to calculation.


In the present examples, basis weight was calculated based on the full dissolvable solid structure having a known area of 17.28 cm2. Thus, the basis weight calculation becomes:







Basis


Weight



(

g

m
2


)


=


Weight


of


pad



(
g
)

×
10
,
000




c


m
2



m
2




17.28


cm
2







Thickness (Caliper) Measurement

The present examples were measured using the Check-Line J-40-V Digital Material Thickness Gauge from Electromatic Equipment Co. (Cedarhurst, NY).


The sample (such as the dissolvable solid structure) is placed between a top and bottom plate of the instrument which has a top plate designed to apply a pressure of 0.5 kPa over a 25 cm2 area. The distance between the plates, to the nearest 0.01 mm, at the time of measurement is recorded as the thickness of the sample. The time of measurement is determined as the time at which the thickness in mm stabilizes or 5 seconds, whichever occurs first.


Equivalent methods are described in detail in compendial method ISO 9073-2, Determination of thickness for nonwovens, or equivalent.


Bulk Density (Density) Determination

Bulk Density is determined by calculation given a Thickness and Basis Weight of the sample (the solid dissolvable structure) (using methods as described above) according to the following:







Bulk



Density





(

g

c


m
3



)


=


Basis


Weight


of


the


pad



(

g

m
2


)



T

h

i

c

kness


of


the


pad



(
mm
)

×

0
.
1




c

m


m

m


×
10
,
000




c


m
2



m
2








Method of Measuring the Footprint of a Dissolvable Solid Structure (or Article)

The footprint of the dissolvable solid structure can be measured by measuring the dimensions of its base so that the base area (that is, the footprint) can be calculated. For example, in the case in which the base of the article is a parallelogram having right angles, the length of the unequal sides of the base (A and B) are measured by a ruler and the area of the base (footprint) is calculated as the product A×B. In the case in which the base of the dissolvable solid structure is a square, the length of a side (C) is measured by a ruler and the area of the base (footprint) is calculated as the square C2. Other examples of shapes can include circle, oval, etc.


Hand Dissolution Test Method
Materials Needed

Dissolvable solid structures to be tested: 3-5 dissolvable solid structure s (finished product samples) are tested so that an average of the number of strokes for each if the individual dissolvable solid structure samples is calculated and recorded as the Average Hand Dissolution value for the dissolvable solid structure. For this method, the entire consumer saleable or consumer use dissolvable solid structure is tested. If the entire consumer saleable or consumer use dissolvable solid structure has a footprint greater than 50 cm2, then first cut the dissolvable solid structure to have a footprint of 50 cm2.


Nitrile Gloves


10 cc syringe


Plastic Weigh boat (˜3 in×3 in)


100 mL Glass beaker


Water (City of Cincinnati Water or equivalent having the following properties: Total Hardness=155 mg/L as CaCO2; Calcium content=33.2 mg/L; Magnesium content=17.5 mg/L; Phosphate content=0.0462 mg/L)


Water used is 7 gpg hardness and 40° C.+/−5° C.


Protocol





    • Add 80 mL of water to glass beaker. Add 300-500 ml of water to glass beaker.

    • Heat water in beaker until water is at a temperature of 40° C.+/−5° C.

    • Transfer 10 mL of the water from the beaker into the weigh boat via the syringe.

    • Within 10 seconds of transferring the water to the weigh boat, place dissolvable solid structure sample in palm of gloved hand (hand in cupped position in non-dominant hand to hold dissolvable solid structure sample).

    • Using dominant hand, add water quickly from the weigh boat to the dissolvable solid structure sample and allow to immediately wet for a period of 5-10 seconds.

    • Rub with opposite dominant hand (also gloved) in 2 rapid circular strokes.

    • Visually examine the dissolvable solid structure sample in hand after the 2 strokes. If dissolvable solid structure sample is completely dissolved, record number of strokes=2 Dissolution Strokes. If not completely dissolved, rub remaining dissolvable solid structure sample for 2 more circular strokes (4 total) and observe degree of dissolution. If the dissolvable solid structure sample contains no solid pieces after the 2 additional strokes, record number of strokes=4 Dissolution Strokes. If after the 4 strokes total, the dissolvable solid structure sample still contains solid pieces of un-dissolved dissolvable solid structure sample, continue rubbing remaining dissolvable solid structure sample in additional 2 circular strokes and check if there are any remaining solid pieces of dissolvable solid structure sample after each additional 2 strokes until dissolvable solid structure sample is completely dissolved or until reaching a total of 30 strokes, whichever comes first. Record the total number of strokes. Record 30 Dissolution Strokes even if solid dissolvable solid structure sample pieces remain after the maximum of 30 strokes.

    • Repeat this process for each of the additional 4 dissolvable solid structure samples.

    • Calculate the arithmetic mean of the recorded values of Dissolution Strokes for the 5 individual dissolvable solid structure samples and record as the Average Hand Dissolution Value for the dissolvable solid structure. The Average Hand Dissolution Value is reported to the nearest single Dissolution Stroke unit.





Fibrous Structures—Fiber Diameter

For fibrous Structures, the diameter of dissolvable fibers in a sample of a web is determined by using a Scanning Electron Microscope (SEM) or an Optical Microscope and image analysis software. A magnification of 200 to 10,000 times is chosen such that the fibers are suitably enlarged for measurement. When using the SEM, the samples are sputtered with gold or a palladium compound to avoid electric charging and vibrations of the fibers in the electron beam. A manual procedure for determining the fiber diameters is used from the image (on monitor screen) taken with the SEM or the optical microscope. Using a mouse and a cursor tool, the edge of a randomly selected fiber is sought and then measured across its width (i.e., perpendicular to fiber direction at that point) to the other edge of the fiber. A scaled and calibrated image analysis tool provides the scaling to get actual reading in microns (μm). Several fibers are thus randomly selected across the sample of the web using the SEM or the optical microscope. At least two specimens from the web (or web inside a product) are cut and tested in this manner Altogether at least 100 such measurements are made and then all data are recorded for statistical analysis. The recorded data are used to calculate average (mean) of the fiber diameters, standard deviation of the fiber diameters, and median of the fiber diameters. Another useful statistic is the calculation of the amount of the population of fibers that is below a certain upper limit. To determine this statistic, the software is programmed to count how many results of the fiber diameters are below an upper limit and that count (divided by total number of data and multiplied by 100%) is reported in percent as percent below the upper limit, such as percent below 1 micron diameter or %-submicron, for example. We denote the measured diameter (in microns) of an individual circular fiber as di.


In case the fibers have non-circular cross-sections, the measurement of the fiber diameter is determined as and set equal to the hydraulic diameter which is four times the cross-sectional area of the fiber divided by the perimeter of the cross of the fiber (outer perimeter in case of hollow fibers). The number-average diameter, alternatively average diameter is calculated as, dnum










i
=
1

n


d
i


n




NON-LIMITING EXAMPLES

The compositions illustrated in the following Examples illustrate specific embodiments of the composition, but are not intended to be limiting thereof. Other modifications can be undertaken by the skilled artisan without departing from the spirit and scope of this invention. These exemplified embodiments of the composition as described herein provide enhanced conditioning benefits to the hair.


All exemplified amounts are listed as weight percents 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.


Conditioner Examples

















Raw Material
Ex 1
Ex 2
Ex 3





















Distilled Water
2.1
1.9
1.6



Behentrimonium
21.1
19.3
24.6



Methosulfate 1



Stearyl Alcohol
46.4
42.4
43.6



1-Hexadecanol
19.0
17.4
17.6



Lauroyl Methyl
0.0
8.7
8.6



Glucamide 2



Polyvinyl
4.2
3.9
3.9



pyrrolidone3



Amodimethicone4
7.2
6.6
0.0



Visible
Y
Y
Y



Homogeneity of



Molten



Composition



Hand Dissolution
20
6
6



Value



Presence of
Y
Y
Y



Lamellar



Structure once



hydrated (Y/N)








1 Behentrimonium Methosulfate - IPA from Croda





2 Glucotain Clean RM from Clariant





3PVP K120 from Ashland





4Amodimethicone from Momentive Performance Materials







Conditioner Examples


























Ex
Ex
Ex
Ex
Ex
Ex
Ex
Ex
Ex
Ex
Ex
Ex
Ex
Ex


Raw Material
4
5
6
7
8
9
10
11
12
13
14
15
16
17





























Distilled Water
2.2
2.4
2.4
2.2
2.3
2.4
2.4
2.2
2.2
2.4
2.2
2.4
2.4
2.4


Behentrimonium
19.4
3.9
3.9
31.0
3.9
31.0
31.0
31.0
3.9
3.9
31.0
31.0
3.9
19.3


Methosulfate 1
















Stearyl Alcohol
42.7
51.9
56.5
35.9
48.4
39.3
32.4
29
60.0
45.5
14.2
16.5
31.7
23.2


1-Hexadecanol
17.5
21.8
21.8
15.5
20.4
16.8
14.1
12.8
23.4
17.4
21.8
25.2
51.5
36.8


