Biodegradable microcapsules containing low log P fragrances
The biodegradable core-shell microcapsules with self-polymerized polyisocyanate shells and modified pea protein encapsulate low log P fragrances, addressing encapsulation challenges and ensuring stability and environmental sustainability.
Patent Information
- Application Number
- JP2025542325
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-01-26
- Filing Date
- 2024-01-23
- Publication Date
- 2026-01-29
AI Technical Summary
Existing microcapsules struggle to encapsulate perfume ingredients with reactive or water-soluble components, leading to loss or poor encapsulation, particularly for low log P fragrances, which are difficult to incorporate due to high water solubility and reactivity with conventional polymer shells.
A biodegradable core-shell microcapsule slurry is developed using self-polymerized polyisocyanate shells with modified pea protein as a dispersant and gum arabic, encapsulating low log P fragrances with a log P value ranging from 0.5 to 2.2, forming a stable and biodegradable microcapsule structure.
The microcapsules effectively encapsulate low log P fragrances, improving stability and preventing leakage, while being biodegradable and suitable for use in consumer products without discoloration issues.
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Figure 2026503597000001_ABST
Abstract
Description
[Technical Field]
[0001] The present disclosure relates to a biodegradable core-shell microcapsule slurry comprising microcapsules. In particular, the microcapsules have walls formed by the self-polymerization of polyisocyanate in the presence of modified pea protein as a dispersant. The microcapsules also have a core containing a low log P perfume. Also disclosed are consumer products containing such core-shell microcapsule slurries and methods for producing such core-shell microcapsule slurries. [Background technology]
[0002] Microcapsules are useful in a variety of applications requiring time-delayed and time-controlled delivery, application, or release of perfume or other actives.
[0003] Conventional microcapsules each have a polymer shell that encapsulates the active substance within the microcapsule core. The polymer shell is typically formed via an interfacial polymerization reaction, i.e., polymerization that occurs at the interface between an aqueous phase and an oil phase. These microcapsules have been developed to provide good performance in various consumer products, such as laundry detergents. See, for example, U.S. Pat. No. 7,491,687, U.S. Pat. No. 6,045,835, U.S. Patent Application Publication No. 2014 / 0287008, and International Publication No. 2015 / 023961. Polyurea microcapsules have been developed to deliver perfumes. Their preparation involves a polymerization reaction between wall-forming materials, such as polyisocyanates and polyamines. During the polymerization reaction, polyisocyanates can react with many perfume ingredients, such as primary alcohols contained in fragrance accords. Additionally, other wall-forming materials, such as polyamines, are reactive toward aldehyde perfume ingredients. Primary alcohols and aldehydes are common components in many fragrance accords. Such perfumes are not suitable for encapsulation by conventional microcapsules. In addition, perfume ingredients that are highly water-soluble are also not suitable for conventional encapsulation because they tend to remain in the aqueous phase instead of being encapsulated in the microcapsule oil core. It remains a challenge to encapsulate perfumes and other active substances without losing either reactive or water-soluble components.
[0004] Methods for incorporating biodegradable polymers into microcapsule compositions have been described. For example, U.S. Patent No. 10,034,819 B2 and U.S. Patent Application Publication No. 2019 / 0240124 A1 teach microcapsules having an inner shell and an outer shell, where the outer shell is produced by complex coacervation of a first polyelectrolyte such as gelatin and a second polyelectrolyte such as carboxymethylcellulose, sodium carboxymethyl guar gum, xanthan gum, and vegetable gum.
[0005] Similarly, EP 2588066 B1 describes coacervated capsules prepared with a coating layer composed of a protein and optionally a non-protein polymer.
[0006] Furthermore, EP 2811846 B1 describes the use of protein aggregates as an interfacial layer around hydrophobic materials.
[0007] EP 1855544 B8 teaches the use of encapsulation of active ingredients in a matrix composed of 0.5-95 wt% anionic polysaccharides and 0.5-95 wt% peptides with molecular weights in the range of 0.3-12 kDa.
[0008] EP 3746217 A1 and WO 2020 / 195132 A1 describe the preparation of core-shell microcapsules by cross-linking proteins into the wall of the microcapsules.
[0009] US Patent No. 10,166,196 B2 discloses the aggregation of primary microcapsules consisting of a primary shell and an outer shell, the outer shell being the primary shell, the outer shell being the product of a complex coacervation reaction between a first protein such as pea or soy protein and a second polymer such as agar, gellan gum, gum arabic, casein, cereal prolamin, pectin, alginate, carrageenan, xanthan gum, canola protein, diutan gum, locust bean gum, or welan gum. Summary of the Invention [Problem to be solved by the invention]
[0010] Therefore, these existing solutions still have limitations and do not adequately teach how to overcome the above-mentioned problems. Thus, there remains a need to develop microcapsule compositions suitable for encapsulating active agents having ingredients that are sustainable and biodegradable. [Means for solving the problem]
[0011] The present disclosure provides a core-shell microcapsule slurry comprising: (a) core-shell microcapsules, the microcapsule core comprising an active substance and the microcapsule shell comprising a self-condensing polyisocyanate; (b) a dispersing agent comprising a modified pea protein; and (c) a hydrocolloid comprising gum arabic; the active substance comprises a low log P fragrance having a log P value ranging from 0.5 to 2.2, the amount of the low log P fragrance being 3% to 18% by weight based on the weight of the active substance; and the core-shell microcapsule slurry is white.
[0012] To improve the understanding of the concepts presented herein, embodiments are illustrated in the accompanying figures. [Brief explanation of the drawings]
[0013] [Figure 1] Figure 1 shows force curves generated in capsule cutting experiments for capsules prepared with whey protein according to Example 7 of WO 2020 / 131875 A2, with citric acid added prior to hardening to achieve a hardening pH of 5 (left diagram, whey); with pea protein according to Example 2 herein (middle diagram, pea); and with pea protein with optimized hardening temperature and pH as described in Example 9 herein (right diagram, temperature and pH optimized pea). This analysis showed that capsule wall properties can be altered by protein choice and, more importantly, by optimizing the hardening profile and pH of the capsule formation reaction. DETAILED DESCRIPTION OF THE INVENTION
[0014] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other features and benefits of any one or more of the embodiments will become apparent from the following detailed description and claims.
[0015] As used herein, the terms "comprise," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent in such process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, "or" means an inclusive or, not an exclusive or. For example, condition A or condition B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and A and B are both true (or exist).
[0016] Additionally, the use of "a" or "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that otherwise is meant.
[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. Additionally, the materials, methods, and examples are illustrative only and not intended to be limiting.
[0018] When an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and / or lower preferred values, this should be understood to specifically disclose all ranges formed by any pairing of any upper or preferred value of the range with any lower or preferred value of the range, regardless of whether the ranges are separately disclosed. When a range of numerical values is recited herein, unless otherwise specified, the range is intended to include the endpoints, and all integers and fractions within the range. For example, if a range of "1 to 10" is recited, this recited range should be interpreted to include ranges such as "1 to 8," "3 to 10," "2 to 7," "1.5 to 6," "3.4 to 7.8," "1 to 2 and 7 to 10," "2 to 4 and 6 to 9," "1 to 3.6 and 7.2 to 8.9," "1 to 5 and 10," "2 and 8 to 10," and "1.5 to 4 and 8."
[0019] The present disclosure illustratively described herein can suitably be practiced in the absence of any element, limitation or limitations not specifically disclosed herein. Although compositions and methods are described herein in terms of "comprising" various components or steps, unless otherwise specified, the compositions and methods can also "consist essentially of" or "consist of" the various components or steps.
[0020] All parts, percentages and proportions referred to in this specification and claims are by weight unless otherwise specified.
[0021] Before addressing the details of the embodiments below, some terms will be defined or clarified.
[0022] As used herein, the term "elevated temperature" means a temperature above room temperature (22°C).
[0023] As used herein, the terms "capsule," "microcapsule," and "core-shell microcapsule" are used interchangeably and refer to a substantially spherical structure having a clearly defined core and a clearly defined envelope or wall or shell. The "core" contains the active substance or substance to be microencapsulated. The terms "wall" and "shell" are used interchangeably to refer to the structure formed by the microencapsulating polymer that surrounds the microencapsulated active substance core.
[0024] The term "logP" as used herein refers to the octanol / water partition coefficient (P) of a perfume ingredient given in the form of the logarithm logP to base 10. The octanol / water partition coefficient of a perfume ingredient is the ratio between the equilibrium concentration of the perfume ingredient in octanol and the equilibrium concentration in water. The logP values of many perfume ingredients are reported, for example, in the Pomona 92 database available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, USA.
[0025] As used herein, the term "self-condensing polyisocyanate" refers to a polyurea formed by the self-polymerization of a polyisocyanate in the presence of water. Those skilled in the art understand that an isocyanate can react with water to form an amine, which can further react with an isocyanate to form a urea bond. Thus, a polyisocyanate can self-polymerize in the presence of water to form a polyurea.
[0026] As used herein, the terms "g," "mg," and "μg" refer to "gram," "milligram," and "microgram," respectively. The terms "L" and "mL" refer to "liter" and "milliliter," respectively.
[0027] Polyisocyanate As used herein, the terms "multifunctional isocyanate" and "polyisocyanate" can be used interchangeably and refer to a compound having two or more isocyanate (-NCO) groups. The polyisocyanate can be aromatic, aliphatic, linear, branched, or cyclic. In some embodiments, the polyisocyanate contains an average of two to four isocyanate groups. In some embodiments, the polyisocyanate contains at least three isocyanate functional groups. In some embodiments, the polyisocyanate is water-insoluble. In certain aspects, the polyisocyanate is an oligomeric polyisocyanate derived from the monomeric diisocyanate hexamethylene diisocyanate (HDI). In certain aspects, the polyisocyanate is an oligomeric polyisocyanate having biuret, isocyanurate, allophanate, uretdione, and / or oligomeric HDI structures. Exemplary polyisocyanates are sold under the trade names TAKENATE® (e.g., TAKENATE® D-110N (Mitsui Chemicals)), DESMODUR® (Covestro), BAYHYDUR® (Covestro), and LUPRANATE® (BASF).
[0028] In some embodiments, the polyisocyanate is an aromatic polyisocyanate. Desirably, the aromatic polyisocyanate contains a phenyl, tolyl, xylyl, naphthyl, or diphenyl moiety as the aromatic component. In some embodiments, the aromatic polyisocyanate is selected from the group consisting of polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of toluene diisocyanate, trimethylolpropane adducts of xylylene diisocyanate, and mixtures thereof.
[0029] In some embodiments, the aromatic polyisocyanate has the structural formula shown below: [ka] (wherein n can vary from 0 to a desired number (e.g., 0 to 50, 0 to 20, 0 to 10, or 0 to 6)), including structural isomers thereof. Preferably, the number n is limited to less than 6. The polyisocyanate may be a mixture of polyisocyanates where the value of n can vary from 0 to 6. When the polyisocyanate is a mixture of various polyisocyanates, the average value of n is preferably 0.5 to 1.5.
[0030] In some embodiments, the aromatic polyisocyanate has the structural formula shown below: [ka] (Wherein, R is C1 to C 10 Alkyl, C1-C 10 ester, or isocyanurate), including its structural isomers. Representative polyisocyanates having this structure are sold under the trade names TAKENATE® D-110N (Mitsui), DESMODUR® L75 (Covestro), and DESMODUR® IL (Covestro).
[0031] The trimethylolpropane adduct of xylylene diisocyanate has the following structural formula: [ka] It has.
[0032] In some embodiments, the aromatic polyisocyanate is selected from the group consisting of 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), xylylene diisocyanate (XDI), tetramethylxylol diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, dialkyldiphenylmethane diisocyanate and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of toluylene diisocyanate (TDI), 4,4'-diisocyanatophenylperfluoroethane, phthalic acid bisisocyanatoethyl ester, aromatic polyisocyanates having reactive halogen atoms, and mixtures thereof. In some embodiments, the aromatic polyisocyanate having reactive halogen atoms is selected from the group consisting of 1-chloromethylphenyl 2,4-diisocyanate, 1-bromomethyl-phenyl 2,6-diisocyanate, 3,3-bischloromethyl ether 4,4′-diphenyl diisocyanate, and mixtures thereof.
[0033] In some embodiments, the polyisocyanate is an aliphatic polyisocyanate selected from the group consisting of a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a biuret of hexamethylene diisocyanate, and mixtures thereof. In some embodiments, the aliphatic polyisocyanate is selected from the group consisting of 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinated aliphatic diisocyanates, brominated aliphatic diisocyanates, phosphorus-containing aliphatic diisocyanates, tetramethoxybutane 1,4-diisocyanate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, and mixtures thereof. In some embodiments, the polyisocyanate comprises a sulfur-containing polyisocyanate, such as may be obtained by reacting hexamethylene diisocyanate with thiodiglycol or dihydroxydihexyl sulfide. In some embodiments, the polyisocyanate is an aliphatic diisocyanate selected from the group consisting of trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,2-diisocyanatododecane, dimeric fatty acid diisocyanates, and mixtures thereof.
