Polyvinyl alcohol composition with eutectic solvent, articles thereof and methods of making the same

Abstract

The present invention relates to a water-soluble film comprising a polyvinyl alcohol polymer (PVOH) and one or more predetermined ratios of a eutectic solvent pair (eutectic solvent).

Description

Technical Field

[0001] This disclosure relates throughout to water-soluble compositions comprising polyvinyl alcohol (PVOH) and a eutectic solvent, and to compositions suitable for contact with liquids, solids, or combinations thereof. This disclosure further relates to methods for preparing articles. Background Technology

[0002] Water-soluble polymer articles formed from polyvinyl alcohol (PVOH), such as containers, granules, and films, are commonly used as packaging materials to simplify the dispersion, pouring, dissolution, and metering of materials to be delivered. Articles may contain or encapsulate active substances released when the article dissolves in water. For example, pouches made from water-soluble films are commonly used to package household care compositions, such as sachets containing laundry detergent or dishwashing liquid.

[0003] Films formed from polyvinyl alcohol (PVOH) have attracted increasing attention due to their high transparency, barrier properties, and non-toxic and environmentally friendly characteristics. Compared to most other polymer films with barrier properties, PVOH offers better flexibility, transparency, toughness, and lower cost, thus it has been used as a barrier film for consumer products. However, strong intermolecular and intramolecular hydrogen bonds exist between the polar hydroxyl groups on the PVOH backbone, resulting in poor flowability of the resulting material. PVOH's high structural regularity and crystallinity lead to a high melting point close to or above its decomposition temperature, making melt processing difficult. Currently, the main method used to prepare PVOH films is solution casting, which results in high costs, complex technology, and inconsistent product quality.

[0004] Modified PVOH compositions are needed to improve melt processing by altering flowability and lowering melting point. This method mainly consists of: (1) blending with other polymers; (2) copolymerization modification; (3) incorporation of post-reactive structural units to reduce structural regularity and improve thermal stability; and (4) addition of low molecular weight plasticizers.

[0005] The selection of plasticizers for a particular system is typically based on the plasticizer's compatibility and durability in the polymer matrix, the amount required for plasticization, and the desired physical properties of the composition. The use of plasticizers has been shown to be quite limited, particularly in film formation, because they generally do not lower the melting temperature of PVOH sufficiently to allow the addition of volatile and temperature-sensitive compounds, such as bittering agents and flavorings. Furthermore, the amount of plasticizer must be strictly controlled, as it can cause articles formed from the composition to become brittle, difficult to process, or prone to breakage; and at higher plasticizer contents, articles may become too soft, fragile, or difficult to process for the desired application.

[0006] What is needed is a product forming aid that lowers the melt temperature of PVOH to allow for melt processing of the product, and optionally includes volatile and temperature-sensitive active substances. Summary of the Invention

[0007] The present invention provides a water-soluble composition comprising a polyvinyl alcohol (PVOH) polymer and a eutectic solvent.

[0008] A method for manufacturing 3D articles is provided, the method comprising the steps of: heating a composition comprising a polyvinyl alcohol (PVOH) polymer and a eutectic solvent to a temperature of about 80°C to about 170°C, and applying pressure to the composition to make it flow.

[0009] A method for preparing a water-soluble membrane is provided, the method comprising providing a polyvinyl alcohol (PVOH) polymer; providing a eutectic solvent; and forming a water-soluble membrane comprising the eutectic solvent and the PVOH polymer. Attached Figure Description

[0010] Although the specification concludes with claims that specifically point out and clearly claim protection for the subject matter of this disclosure, it is believed that this disclosure will be more fully understood through the following description in conjunction with the accompanying drawings. Some of these figures may have been simplified by omitting selected elements for clarity of illustration. Such omissions of elements in some figures do not necessarily indicate the presence or absence of a particular element in any exemplary embodiment unless it is clearly described in the corresponding textual description. The drawings are not to scale.

[0011] Figure 1 This is a side sectional view of the small bag. Detailed Implementation

[0012] This document discloses water-soluble compositions and articles thereof, including films comprising a polyvinyl alcohol polymer (PVOH) and one or more eutectic solvent pairs (eutectic solvents) in a predetermined ratio, such as choline chloride / malic acid, lactic acid / betaine, maleic acid / choline chloride, levulinic acid / choline chloride, lactic acid / propylene glycol, L-arginine / levulinic acid, or trehalose / choline chloride, and delivery pouches formed from or otherwise comprising the film. The eutectic solvent lowers the melt temperature of PVOH more than other typical plasticizers; allows for better extrusion film forming because the plasticizer is less volatile than previously known plasticizers; allows for the addition of volatile and temperature-sensitive compounds, such as bittering agents and flavorings, during extrusion; and lowers the PVOH melt temperature (Tm) while maintaining sufficient physical properties of the film when the film is extruded or solution cast, thereby allowing for further processing advantages, such as improved thermoforming seals with a lower tendency to break.

[0013] As used herein, the articles “a” and “an” when used in a claim are to be understood to refer to one or more things protected or described by the claims. As used herein, the terms “comprising,” “including,” and “containing” are intended to be non-limiting. The compositions of this disclosure may comprise, consist substantially of, or be composed of the components of this disclosure.

[0014] This document may use the term "substantially free of" (or "substantially free from"). This means that the referred material is present in very small amounts, not intentionally added to the composition to form a portion of the composition, or preferably not at analytically detectable levels. It also means that the referred material is present in a composition only as an impurity among other intentionally added materials. If present, the referred material may be present at levels of less than 1%, less than 0.1%, less than 0.01%, or even 0% by weight of the composition.

[0015] Articles of this disclosure formed from water-soluble compositions may contain or encapsulate compositions, such as household care compositions. Compositions may be selected from liquids, solids, or combinations thereof. As used herein, “liquid” includes free-flowing liquids as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light and heavy-duty liquid detergent compositions, fabric strengtheners, detergent gels commonly used in laundry, bleach, and laundry detergent additives. Gases (e.g., suspended bubbles) or solids (e.g., particles) may be contained in the liquid. As used herein, “solid” includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include: granules, microcapsules, beads, strips, and pearlescent microspheres. Solid compositions may provide technically beneficial effects, including but not limited to effects throughout the washing process, pretreatment effects, and / or aesthetic effects.

[0016] As used herein, the term "homogeneous polymer" generally includes polymers having a single type of repeating monomer unit (e.g., polymer chains consisting of or substantially consisting of a single repeating monomer unit). In the specific case of PVOH, the term "homogeneous polymer" (or "PVOH homopolymer" or "PVOH polymer") also includes copolymers having a distribution of vinyl alcohol monomer units and vinyl acetate monomer units, depending on the degree of hydrolysis (e.g., polymer chains consisting of or substantially consisting of vinyl alcohol and vinyl acetate monomer units). In a limiting example of 100% hydrolysis, PVOH homopolymers may include true homopolymers having only vinyl alcohol units.

[0017] As used herein, the term "copolymer" generally includes polymers having two or more types of repeating monomer units (e.g., polymer chains consisting of or substantially consisting of two or more different repeating monomer units, whether they are random copolymers, block copolymers, etc.). In the specific case of PVOH, the term "copolymer" (or "PVOH copolymer") also includes copolymers having a distribution of vinyl alcohol monomer units and vinyl acetate monomer units (depending on the degree of hydrolysis), and at least one other type of repeating monomer unit (e.g., ternary (or longer) polymer chains consisting of or substantially consisting of vinyl alcohol monomer units, vinyl acetate monomer units, and one or more other monomer units (e.g., anionic monomer units). In a limiting example of 100% hydrolysis, a PVOH copolymer may include a copolymer having vinyl alcohol units and one or more other monomer units, but no vinyl acetate units.

[0018] Unless otherwise specified, all temperatures in this document are in degrees Celsius (°C). Unless otherwise specified, all measurements in this document were taken at 20°C and atmospheric pressure.

[0019] In this disclosure, unless otherwise specified, all percentages are by weight of the total composition. Unless otherwise specified, all ratios are by weight.

[0020] Unless otherwise specified, all component or composition levels refer to the active portion of the component or composition and do not include impurities, such as residual solvents or byproducts, that may be present in commercially available sources of such components or compositions.

[0021] It should be understood that each maximum numerical limit given in this specification includes each lower numerical limit, as such lower numerical limits are explicitly stated herein. Each minimum numerical limit given in this specification will include each higher numerical limit, as such higher numerical limits are explicitly stated herein. Each numerical range given in this specification will include each narrower numerical range falling within such a wider numerical range, as all such narrower numerical ranges are explicitly stated herein.

[0022] Polyvinyl alcohol polymer

[0023] The water-soluble composition comprises at least one polyvinyl alcohol (PVOH) polymer, which may include homopolymers thereof (e.g., substantially containing only ethylene alcohol and vinyl acetate monomer units, if present) and copolymers thereof (e.g., containing one or more other monomer units in addition to ethylene alcohol and optional vinyl acetate units). PVOH is a synthetic resin generally obtained by alcoholysis, commonly referred to as the hydrolysis or saponification of polyvinyl acetate. One or more PVOH polymers may be selected as taught herein or blended with a eutectic solvent to form articles soluble in aqueous solutions, such as films. Such water-soluble films may be used, for example, to form resealable pouches for delayed release of cleaning active substances or rinsing additives, such as those found in laundry detergent compositions.

[0024] Completely hydrolyzed PVOH, in which almost all acetate groups have been converted to alcohol groups, is a highly crystalline polymer with strong hydrogen bonds and is soluble only in hot water—above about 140℉ (60°C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, it is known that subsequent PVOH polymers are partially hydrolyzed, with weaker hydrogen bonds and lower crystallinity, and are soluble in cold water—below about 50℉ (10°C). Moderately cold or hot water soluble compositions may contain, for example, moderately partially hydrolyzed PVOH (e.g., with a degree of hydrolysis of about 94% to about 98%), and are readily soluble only in warm water—e.g., rapidly dissolving at temperatures of about 40°C and higher. While the partially hydrolyzed type may be referred to as a vinyl alcohol-vinyl acetate copolymer, both completely and partially hydrolyzed PVOH types are generally referred to as PVOH homopolymers.