Lauroyl Methyl
8.7
11.5
2.0
2.0
11.6
2.0
11.6
11.6
2.0
17.4
17.4
11.5
2.0
8.7


Glucamide 2
















Polyvinyl
3.9
2.9
7.8
7.8
7.8
2.9
2.9
7.8
2.9
7.8
7.8
7.8
2.9
4.0


pyrrolidone3
















Amodimethicone4
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6


Visible
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y


Homogeneity of
















Molten
















Composition
















Fiber Formation
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y






1 Behentrimonium Methosulfate-IPA from Croda




2 Glucotain Clean RM from Clariant




3PVP K120 from Ashland




4Amodimethicone from Momentive Performance Materials







Conditioner Examples


















Raw Material
Ex 18
Ex 19
Ex 20
Ex 21
Ex 22
Ex 23
Ex 24






















Distilled Water
2.4
2.4
2.4
2.4
2.4
2.4
2.4


Stearamidopropyl
0.0
0.0
0.0
15.5
15.5
19.4
31.0


Dimethylamine1









Behenamidopropyl
31.0
31.0
31.0
0.0
0.0
0.0
0.0


Dimethylamine2









Palmitic Acid
0.0
0.0
0.0
0.0
0.0
0.0
9.4


Stearyl Alcohol
35.9
39.3
32.4
45.6
44.9
42.7
26.4


1-Hexadecanol
15.5
16.9
14.1
18.4
18.1
17.5
11.7


Lauroyl Methyl
1.9
1.9
11.6
8.7
8.7
8.7
8.7


Glucamide 3









Polyvinyl
7.8
2.9
2.9
3.9
4.9
3.9
4.9


pyrrolidone4









Amodimethicone5
5.6
5.6
5.6
5.6
5.6
5.6
5.6


Visible
Y
Y
Y
Y
Y
Y
Y


Homogeneity of









Molten









Composition









Fiber Formation
Y
Y
Y
Y
Y
Y
Y






1Stearamidopropyl Dimethylamine from Croda




2Behenamidopropyl Dimethylamine from Croda




3 Glucotain Clean RM from Clariant




4PVP K120 from Ashland




5Amodimethicone from Momentive Performance Materials







Negative Examples





















Comp
Comp
Comp
Comp
Comp
Comp
Comp
Comp
Comp


Raw Material
Ex 1
Ex 2
Ex 3
Ex 4
Ex 5
Ex 6
Ex 7
Ex 8
Ex 9
























Distilled Water
2.4
2.4
0.0
0.0
0.0
0.0
0.0
0.0
0.0


Behentrimonium











Methosulfate 1
0.0
0.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0


Stearamidopropyl











Dimethylamine2

custom character


custom character

0.0
0.0
0.0
0.0
0.0
0.0
0.0


Stearyl Alcohol
39.1
33.1
40.0
40.0
40.0
40.0
40.0
40.0
40.0


1-Hexadecanol
16.4
14.4
20.0
20.0
20.0
20.0
20.0
20.0
20.0


Lauroyl Methyl Glucamide 3
8.7
8.7
0.0
0.0
0.0
0.0
0.0
0.0
0.0


Polyvinyl pyrrolidone4
4.9
4.9
0.0
0.0
0.0
0.0
0.0
0.0
0.0


PEO N60K
0.0
0.0

custom character

0.0
0.0
0.0
0.0
0.0
0.0


Polyacrylic acid5
0.0
0.0
0.0

custom character

0.0
0.0
0.0
0.0
0.0


Polyacrylamide 6
0.0
0.0
0.0
0.0

custom character

0.0
0.0
0.0
0.0


PolyIsobutylene7
0.0
0.0
0.0
0.0
0.0

custom character

0.0
0.0
0.0


Polyacrylic acid copolymer8
0.0
0.0
0.0
0.0
0.0
0.0

custom character

0.0
0.0


Carboxy methyl cellulose 9
0.0
0.0
0.0
0.0
0.0
0.0
0.0

custom character

0.0


Polyethylene Glycol 4000
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

custom character



Amodimethicone10
5.6
5.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0


Visible Homogeneity
N
N
N
N
N
N
N
N
N


of Molten Composition











Fiber Formation
N
N
N
N
N
N
N
N
N






1 Behentrimonium Methosulfate-IPA from Croda




2Stearamidopropyl Dimethylamine from Croda




3 Glucotain Clean RM from Clariant




4PVP K120 from Ashland




5Polyacrylic acid 10,000 g/mol from Aldrich




6 Hyper Floc NF221 from HyChem/SNF




7Polyisobutylene from Aldrich MW = 1.0 e6 g/mol




8Accusol 588 G from Dow




9 Finnfix 2 from CP Kelco




10Amodimethicone from Momentive Performance Materials







Examples/Combinations

A. A dissolvable solid structure comprising:

    • a. fibrous material comprising;
      • 1) a polymeric structurant;
      • 2) a high melting point fatty material having a carbon chain length C12-C22 or mixtures thereof, wherein the melting point is above 25 C; and
      • 3) a cationic surfactant; wherein the polymeric structurant has a weight average molecular weight of from about 10,000 to about 6,000,000 g/mol, and wherein the components of the fibrous material form a homogenous material when molten, and wherein a lamellar structure is formed upon addition of water to the dissolvable solid structure in the ratio of about 5:1.


B. A dissolvable solid structure according to paragraph A comprising:

    • a. fibrous material comprising;
      • 1) from about 1 wt % to about 50 wt % of a polymeric structurant;
      • 2) from about 10 wt % to about 85 wt % of one or more high melting point fatty material having a carbon chain length C12-C22 or mixtures thereof, wherein the melting point is above 25 C;
      • 3) from about 1 wt % to about 60 wt % of a cationic surfactant; wherein the polymeric structurant has a weight average molecular weight of from about 10,000 to about 6,000,000 g/mol, and wherein the components of the fibrous material form a homogenous material when molten, and wherein a lamellar structure is formed upon addition of water to the dissolvable solid structure in the ratio of about 5:1.


C. The structure according to paragraphs A-B, further comprising from about 1 wt % to about 30 wt % of a dispersing agent.


D. The structure according to paragraph A-C, wherein the dispersing agent is selected from the group consisting of a surfactant from the nonionic class of alkyl glucamides, reverse alkyl glucamides, cocoamiodpropyl betaines, alkyl glucoside, triethanol amine, cocamide MEAs and mixtures thereof.


E. The structure according to paragraph A-D, having from about 10 wt % to about 50 wt % of cationic surfactant.


F. The structure according to paragraph A-E, having from about 20 wt % to about 40 wt % of cationic surfactant.


G. The according to paragraph A-F, having from about 1 wt % to about 30 wt % of polymeric structurant.


H. The structure according to paragraph A-G, having from about 1 wt % to about 10 wt % polymeric structurant.


I. The structure according to paragraph A-H, having from about 2 wt % to about 6 wt % of a polymeric structurant.


J. The structure according to paragraph A-I, wherein the fatty amphiphile is selected from the group consisting of a fatty alcohol and a blend of one or more fatty alcohols.


K. The structure according to paragraph A-J, wherein the fatty amphiphile is a fatty acid.


L. The structure according to paragraph A-K, wherein the fatty amphiphile is a fatty amide.


M. The structure according to paragraph A-L, wherein the fatty amphiphile is a fatty ester.


N. The structure according to paragraph A-M, wherein the cationic surfactant is quaternized ammonium salt.


O. The structure according to paragraph A-N, wherein the cationic surfactant is a tertiary amine.


P. The structure according to paragraph A-O, wherein the polymeric structurant is polyvinylpyrrolidone.


Q. The structure according to paragraph A-P, wherein the polymeric structurant is a polyvinylpyrrolidone copolymer.


R. The structure according to paragraph A-Q, wherein the polymeric structurant is polydimethylacrylamide.


S. The structure according to paragraph A-R, wherein the polymeric structurant is polydimethylacrylamide copolymer.


T. The structure according to paragraph A-S, wherein the polymeric structurant is hydroxyl propyl cellulose.


U. The Structure according to paragraph A-T, wherein the Dissolvable Solid Structure dissolves in less than about 30 strokes of the Hand Dissolution Method.


V. The Structure according to paragraph A-U, wherein the Dissolvable Solid Structure dissolves in less than about 20 strokes of the Hand Dissolution Method.


W. The Structure according to paragraph A-V, wherein the Dissolvable Solid Structure dissolves in less than about 15 strokes of the Hand Dissolution Method.