[0034] In some embodiments, the weight average molecular weight of the polyisocyanate ranges from 250 Da to 1000 Da or from 275 Da to 500 Da. In some embodiments, the polyisocyanate used to prepare the microcapsule shell is a single polyisocyanate. In other embodiments, the polyisocyanate is a mixture of polyisocyanates. In some embodiments, the mixture of polyisocyanates includes an aliphatic polyisocyanate and an aromatic polyisocyanate. In some embodiments, the polyisocyanate is a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylene diisocyanate. In some embodiments, the polyisocyanate is an aliphatic polyisocyanate or a combination of aliphatic polyisocyanates without any aromatic polyisocyanate. In some embodiments, the polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate, and the microcapsule shell includes a self-condensed trimethylolpropane adduct of xylylene diisocyanate.
[0035] active substance The microcapsule core contains an encapsulated active, non-limiting examples of which include those described in WO 2016 / 049456. These actives may include fragrances, pro-fragrances, flavors, malodor counteractants, vitamins or derivatives thereof, anti-inflammatory agents, anesthetics, analgesics, antibacterial actives, antivirals, anti-infectives, anti-acne agents, skin lightening agents, insect repellents, animal repellents, bird repellents, emollients, skin moisturizers, wrinkle control agents, UV protection agents, fabric softening actives, hard surface cleaning actives, skin or hair conditioning agents, flame retardants, antistatic agents, taste modulators, cells, live bacteria, antioxidants, self-tanning agents, dihydroxyacetone, coolants, sensates, malodor reactive substances, cosmetic actives, agricultural actives, pesticides, insecticides, herbicides, fungicides, or combinations thereof. Cosmetic actives include vitamins, sun filters and sunscreens, anti-aging agents, anti-wrinkle agents, antioxidants, lifting agents, firming agents, anti-blemish agents, anti-redness agents, thinning agents, draining agents, moisturizers, soothing agents, scrubbing or exfoliating agents, anti-shining agents, sebum regulating agents, skin lightening actives, self-tanning actives, tanning accelerators, or combinations thereof. In some embodiments, the actives include natural extracts and / or essential oils.
[0036] In some embodiments, the active is selected from the group consisting of a fragrance, a pro-fragrance, a malodor counteractant, and combinations thereof. In some embodiments, the active comprises a fragrance. In some embodiments, the active comprises a low log P fragrance having a log P value ranging from 0.5 to 2.2, and the amount of the low log P fragrance is 3% to 18% by weight based on the weight of the active. In some embodiments, the amount of the low log P fragrance is at least 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% by weight based on the weight of the active. In some embodiments, the amount of the low log P fragrance is no more than 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, or 7% by weight based on the weight of the active. In some embodiments, the amount of low log P fragrance ranges from 3% to 15%, 4% to 12%, or 5% to 10% by weight based on the weight of the active.
[0037] In some embodiments, the low log P fragrance has a water solubility of at least 1 g / L, 1.5 g / L, 2 g / L, 2.5 g / L, 3 g / L, or 3.5 g / L as measured at 22.5° C. In some embodiments, the low log P fragrance is selected from the group consisting of ethyl vanillin, coumarin, 4-(4-hydroxyphenyl)butan-2-one (oxyphenylone, CAS number: 5471-51-2), p-anisaldehyde, 2-ethyl-3-hydroxy-4H-pyran-4-one (veltol or ethyl maltol, CAS number: 4940-11-8), benzaldehyde, cinnamaldehyde, and combinations thereof. In some embodiments, the low log P fragrance is selected from the group consisting of coumarin, 4-(4-hydroxyphenyl)butan-2-one (oxyphenylone, CAS number: 5471-51-2), p-anisaldehyde, 2-ethyl-3-hydroxy-4H-pyran-4-one (veltol or ethyl maltol, CAS number: 4940-11-8), benzaldehyde, cinnamaldehyde, and combinations thereof. In some embodiments, the low log P fragrance is selected from the group consisting of coumarin, p-anisaldehyde, benzaldehyde, cinnamaldehyde, and combinations thereof. In some embodiments, the low log P fragrance comprises ethyl vanillin.
[0038] Low log P perfumes are difficult to encapsulate due to their high water solubility. Low log P perfumes also tend to leak from microcapsules, resulting in poor capsule stability and poor capsule performance during the drying stage of laundry. Furthermore, ethyl vanillin can cause discoloration of the slurry and, therefore, the product to which the slurry is added. It has now been discovered that the core-shell microcapsules of the present disclosure can encapsulate actives (e.g., perfumes) containing high levels of low log P perfume ingredients. Accordingly, the present disclosure provides a core-shell microcapsule slurry comprising: (a) core-shell microcapsules; (b) a dispersing agent comprising modified pea protein; and (c) a hydrocolloid comprising gum arabic. In some embodiments, the hydrocolloid comprises gum arabic, which is added to the aqueous phase during the formation of the slurry prior to the emulsification step. In some embodiments, the microcapsule slurry is an aqueous suspension of microcapsules. In some embodiments, the microcapsule slurry is white. The microcapsule slurry can be used directly in consumer products. The microcapsule slurry may also be washed, coated, dried (e.g., spray-dried), and / or combined with one or more other microcapsules, active substances, and / or carrier materials. Core-shell microcapsules comprise a microcapsule core (i.e., core or microcapsule core) and a microcapsule shell (i.e., shell or microcapsule shell). The microcapsule core comprises an active substance, and the microcapsule shell comprises a self-compacting polyisocyanate. Microcapsules of the present disclosure need not be perfectly spherical. In some embodiments, core-shell microcapsules have a diameter of 1 to 100 microns. As used herein with respect to microcapsules, the term "diameter" refers to the diameter of a sphere having the same volume as the microcapsule.
[0039] The microcapsule core contains an active substance. The active substance includes a low log P fragrance having a log P value ranging from 0.5 to 2.2, and the amount of the low log P fragrance is 3% to 18% by weight based on the weight of the active substance. In some embodiments, the microcapsule core further includes an auxiliary core material, such as a solvent, an emollient, and / or a core modifier material. Examples of auxiliary core materials include nanoscale solid particulate materials, polymeric core modifiers, solubility modifiers, density modifiers, stabilizers, humectants, viscosity modifiers, pH modifiers, or combinations thereof. Suitable examples of auxiliary core materials include those described in WO 2016 / 049456 and U.S. Patent Application Publication No. 2016 / 0158121. In some embodiments, the solvent includes caprylic / capric triglyceride. In some embodiments, the solvent includes benzyl benzoate. In some embodiments, the supplemental core material can be present in the wall or on the outside of the capsule in a slurry. In some embodiments, the supplemental core material can be present in the core in an amount of 0.01% to 25% by weight (e.g., 0.5% to 10%) of the capsule.
[0040] The microcapsule shell is formed by the self-polymerization of a polyisocyanate in the presence of water, modified pea protein, and gum arabic. In some embodiments, the polyisocyanate includes or is a trimethylolpropane adduct of xylylene diisocyanate. It has now been discovered that polyisocyanates, such as the trimethylolpropane adduct of xylylene diisocyanate, can self-polymerize in the presence of modified pea protein (as a dispersing agent) when reacted with water to form amine groups, and form a wall material suitable for encapsulating an active substance. In some embodiments, the polyisocyanate does not crosslink with the modified pea protein. In some embodiments, 10%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.2%, or 0.1% or less of the polyisocyanate crosslinks with the modified pea protein. Rather, the modified pea protein appears to function as a scaffold to promote the self-polymerization reaction of the polyisocyanate to form the wall polymer that encapsulates the active substance. Furthermore, gum arabic is added prior to emulsification to promote dissolution of the modified pea protein in the aqueous phase, thereby preventing aggregation. In some embodiments, the microcapsule shell comprises a single type of polymer (i.e., a self-condensing polyisocyanate). In this regard, the microcapsule shell is formed by self-polymerization of one or more polyisocyanates. In some embodiments, the self-condensing polyisocyanates are formed in the absence of exogenous (i.e., added) cross-linking agents, such as polyamines and polyalcohols. In some embodiments, the microcapsule shell is substantially free or free of biopolymers (e.g., pea protein and gum arabic) and / or polyelectrolytes. In some embodiments, the microcapsule shell comprises no more than 15%, 10%, 5%, 3%, 1%, 0.5%, 0.2%, or 0.1% of biopolymer relative to the total weight of the microcapsule shell.In some embodiments, the microcapsule shell comprises no more than 15%, 10%, 5%, 3%, 1%, 0.5%, 0.2%, or 0.1% polyelectrolyte by total weight of the microcapsule shell.
[0041] In some embodiments, the microcapsule shell is biodegradable. The term "biodegradable" as used herein with respect to a material such as an entire microcapsule shell or a polymer of the microcapsule shell means that the material can and / or undergoes physical, chemical, thermal, microbial, biological, and / or ultraviolet or photodegradation without any actual or perceived health and / or environmental hazards. Ideally, a microcapsule shell and / or polymer is considered "biodegradable" if it passes one or more of the following tests: respirometric biodegradation methods in aquatic media available from the Organization for Economic Cooperation and Development (OECD), International Organization for Standardization (ISO), and American Society for Testing and Materials (ASTM) tests, including, but not limited to, OECD 301F or 310 (readily biodegradable), OECD 302 (intrinsic biodegradability), ISO 17556 (solid irritation test), ISO 14851 (freshwater irritation test), ISO 18830 (marine sediment irritation test), OECD 307 (soil irritation test), OECD 308 (sediment irritation test), and OECD 309 (water irritation test). Preferably, the microcapsules are readily biodegradable as determined using the respirometric biodegradation methods in aquatic media, OECD 301F, or OECD 310 tests. More preferably, the microcapsule shell and / or polymer is biodegradable if the shell and / or polymer has a biodegradation rate of at least 20%, 30%, 40%, 50%, or 60%, based on the weight of the shell and / or polymer, within 60 days according to the OECD 301F or OECD 310 test, or most preferably at least 20% biodegradability within 60 days according to the OECD 301F test.
[0042] In some embodiments, the microcapsule shell biodegrades at least 20%, 30%, 40%, 50%, or 60% based on the weight of the shell within 60 days according to OECD 301F or OECD 310. In some embodiments, the microcapsule shell biodegrades at least 20% based on the weight of the shell within 60 days according to OECD 301F or OECD 310.
[0043] The shells of the microcapsules comprise a self-condensing polyisocyanate. In some embodiments, the amount of self-condensing polyisocyanate ranges from 0.1 wt. % to 10 wt. %, preferably from 0.1 wt. % to 8 wt. %, more preferably from 0.2 wt. % to 5 wt. %, and even more preferably from 1.5 wt. % to 3.5 wt. % or from 0.1 wt. % to 5 wt. % based on the weight of the core-shell microcapsule slurry. In some embodiments, the amount of self-condensing polyisocyanate is 1 wt. %, 0.9 wt. %, 0.8 wt. %, 0.7 wt. %, 0.6 wt. %, 0.5 wt. %, 0.4 wt. %, 0.3 wt. %, or 0.2 wt. % or less based on the weight of the core-shell microcapsule slurry.
[0044] In some embodiments, core-shell microcapsules range in diameter from 0.1 microns to 1000 microns (e.g., 0.5 microns to 500 microns, 1 micron to 200 microns, 1 micron to 100 microns, or 1 micron to 50 microns). In some embodiments, core-shell microcapsules are at least 0.1 microns, 0.5 microns, 1 micron, 2 microns, 5 microns, or 20 microns in diameter. In some embodiments, core-shell microcapsules are no greater than 1000 microns, 500 microns, 200 microns, 100 microns, 75 microns, 50 microns, 30 microns, 20 microns, 10 microns, or 5 microns in diameter.
[0045] In some embodiments, the core-shell microcapsule slurry includes a microcapsule-forming aid. In some embodiments, the microcapsule-forming aid is a dispersing agent that promotes the formation of a stable emulsion containing nano- or micro-sized oil droplets to be encapsulated. The microcapsule-forming aid can also improve the performance of the microcapsules by stabilizing the capsules and / or their deposition on a target area or by releasing them into the environment. Performance is measured by the intensity of perfume release during various touchpoints of the user experience, such as the pre-scrub and post-scrub stages of the laundry experience. The pre-scrub stage is when the microcapsules are deposited on fabrics, for example, after a fabric softener containing the microcapsules has been used during a wash cycle. The post-scrub stage is after the microcapsules are deposited on fabrics, where they are broken down by friction or other similar mechanisms. The amount of microcapsule-forming aid can be 0.1% to 40%, 0.1% to 10%, or 0.1% to 5% by weight based on the weight of the microcapsules.
