Biodegradable microcapsules comprising beta-1-4 nonionic polysaccharides

Abstract

The present disclosure relates to a core-shell microcapsule slurry comprising (a) a core-shell microcapsule wherein the core-shell microcapsule has a microcapsule core and a microcapsule shell encapsulating the microcapsule core, the microcapsule core comprising an active material, and the microcapsule shell comprising a self-condensing polyisocyanate and a beta-1-4 nonionic polysaccharide; (b) a dispersant comprising a denatured protein, wherein the denatured protein comprises denatured pea protein and / or denatured whey protein; and (c) a hydrocolloid comprising Arabic gum; wherein the microcapsule shell is characterized by a bursting force of at least 100 [mu] N. The present disclosure also relates to a method of producing such a core-shell microcapsule slurry. The present disclosure also relates to a consumer product containing such a core-shell microcapsule slurry.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to European patent application No. EP 22183276.9 filed on July 6, 2022, the disclosure of which is incorporated herein by reference in its entirety for all purposes. Technical Field

[0003] The present disclosure relates to biodegradable core-shell microcapsule slurries. In particular, the microcapsule shells contain self-condensed polyisocyanates and β-1-4 nonionic polysaccharides (e.g., xyloglucan). The present disclosure also relates to methods for producing such core-shell microcapsule slurries. The present disclosure also relates to consumer products containing such core-shell microcapsule slurries. Background Art

[0004] Microcapsules are useful in a variety of applications where it is desired to deliver, administer, or release a fragrance or other active material in a delayed and controlled manner.

[0005] Conventional microcapsules each have a polymer shell that encapsulates the active material in the microcapsule core. The polymer shell is typically formed via interfacial polymerization (i.e., polymerization occurring at the interface between the aqueous phase and the oil phase). These microcapsules have been developed to provide good performance in various consumer products (such as laundry detergents). See, for example, US 7,491,687, US 6,045,835, US 2014 / 0287008, and WO 2015 / 023961. Polyurea microcapsules have been developed to deliver fragrances. Their preparation involves polymerization between wall-forming materials (e.g., polyisocyanates and polyamines). During the polymerization, polyisocyanates can react with many fragrance ingredients (such as primary alcohols contained in fragrance accords). Another wall-forming material polyamine is also reactive to aldehyde fragrance ingredients. Primary alcohols and aldehydes are common ingredients in many fragrance accords. Such fragrance ingredients are not suitable for conventional microcapsule encapsulation. Furthermore, fragrance ingredients with high water solubility are also not suitable for conventional encapsulation because these ingredients tend to remain in the aqueous phase rather than being encapsulated in the microcapsule oil core. Encapsulation of fragrances and other active materials without loss of reactive and / or water-soluble ingredients remains a challenge.

[0006] Methods for incorporating biodegradable polymers into microcapsule compositions have been described. For example, US 10,034,819 B2 and US 2019 / 0240124 A1 teach microcapsules having an inner shell and an outer shell, wherein the outer shell is produced by complex coacervation of a first polyelectrolyte (such as gelatin) and a second polyelectrolyte (such as carboxymethyl cellulose, sodium carboxymethyl guar gum, xanthan gum, and vegetable gum).

[0007] Similarly, EP 2588066B1 describes coacervate capsules prepared with a coating consisting of a protein and optionally a non-protein polymer. In addition, EP 2811846B1 describes the use of protein aggregates as an interfacial layer around a hydrophobic substance. EP 1855544B2 teaches the use of encapsulating active ingredients in a matrix consisting of 0.5wt%-95wt% of anionic polysaccharides and 0.5wt%-95wt% of peptides with a molecular mass in the range of 0.3-12kDa. EP 3746217A1 and WO 2020 / 195132A1 describe the preparation of core-shell microcapsules by cross-linking proteins into the wall of the microcapsules. US 10,166,196 B2 discloses an agglomerate of primary microcapsules consisting of a primary shell and an outer shell, wherein the outer shell is a primary shell and the outer shell is a product of a complex coacervation reaction of a first protein (such as pea or soybean protein) and a second polymer (such as agar, gellan gum, gum arabic, casein, prolamin, pectin, alginate, carrageenan, xanthan gum, canola protein, dilutan gum, locust bean gum or welan gum).

[0008] Other attempts have proposed the use of xyloglucan as a deposition polymer grafted onto polyurea or melamine formaldehyde microcapsules, primarily to enhance deposition on clothing. For example, WO 2008 / 145547A1 discloses a method of attaching a nonionic deposition polymer that has a direct effect on textiles to core-shell particles. Example 8 provides the attachment of both locust bean gum and xyloglucan nonionic deposition polymers to microcapsules by using various addition polymers. Furthermore, there is no mention of the use of biodegradable proteins for the capsule shell.