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, 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
  • 1. A dissolvable solid fibrous structure comprising a plurality of filaments wherein the filaments comprise: a. a polymeric structurant comprising a weight average molecular weight of from about 10,000 to about 6,000,000 g/mol; wherein the polymeric structurant is free of polyvinyl alcohol;b. a high melting point fatty material having a carbon chain length C12-C22 or mixtures thereof, wherein the melting point is above 25° C.; andc. a cationic surfactant; wherein the components of the filaments form a homogenous material when molten;wherein a lamellar structure is formed upon addition of water to the dissolvable solid structure in the ratio of about 5:1;wherein the plurality of filaments are inter-entangled or otherwise associated with one another to form the fibrous structure;wherein at least 50% of the filaments comprise a diameter of less than 150 microns.
  • 2. The structure of claim 1, wherein the article exhibits rapid dissolution in less than about 30 strokes according to the Hand Dissolution Method.
  • 3. The structure of claim 1, wherein the filaments comprise; a. from about 1 wt % to about 50 wt % of the polymeric structurant;b. from about 10 wt % to about 85 wt % of the high melting point fatty material; andc. from about 1 wt % to about 60 wt % of the cationic surfactant.
  • 4. The structure of claim 3, further comprising from about 1 wt % to about 30 wt % of a dispersing agent.
  • 5. The structure of claim 4, wherein the dispersing agent is chosen from the nonionic class of alkyl glucamides, reverse alkyl glucamides, cocoamidopropyl betaines, alkyl glucoside, triethanol amine, cocamide monoethanolamines (cocamide MEAs), or mixtures thereof.
  • 6. The structure of claim 3, having from about 10 wt % to about 50 wt % of cationic surfactant.
  • 7. The structure of claim 6, having from about 20 wt % to about 40 wt % of cationic surfactant.
  • 8. The structure of claim 3, having from about 1 wt % to about 30 wt % of polymeric structurant.
  • 9. The structure of claim 8, having from about 1 wt % to about 10 wt % polymeric structurant.
  • 10. The structure of claim 3, wherein the high melting point fatty material is chosen from a fatty alcohol and a blend of one or more fatty alcohols.
  • 11. The structure of claim 3, wherein the cationic surfactant is quaternized ammonium salt.
  • 12. The structure of claim 3, wherein the cationic surfactant is a tertiary amine.
  • 13. The structure of claim 3, wherein the polymeric structurant is chosen from polyvinylpyrrolidone, polyvinylpyrrolidone copolymer, polydimethylacrylamide, polydimethylacrylamide copolymer, or mixtures thereof.
  • 14. The structure of claim 1, wherein the dissolvable solid structure dissolves in less than about 20 strokes of the Hand Dissolution Method.
  • 15. The structure of claim 1, wherein the dissolvable solid structure dissolves in less than about 15 strokes of the Hand Dissolution Method.
  • 16. The structure of claim 1, wherein the filaments comprise meltblown filaments.
  • 17. The structure of claim 1, wherein at least 50% of the filaments comprise a diameter of less than 100 microns.
  • 18. The structure of claim 1, wherein at least 50% of the filaments comprise a diameter of less than 10 microns.
  • 19. A dissolvable solid fibrous structure comprising a plurality of filaments wherein the filaments comprise: d. from about 1 wt % to about 10 wt % of a polymeric structurant comprising a weight average molecular weight of from about 10,000 to about 6,000,000 g/mol; wherein the polymeric structurant is free of polyvinyl alcohol;e. from about 20 wt % to about 70 wt % of a high melting point fatty material; wherein the high melting point fatty material comprises cetyl alcohol, stearyl alcohol, behenyl alcohol, or a mixture thereof;f. from about 10 wt % to about 50 wt % of a cationic surfactant comprising behentrimonium methosulfate; wherein the components of the filaments form a homogenous material when molten,wherein a lamellar structure is formed upon addition of water to the dissolvable solid structure in the ratio of about 5:1;wherein the plurality of filaments are inter-entangled or otherwise associated with one another to form the fibrous structure;wherein at least 50% of the filaments comprise a diameter of less than 150 microns.
US Referenced Citations (571)
Number Name Date Kind
1421350 Powell Jun 1922 A
2356168 Mabley Aug 1944 A
2396278 Otto Mar 1946 A
2438091 Lynch Mar 1948 A
2486921 Byerly Nov 1949 A
2486922 Bruce Nov 1949 A
2528378 Mannheimer Oct 1950 A
2613185 Marshall Oct 1952 A
2658072 Milton Nov 1953 A
2694668 Fricke Nov 1954 A
2809971 Jack et al. Oct 1957 A
3152046 Maria Oct 1964 A
3157611 Lindemann Nov 1964 A
3236733 Karsten et al. Feb 1966 A
3293718 Melvin Dec 1966 A
3321425 Karl-ludwig et al. May 1967 A
3332880 Adriaan et al. Jul 1967 A
3426440 Shen et al. Feb 1969 A
3428478 Donaldson et al. Feb 1969 A
3463308 Deneke Aug 1969 A
3489688 Pospischil Jan 1970 A
3570122 Willimas Mar 1971 A
3589007 Walton Jun 1971 A
3653383 Wise Apr 1972 A
3695989 Albert Oct 1972 A
3753196 Kurtz et al. Aug 1973 A
3761418 Parran Sep 1973 A
3859125 Miller Jan 1975 A
3875300 Homm et al. Apr 1975 A
3929678 Laughlin Dec 1975 A
3957921 Iwahashi et al. May 1976 A
3967921 Haberli et al. Jul 1976 A
4020156 Murray et al. Apr 1977 A
4024078 Gilbert et al. May 1977 A
4051081 Jabs et al. Sep 1977 A
4089945 Brinkman et al. May 1978 A
4149551 Benjamin et al. Apr 1979 A
4185125 Kimura et al. Jan 1980 A
4196190 Gehman et al. Apr 1980 A
4197865 Jacquet et al. Apr 1980 A
4206196 Davis Jun 1980 A
4217914 Jacquet et al. Aug 1980 A
4272511 Papantoniou et al. Jun 1981 A
4286016 Dimond Aug 1981 A
4315965 Mason Feb 1982 A
4323525 Bornat Apr 1982 A
4323683 Bolich, Jr. et al. Apr 1982 A
4340583 Wason Jul 1982 A
4342813 Erickson Aug 1982 A
4345080 Bolich, Jr. Aug 1982 A
D266829 Yoshizawa et al. Nov 1982 S
4377615 Suzuki Mar 1983 A
4379753 Bolich, Jr. Apr 1983 A
4381919 Jacquet et al. May 1983 A
4415617 D Nov 1983 A
4422853 Jacquet et al. Dec 1983 A
4448699 Barrat et al. May 1984 A
4470982 Winkler Sep 1984 A
4507280 Pohl et al. Mar 1985 A
4529586 De et al. Jul 1985 A
4536361 Torobin Aug 1985 A
4565647 Llenado Jan 1986 A
D286450 Tovey Oct 1986 S
4635351 Koch et al. Jan 1987 A
4639390 Shoji Jan 1987 A
4663158 Wolfram et al. May 1987 A
4710374 Grollier et al. Dec 1987 A
4723362 Boerger Feb 1988 A
4727410 Higgins, III Feb 1988 A
4822613 Rodero Apr 1989 A