[0046] Examples of microcapsule forming aids include polyvinylpyrrolidone, polyvinyl alcohol, poly(styrene sulfonate), carboxymethyl cellulose, sodium salt of naphthalene sulfonate condensate, copolymers of ethylene and maleic anhydride, alginate, hyaluronic acid, poly(acrylic acid), carboxymethyl cellulose, copolymers of acrylic acid and acrylamide, copolymers of acrylamide and acrylamidopropyltrimonium chloride, terpolymers of (acrylic acid, acrylamide, and acrylamidopropyltrimonium chloride), partially or fully hydrolyzed polyvinyl acetate polymers (i.e., polyvinyl alcohol), or combinations thereof.
[0047] Other microcapsule forming aids include water-soluble salts of alkyl sulfates, alkyl ether sulfates, alkyl isothionates, alkyl carboxylates, alkyl sulfosuccinates, alkyl succinamates, alkyl sulfates such as sodium dodecyl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolysates, acylaspartates, alkyl or alkyl ether or alkylaryl ether phosphate esters, sodium dodecyl sulfate, phospholipids or lecithin, or soap, stearic acid, oleic acid, or sodium, potassium, or ammonium palmitate, alkylarylsulfonates such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, dioctyl sulfosuccinate, sodium dilauryl sulfosuccinate, poly(styrenesulfonate) sodium salt, isobutylene maleic anhydride copolymer, sodium alginate. , cellulose sulfate and pectin, isobutylene maleic anhydride copolymer, gum arabic, carrageenan, pectinic acid, tragacanth gum, almond gum and agar, semi-synthetic polymers such as sulfated cellulose, sulfated methylcellulose, carboxymethyl starch, phosphated starch, lignosulfonic acid, synthetic polymers such as maleic anhydride copolymers (including their hydrolysates), polyacrylic acid, polymethacrylic acid, acrylate butyl acrylate copolymers or crotonic acid homopolymers and copolymers, vinylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid homopolymers and copolymers, and partial amides or partial esters of such polymers and copolymers, carboxy-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and phosphoric acid-modified polyvinyl alcohol, phosphated or sulfated tristyrylphenol ethoxylate.
[0048] In some embodiments, the microcapsule forming aid is a surfactant. Examples of surfactants include, but are not limited to, sulfonated naphthalene-formaldehyde condensates sold under the trade name MORWET® D425 (sodium salt of alkyl naphthalene sulfonate formaldehyde condensates, Akzo Nobel, Fort Worth, TX); partially hydrolyzed polyvinyl alcohols sold under the trade name MOWIOL®, such as MOWIOL® 3-83 (Air Products) or SELVOL® 203 (Sekisui), or polyvinyl alcohols such as Ultalux FP, Ultalux FA, Ultalux AD, OKS-8089 (Sourus); ethylene oxide-propylene oxide block copolymers or poloxomers sold under the trade name PLURONIC®, SYNPERONIC®, or PLURACARE® materials (BASF); FLEXAN® II (Akzo Nobel); ethylene maleic anhydride polymer sold under the trade name ZEMAC® (Vertellus Specialties Inc.); a copolymer of acrylamide and acrylamidopropyltrimonium chloride sold under the trade name SALCARE® SC 60 (BASF); and the Polyquaternium series, such as Polyquaternium 11 ("PQ11"; a copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate; sold by BASF as Luviquat PQ11 AT 1). The surfactant MOWIOL® 3-83 has a viscosity of 2-4 mPa·S (e.g., 3 mPa·S), a degree of hydrolysis of 80-85% (e.g., 83%), an ester value of 170-210 mg KOH / g (e.g., 190 mg KOH / g), and a residual unhydrolyzed acetyl content of 13-18% (e.g., 15%). In certain embodiments, the surfactant is sulfonated polystyrene, for example, the sodium salt of high molecular weight polystyrene sulfonate sold under the trademark FLEXAN® II.
[0049] In some embodiments, the microcapsule formation aid is a processing aid, such as a hydrocolloid, which can improve the colloidal stability of the slurry against coagulation, precipitation, and creaming. In some embodiments, the hydrocolloid is added to the aqueous phase before the emulsification step during the formation of the slurry. The term "hydrocolloid" refers to a broad class of water-soluble or water-dispersible polymers that can be anionic, cationic, zwitterionic, or nonionic in character. Suitable hydrocolloids include polycarbohydrates, such as starch, modified starch, dextrin, maltodextrin, and cellulose derivatives, and their quaternized forms; natural gums, such as alginate esters, carrageenan, xanthan, agar, pectin, pectic acid, gum arabic, tragacanth gum, and karaya gum, guar gum, and quaternized guar gum; gelatin, protein hydrolysates, and their quaternized forms; synthetic polymers and copolymers, such as poly(vinylpyrrolidone-co-vinyl acetate), ... (vinyl alcohol-co-vinyl acetate), poly((meth)acrylic acid), poly(maleic acid), poly(alkyl(meth)acrylate-co-(meth)acrylic acid), poly(acrylic acid-co-maleic acid) copolymer, poly(alkylene oxide), poly(vinyl methyl ether), and poly(vinyl ether-co-maleic anhydride), as well as poly(ethyleneimine), poly((meth)acrylamide), poly(alkylene oxide-co-dimethylsiloxane), poly(aminodimethylsiloxane), Ultrez 20 (acrylates / C10-30 alkyl acrylate crosspolymer), a crosslinked homopolymer of acrylic acid polymerized in cyclohexane and ethyl acetate cosolvent system sold under the trade name CARBOPOL® Ultrez 30, an acrylate copolymer sold under the trade name ACULYN® Excel (acrylate copolymer), and a crosslinked polyacrylic acid polymer (carbomer) sold under the trade name CARBOPOL® 981, and the like, as well as quaternized forms thereof. In certain embodiments, the core-shell microcapsule slurry is prepared in the presence of gum arabic as a hydrocolloid.In certain embodiments, the core-shell microcapsule slurry comprises a hydrocolloid comprising gum arabic.
[0050] In some embodiments, the microcapsule forming aid can be used in combination with carboxymethylcellulose ("CMC"), polyvinylpyrrolidone, polyvinyl alcohol, alkylnaphthalene sulfonate formaldehyde condensate, and / or surfactants during processing to facilitate capsule formation. Examples of surfactants that can be used in combination with the microcapsule forming aid include, but are not limited to, cetyltrimethylammonium chloride (CTAC), poloxomers sold under the trade names PLURONIC® (e.g., PLURONIC® F127), PLURAFAC® (e.g., PLURAFAC® F127), or Miranet-N, a saponin sold under the trade name Q-NATURALE® (National Starch Food Innovation); or gum arabic, such as Seyal or Senegal.
[0051] In certain embodiments, the CMC polymer has a molecular weight ranging from about 90,000 to 1,500,000 daltons, preferably from about 250,000 to 750,000 daltons, and more preferably from 400,000 to 750,000 daltons. The CMC polymer has a degree of substitution ranging from about 0.1 to about 3, preferably from about 0.65 to about 1.4, and more preferably from about 0.8 to about 1.0. The CMC polymer may be present in the microcapsule slurry in an amount of about 0.1% to about 2%, preferably from about 0.3% to about 0.7%, based on the weight of the microcapsule slurry. In other embodiments, the polyvinylpyrrolidone used in the present disclosure is a water-soluble polymer and has a molecular weight ranging from 1,000 to 10,000,000 daltons. Suitable polyvinylpyrrolidones include polyvinylpyrrolidone K12, K15, K17, K25, K30, K60, K90, or combinations thereof. The amount of polyvinylpyrrolidone can be 2-50%, 5-30%, or 10-25% by weight of the microcapsule slurry. Commercially available alkylnaphthalenesulfonate formaldehyde condensates include MORWET® D-425, which is a sodium salt of a naphthalenesulfonate condensate from Akzo Nobel, Fort Worth, TX.
[0052] In some embodiments, the microcapsule forming aid is a food-grade dispersant. The term "food-grade dispersant" refers to a dispersant having qualities suitable for human consumption in food. It may be a natural dispersant or a non-natural dispersant. A natural dispersant refers to a dispersant that exists in nature and is derived from a natural source. Natural dispersants include derivatives that can be salted, desalted, deoiled, fractionated, or modified using natural enzymes or microorganisms. Non-natural dispersants include dispersants that are chemically synthesized by chemical processes that do not involve enzymatic modification.
[0053] Natural dispersing agents include quillaja saponin, lecithin, gum arabic, pectin, carrageenan, chitosan, chondroitin sulfate, modified cellulose, cellulose gum, modified starch, whey protein, pea protein, egg white protein, silk protein, fish gelatin, proteins of porcine or bovine origin, ester gum, fatty acid, or a combination thereof. In certain embodiments, the microcapsule slurry is prepared in the presence of a modified protein as a dispersing agent, such as modified pea protein. In certain embodiments, the core-shell microcapsule slurry contains a dispersing agent comprising a modified protein, such as modified pea protein, particularly modified pea protein isolate.
[0054] In some embodiments, the natural dispersant is a plant storage protein. Plant storage proteins are proteins that accumulate in various plant tissues and function as biological reserves of metal ions and amino acids. Plant storage proteins can be divided into two classes: seed or grain storage proteins and vegetative propagation storage proteins. Seed / grain storage proteins are a set of proteins that accumulate to high levels in seeds / grains during the later stages of seed / grain development, while vegetative propagation storage proteins are proteins that accumulate in vegetative propagation tissues, such as leaves, stems, and tubers (depending on the plant species). During germination, seed / grain storage proteins break down, and the resulting amino acids are used as a nutritional source by the developing seedling. In some aspects, the dispersant used in the preparation of microcapsules is a legume storage protein, particularly a protein extracted from soybean, lupin, pea, chickpea, alfalfa, faba bean, lentil, kidney bean, or a combination thereof. In some embodiments, the plant storage protein is pea protein.
[0055] Pea proteins include pea protein isolates, pea protein concentrates, or combinations thereof. Pea protein isolates and concentrates are generally understood to be composed of several proteins. For example, pea protein isolates and concentrates may include legumin, vicilin, and convicilin proteins. The term "pea protein" is also intended to include partially or fully modified or denatured pea proteins. Individual plant storage proteins (e.g., legumin, vicilin, or convicilin) can also be used in the preparation of the microcapsules of the present disclosure.
[0056] Ideally, the pea proteins of the present disclosure are denatured, preferably without causing gelation of the pea protein. Exemplary conditions for protein (e.g., pea protein) denaturation include, but are not limited to, exposure to heat or cold, changes in pH, exposure to denaturing agents such as detergents, urea, or other chaotropic agents, or mechanical stress, including shear. In some embodiments, the pea protein is partially denatured, for example, 50%, 60%, 70%, 80%, or 85% denatured, based on the total weight of the pea protein. In other embodiments, the pea protein is substantially or completely denatured, for example, at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% denatured, based on the total weight of the pea protein. For example, if an 8% pea protein solution (w / v) is used, the solution can be treated at a temperature of 80°C to 90°C for 20 to 30 minutes (or preferably at 85°C for 25 minutes) to yield substantially denatured pea protein. It is therefore of course possible to use shorter times at higher temperatures, depending on the degree of denaturation desired.
[0057] In particular, chaotropic agents have been found to be particularly useful in providing denatured proteins (e.g., denatured pea proteins) that are useful in preparing the microcapsules of the present disclosure. As is conventional in the art, chaotropic agents are compounds that disrupt hydrogen bonds in aqueous solution, resulting in an increase in entropy. Typically, this reduces the hydrophobic effect that is essential for the three-dimensional structure of proteins. Chaotropes have a positive chaotropic value, i.e., kJ kg on the Hallsworth Scale. -1 An example of a chaotropy value is CaCl2+, which has 92.2 kJ kg -1 , MgCl2kJ kg -1 +54.0, butanol +37.4kJ kg -1 , guanidine hydrochloride + 31.9 kJ kg -1 , and urea + 16.6 kJ kg -1 In a particular embodiment, the chaotropic agent is a guanidinium salt, such as guanidinium sulfate, guanidinium carbonate, guanidinium nitrate or guanidinium chloride. In a particular embodiment, the pea proteins are partially or completely denatured by guanidinium carbonate.