[0025] The degree of hydrolysis (DH) of the PVOH polymer included in the water-soluble compositions of this disclosure can range from about 75% to about 99% (e.g., about 79% to about 92%, about 86.5% to about 89%, or about 88%, such as cold water-soluble compositions; about 90% to about 99%, about 92% to about 99%, or about 95% to about 99%). As the degree of hydrolysis decreases, the film made from the resin will have reduced mechanical strength, but will dissolve more rapidly at temperatures below about 20°C. As the degree of hydrolysis increases, the film made from the polymer will tend to have greater mechanical strength, and thermoforming and / or dissolution will tend to decrease, especially at cooler washing temperatures.

[0026] The degree of hydrolysis of PVOH can be selected, making the water solubility of the polymer temperature-dependent. Therefore, the solubility of the membrane made from the polymer, any compatibilizer polymers, and additional components are also affected. The membrane can be cold-water soluble. Cold-water soluble membranes are soluble in water at temperatures below 10°C and may contain PVOH with a degree of hydrolysis in the range of about 75% to about 90%, or about 80% to about 90%, or about 85% to about 90%. The membrane can also be hot-water soluble. Hot-water soluble membranes are soluble in water at temperatures of at least about 60°C and may contain PVOH with a degree of hydrolysis of at least about 98%.

[0027] The water-soluble polymer (e.g., a PVOH resin blend, alone or in combination with other water-soluble polymers) may be included in the composition in an amount ranging from about 50% by weight, or about 60% by weight, or about 70% by weight, or about 75% by weight, and / or about 80% by weight, or about 85% by weight, or about 90% by weight, or about 95% by weight. For example, the PVOH resin blend may be present in the water-soluble film in an amount ranging from about 50% by weight, or about 65% by weight, or about 70% by weight, or about 75% by weight, and / or about 80% by weight, or about 85% by weight, or about 90% by weight, or about 95% by weight, based on the weight of the composition.

[0028] The water-soluble composition may contain at least about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% by weight and / or at most about 60%, 70%, 80%, 90%, 95%, or 99% by weight of a PVOH polymer or a PVOH polymer blend. Preferably, the polymer blend is present in the composition at about 75% to about 99%, more preferably about 70% to about 95%.

[0029] As detailed below, PVOH polymers are characterized by their viscosity (a value typically associated with the polymer's molecular weight). The viscosity of the polymer is determined by measuring freshly prepared solutions using a Brookfield LV viscometer with a UL adapter, as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield Test Method. Describing the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20°C is international practice. Unless otherwise specified, polymer viscosities in centipoises (cP) listed herein should be understood as referring to the viscosity of a 4% aqueous solution of the water-soluble polymer at 20°C.

[0030] The PVOH polymer is characterized by a 4% solution viscosity (μ) of about 10 cP to about 40 cP, or about 10 cP to about 30 cP, or about 12 cP to about 25 cP, or 14 cP to 20 cP at 20°C. The viscosity μ can be in the range of about 4 cP to about 24 cP (e.g., at least about 4 cP, 8 cP, 10 or 12 cP and / or at most about 12 cP, 16 cP, 20 cP or 24 cP, such as about 10 cP to about 16 cP or about 10 cP to about 20 cP).

[0031] As is well known in the art, the viscosity of PVOH polymers and copolymers is related to the weight-average molecular weight (Mw) of the same PVOH polymer, and viscosity is typically used as a representative of (Mw). Therefore, the weight-average molecular weight of PVOH polymers or copolymers can, for example, range from about 30,000 g / mol to about 175,000 g / mol, or from about 30,000 g / mol to about 100,000 g / mol, or from about 55,000 g / mol to about 85,000 g / mol.

[0032] As described above, the PVOH polymer is characterized by its degree of hydrolysis. The PVOH polymer is characterized by a degree of hydrolysis of about 60% to about 99%, preferably about 80% to about 98%, preferably about 85% to about 95%, and preferably about 87% to about 92%.

[0033] The water-soluble composition may be in the form of a membrane and has a residual value of about 48% by weight or less, as determined by a dissolution chamber test. The water-soluble membrane may have an average tensile strength of at least about 33 MPa, as determined by a tensile strength test; the water-soluble membrane may have a modulus of at least about 12 N / mm², as determined by a modulus test. 2 The modulus value. This article provides various testing methods.

[0034] The compositions described herein may comprise a first PVOH polymer or more than one PVOH polymer, such as a first PVOH polymer and a second PVOH polymer. The specific chemical properties of the first PVOH polymer and the second PVOH polymer are described in more detail below.

[0035] a. First PVOH polymer

[0036] The compositions described herein may comprise a first PVOH polymer. The first PVOH polymer may comprise a first anionic monomer unit. The first PVOH polymer may be a PVOH terpolymer comprising vinyl alcohol monomer units, vinyl acetate monomer units (i.e., when not fully hydrolyzed), and a single type of anionic monomer unit (e.g., wherein the single type of monomer unit may comprise equivalent acid forms, salt forms, and optionally residual ester forms of the anionic monomer unit). The PVOH copolymer may comprise two or more types of anionic monomer units.

[0037] The first anionic monomer unit may be derived from members selected from: vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumarate anhydride, itaconic acid, monomethyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, vinyl sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, salts of the foregoing substances preferably alkali metal salts of the foregoing substances, esters of the foregoing substances, and combinations thereof.

[0038] The anionic monomer unit in the first PVOH polymer may be a carboxylated anionic monomer unit. As used herein, a “carboxylated anionic monomer unit” includes a vinyl polymerization unit, which corresponds to monocarboxylic acid vinyl monomers, their esters and anhydrides, dicarboxylic acid monomers having polymerizable double bonds, their esters and anhydrides, and salts of any of the foregoing substances, preferably alkali metal salts.

[0039] Examples of suitable carboxylated anionic monomer units include vinyl polymerization units corresponding to vinyl anionic monomers, said vinyl anionic monomers including vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, alkali metal salts of the foregoing (e.g., sodium alkali metal salt, potassium alkali metal salt, or other alkali metal salts), esters of the foregoing (e.g., methyl, ethyl, or other C1-C4 or C6 alkyl esters), and combinations thereof (e.g., multiple types of anionic monomers or equivalent forms of the same anionic monomer). Carboxylated anionic monomer units can be derived from maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, and combinations thereof. Carboxylated anionic monomer units can be derived from monoalkyl maleate monomer units. The monoalkyl maleate monomer unit can be derived from members selected from: monomethyl maleate, its alkali metal salts (e.g., sodium salts), and combinations thereof.

[0040] One or more anionic monomer units may be incorporated into or present in a given amount in the first PVOH polymer. Generally, as the anionic monomer content increases, the solubility of the PVOH polymer resin, resin blends, and / or films made from such resins or resin blends also increases. Films containing PVOH polymers with higher anionic monomer content can also have relatively high tackiness, which can indicate greater sealing performance. However, due to the challenges of converting tacky films into pouches, water-soluble films with excessively high tackiness may not be desirable.

[0041] The amount of anionic monomer units can be characterized by the molar content (e.g., expressed as mol%) of the anionic monomer units in the PVOH polymer. One or more anionic monomer units may be present in the first PVOH polymer, individually or collectively, in amounts ranging from about 1 mol% to about 5 mol%, or from about 2 mol% to about 4 mol%, or from about 2 mol% to about 5 mol%, or from about 3 mol% to about 5 mol%, or from about 3.5 mol% to about 4.5 mol%, or from about 4 mol% to about 4.5 mol%. One or more anionic monomer units may be present in the first PVOH polymer in amounts ranging from about 1 mol% to about 4 mol%, or from about 1 mol% to about 3 mol%. The anionic monomer unit may be present in the first PVOH polymer in amounts of at least about 1.0 mol%, 1.5 mol%, 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, or 4.0 mol%, and / or at most about 6.0 mol%, 5.5 mol%, 5.0 mol%, 4.5 mol%, 4.0 mol%, 3.5 mol%, 3.0 mol%, or 2.5 mol%.

[0042] Alternatively or otherwise, the anionic monomer unit may be characterized by the anionic monomer unit present in the PVOH membrane, for example, the molar content (mol%) of the anionic monomer unit compared to the total PVOH polymer in the membrane (e.g., the total PVOH polymer in a PVOH resin blend, including homopolymers and copolymers). The anionic monomer unit may be present in the water-soluble membrane in an amount ranging from about 0.5 mol% to about 5 mol% of the total PVOH polymer in the membrane. The anionic monomer unit may be present in the membrane in an amount of at least about 0.5 mol%, 0.75 mol%, 1.0 mol%, or 1.2 mol%, and / or at most about 5.0 mol%, 4.5 mol%, 4.0 mol%, 3.0 mol%, 2.5 mol%, 2.0 mol%, or 1.7 mol% of the total PVOH polymer in the membrane. For example, a first PVOH polymer containing (carboxylated) anionic monomer units can be blended with a second PVOH polymer, such as a homopolymer, at a ratio of about 30% by weight / 70% by weight to about 70% by weight / 30% by weight to obtain an average blended anionic monomer unit content of about 0.5 mol% to about 3 mol% of the total PVOH polymer. Alternatively or otherwise, the aforementioned anionic monomer unit content may also be applied relative to the content of total water-soluble polymer, PVOH, or other substances in the membrane.

[0043] The first PVOH polymer may be present in an amount ranging from about 10% by weight to about 100% by weight of the total PVOH polymer in the composition, or from about 10% by weight to about 90% by weight of the total PVOH polymer.