4885107 Wetzel Dec 1989 A
4892758 Serbiak Jan 1990 A
4976953 Orr et al. Dec 1990 A
4990280 Thorengaard Feb 1991 A
5034421 Fuisz Jul 1991 A
5052296 Shiba Oct 1991 A
5055384 Kuehnert Oct 1991 A
5061481 Suzuki et al. Oct 1991 A
5062889 Hoehl et al. Nov 1991 A
5062994 Imperatori Nov 1991 A
5094853 Hagarty Mar 1992 A
5098636 Balk Mar 1992 A
5100657 Ansher-jackson et al. Mar 1992 A
5100658 Bolich, Jr. et al. Mar 1992 A
5102129 Roberts Apr 1992 A
5104646 Bolich, Jr. Apr 1992 A
5106609 Bolich, Jr. Apr 1992 A
5112515 Buxton et al. May 1992 A
5166276 Hayama et al. Nov 1992 A
D334420 Copeland et al. Mar 1993 S
5220033 Kamei et al. Jun 1993 A
5230853 Colegrove Jul 1993 A
5261426 Kellett et al. Nov 1993 A
5280079 Allen et al. Jan 1994 A
RE34584 Grote et al. Apr 1994 E
D351345 Geho Oct 1994 S
5364627 Song Nov 1994 A
5391368 Gerstein Feb 1995 A
D357115 Ashley et al. Apr 1995 S
5409703 Mcanalley et al. Apr 1995 A
D358025 Martin et al. May 1995 S
5415810 Lee May 1995 A
5429628 Trinh et al. Jul 1995 A
5444113 Sinclair et al. Aug 1995 A
5446079 Buchanan et al. Aug 1995 A
5455114 Ohmory Oct 1995 A
5457895 Thompson et al. Oct 1995 A
5458433 Stastny Oct 1995 A
5470424 Isaac Nov 1995 A
5470492 Childs et al. Nov 1995 A
5476597 Sakata et al. Dec 1995 A
5501238 Borstel et al. Mar 1996 A
5533636 Reiker Jul 1996 A
5538735 Ahn Jul 1996 A
5580481 Sakata et al. Dec 1996 A
5582786 Brunskill et al. Dec 1996 A
D378180 Hayes Feb 1997 S
5660845 Trinh et al. Aug 1997 A
5672576 Behrens et al. Sep 1997 A
5673576 Chen et al. Oct 1997 A
5674478 Dodd Oct 1997 A
5716692 Warner Feb 1998 A
5750122 Evans May 1998 A
5756438 Rau et al. May 1998 A
5780047 Kamiya et al. Jul 1998 A
5780418 Niinaka Jul 1998 A
D398847 Wyslotsky Sep 1998 S
D399260 Thimote Oct 1998 S
5840675 Yeazell Nov 1998 A
5849378 Gask Dec 1998 A
5879493 Johnson Mar 1999 A
D407640 Crapser et al. Apr 1999 S
D408223 Henry Apr 1999 S
5911224 Berger Jun 1999 A
5925603 D Jul 1999 A
5952286 Puvvada et al. Sep 1999 A
5955419 Barket, Jr. et al. Sep 1999 A
D416103 Hashmi Nov 1999 S
5976454 Sterzel et al. Nov 1999 A
D418415 Hayes Jan 2000 S
D418750 Blin Jan 2000 S
6010719 Remon et al. Jan 2000 A
6028016 Yahiaoui et al. Feb 2000 A
6029808 Peck et al. Feb 2000 A
6034043 Fujiwara Mar 2000 A
6074997 Rau et al. Jun 2000 A
D427902 Hayes Jul 2000 S
6106849 Malkan et al. Aug 2000 A
6177391 Zafar Jan 2001 B1
6200949 Reijmer et al. Mar 2001 B1
D441869 Bloor et al. May 2001 S
D442353 Macias May 2001 S
D442739 Friesenhahn May 2001 S
D443389 Friesenhahn Jun 2001 S
D448802 Lariviere, Jr. et al. Oct 2001 S
D449881 Mock, Sr. Oct 2001 S
D450378 Minakuchi et al. Nov 2001 S
6319510 Yates Nov 2001 B1
6335312 Coffindaffer et al. Jan 2002 B1
6365142 Tamura Apr 2002 B1
6382526 Reneker et al. May 2002 B1
6420625 Jones Jul 2002 B1
6440926 Spadoni et al. Aug 2002 B1
D462900 Yamada et al. Sep 2002 S
6448462 Groitzsch Sep 2002 B2
6458754 Velazquez et al. Oct 2002 B1
D465303 Friesenhahn Nov 2002 S
6503521 Atis et al. Jan 2003 B1
6525034 Dalrymple et al. Feb 2003 B2
6552123 Katayama Apr 2003 B1
D479561 Meyer Sep 2003 S
6623694 Ferguson et al. Sep 2003 B1
D484749 Garraway Jan 2004 S
6723160 Mackey et al. Apr 2004 B2
D489162 Dings-plooij May 2004 S
6790814 Marin Sep 2004 B1
6800295 Fox Oct 2004 B2
6802295 Bedwell et al. Oct 2004 B2
6808375 Kloetzer Oct 2004 B2
6825161 Shefer et al. Nov 2004 B2
6831046 Carew et al. Dec 2004 B2
6846784 Engel et al. Jan 2005 B2
6878368 Ohta et al. Apr 2005 B2
6898819 Tanaka et al. May 2005 B2
D509935 Burt Sep 2005 S
6943200 Corrand et al. Sep 2005 B1
6946506 Bond Sep 2005 B2
D515915 Karim Feb 2006 S
7015181 Lambino Mar 2006 B2
7041369 Mackey et al. May 2006 B1
7115551 Hasenoehrl Oct 2006 B2
7169740 Sommerville-roberts Jan 2007 B2
RE39557 Moe Apr 2007 E
7208460 Shefer et al. Apr 2007 B2
7221900 Reade et al. May 2007 B2
D549051 Nordwall Aug 2007 S
7285520 Krzysik Oct 2007 B2
7291300 Chhabra et al. Nov 2007 B2
7387787 Fox Jun 2008 B2
D576753 Mukai Sep 2008 S
D577332 Moore Sep 2008 S
7429273 De Sep 2008 B2
D578881 Friedland Oct 2008 S
D588332 Phelan Mar 2009 S
7507698 Franzolin Mar 2009 B2
7704328 Bailey et al. Apr 2010 B2
7832552 Newman Nov 2010 B2
7846462 Spadini et al. Dec 2010 B2
7892992 Kamada et al. Feb 2011 B2
7901696 Eknoian et al. Mar 2011 B2
D640921 Caldwell Jul 2011 S
D644541 Schrader et al. Sep 2011 S
8049061 Ehrenreich et al. Nov 2011 B2
D651096 Nakagiri Dec 2011 S
8197830 Helfman et al. Jun 2012 B2
8268764 Glenn, Jr. et al. Sep 2012 B2
8273333 Glenn, Jr. et al. Sep 2012 B2
8288332 Fossum et al. Oct 2012 B2
8309505 Fossum et al. Nov 2012 B2
8349232 Pourdeyhimi Jan 2013 B2
8349341 Glenn, Jr. et al. Jan 2013 B2
8349786 Glenn, Jr. et al. Jan 2013 B2
8349787 Glenn, Jr. et al. Jan 2013 B2
8357728 Butler et al. Jan 2013 B2
8367596 Fossum et al. Feb 2013 B2
D680882 Logue Apr 2013 S
8415287 Glenn, Jr. et al. Apr 2013 B2
D682622 Keys May 2013 S
8453653 Mishra et al. Jun 2013 B2
8461090 Glenn, Jr. et al. Jun 2013 B2
8461091 Glenn, Jr. et al. Jun 2013 B2
8466099 Glenn, Jr. et al. Jun 2013 B2
D685436 Menting Jul 2013 S
8476211 Glenn, Jr. et al. Jul 2013 B2
8541081 Ranganathan et al. Sep 2013 B1
8546640 Popovsky et al. Oct 2013 B2
D694621 Mccarthy Dec 2013 S
8723333 Park et al. May 2014 B2
8765170 Glenn, Jr. Jul 2014 B2
8785361 Sivik Jul 2014 B2
D712159 Clerici et al. Sep 2014 S
D712822 Brusaw et al. Sep 2014 S
8962501 Johnson et al. Feb 2015 B2
8980816 Dreher Mar 2015 B2
9005635 Darcy et al. Apr 2015 B2
9062186 Longdon et al. Jun 2015 B2
D739227 Mitchell et al. Sep 2015 S
9125811 Tojo et al. Sep 2015 B2
D740928 Bruining et al. Oct 2015 S
9163205 Sivik et al. Oct 2015 B2
9173826 Schwartz et al. Nov 2015 B2
9175250 Sivik et al. Nov 2015 B2
9198838 Glenn, Jr. Dec 2015 B2
D748240 Goode Jan 2016 S
9421153 Sivik et al. Aug 2016 B2
D769522 Venet Oct 2016 S
D771788 Duckwitz Nov 2016 S
9480628 Sivik et al. Nov 2016 B2
D774086 Montes et al. Dec 2016 S
D775198 Montes et al. Dec 2016 S
9539444 Kinoshita et al. Jan 2017 B2
9545364 Glenn, Jr. et al. Jan 2017 B2
D778026 Roetheli Feb 2017 S
D793025 Slusarczyk et al. Aug 2017 S
D797551 Chatterton Sep 2017 S
D798143 Chatterton Sep 2017 S
D808583 Zietek Jan 2018 S
9902077 Park et al. Feb 2018 B2
D811922 Lefave Mar 2018 S
D811935 Hughes Mar 2018 S
D819836 Noël Jun 2018 S
D848102 Carlson et al. May 2019 S
D850041 Endle May 2019 S
10294586 Sivik et al. May 2019 B2
D851344 Carlson et al. Jun 2019 S
D857156 Hani Aug 2019 S
D857242 Darrow et al. Aug 2019 S
D857929 Darrow et al. Aug 2019 S
D862020 Gorrell et al. Oct 2019 S
D863600 Chao Oct 2019 S
D864507 Stoughton et al. Oct 2019 S