[0058] In addition to natural dispersing agents, non-natural dispersing agents are useful in preparing the microcapsules of the present disclosure, including N-lauroyl-L-arginine ethyl ester, sorbitan ester, polyethoxylated sorbitan ester, polyglyceryl ester, fatty acid ester, or combinations thereof.
[0059] Other food-safe dispersing agents may also be used in the microcapsule slurries of the present disclosure, such as ammonium phosphatides, acetate esters of mono- and diglycerides (Acetem), lactic acid esters of mono- and diglycerides of fatty acids (Lactem), citric acid esters of mono- and diglycerides of fatty acids (Citrem), monoacetyltartaric acid and diacetyltartaric acid esters of mono- and diglycerides of fatty acids (Datem), succinic acid esters of monoglycerides of fatty acids (SMG), ethoxylated monoglycerides, sucrose esters of fatty acids, sucroglycerides, polyglycerol polyricinoleate, propane-1,2-diol esters of fatty acids, and mono- or diglycerides of fatty acids. Examples of suitable oleic acid or oleic acid esters include thermally oxidized soybean oil, sodium stearoyl lactylate (SSL), calcium stearoyl lactylate (CSL), stearyl tartrate, polyglycerol ester of interesterified castor oil acid (E476), sodium stearoyllatylate, sodium lauryl sulfate, polyoxyethylated hydrogenated castor oil (e.g., as sold under the trade name CREMO-PHOR®), block copolymers of ethylene oxide and propylene oxide (e.g., as sold under the trade name PLURONIC®), polyoxyethylene fatty alcohol ethers, and polyoxyethylene stearic acid esters.
[0060] In some embodiments, the core-shell microcapsule slurry also includes a rheology modifier (e.g., xanthan gum), a preservative, an emulsifier, or a combination thereof. In some embodiments, the core-shell microcapsule slurry also includes a rheology modifier. One or more rheology modifiers or viscosity control agents can be added to the microcapsule slurry to achieve a desired viscosity of the slurry so that the microcapsules remain dispersed in the slurry for an extended period of time. During capsule preparation, the rheology modifier is preferably added prior to emulsification of the aqueous and oil phases, and is typically uniformly dispersed throughout the microcapsule slurry and on the exterior of the microcapsule walls of the microcapsules. Suitable rheology modifiers include acrylate copolymers, cationic acrylamide copolymers, polysaccharides, or a combination thereof. Preferably, the addition of the rheology modifier to the slurry improves the 21s -1 The slurry has a viscosity of less than 600 cps (centipoise) or less than 580 cps at 22°C, measured at a shear rate of 100 cps.
[0061] Commercially available acrylate copolymers include those under the trade name ACULYN® (Dow Chemical Company), such as ACULYN® 22 (copolymer of acrylates and steareth-20 methacrylate), ACULYN® 28 (copolymer of acrylates and beheneth-25 methacrylate), ACULYN® 33 (copolymer of acrylic acid and acrylate), ACULYN® 38 (crosspolymer of acrylates and vinyl neodecanoate), and ACULYN® 88 (crosspolymer of acrylates and steareth-20 methacrylate). Particularly useful acrylate copolymers include anionic acrylate copolymers, such as ACULYN® 33, an alkali-soluble anionic acrylic polymer emulsion (ASE), which is synthesized by emulsion polymerization from acrylic acid and acrylate comonomers. Also suitable for use in the present invention are acrylate copolymers sold under the trade name CARBOPOL®. For example, CARBOPOL® ETD 2020 polymer (acrylate and 10 ~C 30 alkyl acrylate crosspolymer), CARBOPOL® ETD 2691, and CARBOPOL® ETD 2623 (crosslinked acrylate copolymer).
[0062] Polysaccharides are another class of agents suitable as rheology modifiers. In certain embodiments, polysaccharides useful as rheology modifiers include starch, pectin, and vegetable gums such as arginine, guar gum, locust bean gum, and xanthan gum, such as xanthan gum sold under the trade name KELTROL® T (80 mesh food grade), commercially available from CP Kelco, Atlanta, GA. Preferably, the rheology modifier includes or is xanthan gum.
[0063] In some embodiments, the active is a fragrance and the microcapsule slurry comprises: (a) less than 0.3% or less than 0.25% non-encapsulated fragrance, based on the total weight of the fragrance in the slurry; (b) 21s -1 or (c) a combination of (a) and (b).
[0064] In some embodiments, the core-shell microcapsule slurry also includes a capsule deposition aid. The amount of capsule deposition aid in the slurry can range from 0.01% to 25% by weight, more preferably from 5% to 20% by weight, based on the weight of the microcapsules. The capsule deposition aid can be added during capsule preparation or after the capsules are produced.
[0065] Capsule deposition aids are used to aid in the deposition of capsules onto surfaces such as fabric, hair, or skin. Examples of capsule deposition aids include anionically water-soluble, cationically water-soluble, nonionically water-soluble, or amphoterically water-soluble polymers. Suitable capsule deposition aids include polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-16, polyquaternium-22, polyquaternium-24, polyquaternium-28, polyquaternium-39, polyquaternium-44, polyquaternium-46, polyquaternium-47, polyquaternium-53, polyquaternium-55, polyquaternium-67, polyquaternium-68, polyquaternium-69, polyquaternium-73, polyquaternium-74, polyquaternium-77, polyquaternium-78, polyquaternium-80, polyquaternium-82, polyquaternium-83, polyquaternium-84, polyquaternium-85, polyquaternium-86, polyquaternium-87, polyquaternium-88, polyquaternium-89, polyquaternium-90, polyquaternium-91, polyquaternium-92, polyquaternium-93, polyquaternium-94, polyquaternium-95, polyquaternium-96, polyquaternium-97, polyquaternium-98, polyquaternium-99, polyquaternium-100, polyquaternium-101, polyquaternium-102, polyquaternium-103, polyquaternium-104, polyquaternium-105, polyquaternium-106, polyquaternium-107, polyquaternium-108, polyquaternium-109, polyquaternium-110, polyquaternium-111, polyquaternium-112, polyquaternium-113, polyquaternium-114, polyquaternium-115, polyquaternium-116, polyquaternium-117, polyquaternium-118, polyquaternium-119, poly Examples of suitable capsule deposition aids include polyquaternium-79, polyquaternium-80, polyquaternium-81, polyquaternium-82, polyquaternium-86, polyquaternium-88, polyquaternium-101, polyvinylamine, polyethyleneimine, polyvinylamine and vinylformamide copolymer, acrylamidopropyltrimonium chloride / acrylamide copolymer, methacrylamidopropyltrimonium chloride / acrylamide copolymer, polymers containing units derived from polyethylene glycol and terephthalate, polyesters, polymers derived from dicarboxylic acids and polyols, or combinations thereof. Other suitable capsule deposition aids include those described in WO 2016 / 049456, pages 13-27. Additional capsule deposition aids are described in US Patent Application Publication Nos. 2013 / 0330292, 2013 / 0337023, and 2014 / 0017278.
[0066] In some embodiments, the core-shell microcapsule slurry also contains a preservative. One or more preservatives can be added to the microcapsule slurry to prevent damage or inadvertent growth of microorganisms for a specific period of time, thereby extending the shelf life. The preservative can be any organic preservative that does not cause damage to the microcapsule slurry. Suitable water-soluble preservatives include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, parabens, propanediol materials, isothiazolinones, quaternary compounds, and benzoates. Examples of preservatives include low molecular weight alcohols, dehydroacetic acid, phenyl and phenoxy compounds, or combinations thereof.
[0067] A non-limiting example of a commercially available water-soluble preservative is a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and 23% 2-methyl-4-isothiazolin-3-one. Additional antimicrobial preservatives include a 1.5% aqueous solution of Rohm & Haas under the trade name KATHON® CG; 5-bromo available under the trade name BRONIDOX L® from Henkel; 2-bromo-2-nitro-1,3-propanediol available under the trade name BRONOPOL® from Inorex; 1,1'-hexamethylenebis(5-(p-chlorophenyl)biguanide) and its salts, such as acetate and digluconate; 1,3-bis(hydroxy) available under the trade name GLYDANT PLUS® from Ronza; glutaraldehyde; ICI polyaminopropyl biguanide; dehydroacetic acid; and 1,2-benzisothiazolin-3-one sold under the trade name PROXEL® GXL.
[0068] The microcapsule slurry of the present disclosure has been shown to be an effective delivery system that can deliver perfume into consumer products such as fabric conditioner.In addition, the microcapsule slurry also finds utility in a wide range of consumer applications, for example, personal care products, including shampoo, hair conditioner, hair rinse, hair refresher; personal detergents, for example, bar soap, body wash, personal cleaner, and disinfectant; fabric care, for example, fabric refresher, softener, and dryer sheet, ironing water, industrial cleaner, liquid and powder detergent, including unit dose capsule, rinse conditioner, and fragrance booster product; fine fragrance, for example, body mist and Eau de Toilette product; deodorant; roll-on product and aerosol product.
[0069] The present disclosure also provides a method for producing the core-shell microcapsule slurry described herein, comprising: (a) preparing an aqueous phase by (i) denaturing pea protein, (ii) adjusting the pH of the aqueous phase to less than 6, and (iii) adding gum arabic as a hydrocolloid to the aqueous phase; (b) preparing an oil phase comprising an active substance and a polyisocyanate; (c) emulsifying the oil phase with the aqueous phase to form a slurry comprising core-shell microcapsules; and (d) hardening the shells of the microcapsules at a temperature less than 80°C. The resulting core-shell microcapsule slurry comprises: (a) core-shell microcapsules (the microcapsule core comprises an active substance and the microcapsule shell comprises a self-condensing polyisocyanate); (b) a dispersing agent comprising modified pea protein; and (c) a hydrocolloid comprising gum arabic; the active substance comprises a low log P fragrance having a log P value ranging from 0.5 to 2.2, the amount of the low log P fragrance being 3% to 18% by weight based on the weight of the active substance, and the core-shell microcapsule slurry is white in color.
[0070] As demonstrated herein, when polyisocyanates react with water to form amines, they self-polymerize in the presence of modified pea protein as a dispersant and form a wall material suitable for encapsulating active substances in core-shell microcapsules. Without wishing to be bound by theory, it is postulated that the modified pea protein provides a scaffold that promotes the self-polymerization of the polyisocyanates. Advantageously, the inclusion of modified pea protein allows for the use of reduced levels of polyisocyanates, improving the durability and biodegradability of the resulting core-shell microcapsules. Furthermore, desired microcapsule properties, such as good drying performance, low discoloration, and / or reduced aggregation, can be achieved by adjusting the pH of the emulsion or slurry to less than 6 and / or curing the microcapsule shell at a temperature less than 80°C.
[0071] Pea proteins may be denatured in the aqueous phase by exposure to heat or cold, changes in pH, denaturants such as detergents, urea, or other chaotropic agents, or mechanical stress, including shear. In some embodiments, the pea proteins are denatured by heating the aqueous pea protein solution to temperatures between 80°C and 170°C, between 80°C and 140°C, between 80°C and 120°C, between 80°C and 105°C, or between 80°C and 90°C. In some embodiments, the pea proteins are denatured by a denaturing agent. In some embodiments, the pea proteins are denatured by a chaotropic agent. In some embodiments, the chaotropic agent comprises or is a guanidinium salt. In some embodiments, the guanidinium salt is selected from the group consisting of guanidinium sulfate, guanidinium carbonate, guanidinium nitrate, guanidinium chloride, and mixtures thereof. In some embodiments, the chaotropic agent comprises guanidinium carbonate. In some embodiments, the denaturing step (a)(i) comprises mixing the pea protein and guanidine carbonate in an aqueous solution (e.g. an aqueous phase).
[0072] The pH of the aqueous phase (e.g., an aqueous solution containing a mixture of pea protein and guanidine carbonate) is adjusted to less than 6 or less than or equal to 6. In some embodiments, the pH of the aqueous phase is adjusted to less than 5.5 or less than or equal to 5.5. In some embodiments, the pH of the aqueous phase is adjusted to at least 2, 3, 3.5, 4, or 4.5. In some embodiments, the pH of the aqueous phase is adjusted to a range of 2 to 6, 3 to 5.5, 3.5 to 4.5, or 3.8 to 4.2. Gum arabic is added to the aqueous phase as a hydrocolloid.