[0044] b. Second PVOH polymer

[0045] The compositions described herein may comprise a second PVOH polymer. The second PVOH polymer is selected from PVOH polymers comprising: (a) a second anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate unit, or (b) a PVOH homopolymer consisting of a vinyl alcohol monomer unit and optionally a vinyl acetate unit.

[0046] The second PVOH polymer may be a PVOH polymer containing a second anionic monomer unit. The second anionic unit may be different from the first anionic monomer unit, or they may be the same. When the first and second anionic monomer units are the same, the first PVOH polymer and the second PVOH polymer differ in some way, for example, in their respective viscosities or the respective content of incorporated anionic monomer units.

[0047] The second anionic monomer unit may be selected from vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumarate anhydride, itaconic acid, monomethyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, vinyl sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof. The second anionic monomer unit may be selected from acrylamide methylpropanesulfonic acid, its alkali metal salts, and combinations thereof. The first anionic monomer unit in the first PVOH polymer is selected from monomethyl maleate, its alkali metal salt, and combinations thereof, and the second monomer unit in the second PVOH polymer is selected from acrylamide methylpropanesulfonic acid, its alkali metal salt, and combinations thereof. The first PVOH polymer may be present in the composition in the range of about 50% by weight to about 100% by weight, preferably about 70% by weight to about 90% by weight, based on the total PVOH polymer in the composition, wherein the first anionic monomer unit is derived from members selected from: monomethyl maleate, its alkali metal salt, and combinations thereof, wherein the second PVOH polymer is present in the composition in the range of about 10% by weight to about 50% by weight, preferably about 10% by weight to about 30% by weight, based on the total PVOH polymer in the composition, and wherein the second monomer unit is derived from members selected from: acrylamide methylpropanesulfonic acid, its alkali metal salt, and combinations thereof.

[0048] The second anionic monomer unit may be present in the second PVOH polymer in an amount ranging from about 1.0 mol% to about 5.0 mol% of the second PVOH polymer. The second anionic monomer unit may be present in the membrane in an amount ranging from about 0.2 mol% to about 5.0 mol%, or about 0.5 mol% to about 4.5 mol%, or about 1 mol% to about 3 mol% of the total PVOH polymer in the membrane.

[0049] The first PVOH polymer may have a first doping amount (a1) of the first anionic monomer unit, and the second PVOH polymer may have a second doping amount (a2) of the second anionic monomer unit. When the first and second anionic monomer units are the same, the absolute value of |a1–a2| may be greater than zero. The value of (a1–a2) may be greater than zero. This may be: a1 in the range of about 1 mol% to about 5 mol%, preferably about 1 mol% to about 3 mol% of the first PVOH polymer, a2 in the range of about 1 mol% to about 5 mol%, preferably about 1 mol% to about 3 mol% of the second PVOH polymer, and |a1–a2|, preferably a1–a2 in the range of about 0 mol% to about 3 mol%, or about 1 mol% to about 3 mol%.

[0050] The first anionic monomer unit and the second anionic monomer unit may be present in a combined amount of about 2.0 mol% to about 3.5 mol% of the total PVOH polymer in the membrane.

[0051] The second PVOH polymer may be a PVOH homopolymer comprising vinyl alcohol monomer units and optionally vinyl acetate monomer units.

[0052] The second PVOH polymer is characterized by a 4% solution viscosity (μ2) of about 3.0 cP to about 40 cP, or about 7 cP to about 40 cP, or about 10 cP to about 40 cP, or about 10 cP to about 30 cP, or about 12 cP to about 25 cP at 20°C. The first PVOH polymer is characterized by a first 4% solution viscosity (μ1) at 20°C, and the second PVOH polymer is characterized by a second 4% solution viscosity (μ2) at 20°C. The absolute viscosity difference |μ2-μ1| between the first PVOH polymer and the second PVOH polymer can be in the range of 0 cP to about 10 cP, preferably 2 cP to 8 cP.

[0053] The second PVOH polymer may be characterized by a degree of hydrolysis of about 60% to about 99%, preferably about 80% to about 98%, preferably about 83% to about 95%, and preferably about 85% to about 92%.

[0054] The second PVOH polymer may be present in an amount ranging from about 10% to about 90% by weight of the total PVOH polymer in the membrane, preferably from 30% to 80% by weight, and more preferably from 50% to 70% by weight.

[0055] The first PVOH polymer may be present in the composition in the range of about 20% to about 60% by weight, preferably about 30% to about 40% by weight, based on the total weight of the PVOH polymer in the blend, wherein the first anionic monomer unit of the first PVOH polymer is derived from members selected from: monomethyl maleate, its alkali metal salts, and combinations thereof, and wherein the second PVOH polymer is a PVOH homopolymer characterized by a 4% solution viscosity (μ2) of about 10 cP to about 30 cP at 20°C, and present in the PVOH resin blend in the range of about 40% to about 80% by weight, preferably about 60% to about 70% by weight, based on the total weight of the PVOH polymer in the blend.

[0056] Eutectic Solvent

[0057] The compositions of the present invention may contain 1% to 25% by weight of a eutectic solvent, or about 2% to about 22% by weight, or about 5% to about 20% by weight of a eutectic solvent. The eutectic solvent is a mixture of at least one hydrogen bond acceptor (HBA) and at least one hydrogen bond donor (HBD). The melting temperature of the eutectic solvent may be lower than the melting temperature of the HBA and lower than the melting temperature of the HBD.

[0058] Examples of hydrogen bond acceptors include, but are not limited to: amino acids such as arginine, proline, alanine, phenylalanine, glutamine, lysine, glycine, and betaine; non-sugar alcohol polyols such as glycerol and propylene glycol; and amines such as amine oxides, pyridine, pyrrole, and salts of quaternary ammonium compounds (such as choline, 1-ethyl-3-methylimidazolium, and betaine), preferably halide salts.

[0059] HBA can be a small molecule containing about 3 to about 16 carbon atoms, about 4 to about 12 carbon atoms, or about 5 to about 8 carbon atoms.

[0060] In some embodiments, HBA is choline chloride and may be at least about 7.5% by weight, at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight, or at least about 90% by weight, based on the weight of the eutectic solvent.

[0061] Examples of hydrogen bond donors include, but are not limited to, non-quaternary ammonium carboxylic acids such as maleic acid, malic acid, lactic acid, fumaric acid, acetic acid, ascorbic acid, levulinic acid, salicylic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, and citric acid, and their salts; sugars such as sucrose, xylose, trehalose, glucose, and fructose; sugar alcohols such as sorbitol, erythritol, xylitol, and mannitol; and amides such as urea, N-methylurea, dimethylurea, and caprolactam. HBDs may be small molecules containing about 1 to about 12 carbon atoms, about 2 to about 10 carbon atoms, or about 3 to about 8 carbon atoms.

[0062] The amount of hydrogen bond donor may be at least about 1 wt%, at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 50 wt%, at least about 55 wt%, at least about 60 wt%, at least about 65 wt%, at least about 70 wt%, or at least 75 wt%, based on the weight of the eutectic solvent.

[0063] The molar ratio of HBD to HBA in the eutectic solvent can be about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 9:2, 4:1, 7:2, 3:1, 5:2, 2:1, 3:2, 1:1, 2:3, 1:2, 2:5, 1:3, 2:7, 1:4, 2:9, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10. The molar ratio of HBD to HBA can be about 10:1 to about 1:10, or about 5:1 to about 1:5, about 2:1 to about 1:3, or about 1:1. The eutectic solvent is liquid at 25°C. Examples of eutectic solvents are described in Table 1 and can be found in Yizhak Marcus's Deep Eutectic Solvents, published by Springer in 2019.

[0064] Table 1: Examples of eutectic solvents

[0065]

[0066] The eutectic solvent of this invention can be prepared by any method known in the art, but for illustrative purposes, liquid and melt preparation are described herein. For liquid preparation, HBA and HBD are weighed and added to a liquid (typically distilled water) and mixed until dissolved. After solubilization, the mixture is placed on a rotary evaporator to evaporate the liquid and form the eutectic solvent. For melt preparation, HBA and HBD are weighed, combined, heated to a temperature exceeding the melting temperature of HBA and HBD, and then cooled to form the eutectic solvent.

[0067] Beneficial agents

[0068] The composition may further comprise one or more beneficial agents in amounts of about 0.01 wt% to about 45 wt%, about 0.1 wt% to about 35 wt%, or about 0.5 wt% to about 25 wt%. The beneficial agents may be entrained in the composition, thereby allowing for easy transport, but are released when the composition dissolves in water. Examples of suitable beneficial agents include: fragrances, pre-fragrances, finishing aids, odor control and removal agents, odor neutralizers, polymeric dye transfer inhibitors, cationic deposition-enhancing polymers, detergent builders, heavy metal ion chelators, surfactants, foam-stabilizing polymers, pH adjusters, buffers, alkalinity sources, fabric softeners, antistatic agents, dye fixatives, dye abrasion inhibitors, wrinkle reducers, anti-wrinkle agents, wrinkle removers, silicones (e.g., silicone oils, cationic silicones, silicone rubber compounds, high-refractive silicones, and silicone resins), detergents. Polymers, dirt-capturing polymers, flocculants, scale inhibitors, colorants, pigments, aversive agents such as bittering agents, anti-redeposition agents, bleaching activators, bleaching catalysts, bleaching synergists, bleaching agents, photobleaching agents, enzymes, coenzymes, enzyme stabilizers, crystal growth inhibitors, anti-discoloration agents, antioxidants, metal ion salts, corrosion inhibitors, antiperspirants, zinc pyrithione, plant derivatives, plant extracts, plant tissue extracts, plant seed extracts, plant oils, herbal medicines, botanical extracts, essential oils, skin sensitizers, astringents, etc. (e.g., clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel extract), anti-acne agents (salicylic acid), anti-dandruff agents, defoamers, cosmetic astringents, cosmetic bactericides, denaturants, pharmaceutical astringents, topical analgesics, film-forming agents or materials such as polymers that help the film-forming properties and affinity of the composition (e.g., copolymers of eicosene and vinylpyrrolidone), skin bleaching agents and whitening agents (e.g., hydroquinone, kojic acid, ascorbic acid, magnesium ascorbate phosphate, ascorbate glucoside, pyrrolidone, etc.). Panthenol), skin conditioning agents (e.g., moisturizers and occlusive agents), skin soothing and / or healing agents and derivatives (e.g., panthenol and derivatives such as ethyl panthenol, aloe vera juice, pantothenic acid and its derivatives, allantoin, bisabolol and dipotassium glycyrrhizate), skin therapeutic agents (e.g., vitamin D compounds, monoterpenes, diterpenes and triterpenes, β-ionol, cedrol), sunscreens, insect repellents, oral care active substances, personal care active substances, vitamins, antibacterial agents, antimicrobial agents, antifungal agents, their derivatives, and mixtures thereof.