D866105 Carlson et al. Nov 2019 S
D866891 Carlson et al. Nov 2019 S
D866892 Hunt et al. Nov 2019 S
D866893 Hunt et al. Nov 2019 S
D867717 Chavez Nov 2019 S
D868159 Swisher et al. Nov 2019 S
D868953 Mckendree Dec 2019 S
10569286 Anderson et al. Feb 2020 B2
D878694 Carlson et al. Mar 2020 S
10646413 Sivik et al. May 2020 B2
10694917 Dreher et al. Jun 2020 B2
D901115 Carlson et al. Nov 2020 S
D903152 Chao Nov 2020 S
10821056 Swartz et al. Nov 2020 B2
D906802 Chi Jan 2021 S
10894005 Sivik et al. Jan 2021 B2
D910434 Tan et al. Feb 2021 S
D910457 Lee Feb 2021 S
D921166 Meyers Jun 2021 S
D933095 Heiner et al. Oct 2021 S
11351094 Hamersky Jun 2022 B2
11395789 Pratt et al. Jul 2022 B2
11419808 Hilvert Aug 2022 B2
11679066 Song et al. Jun 2023 B2
20010037851 Mortellite Nov 2001 A1
20020044968 Van Apr 2002 A1
20020064510 Dalrymple et al. May 2002 A1
20020077264 Roberts et al. Jun 2002 A1
20020081732 Bowlin et al. Jun 2002 A1
20020081930 Jackson et al. Jun 2002 A1
20020098994 Zafar Jul 2002 A1
20020099109 Dufton et al. Jul 2002 A1
20020161088 Kochvar Oct 2002 A1
20020173213 Chu Nov 2002 A1
20020175449 Chu et al. Nov 2002 A1
20020176827 Rajaiah Nov 2002 A1
20020177621 Hanada et al. Nov 2002 A1
20020187181 Godbey et al. Dec 2002 A1
20030013369 Soane et al. Jan 2003 A1
20030017208 Ignatious Jan 2003 A1
20030018242 Hursh et al. Jan 2003 A1
20030032573 Tanner et al. Feb 2003 A1
20030045441 Hsu et al. Mar 2003 A1
20030054966 Bone et al. Mar 2003 A1
20030069154 Hsu et al. Apr 2003 A1
20030080150 Cowan et al. May 2003 A1
20030099691 Lydzinski et al. May 2003 A1
20030099692 Lydzinski et al. May 2003 A1
20030114332 Ramcharan et al. Jun 2003 A1
20030141662 Kost et al. Jul 2003 A1
20030166489 Van et al. Sep 2003 A1
20030166495 Wang Sep 2003 A1
20030180242 Eccard et al. Sep 2003 A1
20030185872 Kochinke Oct 2003 A1
20030186826 Eccard et al. Oct 2003 A1
20030194416 Shefer Oct 2003 A1
20030199412 Gupta Oct 2003 A1
20030207776 Shefer et al. Nov 2003 A1
20030209166 Vanmaele et al. Nov 2003 A1
20030215522 Johnson et al. Nov 2003 A1
20030224959 Smith Dec 2003 A1
20030232183 Dufton Dec 2003 A1
20040029762 Hensley Feb 2004 A1
20040032859 Miao Feb 2004 A1
20040048759 Ribble et al. Mar 2004 A1
20040048771 Mcdermott Mar 2004 A1
20040053808 Rachse et al. Mar 2004 A1
20040059055 Inada Mar 2004 A1
20040071742 Popplewell Apr 2004 A1
20040071755 Fox Apr 2004 A1
20040082239 Di et al. Apr 2004 A1
20040108615 Foley Jun 2004 A1
20040110656 Casey et al. Jun 2004 A1
20040116018 Fenwick et al. Jun 2004 A1
20040116539 Biercevicz et al. Jun 2004 A1
20040118852 Barmore et al. Jun 2004 A1
20040126585 Kerins et al. Jul 2004 A1
20040170836 Bond Sep 2004 A1
20040175404 Shefer Sep 2004 A1
20040180597 Kamada Sep 2004 A1
20040202632 Gott et al. Oct 2004 A1
20040206270 Vanmaele et al. Oct 2004 A1
20040242097 Hasenoehrl Dec 2004 A1
20040242772 Huth et al. Dec 2004 A1
20040253434 Patel Dec 2004 A1
20040266300 Isele et al. Dec 2004 A1
20050003048 Pearce Jan 2005 A1
20050003991 Macquarrie Jan 2005 A1
20050008776 Chhabra Jan 2005 A1
20050069575 Fox Mar 2005 A1
20050118237 Krzysik et al. Jun 2005 A1
20050136772 Chen et al. Jun 2005 A1
20050136780 Clark et al. Jun 2005 A1
20050137115 Cole et al. Jun 2005 A1
20050137272 Gaserod Jun 2005 A1
20050159730 Kathrani et al. Jul 2005 A1
20050180962 Raz et al. Aug 2005 A1
20050202992 Grandio et al. Sep 2005 A1
20050209574 Boehringer Sep 2005 A1
20050220745 Lu Oct 2005 A1
20050232954 Yoshinari et al. Oct 2005 A1
20050267005 Dasque et al. Dec 2005 A1
20050272836 Yaginuma et al. Dec 2005 A1
20050281757 Ibrahim Dec 2005 A1
20050287106 Legendre Dec 2005 A1
20060002880 Peffly et al. Jan 2006 A1
20060013869 Ignatious Jan 2006 A1
20060052263 Roreger et al. Mar 2006 A1
20060064510 Low et al. Mar 2006 A1
20060078528 Yang et al. Apr 2006 A1
20060078529 Uchida et al. Apr 2006 A1
20060083784 Ignatious Apr 2006 A1
20060128592 Ross Jun 2006 A1
20060134412 Mackey Jun 2006 A1
20060159730 Simon Jul 2006 A1
20060160453 Suh Jul 2006 A1
20060228319 Vona, Jr. et al. Oct 2006 A1
20060274263 Yacktman et al. Dec 2006 A1
20070028939 Mareri et al. Feb 2007 A1
20070054579 Baker, Jr. Mar 2007 A1
20070098749 Eknoian et al. May 2007 A1
20070099813 Luizzi May 2007 A1
20070110792 Simon May 2007 A9
20070135528 Butler et al. Jun 2007 A1
20070149435 Koenig et al. Jun 2007 A1
20070225388 Cooper et al. Sep 2007 A1
20070269651 Denome et al. Nov 2007 A1
20070298064 Koslow Dec 2007 A1
20080008906 Catalfamo Jan 2008 A1
20080019935 Khan Jan 2008 A1
20080035174 Aubrun-sonneville Feb 2008 A1
20080083420 Glenn et al. Apr 2008 A1
20080090939 Netravali et al. Apr 2008 A1
20080131695 Aouad et al. Jun 2008 A1
20080138492 Cingotti Jun 2008 A1
20080149119 Shen Jun 2008 A1
20080152894 Beihoffer et al. Jun 2008 A1
20080153730 Tsaur Jun 2008 A1
20080215023 Scavone et al. Sep 2008 A1
20080269095 Aubrun-sonneville Oct 2008 A1
20080276178 Fadell et al. Nov 2008 A1
20080279905 Kawamoto et al. Nov 2008 A1
20080292669 Deng et al. Nov 2008 A1
20080293839 Stobby Nov 2008 A1
20090004254 Maibach Jan 2009 A1
20090041820 Wu et al. Feb 2009 A1
20090054860 Young et al. Feb 2009 A1
20090061225 Bailey et al. Mar 2009 A1
20090061496 Kuhn Mar 2009 A1
20090061719 Shibutani Mar 2009 A1
20090144913 Yu et al. Jun 2009 A1
20090155326 Mack Jun 2009 A1
20090155383 Kitko et al. Jun 2009 A1
20090181587 Kang Jul 2009 A1
20090197787 Venet et al. Aug 2009 A1
20090232873 Glenn, Jr. et al. Sep 2009 A1
20090249558 Fileccia Oct 2009 A1
20090258099 Brown et al. Oct 2009 A1
20090263342 Glenn, Jr. et al. Oct 2009 A1
20090285718 Privitera Nov 2009 A1
20090291282 Kitamura et al. Nov 2009 A1
20090293281 Bruno Dec 2009 A1
20100018641 Branham Jan 2010 A1
20100021517 Ahlers Jan 2010 A1
20100098745 Staab Apr 2010 A1
20100105821 Verrall Apr 2010 A1
20100135921 Hughes et al. Jun 2010 A1
20100150976 Schnitzler Jun 2010 A1
20100166854 Michniak-kohn Jul 2010 A1
20100167971 Glenn, Jr. et al. Jul 2010 A1
20100173817 Glenn, Jr. et al. Jul 2010 A1
20100179083 Glenn, Jr. et al. Jul 2010 A1
20100196440 Stark Aug 2010 A1
20100266668 Coffee Oct 2010 A1
20100279905 Glenn, Jr. Nov 2010 A1
20100285101 Moore Nov 2010 A1
20100286011 Glenn, Jr. et al. Nov 2010 A1
20100291165 Glenn, Jr. et al. Nov 2010 A1
20100298188 Glenn, Jr. et al. Nov 2010 A1
20110014252 Sagel et al. Jan 2011 A1
20110023240 Fossum Feb 2011 A1
20110027328 Baig et al. Feb 2011 A1
20110028373 Fossum et al. Feb 2011 A1
20110028374 Fossum et al. Feb 2011 A1
20110033509 Simon Feb 2011 A1
20110045041 Golubovic-Liakopoulos et al. Feb 2011 A1
20110123596 Baecker et al. May 2011 A1
20110129510 Liebmann Jun 2011 A1