[0073] The oil phase can be prepared by mixing an active material and a polyisocyanate. In some embodiments, an auxiliary core material (e.g., a solvent) is also mixed with the active material and the polyisocyanate. In some embodiments, the polyisocyanate is dissolved in a solution containing a solvent (e.g., caprylic / capric triglyceride) and an active material. In some embodiments, the active material is selected from the group consisting of perfume, pro-fragrance, malodor counteractant, and combinations thereof. The active material comprises a low log P perfume having a log P value ranging from 0.5 to 2.2, and the amount of the low log P perfume is 3% to 18% by weight based on the weight of the active material. In some embodiments, the active material is a perfume, and the slurry contains (a) less than 0.3% or less than 0.25% non-encapsulated perfume based on the total weight of the perfume, (b) 21s -1or (c) a combination of (a) and (b). In some embodiments, the amount of polyisocyanate used to prepare the microcapsules and microcapsule slurries ranges from 0.1% to 8% by weight, based on the weight of the core-shell microcapsule slurry. In some embodiments, the amount of polyisocyanate used to prepare the microcapsules and microcapsule slurries ranges from 0.1% to 10% by weight, 0.1% to 8% by weight, 0.2% to 5% by weight, 1.5% to 3.5% by weight, or 0.1% to 5% by weight, based on the weight of the core-shell microcapsule slurry. In some embodiments, the amount of polyisocyanate used in preparing the microcapsules and microcapsule slurries is 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, or 0.2 wt% or less, based on the weight of the core-shell microcapsule slurry. In some embodiments, the polyisocyanate includes or is a trimethylolpropane adduct of xylylene diisocyanate.
[0074] In step (c), the oil phase is emulsified with the aqueous phase to form a slurry containing core-shell microcapsules. In some embodiments, the slurry is an emulsion. In step (d), the microcapsule shells are hardened at a temperature below 80°C (e.g., in the range of 63°C to 67°C). As used herein, the term "hardening" refers to a polymer toughening or hardening process brought about by heat, chemical additives, and / or light irradiation. In some embodiments, the microcapsule shells are hardened at elevated temperatures. In some embodiments, the microcapsule shells are hardened at temperatures below 80°C or below 70°C. In some embodiments, the microcapsule shells are hardened at temperatures ranging from 15°C to 80°C, 55°C to 65°C, 55°C to 70°C, 55°C to 80°C, or 63°C to 67°C. In some embodiments, the microcapsule shells may be hardened for 1 minute to 10 hours, 0.1 hours to 5 hours, 0.2 hours to 4 hours, or 0.5 hours to 3 hours. In some embodiments, the microcapsule slurry can be heated to the desired curing temperature at a linear rate of 0.5-20°C per minute (e.g., 1-5°C per minute, 2-8°C per minute, or 2-10°C per minute).
[0075] In some embodiments, the method of producing the microcapsule slurry further comprises adding a rheology modifier, a preservative, an emulsifier, or a combination thereof to the microcapsule slurry. In some embodiments, a rheology modifier (e.g., xanthan gum) is added to the aqueous phase prior to step (c).
[0076] In some embodiments, a catalyst, such as 1,4-diazabicyclo[2,2,2]octane (DABCO), N-methylimidazole, diaminobicyclooctane, or 2,2'-dimorpholinodiethyl ether, is not used to form the microcapsule shell. In some embodiments, the amount of catalyst for shell formation is 50 wppm (parts per million by weight), 20 wppm, 10 wppm, 5 wppm, 2 wppm, 1 wppm, 0.5 wppm, or 0.2 wppm or less, based on the weight of the microcapsule slurry.
[0077] The microcapsule slurries of the present disclosure can be formulated into microcapsule delivery systems for use in consumer products. The microcapsule delivery system can be a microcapsule slurry suspended in an external solvent (e.g., water, ethanol, or a combination thereof), with the microcapsules present at a level of 0.1% to 80% (e.g., 70-75%, 40-55%, 50-90%, 1% to 65%, or 5% to 45%) by weight of the microcapsule delivery system.
[0078] Alternatively or additionally, microcapsules and slurries thereof prepared according to the present disclosure can then be purified (see U.S. Patent Application Publication No. 2014 / 0017287). Purification can be achieved by washing the microcapsule slurry with water until a neutral pH is obtained.
[0079] The microcapsule delivery system may optionally contain one or more other delivery systems, such as polymer-assisted delivery compositions (see U.S. Pat. No. 8,187,580), fiber-assisted delivery compositions (U.S. Patent Application Publication No. 2010 / 0305021), cyclodextrin host-guest complexes (U.S. Pat. No. 6,287,603 and U.S. Patent Application Publication No. 2002 / 0019369), pro-fragrances (WO 2000 / 072816 and EP 0922084), or combinations thereof. The microcapsule delivery system may also contain one or more (e.g., two, three, four, five, or six or more) different microcapsules, including the various microcapsules of the present disclosure, as well as other microcapsules, such as aminoplast, hydrogel, sol-gel, polyurea / polyurethane microcapsules, and melamine formaldehyde microcapsules. More exemplary delivery systems that can be incorporated include coacervate microcapsules (see WO 2004 / 022221) and cyclodextrin delivery systems (see WO 2013 / 109798 and U.S. Patent Application Publication No. 2011 / 03085560).
[0080] The microcapsule slurries of the present disclosure are suitable for incorporation into any of a variety of consumer products in which controlled release of an active (e.g., a fragrance or flavor) is desired. The present disclosure also provides consumer products comprising the core-shell microcapsule slurries of the present disclosure. In some embodiments, the consumer product is selected from the group consisting of fabric conditioners, fabric softeners, fabric refreshers, liquid laundry detergents, powder detergents, scent boosters, body washes, body soaps, shampoos, hair conditioners, body sprays, hair refresher sprays, hair dyes, hair moisturizers, skin moisturizers, hair treatments, antiperspirants, deodorants, skin treatments, insect repellents, candles, surface cleaners, bathroom cleaners, bleach, cat litter, refresher sprays, pesticides, insecticides, herbicides, fungicides, paints, and combinations thereof.
[0081] Purpose The microcapsule slurries and delivery systems of the present disclosure are suitable for use in, but not limited to, laundry detergents, liquid laundry detergents, powder laundry detergents, tablet laundry detergents, laundry detergent bars, laundry detergent creams, hand wash laundry detergents, fabric conditioners or softeners, fabric refreshers, scent boosters, shampoos, hair conditioners, bar soaps, shower gels, body washes, antiperspirants, body sprays, body mists, lotions, candles, or textile products.
[0082] More particularly, the microcapsules of the present disclosure can be used in the following products:
[0083] A) Fabric care products, such as rinse conditioners (containing 1 to 30% by weight of a fabric conditioning active), liquid fabric conditioners (containing 1 to 30% by weight of a fabric conditioning active), tumble dryer sheets, fabric refreshers, fabric refresher sprays, ironing liquids, and fabric softener systems, e.g., U.S. Pat. No. 6,335,315, U.S. Pat. No. 5,674,832, U.S. Pat. No. 5,759,990 , U.S. Patent Nos. 5,877,145, 5,574,179, 5,562,849, 5,545,350, 5,545,340, 5,411,671, 5,403,499, 5,288,417, 4,767,547, and 4,424,134.
[0084] The liquid dough softener / freshener preferably comprises at least one dough softener present in a concentration of 1 to 30% by weight of the liquid dough softener / freshener (e.g., 4% to 20%, 4% to 10%, and 8% to 15%). The ratio of active to dough softener can be 1:500 to 1:2 (e.g., 1:250 to 1:4 and 1:100 to 1:8). By way of example, if the dough softener is 5% by weight of the dough softener, the active is 0.01% to 2.5%, preferably 0.02% to 1.25%, more preferably 0.1% to 0.63%. As another example, if the dough softener is 20% by weight of the dough softener, the active is 0.04% to 10%, preferably 0.08% to 5%, more preferably 0.4% to 2.5%. The active material may be a fragrance, a malodor counteractant, or a combination thereof. The liquid dough softener may have 0.15% to 15% capsules (e.g., 0.5% to 10%, 0.7% to 5%, and 1% to 3%). With capsules at these levels, the neat oil equivalent (NOE) in the softener is 0.05% to 5% (e.g., 0.15% to 3.2%, 0.25% to 2%, and 0.3% to 1%).
[0085] Suitable fabric softeners include cationic surfactants, non-limiting examples of which include quaternary ammonium compounds (QACs), such as alkylated quaternary ammonium compounds, cyclic or cyclic quaternary ammonium compounds, aromatic quaternary ammonium compounds, diquaternary ammonium compounds, alkoxylated quaternary ammonium compounds, amidoamine quaternary ammonium compounds, ester quaternary ammonium compounds, or combinations thereof.
[0086] Dough softening products include water-based QACs characterized by: a) the viscosity of the final product ranges from 5 to 300 cps at 10 s, preferably from 20 to 150 cps; b) The level of QAC ranges from 0.5 to 20 wt% of the softening active, preferably 1 to 16 wt%, more preferably 6 to 12 wt%. Typical preferred cationic dough softening components include water-insoluble quaternary ammonium dough softeners, the most commonly used being di-long alkyl chain ammonium chloride or methyl sulfate. Preferred cationic softeners include, but are not limited to: a. Rapidly biodegradable quaternary ammonium compounds containing one or more ester bonds located between the quaternary ammonium group and a long alkyl chain (e.g., TEA ester quats, DEEDMAC, and HEQ); b. Non-ester quaternary ammonium compounds (e.g., ditallowdimethylammonium chloride (DTDMAC), dihydrogenated tallowdimethylammonium chloride, dihydrogenated tallowdimethylammonium methyl sulfate, distearyl dimethylammonium chloride, dioleyl dimethylammonium chloride, dipalmityl hydroxyethyl methylammonium chloride, stearyl benzyl dimethyl ammonium chloride, tallow trimethylammonium chloride, hydrogenated tallow trimethylammonium chloride, C12-14 alkyl hydroxyethyl dimethylammonium chloride, C12-18 alkyl dihydroxyethyl methylammonium chloride, di(stearoyloxyethyl)dimethylammonium chloride (DSOEDMAC), di(tallowoyloxyethyl)dimethylammonium chloride, ditertiary imidazolinium methyl sulfate, 1-(2-tallowylamidoethyl)-2-tallowylimidazolinium methyl sulfate).
[0087] A first group of quaternary ammonium compounds (QACs) suitable for use in accordance with the present disclosure are represented by formula (I): [ka] (wherein each R is independently C1 to C 35 R is selected from alkyl or alkenyl groups; 1 represents a C1-C4 alkyl, C2-C4 alkenyl, or C1-C4 hydroxyalkyl group; T is typically O-CO (i.e., an ester group bonded to R through its carbon atom), but can alternatively be CO-O (i.e., an ester group bonded to R through its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1, 2, or 3; and X is an anionic counterion, such as a halide or alkyl sulfate, e.g., chloride or methyl sulfate. Diester variants of formula (I) (i.e., m=2) are preferred, and typically have mono- and triester analogs associated therewith.
[0088] Particularly preferred agents are formulations rich in diesters of triethanolammonium methyl sulfate, also known as "TEA ester quats." Commercial examples include, for example, Stepan's STEPANTEX® UL85, e.g., Clariant's Prapagen™ TQL, and e.g., Kao's Tetranyl™ AHT-1 (all di[hardened tallow esters] of triethanolammonium methyl sulfate), e.g., Kao's AT-1 (di[tallow esters] of triethanolammonium methyl sulfate) and L5 / 90 (di-[coconut esters] of triethanolammonium methyl sulfate), both of which are also e.g., Kao's REWOQUAT® WE15 (C10-C16). 20 and C 16 ~C 18 Diesters of triethanolammonium methyl sulfate with fatty acyl residues derived from unsaturated fatty acids.
[0089] Also suitable are soft quaternary ammonium actives such as STEPANTEX® VK90, STEPANTEX® VT90, SP88 (e.g., Stepan), Prapagen™ TQ (e.g., Clariant), DEHYQUART® AU-57 (e.g., Cognis), REWOQUAT® WE18 (e.g., Degussa), Tetranyl™ L190P, Tetranyl™ L190SP, and Tetranyl™ L190S (all e.g., Kao).
[0090] A second group of QACs suitable for use in accordance with the present disclosure are those of formula (II): (R 1 )2-N + -[(CH2) n -TR 2 ]2X - (II) (In the formula, each R 1 The group is C l 1 to 4 alkyl or C2 to C4 alkenyl group, and each R 2 The group is C8-C28 and n, T, and X are independently selected from alkyl or alkenyl groups, and are as defined above. Preferred materials in this second group include bis(2-tallowyloxyethyl)dimethylammonium chloride and cured versions thereof.
[0091] A third group of QACs suitable for use in accordance with the present disclosure are those of formula (III): [ka] (In the formula, each R 1 groups are independently selected from C1-C4 alkyl, hydroxyalkyl, or C2-C4 alkenyl groups, and each R 2 The group is C8-C 28 and n, T, and X are independently selected from alkyl or alkenyl groups, and n, T, and X are as defined above. Preferred materials in this second group include 1,2-bis[tallowyloxy]-3-trimethylammonium propane chloride, 1,2-bis[hardened tallowyloxy]-3-trimethylammonium propane chloride, 1,2-bis[oleoyloxy]-3-trimethylammonium propane chloride, and 1,2-bis[stearoyloxy]-3-trimethylammonium propane chloride. Such materials are described in U.S. Pat. No. 4,137,180 (Lever Brothers). Preferably, these materials also contain an amount of the corresponding monoester.