[0069] In one embodiment, the beneficial agent may be at least partially surrounded by a wall material to form microcapsules. In one aspect, the microcapsule wall material may comprise: melamine, polyacrylamide, silicone, silica, polystyrene, polyurea, polyurethane, polyacrylate-based materials, gelatin, styrene malic anhydride, polyamide, and mixtures thereof. In one aspect, the melamine wall material may comprise melamine crosslinked with formaldehyde, melamine-dimethoxyethanol crosslinked with formaldehyde, and mixtures thereof. In one aspect, the polystyrene wall material may comprise polystyrene crosslinked with divinylbenzene. In one aspect, the polyurea wall material may comprise urea crosslinked with formaldehyde, urea crosslinked with glutaraldehyde, and mixtures thereof. In one aspect, the polyacrylate-based material may include polyacrylates formed from methyl methacrylate / dimethylamino methacrylate, polyacrylates formed from aminoacrylates and / or methacrylates with a strong acid, polyacrylates formed from carboxylic acid acrylates and / or methacrylate monomers with a strong base, polyacrylates formed from aminoacrylates and / or methacrylate monomers with carboxylic acid acrylates and / or carboxylic acid methacrylate monomers, and mixtures thereof. In one aspect, the fragrance microcapsules may be coated with a deposition aid, a cationic polymer, a nonionic polymer, anionic polymer, or a mixture thereof. Suitable polymers may be selected from polyethylene formaldehyde, partially hydroxylated polyethylene formaldehyde, polyethyleneamine, polyethyleneimine, ethoxylated polyethyleneimine, polyvinyl alcohol, polyacrylates, and combinations thereof. In one aspect, one or more types of microcapsules may be used, for example, two types of microcapsules with different beneficial agents.

[0070] In the implementation scheme, the beneficial agent may be a fragrance oil and may contain materials selected from: 3-(4-tert-butylphenyl)-2-methylpropanal, 3-(4-tert-butylphenyl)-propanal, 3-(4-isopropylphenyl)-2-methylpropanal, 3-(3,4-methylenedioxyphenyl)-2-methylpropanal, and 2,6-dimethyl-5-heptenal, α-dihydrodamascone, β-dihydrodamascone, δ-dihydrodamascone Ketones, β-dihydrodamascone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, methyl-7,3-dihydro-2H-1,5-benzodioxane-3-one, 2-[2-(4-methyl-3-cyclohexenyl-1-yl)propyl]cyclopentan-2-one, 2-sec-butylcyclohexanone, and β-dihydroionone, linalool, ethyl linalool, tetrahydrolinalool, and dihydromyrcenol. Suitable flavoring materials are available from Givaudan Corp. (Mount Olive, NJ, USA), International Flavors & Fragrances Corp. (South Brunswick, NJ, USA), or Quest Corp. (Naarden, Netherlands). In one aspect, the beneficial agent is flavoring microcapsules. Flavors are generally volatile and may evaporate or cause a flammability hazard during the melt processing of PVOH. The lower melting and processing temperatures of PVOH eutectic compositions can facilitate the incorporation of fragrances.

[0071] In one embodiment, the beneficial agent may be encapsulated in a shell. In one embodiment, the encapsulated beneficial agent is a fragrance oil, and the shell is a polymer.

[0072] In this embodiment, the beneficial agent may be an enzyme. Enzymes are typically temperature-sensitive and may be inactivated or decomposed when melt-processed with PVOH. The lower melting temperature of the PVOH eutectic composition allows for the incorporation of enzymes while minimizing denaturation or decomposition. Suitable enzymes include proteases, amylases, cellulases, lipases, xyloglucanases, pectic acid lyases, mannanases, bleaching enzymes, keratinases, and mixtures thereof.

[0073] In embodiments, the beneficial agent may be a flavoring agent, a bittering agent, or an aversive agent. Flavoring agents may be included to encourage human consumption of the composition. This is particularly useful for health and oral care compositions. Bittering agents and aversive agents may be incorporated into the composition to deter animals, especially humans, from consuming it. Flavoring agents and bittering agents may decompose at elevated temperatures, making them difficult to incorporate into PVOH compositions. The lower melting and processing temperatures of the PVOH eutectic compositions of the present invention allow for the incorporation of flavoring agents, bittering agents, or aversive agents while retaining their efficacy.

[0074] In the embodiments, the beneficial agent may be an organosilicon. The available organosilicon may be a compound containing any organosilicon. In one embodiment, the organosilicon polymer is selected from cyclic organosilicones, polydimethylsiloxanes, amino organosilicones, cationic organosilicones, organosilicon polyethers, organosilicon resins, organosilicon carbamates, and mixtures thereof. In one embodiment, the organosilicon is a polydialkyl organosilicon, or a polydimethylsiloxane (polydimethylsiloxane or “PDMS”), or derivatives thereof. In another embodiment, the organosilicon is selected from amino-functionalized organosilicones, amino-polyether organosilicones, alkoxylated organosilicones, cationic organosilicones, ethoxylated organosilicones, propoxylated organosilicones, ethoxylated / propoxylated organosilicones, quaternary organosilicones, or combinations thereof.

[0075] In the implementation plan, the beneficial agent may be an oral care active substance. Suitable oral care active substances include preventive agents, including but not limited to: sodium fluoride, stannous fluoride, sodium monofluorophosphate; dental hypersensitivity treatment agents, including but not limited to: potassium nitrate, strontium chloride, and stannous fluoride; gingivitis preventive and treatment agents, including but not limited to stannous fluoride, triclosan, hexadecylpyridinium chloride, and chlorhexidine; dental erosion preventive agents, including but not limited to: sodium fluoride, stannous fluoride, and sodium polyphosphate; periodontitis treatment agents, including but not limited to chlorhexidine, tetracycline, doxycycline, and ketoprofen; and dry mouth improvers, including but not limited to pilocarpine and senna.

[0076] In the implementation plan, the beneficial agents may be personal health-promoting active substances. Suitable personal health-promoting active substances include personal health care products such as: treatments for colds and flu, including but not limited to antihistamines such as diphenhydramine hydrochloride, doxylamine succinate, chlorpheniramine maleate, fexofenadine, terfenadine, and cetirizine decongestants; desmopressin such as phenylephrine hydrochloride, pseudoephedrine, oxymetazoline; expectorants such as guaifenesin; antitussives such as dextromethorphan hydrobromide; antipyretics and analgesics such as acetaminophen, ibuprofen, naproxen, and aspirin; antacids, including but not limited to acid-reducing agents such as magnesium hydroxide, aluminum hydroxide, calcium carbonate, sodium bicarbonate, and dimethyl silicone oil; H2 antagonists such as cimetidine, ranitidine, and famotidine; proton pump inhibitors such as omeprazole and pantoprazole; and antidiarrheals, including but not limited to bismuth subsalicylate and loperamide. Probiotics, including but not limited to Bifidobacterium infantis and Lactobacillus acidophilus. Volumetric fibers, including but not limited to psyllium husk.

[0077] In the implementation scheme, the beneficial agent may be a temperature-sensitive beneficial agent. A temperature-sensitive beneficial agent is one that poses a processing challenge at temperatures associated with the melt processing of the PVOH composition. Temperature-sensitive beneficial agents may have high vapor pressures, causing them to volatilize and / or thermally degrade at temperatures close to the processing temperature of the PVOH composition during processing. Examples of temperature-sensitive beneficial agents include enzymes, proteins, flavorings, flavoring agents, and color dyes. An example of a temperature-sensitive beneficial agent is the flavoring bittering agent denatammonium benzoate, which can... Commercially available. It can be added to compositions as an inhibitor of accidental ingestion in animals. The thermal decomposition temperature of denatum benzoate is about 180°C. Temperature-sensitive beneficial agents are characterized by a thermal degradation temperature of less than 200°C, or about 100°C to about 190°C, or about 110°C to about 185°C, or about 120°C to about 180°C.

[0078] The 3D product and its preparation method of the present invention

[0079] The compositions of the present invention are suitable for melt flow processing into 3D articles. Examples of suitable melt flow processing include, but are not limited to, injection molding, blow molding, filament extrusion and optionally granulation, film extrusion, melt spinning of fibers and / or nonwoven substrates, 3D printing, rotational molding, and granulation. The eutectic helps to lower the melt temperature and processing temperature of the composition, enabling melt flow processing at temperatures below those of PVOH alone. The compositions of the present invention can be melt-processed by heating the composition to temperatures of about 80°C to about 185°C, or about 85°C to about 160°C, or about 90°C to about 150°C to soften or melt the composition and applying pressure to the composition to allow it to flow.