20110136719 Jalbert Jun 2011 A1
20110159267 Lee Jun 2011 A1
20110165110 Kinoshita et al. Jul 2011 A1
20110182956 Glenn, Jr. et al. Jul 2011 A1
20110189246 Glenn, Jr. et al. Aug 2011 A1
20110189247 Glenn, Jr. Aug 2011 A1
20110195098 Glenn, Jr. et al. Aug 2011 A1
20110223381 Sauter Sep 2011 A1
20110230112 Rose Sep 2011 A1
20110250256 Hyun-oh et al. Oct 2011 A1
20110287687 Kramer et al. Nov 2011 A1
20110301070 Ochomogo Dec 2011 A1
20120021026 Glenn, Jr. Jan 2012 A1
20120027838 Gordon et al. Feb 2012 A1
20120048769 Sivik Mar 2012 A1
20120052036 Glenn, Jr. Mar 2012 A1
20120052037 Sivik et al. Mar 2012 A1
20120053103 Sivik Mar 2012 A1
20120053108 Glenn, Jr. Mar 2012 A1
20120058100 Shastri et al. Mar 2012 A1
20120058166 Glenn, Jr. Mar 2012 A1
20120082037 Wang Apr 2012 A1
20120107534 Wnuk et al. May 2012 A1
20120172831 Darcy Jul 2012 A1
20120215148 Ewert Aug 2012 A1
20120237576 Gordon Sep 2012 A1
20120258902 Parrish et al. Oct 2012 A1
20120270029 Glenn, Jr. et al. Oct 2012 A1
20120288693 Stanley et al. Nov 2012 A1
20120294823 Aramwit Nov 2012 A1
20120321580 Glenn, Jr. Dec 2012 A1
20130052277 Weiss et al. Feb 2013 A1
20130142852 Tojo et al. Jun 2013 A1
20130171421 Weisman Jul 2013 A1
20130230482 Saguchi et al. Sep 2013 A1
20130236520 Popovsky et al. Sep 2013 A1
20130280979 Mckee Oct 2013 A1
20130303419 Glenn, Jr. et al. Nov 2013 A1
20140017402 Kleinwaechter et al. Jan 2014 A1
20140039114 Hagihara et al. Feb 2014 A1
20140105946 Glenn, Jr. et al. Apr 2014 A1
20140127145 Deckner May 2014 A1
20140128345 Woodrow et al. May 2014 A1
20140265007 Bruning et al. Sep 2014 A1
20140271744 Glenn, Jr. et al. Sep 2014 A1
20140271745 Glenn, Jr. et al. Sep 2014 A1
20140329428 Glenn, Jr. Nov 2014 A1
20150044157 Kulkarni et al. Feb 2015 A1
20150071572 Dreher Mar 2015 A1
20150102307 Tajima et al. Apr 2015 A1
20150297494 Mao Oct 2015 A1
20150313803 Lynch et al. Nov 2015 A1
20150313804 Lynch et al. Nov 2015 A1
20150313805 Lynch et al. Nov 2015 A1
20150313806 Lynch et al. Nov 2015 A1
20150313807 Lynch et al. Nov 2015 A1
20150313808 Lynch et al. Nov 2015 A1
20150313809 Lynch et al. Nov 2015 A1
20150315350 Mao et al. Nov 2015 A1
20160008235 Sivik et al. Jan 2016 A1
20160101026 Pratt Apr 2016 A1
20160101204 Lynch Apr 2016 A1
20160143827 Castan Barberan et al. May 2016 A1
20160250109 Dreher et al. Sep 2016 A1
20160324741 Baig Nov 2016 A1
20160367104 Dreher et al. Dec 2016 A1
20170121641 Smith May 2017 A1
20170335080 Mao et al. Nov 2017 A1
20180015643 Patel et al. Jan 2018 A1
20180104177 Constantine et al. Apr 2018 A1
20180110710 Zhao et al. Apr 2018 A1
20180140469 Kane et al. May 2018 A1
20180163325 Glenn, Jr. et al. Jun 2018 A1
20180258555 Glenn, Jr. Sep 2018 A1
20180311135 Chang et al. Nov 2018 A1
20180333339 Hamersky Nov 2018 A1
20180334644 Hamersky et al. Nov 2018 A1
20190015875 Gardner, Jr. et al. Jan 2019 A1
20190105243 Song et al. Apr 2019 A1
20190282457 Pratt Sep 2019 A1
20190282461 Glassmeyer Sep 2019 A1
20190350819 Hamersky Nov 2019 A1
20200071851 Glenn, Jr. et al. Mar 2020 A1
20200093710 Hamersky Mar 2020 A1
20200214946 Chan et al. Jul 2020 A1
20200261326 Sivik et al. Aug 2020 A1
20200275818 Gamble Sep 2020 A1
20200308360 Mao et al. Oct 2020 A1
20200405587 Song Dec 2020 A1
20210000733 Hilvert Jan 2021 A1
20210094744 Benson et al. Apr 2021 A1
20210107263 Bartolucci et al. Apr 2021 A1
20210121373 Tan et al. Apr 2021 A1
20210128417 Sivik et al. May 2021 A1
20210137798 Sivik et al. May 2021 A1
20210147763 Tan et al. May 2021 A1
20210189602 Glenn, Jr. et al. Jun 2021 A1
20210322290 Lynch et al. Oct 2021 A1
20210401677 Song Dec 2021 A1
20220054365 Xu et al. Feb 2022 A1
20220323309 Pratt et al. Oct 2022 A1
20230190588 Song Jun 2023 A1
Foreign Referenced Citations (169)
Number Date Country
2004202461 Nov 2007 AU
2300638 Aug 2000 CA
2524099 Apr 2006 CA
2695068 Sep 2010 CA
166297 May 2018 CA
169627 May 2018 CA
1138091 Dec 1996 CN
1219388 Jun 1999 CN
1268558 Oct 2000 CN
1357613 Jul 2002 CN
1454231 Nov 2003 CN
1473194 Feb 2004 CN
1530431 Sep 2004 CN
1583991 Feb 2005 CN
1726074 Jan 2006 CN
3648760 May 2007 CN
101161877 Apr 2008 CN
101424009 May 2009 CN
102006852 Apr 2011 CN
301666535 Sep 2011 CN
102647973 Aug 2012 CN
103282015 Sep 2013 CN
103735428 Apr 2014 CN
104040061 Sep 2014 CN
304115833 Apr 2017 CN
106726634 May 2017 CN
106728634 May 2017 CN
106916659 Jul 2017 CN
304537587 Mar 2018 CN
109589279 Mar 2020 CN
19607851 Sep 1997 DE
10331767 Feb 2005 DE
100932 Apr 2018 DE
100938 Apr 2018 DE
101063 May 2018 DE
101100 May 2018 DE
101101 May 2018 DE
0392608 Oct 1990 EP
609808 Aug 1994 EP
0858828 Aug 1998 EP
0948960 Oct 1999 EP
1214879 Jun 2002 EP
1227152 Jul 2002 EP
1217987 Dec 2004 EP
1574561 Sep 2005 EP
1160311 Mar 2006 EP
1887036 Feb 2008 EP
1958532 Aug 2008 EP
2085434 Aug 2009 EP
1317916 Oct 2010 EP
2246031 Nov 2010 EP
2871685 Dec 2005 FR
2886845 Dec 2006 FR
2107579 May 1983 GB
2235204 Feb 1991 GB
2355008 Apr 2001 GB
2378407 Feb 2003 GB
20150354411 May 2017 IN
S4912158 Feb 1974 JP
58021608 Feb 1983 JP
S58216109 Dec 1983 JP
S59163458 Sep 1984 JP
S6272609 Apr 1987 JP
S6272610 Apr 1987 JP
S6281432 Apr 1987 JP
S6281462 Apr 1987 JP
S6346251 Feb 1988 JP
S63156715 Jun 1988 JP
H01172319 Jul 1989 JP
H01229805 Sep 1989 JP
H01313418 Dec 1989 JP
H0275650 Mar 1990 JP
H05344873 Dec 1993 JP
H0617083 Jan 1994 JP
0753349 Feb 1995 JP
H0789852 Apr 1995 JP
H07173724 Jul 1995 JP
H08325133 Dec 1996 JP
H09216909 Aug 1997 JP
10158700 Jun 1998 JP
H10251371 Sep 1998 JP
H10251952 Sep 1998 JP
H11513053 Nov 1999 JP
2000053998 Feb 2000 JP
2000169896 Jun 2000 JP
2000212828 Aug 2000 JP
2000229841 Aug 2000 JP
2001302868 Oct 2001 JP
2001519376 Oct 2001 JP
2001520983 Nov 2001 JP
2002201531 Jul 2002 JP
2002226895 Aug 2002 JP
2003073700 Mar 2003 JP
2003082397 Mar 2003 JP
2004509198 Mar 2004 JP
2004256799 Sep 2004 JP
2004533551 Nov 2004 JP
2004345983 Dec 2004 JP
2005171063 Jun 2005 JP
2005538202 Dec 2005 JP
2006002337 Jan 2006 JP
2006056835 Mar 2006 JP
3828217 Jul 2006 JP
2007001889 Jan 2007 JP
2007091954 Apr 2007 JP
2007197365 Aug 2007 JP
2007197540 Aug 2007 JP
2007528748 Oct 2007 JP
4128580 May 2008 JP
2008156807 Jul 2008 JP
2008525436 Jul 2008 JP
2009079329 Apr 2009 JP
2009533569 Sep 2009 JP
4510221 May 2010 JP
2010100966 May 2010 JP
2010126856 Jun 2010 JP
2013505375 Feb 2013 JP
2013099467 May 2013 JP
5344873 Aug 2013 JP
2013531145 Aug 2013 JP
2013531748 Aug 2013 JP
2015509147 Mar 2015 JP
5821609 Oct 2015 JP
6272610 Jan 2018 JP
20020003442 Jan 2002 KR
20040094520 Nov 2004 KR
232027 Oct 1994 TW
8301943 Jun 1983 WO
9514495 Jun 1995 WO
9918182 Apr 1999 WO
9951715 Oct 1999 WO
9957155 Nov 1999 WO