[0092] Co-softeners. Co-softeners (also referred to as co-softeners and fat complexing agents) can be used in the fabric conditioner compositions of the present disclosure. When used, co-softeners are typically present at 0.1 to 20%, especially 0.1 to 5%, based on the total weight of the composition. Preferred co-softeners include fatty alcohols, fatty esters, and fatty N-oxides. Fatty esters that can be used include fatty monoesters such as glycerol monostearate, and fatty sugar esters such as those disclosed in WO 01 / 46361 (Unilever).
[0093] In some embodiments, the compositions of the present disclosure may contain a co-active. Particularly suitable fat-complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred. Without being bound by theory, it is believed that the fat-complexing agent improves the viscosity profile of the composition by complexing with the monoester component of the fabric conditioner material, thereby providing a composition with relatively high levels of diester- and triester-linked components. Diester- and triester-linked components are more stable and do not adversely affect initial viscosity as much as monoester components. It is also believed that the higher levels of monoester-linked components present in compositions containing TEA-based quaternary ammonium materials can potentially destabilize the composition due to depletion flocculation. By using a co-active that complexes with the monoester-linked components, depletion flocculation is significantly reduced. In other words, in some embodiments, as required by the present disclosure, increased levels of the co-active "neutralize" the monoester-linked components of the quaternary ammonium material. This in situ diester formation from the monoester and fatty alcohol also improves the softening properties of the composition.
[0094] Silicone. In some embodiments, the composition of the present disclosure may further contain a silicone-based fabric softener. Preferably, the fabric softening silicone is polydimethylsiloxane. Fabric softening silicones include, but are not limited to, 1) non-functional silicones such as polydimethylsiloxane (PDMS) or alkyl (or alkoxy) functionalized silicones; and 2) functionalized silicones or copolymers having one or more different types of functional groups, such as amino, phenyl, polyether, acrylate, silicon hydride, carboxylic acid, and quaternized nitrogen. Suitable silicones may be selected from polydialkylsiloxanes, preferably polydimethylsiloxanes, more preferably amino-functionalized silicones, anionic silicones, and carboxyl-functionalized silicones. Aminosilicones may also be used, such as Arristan 64, e.g., CHT, or Wacker CT45E, e.g., Wacker.
[0095] For silicone emulsions, particle sizes can range from about 1 nm to 100 microns, preferably from about 10 nm to 10 microns, including microemulsions (<150 nm), standard emulsions (about 200 nm to about 500 nm), and macroemulsions (about 1 micron to about 20 microns).
[0096] Nonionic Surfactants. In some embodiments, the composition may further comprise a nonionic surfactant. Typically, these are included for the purpose of stabilizing the composition. Suitable nonionic surfactants include addition products of ethylene oxide with fatty alcohols, fatty acids, and fatty amines. Any of the specific types of alkoxylated materials described below may be used as nonionic surfactants. Suitable surfactants are substantially water-soluble surfactants of the general formula (V): RY-(C2H4O)z-CH2-CH2-OH(V), where R is selected from the group consisting of primary, secondary, and branched-chain alkyl and / or acyl hydrocarbyl groups, primary, secondary, and branched-chain alkenyl hydrocarbyl groups, and primary, secondary, and branched-chain alkenyl-substituted phenolic hydrocarbyl groups, and the chain length of the hydrocarbyl group is 8 to about 25, preferably 10 to 20, e.g., 14 to 18, carbon atoms. In the general formula for ethoxylated nonionic surfactants, Y is typically -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R, where R has the meaning given above for formula (V) or can be hydrogen, and Z is at least about 8, preferably at least about 10 or 11.
[0097] Preferably, the nonionic surfactant has an HLB of about 7 to about 20, more preferably 10 to 18, e.g., 12 to 16. GENAPOL® C200 (Clariant), based on a coco chain and 20 EO groups, is an example of a suitable nonionic surfactant. If present, the nonionic surfactant is present in an amount of 0.01 to 10 wt. %, more preferably 0.1 to 5 wt. %, based on the total weight of the composition. LUTENSOL® AT25 (BASF), based on a coco chain and 25 EO groups, is an example of a suitable nonionic surfactant. Other suitable surfactants include RENEX® 36 (Trideceth-6), e.g., from Croda; TERGITOL® 15-S3, e.g., from Dow Chemical Co.; Dihydrol LT7, e.g., from Thai Ethoxylate Ltd.; CREMOPHOR® CO40, e.g., from BASF; and NEODOL® 91-8, e.g., from Shell.
[0098] Cationic polysaccharides. In some embodiments, the composition may further comprise at least one cationic polysaccharide. Cationic polysaccharides can be obtained by chemically modifying polysaccharides, typically natural polysaccharides. Such modifications can introduce cationic side groups into the polysaccharide backbone. Cationic polysaccharides include, but are not limited to, cationic cellulose and its derivatives, cationic starch and its derivatives, cationic cellulose and its derivatives, cationic xylan and its derivatives, cationic mannan and its derivatives, and cationic galactomannan and its derivatives, such as cationic guar and its derivatives. Suitable cationic celluloses include cellulose ethers containing quaternary ammonium groups, cationic cellulose copolymers, or cellulose grafted with water-soluble quaternary ammonium monomers.
[0099] Cellulose ethers containing quaternary ammonium groups are described in French Patent Application Publication No. 1,492,597, including, in particular, the polymers sold by Dow under the names "JR" (JR400, JR125, JR30M) or "LR" (LR400, LR30M). These polymers are also defined in the CTFA dictionary as hydroxyethyl cellulose quaternary ammonium reacted with an epoxide substituted with a trimethylammonium group. Suitable cationic celluloses also include Solvay's LR3000KC. Cationic cellulose copolymers, or celluloses grafted with water-soluble quaternary ammonium monomers, are described, inter alia, in U.S. Pat. No. 4,131,576, including, for example, hydroxyalkyl celluloses, such as hydroxymethyl-, hydroxyethyl-, or hydroxypropyl celluloses grafted with, inter alia, methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, or dimethyldiallylammonium salts.
[0100] Commercially available products corresponding to this definition are more particularly those sold under the names CELQUAT® L200 and CELQUAT® H100 by Akzo Nobel. Cationic starches suitable for the present disclosure include products sold under the names POLYGELO® (cationic starch from Sigma), SOFTGEL®, AMYLOFAX®, and SOLVITOSE® (cationic starch from Avebe), and CATO from National Starch. Suitable cationic galactomannans may be derived from fenugreek gum, konjac gum, tara gum, cassia gum, or guar gum.
[0101] In some embodiments, the cationic polysaccharides of the present disclosure can have an average molecular weight (Mw) of 100,000 Daltons to 3,500,000 Daltons, preferably 100,000 Daltons to 1,500,000 Daltons, and more preferably 100,000 Daltons to 1,000,000 Daltons.
[0102] In some embodiments, the fabric conditioner composition of the present disclosure preferably comprises 0.01 to 2 wt% of cationic polysaccharide based on the total weight of the composition. More preferably, it comprises 0.025 to 1 wt% of cationic polysaccharide based on the total weight of the composition. Most preferably, it comprises 0.04 to 0.8 wt% of cationic polysaccharide based on the total weight of the composition. In the context of this application, the term "degree of substitution (DS)" of a cationic polysaccharide, such as cationic guar, refers to the average number of substituted hydroxyl groups per saccharide unit. DS may, inter alia, refer to the number of carboxymethyl groups per saccharide unit. DS can be determined by titration.
[0103] The DS of the cationic polysaccharide is preferably in the range of 0.01 to 1, more preferably 0.05 to 1, and most preferably 0.05 to 0.2. In the context of this application, the "charge density (CD)" of a cationic polysaccharide, such as cationic guar, refers to the ratio of the number of positive charges on the monomer units constituting the polymer to the molecular weight of said monomer units. The CD of a cationic polysaccharide, such as cationic guar, is preferably in the range of 0.1 to 3 (meq / gm), more preferably 0.1 to 2 (meq / gm), and most preferably 0.1 to 1 (meq / gm).
[0104] Nonionic Polysaccharides. In some embodiments, the fabric conditioner composition may further comprise at least one nonionic polysaccharide. The nonionic polysaccharide may be a modified or unmodified nonionic polysaccharide. The modified nonionic polysaccharide may include hydroxyalkylation and / or esterification. In the context of the present disclosure, the modification level of the nonionic polysaccharide may be characterized by molar substitution (MS), which refers to the average number of moles of substituents, such as hydroxypropyl groups, per mole of monosaccharide unit. MS can be determined by the Zeisel-GC method, particularly based on the following reference: Hodges, et al. (1979) Anal. Chem. 51(13). Preferably, the MS of the modified nonionic polysaccharide is in the range of 0 to 3, more preferably 0.1 to 3, and most preferably 0.1 to 2.
[0105] In some embodiments, the nonionic polysaccharides of the present disclosure may be selected from, inter alia, glucans, modified or unmodified starches (e.g., from cereals such as wheat, corn, or rice, vegetables such as yellow peas, and tubers such as potato or cassava), amylose, amylopectin, glycogen, dextran, cellulose and its derivatives (methylcellulose, hydroxyalkylcellulose, ethylhydroxyethylcellulose), mannan, xylan, lignin, araban, galactan, galacturonan, chitin, chitosan, glucuronoxylan, arabinoxylan, xyloglucan, glucomannan, pectic acid and pectin, arabinogalactan, carrageenan, agar, gum arabic, tragacanth gum, gum ghatti, karaya gum, locust bean gum, galactomannans such as guar and its nonionic derivatives (hydroxypropyl guar), and mixtures thereof.
[0106] Among the celluloses that can be used are hydroxyethyl cellulose and hydroxypropyl cellulose. Suitable non-limiting examples include products sold under the trade names KLUCEL® EF, KLUCEL® H, KLUCEL® LHF, KLUCEL® MF, and KLUCEL® G from Aqualon, CELLOSIZE® Polymer PCG-10 from Amerchol, and HEC, HPMC K200, and HPMC K35M from Ashland.
[0107] In some embodiments, the fabric conditioner composition of the present disclosure preferably comprises 0.01 to 2 wt% of nonionic polysaccharide based on the total weight of the composition. More preferably, it comprises 0.025 to 1 wt% of nonionic polysaccharide based on the total weight of the composition. Most preferably, it comprises 0.04 to 0.8 wt% of nonionic polysaccharide based on the total weight of the composition. Preferably, the fabric conditioner composition comprises 0.02 to 4 wt%, more preferably 0.05 to 2 wt%, and most preferably 0.08 to 1.6 wt% of the combined weight of cationic polysaccharide and nonionic polysaccharide. Preferably, the ratio of the weight of cationic polysaccharide in the composition to the weight of nonionic polysaccharide in the composition is 1:10 to 10:1, more preferably 1:3 to 3:1.
[0108] In a preferred embodiment, the cationic polysaccharide and the nonionic polysaccharide are mixed before being added to the fabric conditioner composition. Preferably, the mixture is prepared as a suspension in water. Preferably, the ratio of the weight of the quaternary ammonium compound in the composition to the total weight of the cationic polysaccharide and the nonionic polysaccharide in the composition is from 100:1 to 2:1, more preferably from 30:1 to 5:1.
[0109] Water. In some embodiments, the fabric conditioner composition of the present disclosure comprises water. The composition is a softening composition with added rinse, suitable for use in laundry processes. The composition is a pourable liquid. The liquid composition has a pH ranging from about 2.0 to about 7, preferably from about 2 to about 4, more preferably from about 2.5 to about 3.5. The composition may also contain a pH modifier, preferably hydrochloric acid, lactic acid, or sodium hydroxide. The composition is preferably a ready-to-use liquid comprising an aqueous phase. The aqueous phase may contain water-soluble species such as mineral salts or short-chain (C1-C4) alcohols. The composition is preferably for use in the rinse cycle of a domestic textile washing operation, and can be added undiluted directly to the washing machine, for example, through a dispenser drawer or, for top-loading washing machines, directly into the drum. The composition can also be used in a domestic hand washing operation.