[0009] WO 2012 / 007438A1 discloses a particle containing a beneficial agent comprising a multilayer shell, wherein the outer shell may be a polyurea having a deposition polysaccharide polymer (e.g., xyloglucan) on the outside of the shell (see claim 4 and pages 28-30). The deposition aid is grafted onto the particle via heating and stirring at 80°C in the presence of ascorbic acid and methyl acrylate.

[0010] WO 2012 / 038144 A1 discloses the attachment of xyloglucan deposition agents to preformed melamine formaldehyde fragrance microcapsules via a polyvinyl acetate formulation to enhance deposition on clothing even in the presence of mannanase (see Example 3).

[0011] WO 2016 / 177607A1 discloses polyurea microcapsules containing a beneficial agent (e.g., a fragrance) within a polyurea shell, the polyurea shell being characterized in that a xyloglucan deposition polymer is grafted thereon, which helps to reduce agglomeration of the microcapsules to improve dispersion in surfactant-containing products. The xyloglucan deposition polymer is added at different time points (7 min, 15 min, 30 min, 45 min, or 60 min) after the start of the encapsulation process and before the curing step (see Example 1). There is also no mention of the use of plant proteins, or specifically pea proteins, for the capsule shell.

[0012] WO 2007 / 062833A1 discloses the use of polyxyloglucan as an uncharged polysaccharide material on melamine formaldehyde as a shell material for core-shell polymer particles containing a benefit agent (eg, fragrance). There is no mention of the use of plant or pea protein for capsule shells.

[0013] These existing solutions still have limitations and do not adequately teach how to overcome the above-mentioned problems.Therefore, there is a need to develop microcapsule compositions suitable for encapsulating active materials with sustainable and biodegradable ingredients. Summary of the invention

[0014] The present disclosure provides a core-shell microcapsule slurry. The core-shell microcapsule slurry comprises: (a) a core-shell microcapsule, wherein the core-shell microcapsule has a microcapsule core and a microcapsule shell encapsulating the microcapsule core, the microcapsule core comprises an active material, and the microcapsule shell comprises a self-condensed polyisocyanate and a β-1-4 nonionic polysaccharide; (b) a dispersant comprising a denatured protein, wherein the denatured protein comprises denatured pea protein and / or denatured whey protein; and (c) a hydrocolloid comprising gum arabic; wherein the microcapsule shell is characterized by a rupture force of at least 100 μN.

[0015] The present disclosure also provides a method for producing a core-shell microcapsule slurry. The method comprises: (a) providing an aqueous phase comprising a denatured protein and gum arabic, wherein the denatured protein comprises a denatured pea protein and / or a denatured whey protein; (b) providing an oil phase comprising an active material and a polyisocyanate; (c) emulsifying the oil phase with the aqueous phase to form an emulsion; (d) adding all of the β-1-4 nonionic polysaccharide to the emulsion within 5 minutes after the start of the emulsification step (c) to form a microcapsule slurry comprising core-shell microcapsules; and (e) curing the shell of the microcapsule at a temperature in the range of 40°C to 90°C. The present disclosure also provides a core-shell microcapsule slurry obtainable by such a method. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Embodiments are illustrated in the accompanying drawings to improve understanding of the concepts as presented herein.

[0017] Figure 1 Shown is the sensory performance evaluation of microcapsules 1-4 (prepared with xyloglucan added at different times) side dosed into powder detergent and hand washed compared to control microcapsule 14 (no xyloglucan).

[0018] Figure 2 Shown is the sensory performance evaluation of microcapsules 1 and 7 side-dosed into powder detergent and hand washed.

[0019] Figure 3 Shown is the sensory performance evaluation of microcapsule 1 (made using denatured pea protein as dispersant) compared to microcapsules 10-12 (made using modified starch as dispersant) and microcapsule 13 (commercial melamine formaldehyde microcapsules). The microcapsules were sprayed onto powder detergent and washed according to the hand wash regimen.

[0020] Figure 4 Shown is the sensory performance evaluation of microcapsules 8 and 9 (comprising xyloglucan) after spraying into a powdered detergent and evaluated in a hand wash application, compared to comparative microcapsule 14 (without xyloglucan). DETAILED DESCRIPTION

[0021] The foregoing general description and the following detailed description are exemplary and explanatory only and do not limit the invention as defined by the appended claims. Other features and benefits of any one or more embodiments will be apparent from the following detailed description and from the claims.

[0022] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," 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, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. In addition, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or 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 both A and B are true (or exist).

[0023] Moreover, "a / an" is used to describe the elements and components described herein. This is done only for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one / a or at least one / a, and the singular also includes the plural, unless it is obvious that it is otherwise intended.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those of ordinary skill in the art to which the present invention belongs. In the event of a conflict, this specification, including definitions, shall prevail. 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. In addition, materials, methods and examples are illustrative only and are not intended to be restrictive.