0042992 Jul 2000 WO
0107194 Feb 2001 WO
0119948 Mar 2001 WO
0125322 Apr 2001 WO
0125393 Apr 2001 WO
200125322 Apr 2001 WO
2001024770 Apr 2001 WO
200154667 Aug 2001 WO
2001054667 Aug 2001 WO
0183657 Nov 2001 WO
0238722 May 2002 WO
2004032859 Apr 2004 WO
2004041991 May 2004 WO
2005003423 Jan 2005 WO
2005070374 Aug 2005 WO
2005075547 Aug 2005 WO
2006106514 Oct 2006 WO
2006130647 Dec 2006 WO
2007022229 Feb 2007 WO
2007033598 Mar 2007 WO
2007093558 Aug 2007 WO
2007093619 Aug 2007 WO
2007102119 Sep 2007 WO
2008015641 Feb 2008 WO
2008049242 May 2008 WO
2008104954 Sep 2008 WO
2009019571 Feb 2009 WO
2009095891 Aug 2009 WO
2010006708 Jan 2010 WO
2010077627 Jul 2010 WO
2010085569 Jul 2010 WO
2012120199 Sep 2012 WO
2014158472 Oct 2014 WO
2015034975 Mar 2015 WO
2015153185 Oct 2015 WO
2019001940 Jan 2019 WO
2020192519 Oct 2020 WO
Non-Patent Literature Citations (103)
Entry
Afifi-Effat et al., Polymer Letters, 9: 651-655 (1971).
All Office Actions; U.S. Appl. No. 13/173,639, filed Jun. 30, 2011.
All Office Actions; U.S. Appl. No. 13/229,825, filed Sep. 12, 2011.
All Office Actions; U.S. Appl. No. 14/334,862, filed Jul. 18, 2014.
All Office Actions; U.S. Appl. No. 15/170,125, filed Jun. 1, 2016.
All Office Actions; U.S. Appl. No. 15/374,486, filed Dec. 9, 2016.
All Office Actions; U.S. Appl. No. 15/978,503, filed May 14, 2018.
All Office Actions; U.S. Appl. No. 16/674,837, filed Nov. 5, 2019.
All Office Actions; U.S. Appl. No. 17/184,712, filed Feb. 25, 2021.
Ashland, Klucel hydroxypropylcelllose, accessed at http://www.ashland.com/Ashland/Static/Documents/ASI/PC_11229_Klucel_HPC.pdf on Apr. 20, 2016.
Francis Ignatious, Linghong Sun, Chao-Pin Lee, and John Baldoni. Electrospun Nanofibers in Oral Drug Delivery—ExpertReview. Pharmaceutical Research, vol. 27, No. 4, Apr. 2010, pp. 576-588. Published online Feb. 9, 2010.
Gemz Hair Care. Perfect Pairs. Publication date unavailable. Visited Jan. 26, 2022. https://shopgemz.com/collections/perfect-pairs (Year: 0).
Makadia, et al., “Poly Lactic-co-Glycolic Acid (PLGA) as Biodegradable ControlledDrug Delivery Carrier”, Polymers, 3, pp. 1377-1397 (2011).
Menard et al., “Gnotobiotic Mouse Immune Response Induced by Bifidobacterium sp. Strains Isolated from Infants”, Applied and Environmental Microbiology, vol. 74, Issue 3, Feb. 1, 2008, pp. 660-666.
Minifibers, Inc., accessed on line at http://www.minifibers.com/documents/Choosing-the-Proper-Short-Cut-Fiber.pdf Oct. 3, 2016.
Overview of pharmaceutical excipients used in tablets and capsules in Drug Topics, dated Oct. 24, 2008. Downloaded Sep. 20, 2016 from http://drugtopics.modernmedicine.com/drugtopics/news/modernmedicine/ modernmedicinenews/overviewpharmaceuticalexcipientsusedtablets.
Smith, et al., “Nanofibrous Scaffolds and Their Biological Effects”, Nanotechnologiesfor the Life Sciences, vol. 9, pp. 188-215 (2006).
W S Ratnayake and D S Jackson. Gelatinization and solubility of corn starch during heating in excess water. Faculty u Publications in Food Science and Technology, Jan. 1, 2006. Also published in Journal of Agricultural and Food Chemistry 54:1 O(2006), pp. 3712-3716.
Yasuhiro Hiramatsu et al. “Bifidobacterium Components Have Immunomodulatory Characteristics Dependent on the Method of Preparation” Cytotechnology, Kluwer Academic Publishers, Do, vol. 55, Issue No. 2-3, Nov. 1, 2007, p. 79-87.
“Green Chemistry”, Huazhong University of Science and Technology Press, published on Jun. 30, 2008, pp. 6.
Adhesives Research (Pennsylvania, http://12.4.33.51/news/apresmed.htm).
All final and non-final office actions for U.S. Appl. No. 29/728,688 (P&G Case D-02862).
All Office Actions; U.S. Appl. No. 14/690,593, filed Apr. 20, 2015.
All Office Actions; U.S. Appl. No. 15/665,886, filed Aug. 1, 2017.
All Office Actions; U.S. Appl. No. 15/979,961, filed May 15, 2018.
All Office Actions; U.S. Appl. No. 15/981,096, filed May 16, 2018.
All Office Actions; U.S. Appl. No. 16/431,028, filed Jun. 4, 2019.
All Office Actions; U.S. Appl. No. 16/431,115, filed Jun. 4, 2019.
All Office Actions; U.S. Appl. No. 16/577,120, filed Sep. 20, 2019.
All Office Actions; U.S. Appl. No. 16/589,504, filed Oct. 1, 2019.
All Office Actions; U.S. Appl. No. 16/901,548, filed Jun. 15, 2020.
All Office Actions; U.S. Appl. No. 16/912,876, filed Jun. 26, 2020.
All Office Actions; U.S. Appl. No. 16/918,292, filed Jul. 1, 2020.
All Office Actions; U.S. Appl. No. 16/953,975, filed Nov. 20, 2020.
All Office Actions; U.S. Appl. No. 17/070,205, filed Oct. 14, 2020.
All Office Actions; U.S. Appl. No. 17/357,119, filed Jun. 24, 2021.
All Office Actions; U.S. Appl. No. 29/672,822, filed Dec. 10, 2018.
All Office Actions; U.S. Appl. No. 29/676,338, filed Jan. 10, 2019.
All Office Actions; U.S. Appl. No. 29/707,807, filed Oct. 1, 2019.
All Office Actions; U.S. Appl. No. 29/707,809, filed Oct. 1, 2019.
All Office Actions; U.S. Appl. No. 29/728,687, filed Mar. 20, 2020.
All Office Actions; U.S. Appl. No. 29/766,885, filed Jan. 19, 2021.
All Office Actions; U.S. Appl. No. 29/815,500, filed Nov. 15, 2021.
All Office Actions; U.S. Appl. No. 29/819,499, filed Dec. 15, 2021.
Amerilab Technologies, Inc. (Minnesota, http://www.amerilabtech.comm/).
Anonymous “P8136 Poly(vinyl alcohol)” Internet article, [Online] XP002538935, Retrieved from the Internet: URL:hllp/20 NWW.sigmaaldrich.com/catalog/ProductDetail.do?D7=0%N25-SEARCH_ CONCAT PNOIBRAND KEY%N4=P8136%7SCIAL%N25=0%QS=ON%F=SPEC retrieved on Jul. 28, 2009, year 2009, 1 pg.
Briscoe et al. “The effects of hydrogen bonding upon the viscosity of aqueous poly( vinyl alcohol) solutions,” from Polymer, 41 (2000), pp. 3851-3860.
Cardinal Health (Dublin, Ohio, http://spd.cardinal.com/).
Cima Labs, Inc. (Minnesota, http://www.cimalabs.com/).
Color Keeper [online], [site visited Oct. 18, 2021]. Available from internet, URL: https://shopgemz.com/products/color-keeper?variant=13094595002434&utm_source=google&utm_medium=cpc&utm_campaign=Shopping&gclid=Cj0KCQjw5JSLBhCxARIsAHgO2SdAT7LTehpyxM1qTGtnFETDalNuo9_cQSOpPwCmsmmdGA1YOUSekQEaAh0iEALw_wcB (Year: 2021).
Definition of Derivative by Merriam Webster Online Dictionary, Year, 2021.
Design of “Detergent tablets” (Design Registration No. 000634142-0003), (No. of Publicly known information: HH18274488), Registered Community Designs Bulletin, published by EUIPO on Jan. 9, 2007, 4 pgs.
Design of “Detergent tablets” (Design Registration No. 000634142-0004), (No. of Publicly known information: HH18274489), Registered Community Designs Bulletin, published by EUIPO on Jan. 9, 2007, 4 pgs.