[0110] Fabric conditioner compositions can typically be made by combining a melt containing fabric softeners with an aqueous phase. The polymer can be combined with the aqueous phase or can be post-introduced into the composition after the melt and aqueous phase are combined. A preferred method of preparation is as follows: 1. Heat the water to about 40-50°C, preferably above 45°C. 2. Add the rheology modifier to the water slowly, preferably over a period of about 1 minute, with stirring. 3. Mix thoroughly, preferably for 1 to 10 minutes. 4. Add any minor ingredients such as antifoaming agents, sequestering agents, and preservatives. 5. Melting the emollient active and optional fatty alcohol together to form a co-melt. 6. Add the co-melt to the heated water. 7. If necessary, add acid until desired pH is achieved. 8. Add dyes and perfumes. 9. Cooling.
[0111] B) Liquid dish detergents such as those described in U.S. Pat. No. 6,069,122 and U.S. Pat. No. 5,990,065.
[0112] C) Automatic dish detergents such as those described in U.S. Pat. Nos. 6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902,781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169,552, and 4,714,562.
[0113] D) Bucket dilutable cleaners and all-purpose cleaners, including toilet cleaners, bathroom cleaners, bath tissue, rug fresheners, candles (e.g., scented candles), room fresheners, floor cleaners, disinfectants, window cleaners, trash bag / trash can liners, air fresheners (e.g., room fresheners, car fresheners, sprays, scented oil air fresheners, auto spray air fresheners, and neutralizing gel beads), moisture absorbers, household appliances (e.g., paper towels and disposable wipes), and insect repellents / traps / cakes.
[0114] E) Personal Care Products: Cosmetics or Pharmaceuticals. More particularly, personal cleansers (e.g., bar soaps, body washes, and shower gels), shower conditioners, sunscreens (e.g., sprays, lotions, and sticks), insect repellents, hand sanitizers, anti-inflammatories (e.g., balms, ointments, and sprays), antibacterials (e.g., ointments and creams), sensates, deodorants and antiperspirants (including aerosols, pump sprays, and wax-based), lotions, body and foot powders, body mists or body sprays, shaving creams and men's grooming products, bath soaks, exfoliating scrubs.
[0115] F) Hair care products, more particularly shampoos (liquid and dry powder), hair conditioners (rinse-off, leave-in, and cleansing conditioners), hair rinses, hair refreshers, hair perfumes, hair straightening products, hair styling products, hair fixatives and styling aids, hair combing creams, hair waxes, hair foams, hair gels, non-aerosol pump sprays, hair bleaches, dyes and colorants, perms, and hair wipes.
[0116] In certain embodiments, the core-shell microcapsule slurries of the present disclosure are used to improve the freshness of fabrics. Thus, in certain embodiments, the microcapsules of the present disclosure are included in a fabric conditioner or softener having a pH of 2 to 4, preferably a pH of 2.5 to 3.5.
[0117] Many aspects and embodiments have been described above, by way of example only and not limitation, and after reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention. [Example]
[0118] The following non-limiting examples are provided to further illustrate the present invention and should not be construed as limitations thereof, since many variations of the present invention are possible without departing from the spirit or scope of the invention.
[0119] overview The caprylic / capric triglyceride used in the examples is a commercial product of Stepan, Chicago, IL under the trade name NEOBEE® M-5. The polyisocyanate used in the examples is a trimethylolpropane adduct of xylylene diisocyanate, commercially available under the trade name TAKENATE® D110N from Mitsui Chemicals Inc., Japan. Those skilled in the art will understand that some commercially available polyisocyanates are solutions of polyisocyanate in solvents. The amount of polyisocyanate (e.g., TAKENATE® D110N) shown in this disclosure refers to the amount of polyisocyanate itself, i.e., excluding the amount of solvent.
[0120] Example 1: Synthesis of reference microcapsules Melamine-formaldehyde capsules were prepared as described in Example 1 of U.S. Patent Application Publication No. 2012 / 0093899. Briefly, 80 parts by weight of Helion fragrance (International Flavors & Fragrance Inc., Union Beach, NJ) was mixed with 20 parts by weight of caprylic / capric triglyceride solvent to form a fragrance / solvent composition. Uncoated capsules were prepared by forming a polymer wall to encapsulate the fragrance / solvent composition droplets. A copolymer of acrylamide and acrylic acid (sold under the trade name ALCAPSOL® 200) was first dispersed in water along with a methylated melamine-formaldehyde resin (sold under the trade name CYMEL® 385). These two components were allowed to react under acidic conditions for at least 1 hour.
[0121] Subsequently, the perfume / solvent composition was added to the wall polymer solution, and droplets of the desired size were achieved by high-shear homogenization. For the microcapsule slurry, hardening of the polymer layer around the perfume / solvent composition droplets was carried out at 125°C. After cooling to room temperature, ethylene urea was added into the microcapsule slurry. In addition, rheology modifiers and preservatives were added. The pH was adjusted using NaOH. The components of the slurry are listed in Table 1. The slurry contained 28.0% total perfume.
[0122] [Table 1]
[0123] Example 2: Preparation of polyisocyanate microcapsules in the presence of modified pea protein, modified starch / polystyrene sulfonate sodium salt An oil phase was prepared by mixing 80 parts by weight of Helion fragrance with 20 parts by weight of caprylic / capric triglyceride solvent, thereby forming a fragrance / solvent composition. An aqueous phase was prepared by dispersing pea protein powder (15.4% by weight) in water. Guanidine carbonate was added as a denaturant, and the pH was adjusted to 5 using citric acid. These components were allowed to react for 15 minutes.
[0124] Subsequently, modified starch sold under the trade name PURITY GUM® Ultra (Ingredion, Westchester, IL) and high molecular weight polystyrene sulfonate (sold under the trade name FLEXAN® II, sodium salt) were added to the aqueous phase as emulsifiers, and the mixture was mixed for 15 minutes. Tanal-02 (high molecular weight multipurpose hydrolyzable tannin; Ajinomoto Natural Specialties, Tokyo, Japan) was then added to the aqueous phase.
[0125] Polyisocyanate was added to the oil phase at 5 wt%. Subsequently, the oil phase was emulsified into the aqueous phase under a shear rate of 7400 revolutions per minute ("RPM") for 3 minutes to form an oil-in-water emulsion (i.e., microcapsule slurry). For the microcapsule slurry, curing of the polymer layer (i.e., shell) around the perfume / solvent composition droplets was carried out at 55°C for 3.5 hours and then at 80°C for 30 minutes. Then, a rheology modifier and a preservative (1,2-benzisothiazolin-3-one) were added. The components of the slurry are listed in Table 2. The slurry contained 31.2% total perfume.
[0126] [Table 2]
[0127] Example 3: Preparation of polyisocyanate microcapsules in the presence of modified pea protein, modified starch / polystyrene sulfonate sodium salt at pH 4 and curing temperature 65°C The general procedure of Example 2 was followed with the following changes: the pH of the aqueous phase was adjusted to 4 instead of 5, and curing was carried out at 65° C. for 4 hours. The components of the slurry are listed in Table 3. The slurry contained 31.2% total perfume.
[0128] [Table 3]
[0129] Example 4: Preparation of microcapsules with reduced levels of modified pea protein The general procedure of Example 3 was carried out with a reduced concentration of pea protein. The components of the slurry are listed in Table 4. The slurry contained a total flavor content of 31.2%.
[0130] [Table 4]
[0131] Example 5: Preparation of microcapsules under lower pH conditions The general procedure of Example 3 was followed, except that the pH of the aqueous phase was adjusted to 3 instead of 4. The components of the slurry are listed in Table 5. The slurry contained 30.3% total perfume.
[0132] [Table 5]
[0133] Example 6: Preparation of pH-adjusted microcapsules by using phosphoric acid The general procedure of Example 3 was followed, except that the pH of the aqueous phase was adjusted by using phosphoric acid instead of citric acid. The components of the slurry are listed in Table 6. The slurry contained 32.2% total flavor.
[0134] [Table 6]
[0135] Example 7: Preparation of microcapsules with increased perfume content The general procedure of Example 3 was followed with a reduced amount of water. The components of the slurry are listed in Table 7. The slurry contained 34.6% total perfume.
[0136] [Table 7]
[0137] Example 8: Preparation of microcapsules with higher surfactant concentrations The general procedure of Example 3 was followed with a higher amount of surfactant. The components of the slurry are listed in Table 8. The slurry contained 28.6% total perfume.
[0138] [Table 8]
[0139] Example 9: Microcapsules prepared with modified pea protein and gum arabic An oil phase was prepared by mixing 80 parts by weight of Helion perfume with 20 parts by weight of caprylic / capric triglyceride solvent, thereby forming a perfume / solvent composition. Polyisocyanate was added to the oil phase at 5% by weight.
[0140] An aqueous phase was prepared by dispersing 12.43 grams of pea protein powder in 124 grams of water and adjusting the pH to 9-9.5 using 0.3 grams of 25% sodium hydroxide solution. To promote dissolution and inhibit aggregation of the pea protein isolate (Liu, et al. (2010) Food Res. International. 43:489-495), 85 grams of gum arabic Instant AA (Nexira, Somerville, NJ; 10% solution) was included as a hydrocolloid. The aqueous mixture was high-sheared at 7400 rpm for 20 seconds. High-molecular-weight polystyrene sulfonate sodium salt sold under the trade name FLEXAN® II (15 grams of a 10% solution) was added, and the resulting aqueous mixture was high-sheared at 7400 rpm for 20 seconds. In a separate beaker, 38 grams of guanidine carbonate solution (20%) was adjusted to pH 4 using 31 grams of 50% citric acid solution and the resulting solution was allowed to foam out. The resulting guanidine citrate solution was added to the aqueous pea protein / gum arabic mixture and allowed to react for 15 minutes at room temperature. Afterwards, 48 grams of a 1% xanthan gum solution was added to the aqueous phase followed by 10 grams of a 30% Tanal-02 solution.
[0141] Subsequently, the oil phase was emulsified into the aqueous phase under a shear rate of 7400 rpm for 3 minutes to form an oil-in-water emulsion (i.e., microcapsule slurry). For the microcapsule slurry, hardening of the polymer layer (i.e., shell) around the perfume / solvent composition droplets was carried out at 65°C for 4 hours. In addition, a preservative was added to the slurry. The components of the slurry are listed in Table 9. The slurry contained 31.2% total perfume amount.
[0142] [Table 9]
[0143] The same microcapsule slurry was prepared, but without gum arabic. However, without gum arabic, the emulsion failed completely and no microcapsules were formed, demonstrating that polyisocyanate / pea protein microcapsules cannot be formed in the absence of gum arabic.
[0144] Example 10: Fabric conditioner samples containing microcapsules Using a model unscented dough conditioner with 10% holes in the formulation, water and microcapsules were added. The microcapsules described in Examples 1-3 were each premixed with water before being added to the model dough conditioner. The resulting samples were homogenized at 300 rpm using an overhead agitator. The finished dough conditioner samples contained 0.2% neat oil equivalent. This resulted in 0.65% by weight of encapsulated perfume for the microcapsules in Examples 2 and 3, and 0.72% by weight of encapsulated perfume for the reference microcapsules in Example 1.
[0145] Thirty-five grams of finished fabric conditioner containing the above dosage of microcapsules was added to a front-load Miele Professional PW 6065 Vario washing machine. The wash load contained 2.2 kg of laundry, including eight large towels for evaluation, two T-shirts, two pillowcases, two dish towels, and two mini towels. The wash temperature was set at 40°C, and 15.5 L of water was used for the main wash and 34 L of total water for the two rinses. The total wash cycle was 60 minutes. Some towels were stored for humidity evaluation, and the remainder were line-dried at room temperature for dryness evaluation.
[0146] Randomly selected wet samples were evaluated by several experts using an intensity scale of 0 to 5, with 0 being "no performance" and 5 being "strong performance." Evaluations were performed "blind" such that each sample had a randomly assigned number. Dry evaluations were performed the day after the wet evaluations and were performed by the same experts using the same intensity scale of 0 to 5. Sensory scores were recorded before and after gentle handling of each of the randomly selected fabrics (contained in separate polyethylene bags). The results of these analyses are shown in Table 10.
[0147] The low pH and low cure temperature pea protein / isocyanate microcapsules of Example 3 performed better than both the high pH and high cure temperature melamine formaldehyde microcapsules (Example 1) and the pea protein / isocyanate microcapsules (Example 2) by achieving a strong perfume burst during the drying evaluation (after handling). Furthermore, the microcapsules of Example 3 demonstrated that they did not lose efficacy after the damp stage on fabric, even though they were relatively weak compared to the microcapsules of Example 2. Furthermore, when compared to the microcapsules of Examples 1 and 2, the microcapsules of Example 3 demonstrated improved processability, no agglomerate formation, and improved slurry color.
[0148] [Table 10]
[0149] Example 11: Analytical evaluation of various microcapsules The characteristics of the microcapsules produced in Examples 1, 3, 4, 5, 6, and 9 were determined, including perfume content, encapsulation efficiency, free oil, viscosity, and size. The results of these analyses are shown in Table 11.