[0080] In the implementation plan, the three-dimensional article of manufacture may be a consumer product. Examples of consumer products include baby care products, beauty care products, fabric care products, household care products, feminine care products, health care products, and products or devices intended for use or consumption for sale and not intended for subsequent commercial manufacture or modification. Such products include, but are not limited to, fabric softeners, fabric strengtheners, laundry detergent additives, conditioning agents, hair colorants, bath products, shampoos, facial cleansers, dishwashing liquids, and products and / or methods for treating hair-related heavy-duty laundry detergents (human, dog, and / or cat), including bleaching, coloring, dyeing, conditioning, shampooing, styling; personal care; cosmetics; skin care, including the application of creams, lotions, and other topical products for consumer use; and shaving products, involving products and / or methods for treating fabrics, hard surfaces, and any other surfaces in fabric or home care areas, including: air care, car care, dishwashing, fabric conditioning (including softening), laundry detergent cleaning, laundry detergent rinse additives and / or conditioning, hard surface cleaning and / or treatment; products and / or methods involving oral care, including toothpaste, teething gel, teeth cleaner, denture adhesives, teeth whitening; over-the-counter health products, including cough and cold medicines, pain relievers, pet health and nutrition, and purified water.

[0081] In one embodiment, the three-dimensional object includes a container filled with one or more beneficial agents. The container may be at least partially composed of the components of the present invention to provide water solubility to at least a portion of the container to release the beneficial agent. The beneficial agent may include a single solid element, a collection of solid powder elements, a liquid, or a gas.

[0082] In this example, a PVOH eutectic composition was formed and extruded using a Thermo Fischer Scientific Pharma 11HME assembly equipped with an 11mm twin-screw with a length-to-diameter ratio of 40:1, operating at 200 rpm, a single-hole circular die, and eight heating zones. The first heating zone was shut off, and the temperatures of zones two through eight were uniformly increased, with zone two heated to 80°C and zone eight heated to 120°C. The die temperature was maintained at 110°C. The PVOH polymer was SELVOL, sold by Sekisui Specialty Chemicals LLC, Dallas, TX. TM The dry powder of polyvinyl alcohol 205 has a reported degree of hydrolysis of 88 mol%, a viscosity of 5.7 cP for a 4 wt% solution, a weight-average molecular weight of about 50,000 g / mol, and a melting temperature of about 180°C to about 190°C. The eutectic solvent is L-arginine:levulinic acid in a 1:1 molar ratio. The PVOH powder and the eutectic liquid are mixed in an extruder to form a composition of 74 wt% PVOH and 26 wt% eutectic solvent, and extruded through a 3 mm die.

[0083] In the example, Thermo Fischer Scientific Pharma 11HME, equipped with an 11mm twin-screw with a length-to-diameter ratio of 40:1, operating at 200 rpm, a single-hole circular die, and eight heating zones, was used to form and extrude PVOH, eutectic, and temperature-sensitive additives. The composition contains 74% by weight of SELVOL, sold by Sekisui Specialty Chemicals LLC, Dallas, TX. The eight heating zones from the hopper to the die are set at temperatures of 80°C, 105°C, 120°C, 120°C, 120°C, 115°C, 110°C, and 110°C. TM Polyvinyl alcohol 205, with a reported degree of hydrolysis of 88 mol%, a viscosity of 5.7 cP for a 4 wt% solution, a weight-average molecular weight of about 50,000 g / mol, and a melting temperature of about 180°C to about 190°C. It also contains 25.6 wt% of a eutectic solvent comprising a 1:1 molar ratio of L-arginine to levulinic acid and 0.4 wt% of a commercially available solvent from TCI America. PVOH powder, eutectic liquid and The mixture was prepared in an extruder and extruded through a 3mm die. Mass spectrometry was used to confirm the presence of [unspecified components] in the extruded product. The presence and absence of degradation.

[0084] Water-soluble membrane

[0085] In this embodiment, the 3D article may be a water-soluble membrane. The water-soluble membrane may at least partially or completely encapsulate the home care composition in the compartment. The membrane described herein comprises PVOH homopolymers, PVOH copolymers, and PVOH resin blends. The PVOH resin blends comprise at least a first PVOH polymer and a second PVOH polymer, as detailed below.

[0086] Other membrane components / properties

[0087] In addition to the polyvinyl alcohol polymers described above, the water-soluble films disclosed herein may contain other components.

[0088] The membranes disclosed herein may contain other water-soluble polymers. In addition to PVOH polymers and PVOH copolymers, other water-soluble polymers used in the blends may include, but are not limited to, modified polyvinyl alcohol, polyacrylates, water-soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, pullulan, water-soluble natural polymers including, but not limited to, guar gum, acacia gum, xanthan gum, carrageenan, and starch, water-soluble polymer derivatives including, but not limited to, modified starch, ethoxylated starch, and hydroxypropylated starch, the aforementioned copolymers, and any combination of the aforementioned substances. However, other water-soluble polymers may include polyalkylene oxides, polyacrylamide, polyacrylic acid and its salts, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and their salts, polyamino acids, polyamides, gelatin, methylcellulose, carboxymethylcellulose and its salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, and polymethyl methacrylate. Such water-soluble polymers, whether PVOH or other polymers, are commercially available from a variety of sources. Any of the aforementioned water-soluble polymers is generally suitable as a film-forming polymer. Generally speaking, water-soluble films may contain copolymers and / or blends of the aforementioned resins.

[0089] The water-soluble polymers (including, but not limited to, PVOH polymers and PVOH copolymers) used in the membranes described herein may be characterized by viscosities, for example, in the range of about 3.0 cP to about 27.0 cP, about 4.0 cP to about 24.0 cP, about 4.0 cP to about 23.0 cP, about 4.0 cP to about 15 cP, or about 6.0 cP to about 10.0 cP. The viscosity of the polymer is determined by measuring a freshly prepared solution using a Brookfield LV viscometer with a UL adapter, as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield Test Method. It is international practice to describe the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20°C. Unless otherwise specified, polymer viscosities listed herein in cP should be understood as referring to the viscosity of a 4% aqueous solution of the water-soluble polymer at 20°C.

[0090] As is well known in the art, the viscosity of water-soluble polymers (PVOH or other polymers) is similar to the weight-average molecular weight of the same PVOH polymer. Related, and viscosity is usually used as Therefore, the weight-average molecular weight of the water-soluble polymer comprising the first PVOH copolymer and the second PVOH polymer can be, for example, in the range of about 30,000 to about 175,000, or about 30,000 to about 100,000, or about 55,000 to about 85,000.

[0091] Water-soluble membranes may contain other additives and processing agents, such as, but not limited to, surfactants, lubricants, strippers, fillers, extenders, crosslinking agents, antiblocking agents, antioxidants, anti-sticking agents, defoamers, nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite, or others), aversive agents such as bittering agents (e.g., denatamine salts such as denatamine benzoate, denatamine saccharin, and denatamine chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringin; and quassinolides such as quassinolide and strychnine), and stimulants (e.g., capsaicin, piperazine, isothiocyanates, and transgenic toxins), and other functional ingredients, in amounts suitable for their intended purpose. Membranes including plasticizers are beneficial. The amounts of these agents, individually or collectively, may be up to about 50% by weight, 20% by weight, 15% by weight, 10% by weight, 5% by weight, 4% by weight, and / or at least 0.01% by weight, 0.1% by weight, 1% by weight, or 5% by weight. Preferably, the total amount of such additives and processing aids in the membrane is about 20% to about 50%, more preferably about 25% to about 40%.

[0092] Water-soluble membranes may be substantially free of conventional plasticizers such as glycerin, diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, up to 400 MW of polyethylene glycol, neopentyl glycol, trimethylolpropane, polyether polyols, sorbitol, 2-methyl-1,3-propanediol, cholinesterase, and mixtures thereof. Based on the total membrane weight, the total amount of conventional plasticizers can be less than about 1%, or less than about 0.1%, or less than about 0.01%, or even 0%.

[0093] Suitable surfactants may include nonionic, cationic, anionic, and amphoteric classes. Suitable surfactants include, but are not limited to, polyoxyethyleneized polypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenols and alkanolamides (nonionic), polyoxyethyleneized amines, quaternary ammonium salts and polyoxyethyleneized quaternary ammoniums (cationic), and amine oxides, N-alkyl betaine and sulfobetaine (amphoteric). Other suitable surfactants include sodium sulfosuccinate, acylated fatty acid esters of glycerol and propylene glycol, lactams of fatty acids, sodium alkyl sulfate, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, acetylated fatty acid esters, and combinations thereof. The amount of surfactant in the water-soluble film may range from about 0.1% by weight to 2.5% by weight, optionally from about 1.0% by weight to 2.0% by weight.

[0094] Suitable lubricants / strippers may include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty acid esters, fatty amines, fatty amine acetates, and fatty amides. Preferred lubricants / strippers are fatty acids, fatty acid salts, and fatty amine acetates. The amount of lubricant / stripper in the water-soluble film may be in the range of about 0.02% by weight to about 1.5% by weight, optionally from about 0.1% by weight to about 1% by weight.

[0095] The membrane may contain an aversive agent such as a bittering agent, for example denatam benzoate and / or its derivatives. Prior to membrane preparation, the aversive agent may be mixed with polymeric materials and / or other auxiliaries (e.g., before casting or extruding the membrane). Alternatively or otherwise, the aversive agent may be added to the membrane or pouch, for example by coating, printing, spraying, or other coating methods.

[0096] Suitable fillers / expanders / antiblocking agents / anti-sticking agents include, but are not limited to, starch, modified starch, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, and mica. Preferred materials are starch, modified starch, and silica. The amount of filler / expander / antiblocking agent / anti-sticking agent in the water-soluble film can range from about 0.1 wt% to about 25 wt%, or about 1 wt% to about 10 wt%, or about 2 wt% to about 8 wt%, or about 3 wt% to about 5 wt%. In the absence of starch, a preferred range for suitable filler / expander / antiblocking agent / anti-sticking agent is about 0.1 wt% or 1 wt% to about 4 wt% or 6 wt%, or about 1 wt% to about 4 wt%, or about 1 wt% to about 2.5 wt%.