Design of “Soaps” accepted on Jul. 11, 1986, Publishing Office: Korean Intellectual Property Office (KIPO), Document Name: Design Gazette (Application No. 3019850005996), Publication Date: Jun. 9, 1986, (No. of Publicly known information: HG21900612), 3 pgs.
Dissolving Soap Strips (Ranir LLC, Michigan, www.ranir.com).
Dow, UCARE™ Polymer LR-400, Technical Data Sheet, Downloaded in Mar. 2022, 4 pages.
Encyclopedia of Polymer Science and Engineering, vol. 15, 2nd ed., p. 204 308 Silicones, year 1989.
Final Office Action; U.S. Appl. No. 14/690,593 dated Aug. 17, 2017.
Final Office Action; U.S. Appl. No. 14/690,593 dated Jul. 21, 2016.
Final Office Action; U.S. Appl. No. 15/665,886 dated Dec. 28, 2107.
Guerrini et al. “Thermal and Structural Characterization of Nanofibers of Poly( vinyl alcohol) Produced by Electrospinning”, Journal of Applied Polymer Science, vol. 112, Feb. 9, 2009, pp. 1680-1687.
Hexagon 4 ward soap mold, Soap, Cosmetics, NEW Silicon mold, Published on Sep. 29, 2016, Retrieved from Internet : http://candle-box.com/product/%EC%9C%A1%EA%B0%81-4%EA%B5%AC-%EB%B9%84%EB%88%84%EB%AA%B0 %EB%93%9C/2206/?page_4=3#none, dated Sep. 10, 2019, 16 pgs.
Hildebrand, T., et al. “Quantification of bone microarchitecture with the structure mode index”, Computer Methods in Biomechanics and Biomedical Engineering, vol. 1, Jan. 14, 1997, pp. 15-23.
How Gemz work?, Gemz Hair Care, published on Oct. 1, 2018, retrieved on Apr. 27, 2021, retrieved from the Internet URL: https:// www.youtube.com/watch?v=ts1waYk43g4, 3 pgs.
Japanese Paper Soap (http://www.wishingfish.com/papersoap.html).
Karen Duis et al, “Environmental fate and effects of water-soluble synthetic organic polymers used in cosmetic products”, Environmental Sciences Europe, vol. 33, Article No. 21, Feb. 16, 2021, 78 pages.
Kuraray: “Mowiol—Technical data sheet”, Jun. 1, 2010 (Jun. 1, 2010),pp. 1-4, XP055119891, Retrieved from the Internet: URL:http://www.kuraray.eu/fileadmin/Downloads/mowiol/TDS_Mowiol_en_20110624.pdf [retrieved on May 23, 2014].
Le Laboratoire du Bain (France, http://www.laboudubain.com/).
M.K. Industries (Gujarat India, http://www.soapstrips.com).
Megulars Car Wash Strips: Megulars Inc. California, http://www.automotivedigesl.com/view_art.asp?articles!D=12414.
Michelle Villett, Why You Need a Sulfate-Free Shampoo, The Skincare Edit, updated date: Jan. 25, 2019, Original publication date: Feb. 22, 2016 (Year: 2016), 7 pages. Mar. 23, 2021.
MOVA Pharmaceutical and Kosmos (USA, http:/lwww.icon-pr.com/news/news/prinl.cfm?inv_id=256-1).
Ni Genshan et al. “Drug Classification and Pharmacology Summary”, PLA Press, published on Apr. 30, 1988, pp. 3.
Non-Final Office Action; U.S. Appl. No. 17/070,205 dated Nov. 23, 2021.
Non-Final Office Action; U.S. Appl. No. 16/901,548 dated Aug. 3, 2021.
Non Final Office Action; U.S. Appl. No. 14/690,593 dated Mar. 1, 2016.
Non Final Office Action; U.S. Appl. No. 14/690,593 dated Nov. 22, 2016.
Non Final Office Action; U.S. Appl. No. 15/665,886 dated Sep. 1, 2107.
Notice of Allowance; U.S. Appl. No. 15/665,886 dated Jun. 10, 2020.
Notice of Allowance; U.S. Appl. No. 16/901,548 dated Jan. 6, 2022.
Okasaka et al., “Evaluation Of Anionic Surfactants Effects On The Skin Barrier Function Based On Skin Permeability”, Pharmaceutical Development and Technology, vol. 24, No. 1, Jan. 23, 2018, pp. 99-104.
Paper Pieces Hexagons, announced 2018 [online], [site visited Oct. 14, 2021]. Available from internet, URL:https://www.amazon.com/Paper-Pieces-HEX100B-Hexagons-1200pc/dp/B07DVYV2HN/(Year: 2018).
PCT International Search Report and Written Opinion for PCT/US2018/030762 dated Aug. 7, 2018.
Product Review: Gemz Solid Shampoo, Travel As Much, published on Mar. 19, 2019, retrieved on Apr. 27, 2021, retrieved from the Internet URL: https://travelasmuch.com/gemz-solid-shampoo-review/, 14 pgs.
Pure Soap Leafz: (Soap UNLTD. Netherlands, http://www.upandunder.com.uk/eshop/catalogue/testbs.asp?Manufacturer_ID=252&Activity_ID=33&Description_ID=157).
Raymond C Rowe et al., Polyvinyl Alcohol, Handbook of Pharmaceutical Excipients, 2009, Sixth Edition, Pharmaceutical Press, 564-565.
Retrieved from: https ://www.craftcuts.com/hexagon-craft-shape. html Hexagon wood cutouts, www.craftcuts.com, 1 page, reviewed as early as May 2018 (Year: 2018), 16 pgs.
Rounded hexagon shape, announced 2016 [online], [site visited Oct. 20, 2021], Available from internet, URL:https://www.vexels.com/png-svg/preview/139199/rounded-hexagon-shape (Year: 2016).
Sahin et al. “A Study on Physical and Chemical Properties of Cellulose Paper Immersed in Various Solvent Mixtures” International Journal Of Molecular Sciences, Jan. 2008; 9(1): 78-88.
Sanipro Sanitary Products (Italy, http://www.sanipro.iit).
Solublon (Toyohashi Japan, http://www.solublon.com).
SPI Pharma (Delaware, http://www.spipharma.com).
Travelers Passport Paper Soap Sheets (http://www.weddingflavornow.com/index.asp?PageAction=VIEWPROD&PROD&ProdID=510).
Vaughan, C.D. “Solubility, Effects in Product, Package, Penetration and Preservation”, Cosmetics and Toiletries, vol. 103, Oct. 1988, 24 pgs.
Vesterby, A.: “Star Volume in Bone Research: A Histomorphometric Analysis Of Trabecular Bone Structure Using Vertical Sections”, Anal Rec: Feb. 1993, 232(2), pp. 325-334.
Wenda (China, http://www.wenda.com).
Wermuth et al. Drug Discovery, “Drug Discovery Today, 2006”, vol. 11 7/8, 348-354, Year 2006.
Zhang et al. “Study on Morphology of Electrospun Poly( vinyl alcohol) Mats,” European Polymer Journal 41 (2005), pp. 423-432.
Hiroshi Yagi & 4 Others, Research Study of a Friction Protector for Preventing a Tow Line From Breaking, Working Papers for Fiscal 2006 | Japan | Japan Coast Guard Dec. 2007, pp. 1-8.
Latorre Carmen, Nanotribological Effects of Hair Careproducts and Environment on Human Hair Using Atomic Forcemicroscopy,Journal of Vacuum Science and Technology: Part A, U.S.A, AVS/AIP , Jun. 28, 2005 , V2 3 N 4, p. 1034-1045.
Pattama Taepaiboon, et al., “Effect of Cross-linking on Properties and Release Characteristics of Sodium Salicylate-loaded Electrospun Poly(Vinyl Alcohol) Fibre Mats”, Nanotechnology, vol. 18, No. 17, Apr. 2, 2007.
Wikipedia “Polyvinyl alcohol,” last modified Mar. 30, 2017; https://en.wikipedia.org/wiki/Polyvinyl_alcohol.
“Prill”, wikipedia, https://en.wikipedia.org/wiki/Prill, No Known date, 1 Page.
Related Publications (1)
Number Date Country
20220257476 A1 Aug 2022 US
Provisional Applications (1)
Number Date Country
62506777 May 2017 US
Continuations (1)
Number Date Country
Parent 15979961 May 2018 US
Child 17730390 US