[0150] [Table 11]
[0151] Additionally, the wall strength of the microcapsules prepared in Example 9 was compared with that of whey microcapsules prepared according to Example 7 and Example 2 in WO 2020 / 131875 A2. Wall strength was measured by contacting a probe tip and progressively compressing a single microcapsule. This analysis, shown in Figure 1, demonstrates that protein selection has a smaller effect on wall strength and microcapsule flexibility. The pH and cure profile have a stronger effect on wall strength while maintaining wall flexibility (deformation). This combination allows for minimal wet performance but a very strong burst with minimal friction during the dry phase. While the wall strength is weak and requires minimal energy to break, flexibility is sufficient to survive a wash cycle in an EU washing machine and the wet phase on fabrics. Although the polyisocyanate / pea protein based microcapsules are relatively weak compared to whey or melamine formaldehyde microcapsules, the polyisocyanate / pea protein based microcapsules provide good stability in the product and the processability of the slurry is maintained. In Figure 1, the X (horizontal) axis is the position or displacement of the probe tip and the Y (vertical) axis is the force of the probe tip applied to the microcapsule surface.
[0152] Example 12: Malodor Absorption Capacity To test the malodor absorption capacity of the microcapsules disclosed herein, diethyl phthalate and caprylic / capric triglyceride solvents were encapsulated according to the methods presented in Example 1 (melamine formaldehyde) and Example 9 (polyisocyanate microcapsules prepared with pea protein and gum arabic), respectively, to produce odorless microcapsules.
[0153] The microcapsules were exposed to malodors, and the reduction in malodor concentration was measured via headspace analysis. More specifically, 100 grams of a 1.5% malodor solution was placed in a jar and allowed to equilibrate for 30 minutes. The towels were "activated" by rubbing them five times with a tongue depressor against the side marked with an "X." The "activated" towel, with the "X" facing up, was placed in a second jar (16 oz) fitted with a septum injection lid. 100 mL of malodor vapor was transferred into the second jar containing the towel sample using a 100 mL gas-tight syringe. The towel sample was stored for 1.5 hours, after which the headspace was sampled and analyzed using a SKC pump at a flow rate of 150 ml / min into a Tenax tube for 10 minutes.
[0154] The results of this analysis (Table 12) show that polyisocyanate microcapsules prepared with pea protein and gum arabic have a malodor absorption capacity comparable to that of melamine formaldehyde microcapsules.
[0155] [Table 12]
[0156] Example 13: Microcapsules prepared with oils containing high concentrations of natural components The performance of microcapsules encapsulating natural flavors (i.e., extracts derived from plants or distilled products) or naturally derived flavors (i.e., chemically modified natural flavors) was also evaluated (Table 13). These microcapsules were prepared according to the method described in Example 9.
[0157] [Table 13-1] [Table 13-2]
[0158] Perfume leakage from microcapsules prepared according to the method described in Example 9 was evaluated after storage in a fabric conditioner at 37° C. The results of this analysis (Table 14) show stable encapsulation of oils and essential oils containing high amounts of natural extracts.
[0159] The performance of polyisocyanate microcapsules prepared according to the method described in Example 9 was compared with melamine formaldehyde microcapsules (Example 1) in wet, pre-dry, dry GH (gentle handling), and post-dry stages. "Pre-dry" refers to the stage after drying but before folding the fabric. "Dry GH" refers to the stage at which the fabric is folded twice and then evaluated by panelists. "Post-dry" refers to the stage at which both hands are used to rub the fabric at least once to rupture the test microcapsules, followed by vigorous mechanical force and evaluation for signs of fragrance release. Fragrance intensity was judged on a scale of 0 to 5, with 0 being no performance and 5 being maximum. Intensity and hedonicity were evaluated by perfumers and fragrance design managers.
[0160] [Table 14]
[0161] Expert evaluation by scent designers and perfumers showed that hedonic stability was observed for oils containing high levels of natural products in microcapsules produced by the method described in Example 9 (Table 14). In comparison, melamine formaldehyde microcapsules did not exhibit good encapsulation or stable performance over time in the product.
[0162] Example 14: Microcapsules containing low log P fragrances The stability and performance of microcapsules encapsulating low log P perfumes were also evaluated (Tables 16 and 17). These test microcapsules were prepared according to the methods described in Example 1 (melamine formaldehyde capsules) and Example 9 (polyisocyanate capsules), respectively, except that the perfume compositions encapsulated in these examples were blends of the perfume base and low log P perfumes shown in Tables 16 and 17. Ethyl vanillin has a log P value of 1.55, benzaldehyde has a log P value of 1.70, cinnamaldehyde has a log P value of 1.82, oxyphenylone has a log P value of 1.48, Vertol has a log P value of 0.50, coumarin has a log P value of 1.51, and obepin has a log P value of 2.20. The perfume base has the composition shown in Table 15 below. The perfume base components have log P values ranging from 2.26 to 7.17.
[0163] [Table 15]
[0164] Preparation of dough softener samples containing test microcapsules: Microcapsule slurries prepared according to the methods described in Example 1 or Example 9 (except that the perfume composition differs as described above) were diluted in water and added to an unscented dough softener base. The resulting mixture was homogenized for 15 minutes at 300 rpm using an overhead stirrer. The finished dough softener samples contained 0.1% neat oil equivalent. The samples were prepared one day before the washing experiment.
[0165] Stability Testing: Finished dough softener samples were stored at 37°C for up to 8 weeks. Test samples were removed at 4 and 8 weeks, respectively, for sensory evaluation and measurement of perfume leakage. "Fresh" (Performance) in Table 17 means that the finished dough softener samples were evaluated when fresh and before being stored at 37°C for an extended period of time.
[0166] Sensory Performance Evaluation: The perfume intensity of the perfume compositions encapsulated by the test microcapsules was evaluated by conducting a wash experiment using a European washing machine (Miele) with finished fabric softener samples using a certified experimental protocol. Terry towels were used for the wash experiment and washed with finished fabric softener samples containing the test microcapsules. The washed terry towel samples were removed from the washing machine and line-dried overnight. Randomly selected wet towel samples were evaluated by several experts using an intensity scale of 0 to 5, with 0 meaning "no performance" and 5 meaning "strong performance." The evaluation was performed "blind," with each sample having a randomly assigned number. The dry evaluation was performed the day after the wet evaluation and was performed by the same experts using the same intensity scale of 0 to 5.
[0167] [Table 16]
[0168] [Table 17]
[0169] This example demonstrates that core-shell microcapsules of the present disclosure can successfully encapsulate perfume ingredients with low log P (0.5-2.2). Polyisocyanate microcapsules prepared according to the method described in Example 9 successfully encapsulated perfumes containing 15% ethyl vanillin, 15% oxyphenylon, or 15% coumarin. Such microcapsules demonstrated high encapsulation efficiency (low free oil) for low log P perfume ingredients, good dry feel performance, and stability. In comparison, melamine formaldehyde microcapsules prepared according to the method described in Example 1 exhibited low encapsulation efficiency (high free oil), high leakage, and poor dry feel performance for low log P perfume ingredients. High leakage of ethyl vanillin caused the slurry to turn brown, which also discolored the product to which the slurry was added. Thus, the core-shell microcapsules of the present disclosure provide a better delivery system to deliver low log P perfumes and provide caring, creamy, sweet, oriental, sensory, and luxurious benefits to consumer products.
[0170] It should be noted that not all of the acts described above in the general description or examples are required, that some of the specific acts may not be required, and that one or more additional acts may be performed in addition to those described. Furthermore, the order in which the acts are listed is not necessarily the order in which the acts are performed.
[0171]
[0013] In the foregoing specification, the concepts have been described with reference to specific embodiments. However, those skilled in the art will recognize that various modifications and changes can be made without departing from the scope of the invention as set forth in the following claims. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.
[0172] Benefits, other advantages, and solutions to problems have been described above with respect to particular embodiments. However, the benefits, advantages, solutions to problems, and any features that may give rise to or make more pronounced any benefit, advantage, or solution should not be construed as critical, necessary, or essential features of any or all of the claims.
[0173] It should be understood that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.
[0174] Any references, including any patents or applications cited, cross-referenced, or related herein, and any patent application or patent to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly excluded or otherwise limited. The citation of any reference is not an admission that it is prior art with respect to any invention disclosed or claimed herein, or that it alone, or in any combination with any other reference, teaches, suggests, or discloses any such invention. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control.
Claims
1. (a) a core-shell microcapsule, wherein the core of the microcapsule comprises an active substance and the shell of the microcapsule comprises a self-condensing polyisocyanate; (b) a dispersing agent comprising denatured pea protein; (c) a hydrocolloid containing gum arabic; A core-shell microcapsule slurry comprising: The core-shell microcapsule slurry, wherein the active material comprises a low log P perfume having a log P value ranging from 0.5 to 2.2, the amount of the low log P perfume being 3% to 18% by weight based on the weight of the active material, and the core-shell microcapsule slurry is white in color.
2. 2. The core-shell microcapsule slurry of claim 1, wherein the low log P fragrance is selected from the group consisting of ethyl vanillin, coumarin, 4-(4-hydroxyphenyl)butan-2-one, p-anisaldehyde, 2-ethyl-3-hydroxy-4H-pyran-4-one, benzaldehyde, cinnamaldehyde, and combinations thereof.
3. 3. The core-shell microcapsule slurry according to claim 1, wherein the low log P perfume is selected from the group consisting of coumarin, p-anisaldehyde, benzaldehyde, cinnamaldehyde, and combinations thereof.
4. The core-shell microcapsule slurry according to any one of claims 1 to 3, wherein the polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.
5. The core-shell microcapsule slurry of any one of claims 1 to 4, further comprising a rheology modifier, a preservative, an emulsifier, or a combination thereof.
6. 6. The core-shell microcapsule slurry of claim 5, wherein the rheological modifier comprises xanthan gum.
7. 7. The core-shell microcapsule slurry of claim 1, wherein the self-condensing polyisocyanate is present in an amount of 0.1% to 8% by weight of the core-shell microcapsule slurry.
8. The core-shell microcapsule slurry of any one of claims 1 to 7, wherein the active material is a perfume, a pro-fragrance, a malodor counteractant, or a combination thereof.
9. The active is a fragrance, and the slurry comprises: (a) less than 0.3% or less than 0.25% non-encapsulated fragrance, based on the total weight of the fragrance in the slurry; (b) 21s -1 9. The core-shell microcapsule slurry of claim 8, having a viscosity of less than 600 cps or less than 580 cps at 22°C, measured at a shear rate of 100 cps, or (c) a combination of (a) and (b).
10. 10. A consumer product comprising the core-shell microcapsule slurry of any one of claims 1 to 9, wherein the consumer product is preferably a fabric conditioner, a fabric softener, a fabric refresher, a liquid laundry detergent, or a powder detergent.
11. 10. A method for producing the core-shell microcapsule slurry of claim 1, comprising: (a) (i) denaturing pea proteins, (ii) adjusting the pH of the aqueous phase to less than 6; (iii) adding gum arabic as a hydrocolloid to the aqueous phase preparing the aqueous phase by: (b) preparing an oil phase comprising an active material and a polyisocyanate; (c) emulsifying the oil phase with the aqueous phase to form a slurry containing core-shell microcapsules; (d) hardening the shells of the microcapsules at a temperature less than 80°C; A method comprising:
12. The method of claim 11, wherein the polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.
13. 13. The method of claim 11 or 12, wherein the pH in (a)(ii) is adjusted to between 4.5 and 3.
5.
14. 14. The method of any one of claims 11 to 13, wherein the shells of the microcapsules in (d) are cured at a temperature of from 63°C to about 67°C.
15. The method of any one of claims 11 to 14, wherein the active is a perfume, a pro-fragrance, a malodor counteractant, or a combination thereof.
16. The active is a fragrance, and the slurry comprises: (a) less than 0.3% or less than 0.25% non-encapsulated fragrance, based on the total weight of the fragrance; (b) 21s -1 16. The method of claim 15, wherein the composition has a viscosity of less than 600 cps or less than 580 cps at 22°C, measured at a shear rate of 100 cps or less, or (c) a combination of (a) and (b).
17. 17. The method of any one of claims 11 to 16, further comprising adding a rheology modifier, a preservative, an emulsifier, or a combination thereof.
18. 18. The method of claim 17, wherein the rheological modifier is added before step (c), preferably the rheological modifier is xanthan gum.
19. The method according to any one of claims 11 to 18, wherein the amount of polyisocyanate is from 0.1% to 8% by weight of the core-shell microcapsule slurry.