[0097] As determined by Karl Fischer titration, the water-soluble membrane may also have a residual water content of at least 4% by weight, preferably in the range of about 4% by weight to about 10% by weight.

[0098] The film can be opaque, transparent, or translucent. The film may include printed areas. These printed areas may cover an uninterrupted portion of the film or a portion thereof. The printed areas may include inks, pigments, dyes, bluing agents, or mixtures thereof. The printed areas may include a single color, or may include multiple colors, even three colors. The print may exist as a layer on the surface of the film, or may at least partially penetrate into the film. The film will include a first side and a second side. The printed areas can be achieved using standard techniques such as flexographic printing or inkjet printing. The printed areas may be on either side or both sides of the film. Alternatively, inks or pigments may be added during film manufacturing to color all or at least part of the film.

[0099] Other features of the water-soluble polymer composition, such as those of a film, can be found in U.S. Patent Publication 2011 / 0189413 and U.S. Patent Application 13 / 740,053, both of which are incorporated herein by reference in their entirety.

[0100] Film forming method

[0101] One type of contemplated embodiment is characterized in that the water-soluble film is formed, for example, by mixing, co-casting, or welding a PVOH polymer (or, in the case of a blend system), together with a co-melting solvent and any optional second additive described herein. If the polymers are mixed first, the water-soluble film is preferably formed by casting the resulting mixture (e.g., together with other plasticizers and other additives). If the polymers are welded, the water-soluble film can be formed by, for example, solvent or thermal welding. Another type of contemplated embodiment is characterized in that the water-soluble film is formed by extrusion, for example, blow molding. In a contemplated non-limiting embodiment, a blend film of a PVOH polymer and an acrylamide methylpropanesulfonic acid PVOH terpolymer is formed by blow molding.

[0102] Water-soluble films can be formed, for example, by mixing, co-casting, or welding a first PVOH copolymer and a second PVOH polymer of the type and amount described herein, along with a preferred and optional second additive described herein. If the polymers are mixed first, the water-soluble film is preferably formed by casting the resulting mixture (e.g., together with other plasticizers and other additives). If the polymers are welded, the water-soluble film can be formed by, for example, solvent or thermal welding. Water-soluble films can be formed by extrusion, such as blow molding.

[0103] The membrane can have any suitable thickness. For example, the membrane can have a thickness in the range of about 5 μm to about 200 μm, or in the range of about 20 μm to about 100 μm, or in the range of about 40 μm to about 85 μm (e.g., 76 μm). When the pouch is prepared, for example, by thermoforming as described below, the membrane can be deformed, resulting in different membrane thicknesses within the pouch. Therefore, the undeformed thickness of the membrane can be determined prior to deformation and / or pouch formation.

[0104] Water-soluble membranes can also be self-standing membranes composed of one or more similar layers.

[0105] The membranes described herein can also be used to prepare articles such as small packages having two or more compartments, the compartments being made from a combination of the same membrane or other polymeric materials. As is known in the art, additional membranes can be obtained, for example, by casting, blow molding, extrusion, or blow extrusion of the same or different polymeric materials. Polymers, copolymers, or derivatives thereof suitable as additional membranes may be selected from polyvinyl alcohol, polyvinylpyrrolidone, polyepoxides, polyacrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic acid / acrylic acid copolymers, polysaccharides (including starch and gelatin), natural gums such as xanthan gum, and carrageenan. For example, polymers may be selected from polyacrylate and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethyl cellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, polymethyl methacrylate, and combinations thereof, or selected from polyvinyl alcohol, polyvinyl alcohol copolymers and hydroxypropyl methylcellulose (HPMC), and combinations thereof. One type of envisioned membrane is characterized in that the content of a polymer, such as the PVOH resin blend described above, in the pouch material is at least 60%.

[0106] The weight ratio of all water-soluble polymers, compared to the combined amount of all plasticizers, compatibilizers, and second additives, can range, for example, from about 0.5 to about 18, from about 0.5 to about 15, from about 0.5 to about 9, from about 0.5 to about 5, from about 1 to 3, or from about 1 to 2. Preferably, the ratio is from about 1 to about 3, more preferably from about 1.3 to about 2.5. Specific amounts of plasticizers and other non-polymer components can be selected based on the intended use of the water-soluble membrane in particular embodiments to adjust the membrane's flexibility and impart beneficial processing effects according to desired mechanical membrane properties.

[0107] pouch

[0108] The membrane can be formed into a pouch having one or more compartments, which can at least partially or completely encapsulate the composition. The composition can be a home care composition at least partially encapsulated in the compartments by a water-soluble membrane. Suitable membranes and home care compositions are detailed herein.

[0109] The pouch typically includes at least one sealed compartment. The pouch may include a single compartment or multiple compartments, such as at least two compartments or at least three compartments. Figure 1An article is shown in which a water-soluble pouch 100 is formed from a water-soluble polymer membrane 10, 20 sealed at interface 30. One or both of the membranes 10, 20 comprise a PVOH resin blend of a first PVOH polymer and a second PVOH polymer. The membranes 10, 20 define an inner pouch container volume 40 containing any desired composition 50 to be released into an aqueous environment. The composition 50 is not specifically limited and may include, for example, any of the various compositions described below. In embodiments comprising multiple compartments, each compartment may contain the same and / or different compositions. Subsequently, the compositions may be in any suitable form, including but not limited to liquids, solids, and combinations thereof (e.g., solids suspended in a liquid). The pouch may include a first compartment, a second compartment, and a third compartment, each containing a different first composition, a second composition, and a third composition, respectively.

[0110] The compartments of the multi-compartment pouch may have the same or different sizes and / or volumes. The compartments of the multi-compartment pouch of the present invention may be separate or joined in any suitable manner. A second and / or third and / or subsequent compartment may be stacked on top of a first compartment. A third compartment may be stacked on top of a second compartment, which may then be stacked on top of the first compartment in a sandwich configuration. Alternatively, the second and third compartments may be stacked on top of the first compartment. However, it is also conceivable that the first, second, and optionally third compartments, as well as subsequent compartments, may be connected to each other in a side-by-side relationship. The compartments may be strung together, with each compartment individually separable by perforated thread. Thus, each compartment can be individually torn off by the end user from the remainder of the string, for example, to pre-treat or post-treat fabrics with the composition from the compartments. The first compartment may be at least surrounded by the second compartment, for example, forming a tire-hub configuration or a pouch-within-a-pouch configuration.

[0111] A multi-compartment pouch may comprise three compartments: a first large compartment and two smaller compartments. The second and third smaller compartments are stacked on top of the first large compartment. The size and geometry of the compartments are chosen to enable this arrangement. The compartment geometries may be identical or different. The second and optional third compartments may each have different geometries and shapes compared to the first compartment. The second and optional third compartments may be arranged in a specific design on top of the first compartment. This design may be decorative, educational, or illustrative, such as illustrating a concept or usage, and / or indicating the product's origin. The first compartment may be the largest, having two large, perimeter-sealed surfaces, and the second compartment is smaller, covering less than about 75% or less than about 50% of the surface area of ​​one side of the first compartment. When a third compartment is present, the above structure may be the same, but the second and third compartments cover less than about 60%, or less than about 50%, or less than about 45% of the surface area of ​​one side of the first compartment.

[0112] The articles, pouches, and / or packets disclosed herein may include one or more different films. For example, when a pouch comprises a single compartment, the pouch may be made of a single wall that is folded over itself and sealed at the edges, or alternatively, of two walls that are sealed together at the edges. When a pouch comprises multiple compartments, the pouch may be made of one or more films, such that any given pouch compartment may comprise a wall made of a single film or multiple films with different compositions. A multi-compartment pouch may include at least three walls: an outer upper wall; an outer lower wall; and a partition wall. The outer upper wall and outer lower wall are generally opposite each other and form the exterior of the pouch. The partition wall is located inside the pouch and is fixed along a sealing line to the generally opposite outer wall. The partition wall divides the interior of the multi-compartment pouch into at least a first compartment and a second compartment.

[0113] Articles such as pouches and packets can be prepared using any suitable equipment and methods. For example, single-compartment pouches can be prepared using vertical forming fill, horizontal forming fill, or roller filling techniques commonly known in the art. Such methods can be continuous or intermittent. The film can be wetted and / or heated to increase its stretchability. The method may also involve using a vacuum to draw the film into a suitable mold. When the film is on a horizontal portion of the surface, a vacuum can be applied to draw the film into the mold for about 0.2 seconds to about 5 seconds, or about 0.3 seconds to about 3 seconds, or about 0.5 seconds to about 1.5 seconds. This vacuum allows it to provide a negative pressure, for example, in the range of 10 mbar to 1000 mbar, or 100 mbar to 600 mbar.

[0114] The molds used to produce products such as pouches can have any shape, length, width, and depth, depending on the desired pouch size. If desired, the molds can also differ in size and shape from one another. For example, the final pouch volume can be from about 5 mL to about 300 mL, or from about 10 to 150 mL, or from about 20 mL to about 100 mL, and the mold size can be adjusted accordingly.

[0115] The pouch may include a first sealed compartment and a second sealed compartment. The second compartment may generally be stacked on top of the first sealed compartment, such that the second sealed compartment and the first sealed compartment share the internal partition wall of the pouch.

[0116] The pouch may include a first compartment and a second compartment, as well as a third sealed compartment. The third sealed compartment is generally stacked on top of the first sealed compartment, such that the third sealed compartment and the first sealed compartment share the internal partition wall of the pouch.

[0117] The first and second compositions may be selected from one of the following combinations: liquid, liquid; liquid, powder; powder, powder; and powder, liquid. The first, second, and third compositions may be selected from one of the following combinations: solid, liquid, liquid; and liquid, liquid, liquid; liquid, solid, liquid; solid, liquid, solid; and solid, solid, solid.

[0118] A single compartment or multiple sealed compartments may contain the composition. Multiple compartments may each contain the same or different compositions. The composition may be in the form of a liquid, a solid, or a combination thereof. The composition may be in the form of a solid, a liquid, a powder, beads, or a mixture thereof.

[0119] The composition may be a household care composition, such as selected from the following household care compositions: light-duty liquid detergent compositions, heavy-duty liquid detergent compositions, hard-surface compositions (including hand-washing dishwashing or automatic dishwashing compositions), detergent gels commonly used for laundry, bleach compositions, laundry detergent additives, fabric strengthening compositions, shampoos, bath products, other personal care compositions, and mixtures thereof.

[0120] The pouch can be prepared by any suitable method. For example, the method may include the steps of: providing a water-soluble membrane as described herein; shaping the membrane to form an open compartment; providing the composition to the open compartment; and sealing the open compartment, for example, with a second water-soluble membrane to form a pouch having a sealed compartment containing the composition encapsulated therein.

[0121] Different compartments of multi-compartment pouches can be prepared together in a parallel manner, wherein the resulting pouches, linked together, can be separated by cutting or not. Alternatively, the compartments can be prepared individually.

[0122] The pouch can be prepared according to a method comprising the following steps: a) forming a first compartment (as described above); b) forming notches in some or all of the closed compartments formed in step (a) to create a second molded compartment, which is superimposed on top of the first compartment; c) filling and sealing the second compartment with a third membrane; d) sealing the first, second, and third membranes; and e) cutting the membranes to produce a multi-compartment pouch. The notches formed in step (b) can be obtained by applying a vacuum to the compartments obtained in step (a).

[0123] The second and / or third compartments may be prepared in separate steps and then combined with the first compartment, as described in European Patent Application No. 08101442.5 or WO 2009 / 152031.

[0124] The pouch can be prepared according to a method comprising the following steps: a) using heat and / or vacuum, on a first molding machine, to form a first compartment using a first film; b) filling the first compartment with a first composition; c) on a second molding machine, optionally using heat and vacuum, deforming a second film to prepare a second molded compartment and optionally a third molded compartment; d) filling the second compartment and optionally the third compartment; e) sealing the second compartment and optionally the third compartment using a third film; f) placing the sealed second compartment and optionally the third compartment on the first compartment; g) sealing the first, second, and optionally third compartments; and h) cutting the film to produce a multi-compartment pouch.

[0125] The first and second molding machines can be selected based on their suitability for performing the above methods. The first molding machine can be a horizontal molding machine, and the second molding machine can be a rotary drum molding machine, for example, located above the first molding machine.

[0126] It should be understood that by using appropriate feed stations, it is possible to manufacture multi-compartment pouches containing many different or distinct compositions and / or different or distinct liquid, gel, or paste compositions.

[0127] The film and / or pouches can be sprayed or coated with suitable materials (such as surfactants, lubricants, repellents, or mixtures thereof). The film and / or pouches can be printed, for example, with inks and / or surfactants.

[0128] The film-encapsulated compositions described herein can have any suitable viscosity, depending on factors such as the formulation and the purpose of the composition. The composition can be produced in 20 seconds. -1 It exhibits high shear viscosity values ​​of 100 cP to 3,000 cP, 300 cP to 2,000 cP, or 500 cP to 1,000 cP at a shear rate and a temperature of 20°C, and within 1 second... -1 The viscosity has a low shear viscosity value of 500 cP to 100,000 cP, or 1,000 cP to 10,000 cP, or 1,300 cP to 5,000 cP at a shear rate and a temperature of 20°C. Methods for measuring viscosity are known in the art. According to this disclosure, viscosity measurements are performed using a rotational rheometer (e.g., TA Instruments AR550). This instrument includes a 40 mm 2° or 1° tapered clamp with a gap of approximately 50 μm to 60 μm for isotropic liquids, or a 40 mm flat steel plate with a 1000 μm gap for containing liquid particles. Measurements are performed using a process that includes a conditioning step, peak holding, and a continuous gradient step. The conditioning step involves setting the measurement temperature at 20°C and, in 10 s… -1 A 10-second pre-shear was performed at the selected shear rate, followed by 60 seconds of equilibration at the chosen temperature. Peak retention involved applying a 0.05-second pre-shear at 20°C. -1The shear rate was set for 3 minutes, with samples taken every 10 seconds. A continuous gradient step was performed at 20°C at 0.1 s⁻¹. -1 up to 1200s -1 The shear rate was set for 3 minutes to obtain full flow characteristics.

[0129] When in the form of sachets, the compositions disclosed herein may contain the components described in more detail below.

[0130] spices

[0131] Flavors may include pure flavorings, encapsulated flavorings, or mixtures thereof. Preferably, flavorings include pure flavorings. A portion of the flavoring may be encapsulated in a core-shell encapsulator.

[0132] As used herein, the term "fragrance" includes fragrance raw materials (PRMs) and fragrance harmonizers. As used herein, the term "fragrance raw material" refers to a compound having a molecular weight of at least about 100 g / mol, and which may be used alone or in combination with other fragrance raw materials to impart odor, aroma, flavor, or fragrance. As used herein, the terms "fragrance component" and "fragrance raw material" are interchangeable. As used herein, the term "fragrance harmonizer" refers to a mixture of two or more PRMs.

[0133] A portion of the fragrance may be an encapsulated fragrance. The fragrance may be encapsulated in a core-shell encapsulation. The encapsulation may include a core and walls, wherein the walls act as a shell at least partially surrounding the core. The core may contain beneficial agents such as fragrance. The walls may include an outer surface, which may include a coating. The coating may contain a functional polymer. These elements are discussed in more detail below.

[0134] The encapsulation may have a wall that at least partially surrounds the core. The wall may include a wall material selected from polyethylene; polyamide; polystyrene; polyisoprene; polycarbonate; polyester; polyacrylate; acrylics; amino plastics; polyolefins; polysaccharides such as alginate and / or deacetylated chitosan; gelatin; shellac; epoxy resins; vinyl polymers; water-insoluble inorganic substances; siloxanes; and mixtures thereof. The wall material may be selected from amino plastics, acrylics, acrylates, and mixtures thereof.

[0135] The outer wall of the encapsulation may include a coating. Some coatings can improve deposition on a target surface, such as a fabric. The encapsulation may have a coating-to-wall weight ratio of about 1:200 to about 1:2, about 1:100 to about 1:4, or even about 1:80 to about 1:10.

[0136] The coating may contain functional polymers. The coating may contain cationic functional polymers. Cationic polymers may be selected from polysaccharides, cationic modified starch, cationic modified guar gum, polysiloxanes, copolymers of polydiallyldimethylammonium halide, polydiallyldimethylammonium chloride and vinylpyrrolidone, acrylamide, imidazole, imidazoline halides, imidazolonium halides, polyethyleneamine, polyethyleneformamide, polyallylamine, copolymers thereof, and mixtures thereof. The coating may contain polymers selected from polyvinyl alcohol, polyethyleneformamide, polyallylamine, copolymers thereof, and mixtures thereof.

[0137] The core of the encapsulation may contain beneficial agents. Suitable beneficial agents may include fragrance ingredients, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lipids, skin coolants, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleaching agent particles, silica particles, odor reducers, odor control materials, chelating agents, antistatic agents, softeners, insect and moth repellents, colorants, antioxidants, chelating agents, base agents, sterilizing cover sheets and shape control agents, smoothers, wrinkle control agents, hygiene treatment agents, disinfectants, microbial control agents, mold control agents, mildew control agents, antiviral agents, desiccants, stain repellents, detergents, and fabric fresheners. Agents and freshness prolonging agents, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retainers, optical brighteners, color restorers / restorers, anti-fading agents, whitening enhancers, anti-abrasion agents, anti-friction agents, fabric insulators, anti-pilling agents, defoamers, anti-foaming agents, UV protectants, light fading inhibitors, anti-allergens, enzymes, waterproofing agents, fabric comfort agents, shrinkage inhibitors, stretch inhibitors, stretch recovery agents, skin care agents, glycerin, and natural active substances, antibacterial active substances, antiperspirant active substances, cationic polymers, dyes, and mixtures thereof. Beneficial agents may include fragrance ingredients.

[0138] The encapsulation may include a core containing fragrance ingredients and a wall containing melamine formaldehyde and / or cross-linked melamine formaldehyde, wherein the wall also includes a coating on the outer surface of the wall, wherein the coating contains a functional polymer such as polyvinyl formamide.

[0139] organic solvents

[0140] Organic solvents can be used in the pouch compositions of this disclosure, for example, to enhance product stability. However, organic solvent loss in the pouches described herein can cause problems such as product instability, sticky or greasy pouches. The water-soluble film of this disclosure, together with the compositions and containers of this disclosure, is believed to minimize organic solvent loss while providing other beneficial pouch effects such as pouch integrity, film plasticity, dissolution in use, and / or fragrance release.

[0141] Other ingredients

[0142] The pouch compositions described herein may contain one or more of the following non-limiting ingredients: fabric care aids; stain-removing enzymes; deposition aids; rheology modifiers; detergent builders; bleach; bleaching agents; bleaching precursors; bleaching synergists; bleaching catalysts; fragrance-loaded zeolites; starch encapsulation blends; polyglycerol esters; whitening agents; pearlescent agents; enzyme stabilizing systems; scavenging agents; fixatives containing anionic dyes; complexing agents containing anionic surfactants; and mixtures thereof; optical brighteners. Or fluorescent agents; polymers, including but not limited to detergency polymers and / or dirt-suspending polymers; dispersants; defoamers; non-aqueous solvents; fatty acids; defoaming agents, such as silicone defoaming agents; cationic starch; scum dispersants; direct dyes; tinting dyes; colorants; opacifiers; antioxidants; water-soluble growth promoters, such as toluenesulfonate, isopropylbenzenesulfonate, and naphthalenesulfonate; colored patches; colored beads, spheres, or extrudates; clay softeners; antibacterial agents; in addition to or alternatively, the composition may contain surfactants, quaternary ammonium compounds, and / or solvent systems. Quaternary ammonium compounds may be present in fabric reinforcing agent compositions, such as fabric softeners, and contain quaternary ammonium cations with the structure NR4. + A positively charged polyatomic ion, wherein R is an alkyl group or an aryl group.

[0143] How to use

[0144] The container system described herein is suitable for storing, transporting, and / or selling the small bags contained therein.

[0145] Any pouch described herein and the household composition contained therein can be used to treat a substrate, such as a fabric or a hard surface, for example, by contacting the substrate with a film, article, and / or composition contained therein. The contact step can be performed manually or in an automatic machine, such as an automatic (top- or front-loaded) washing machine or an automatic dishwasher. The contact step can be performed in the presence of water, which can be at a temperature of up to about 80°C, or up to about 60°C, or up to about 40°C, or up to about 20°C, or up to about 15°C, or up to about 10°C, or up to about 5°C. Multiple rinsing cycles or even a single rinsing cycle can be performed after the contact step. The method may include the step of opening a closed container and contacting the pouch contained therein. The method may also include the step of closing the container.

[0146] This disclosure further relates to the use of a water-soluble film that provides a pleasant fragrance experience when the container is opened, wherein the water-soluble film forms a pouch and at least partially encapsulates a home care composition comprising fragrance and an organic solvent within a compartment, and wherein the water-soluble film comprises a polyvinyl alcohol (PVOH) resin blend comprising a first PVOH polymer comprising a first anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate unit, and the PVOH resin blend further comprising a second PVOH polymer selected from: a) a PVOH polymer comprising a second anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate unit, or b) a PVOH homopolymer consisting essentially of a vinyl alcohol monomer unit and optionally a vinyl acetate unit.

[0147] Example

[0148] The effect of eutectic type and amount on reducing the melting temperature of PVOH was investigated by preparing PVOH compositions with different amounts of eutectic solvent. Compositions of PVOH polymer and conventional plasticizer propylene glycol were also prepared as controls. The compositions were prepared by dissolving a specific ratio of PVOH polymer and eutectic solvent component in water and drying to form a film to remove excess water, followed by solution casting of the film. Table 2 illustrates the use of SELVOL, sold by Sekisui Specialty Chemicals LLC, Dallas, TX. TM The composition prepared from polyvinyl alcohol 205 has a reduced melting temperature. It has a degree of hydrolysis of 88 mol%, a solution viscosity of 5.7 cP at 4 wt%, a weight-average molecular weight of about 50,000 g / mol, and a reported melting temperature of about 180 °C to about 190 °C.

[0149] Table 2: Melt content of PVOH compositions containing different amounts of conventional plasticizers and eutectic solvents as measured by DSC temperature

[0150]

[0151] *PVOH is SELVOL TM Polyvinyl alcohol 205

[0152] **It was observed that the membranes formed from these compositions had lower mechanical strength than other membranes in the dataset.**

[0153] Table 3 illustrates the melting temperatures of compositions prepared using blends of PVOH polymers, wherein the PVOH blends consist of 50 wt% PVOH with a MW of 85 K to 125 K and a degree of hydrolysis of 87 mol% to 89 mol% and 50 wt% PVOH with a MW of 145 K to 185 K and a degree of hydrolysis of 87 mol% to 89 mol%.

[0154] Table 3: Melt content of PVOH compositions containing different amounts of conventional plasticizers and eutectic solvents as measured by DSC. temperature

[0155]

[0156] * indicates that no sample was prepared.

[0157] The melting temperature of compositions containing PVOH polymers is not affected by the propylene glycol content of 5% to 15% by weight. Compared to PVOH alone and PVOH / propylene glycol controls, compositions containing different types of eutectic solvents exhibit a lower melting temperature.

[0158] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​cited. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0159] Unless expressly excluded or otherwise limited, every reference cited herein, including any cross-references or related patents or patent applications, and any patent application or patent claiming priority to or benefiting from it, is incorporated herein by reference in its entirety. Reference to any reference is not an endorsement of it as prior art to any disclosed or protected art herein, nor is it an endorsement of any such invention, either on its own or in combination with any one or more references. Furthermore, where any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in referenced documents, the meaning or definition given to that term in this invention shall prevail.

[0160] While specific embodiments of the invention have been illustrated and described by way of example, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications falling within the scope of the invention be covered by the appended claims.

Claims

1. A water-soluble membrane composition, said water-soluble membrane composition comprising: Polyvinyl alcohol (PVOH) polymer; Eutectic solvent, The water-soluble film composition of the aforementioned water-soluble film contains less than 1% by weight of a conventional plasticizer selected from glycerol, diglycerol, sorbitol, ethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, polyether polyol, 2-methyl-1,3-propanediol, cholinesterase, and mixtures thereof. The eutectic solvent comprises a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA), wherein the HBD is selected from: maleic acid, malic acid, lactic acid, fumaric acid, acetic acid, ascorbic acid, levulinic acid, salicylic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, citric acid, and their salts; sucrose, xylose, trehalose, glucose, and fructose; erythritol, xylitol, and mannitol; and urea, N-methylurea, dimethylurea, and caprolactam, and the HBA is selected from: arginine, proline, alanine, phenylalanine, glutamine, lysine, glycine, betaine, amine oxide, pyridine, pyrrole, and quaternary ammonium compound salts.

2. The water-soluble membrane composition according to claim 1, wherein the polyether polyol comprises up to 400 MW of polyethylene glycol.

3. The water-soluble film composition according to claim 1, wherein the polyether polyol comprises diethylene glycol, triethylene glycol or tetraethylene glycol.

4. The water-soluble membrane composition according to claim 1, wherein the HBD and the HBA are present in a molar ratio of 1:1 to 1:

3.

5. The water-soluble film composition according to claim 1, wherein the composition has a melting temperature of less than 170°C.

6. The water-soluble film composition according to claim 1, wherein the composition comprises 1% to 20% by weight of the eutectic solvent.

7. The water-soluble membrane composition according to claim 1, wherein the composition further comprises 0.01% to 20% by weight of a beneficial agent.

8. The water-soluble membrane composition according to claim 7, wherein the beneficial agent is at least one of the following: fragrance, finishing aid, odor control and removal agent, odor neutralizer, polymer dye transfer inhibitor, cationic deposition enhancing polymer, detergent, heavy metal ion chelating agent, surfactant, foam stabilizing polymer, pH adjuster, fabric softener, antistatic agent, dye fixing agent, dye abrasion inhibitor, antiwrinkle agent, silicone, detergent polymer, dirt-capturing polymer, flocculant polymer, scale repellent, colorant, anaerobic agent. Anti-redeposition agents, bleaching activators, bleaching catalysts, bleaching synergists, bleaching agents, enzymes, coenzymes, enzyme stabilizers, crystal growth inhibitors, anti-discoloration agents, antioxidants, metal ion salts, corrosion inhibitors, antiperspirants, plant derivatives, plant extracts, skin sensitizers, astringents, anti-acne agents, anti-dandruff agents, defoamers, cosmetic bactericides, denaturing agents, topical analgesics, film-forming agents or materials, skin conditioning agents, skin treatment agents, sunscreens, insect repellents, antimicrobial agents, their derivatives, and mixtures thereof.

9. The water-soluble film composition according to claim 7, wherein the beneficial agent is at least one of the following: essential oils, buffers, anti-wrinkle agents, pigments, zinc pyrithione, cosmetic astringents, pharmaceutical astringents, skin bleaching agents and whitening agents, skin soothing and / or healing agents and derivatives thereof, derivatives thereof, and mixtures thereof.

10. The water-soluble film composition according to claim 7, wherein the beneficial agent is at least one of the following: anti-wrinkle agent, pre-fragrance, alkalinity source, silicone oil, cationic organosilicon, silicone rubber compound, bittering agent, photobleaching agent, plant tissue extract, vegetable oil, herbal medicine, salicylic acid, copolymer of eicosene and vinylpyrrolidone, hydroquinone, kojic acid, magnesium ascorbate phosphate, ascorbate glucoside, pyridoxine, humectant, monoterpene, diterpene, triterpene, β-ionol, cedrol, vitamin, antibacterial agent, antifungal agent, derivatives thereof, and mixtures thereof.

11. The water-soluble membrane composition according to claim 7, wherein the beneficial agent is at least one of the following: high-refractive-index organosilicon, plant seed extract, ascorbic acid, panthenol and its derivatives, pantothenic acid and its derivatives, occlusive agents, their derivatives, and mixtures thereof.

12. The water-soluble film composition according to claim 7, wherein the beneficial agent is at least one of the following: organosilicon resin, botanical extract, menthyl lactate, ethyl panthenol, allantoin, bisabolol, dipotassium glycyrrhizate, vitamin D compound, derivatives thereof, and mixtures thereof.

13. The water-soluble membrane composition according to claim 12, wherein the botanical extract is menthol, camphor, or eugenol.

14. The water-soluble film composition according to claim 7, wherein the beneficial agent is at least one of the following: clove oil, eucalyptus oil, witch hazel extract, aloe vera juice, derivatives thereof, and mixtures thereof.

15. The water-soluble film composition according to claim 7, wherein the beneficial agent is temperature-sensitive.

16. A method for melt flow processing of the water-soluble film composition according to claim 1, wherein the method is selected from the group consisting of injection molding, blow molding, filament extrusion and optionally granulation, film extrusion, melt spinning of fibers and / or nonwoven substrates, 3D printing, rotational molding and granulation.

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