[0025] When amount, concentration or other values ​​or parameters are given with scope, preferred range or a series of upper preferred values ​​and / or lower preferred values, this should be understood as particularly disclosing all scopes formed by any pairing of any upper range limit or preferred value and any lower range limit or preferred value, and whether these scopes are disclosed separately.When numerical range is enumerated herein, unless otherwise indicated, the scope is intended to include all integers and fractions in its endpoints and the scope.For example, when enumerating the scope of "1 to 10", the enumerated scope should be interpreted as including "1 to 8", "3 to 10", "2 to 7", "1.5 to 6", "3.4 to 7.8", "1 to 2 and 7-10", "2 to 4 and 6 to 9", "1 to 3.6 and 7.2 to 8.9", "1-5 and 10", "2 and 8 to 10", "1.5-4 and 8" and other scopes.

[0026] The present disclosure illustratively described herein may suitably be practiced without any element or elements, limitation or limitations not specifically disclosed herein. Although compositions and methods are described herein as "comprising" various components or steps, unless otherwise indicated, these compositions and methods may also "consist essentially of" or "consist of" the various components or steps.

[0027] Unless otherwise indicated, all parts, percentages and ratios referred to herein and in the claims are by weight.

[0028] The values ​​and dimensions disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such value is intended to mean the recited value and a functionally equivalent range around that value. For example, a value disclosed as "50%" is intended to mean "about 50%".

[0029] Before presenting details of the following embodiments, some terms are defined or clarified.

[0030] The terms "obtainable" and "obtained" are used interchangeably in the present disclosure and are not meant to indicate that, for example, a product must be obtained by, for example, the sequence of steps following the term "obtained", although such limited understanding is always included in the term as a preferred aspect of the present disclosure.

[0031] As used herein, the term "rupture force" means the force required to rupture a microcapsule. It can be measured according to the method described in the section "Method for measuring rupture force" of the present disclosure.

[0032] As used herein, the term "microcapsule slurry" means an aqueous suspension of biodegradable core-shell microcapsules. In some embodiments, the biodegradable core-shell microcapsule product produced according to the methods and examples described in the present disclosure is in the form of a microcapsule slurry. The microcapsule slurry can be used directly in consumer products. The microcapsule slurry can also be washed, coated, dried (e.g., spray dried) and / or combined with one or more other microcapsules, active materials, and / or carrier materials.

[0033] As used herein, the term "self-condensing polyisocyanate" means a polyurea formed by 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 linkage. Thus, a polyisocyanate can self-polymerize in the presence of water to form a polyurea.

[0034] As used herein, the terms "capsule", "microcapsule" and "core-shell microcapsule" are used interchangeably and refer to a substantially spherical structure having a well-defined core and a well-defined envelope or wall or shell. The "core" contains the active material or microencapsulated material. The terms "wall" and "shell" are used interchangeably to refer to a structure formed by a microencapsulating polymer surrounding a core of microencapsulated active material.

[0035] As used herein, the term "w / w" means weight by weight and the term "w / v" means weight per volume. As used herein, the term "wt%" means weight percent.

[0036] As used herein, the terms "g", "mg" and "μg" refer to "gram", "milligram" and "microgram", respectively. The terms "L", "mL", and "μL" refer to "liter", "milliliter" and "microliter", respectively. The terms "cm", "mm" and "μm" refer to "centimeter", "millimeter" and "micrometer", respectively. The terms "mN" and "μN" refer to "millinewton" and "micronewton", respectively.

[0037] Polyisocyanate

[0038] As used herein, the terms "multifunctional isocyanate / polyfunctional isocyanate" and "polyisocyanate" can be used interchangeably and refer to compounds with two or more isocyanate (-NCO) groups. Polyisocyanates can be aromatic, aliphatic, linear, branched or cyclic. In certain embodiments, polyisocyanates contain an average of 2 to 4 isocyanate groups. In certain embodiments, polyisocyanates contain at least three isocyanate functional groups. In certain embodiments, polyisocyanates are water-insoluble. In certain aspects, polyisocyanates are oligomeric polyisocyanates obtained from hexamethylene diisocyanate (HDI) (which is a monomeric diisocyanate). In certain aspects, polyisocyanates are oligomeric polyisocyanates with biuret, isocyanurate, allophanate, uretdione and / or oligomeric HDI structures. Exemplary polyisocyanates are sold under the following trade names: (For example, D-110N; Mitsui Chemicals Co., Ltd.), (Covestro), (Covestro) and (BASF).

[0039] In certain embodiments, polyisocyanate is an aromatic polyisocyanate. Desirably, the aromatic polyisocyanate comprises phenyl, tolyl, xylyl, naphthyl or diphenyl moieties as aromatic components. In certain 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.

[0040] In some embodiments, the aromatic polyisocyanate has the structural formula shown below, and includes structural isomers thereof

[0041]

[0042] Wherein n can vary from 0 to a desired number (e.g., 0-50, 0-20, 0-10, or 0-6). Preferably, the value of n is limited to less than 6. The polyisocyanate may also be a mixture of polyisocyanates, wherein the value of n can vary from 0 to 6. In the case where the polyisocyanate is a mixture of various polyisocyanates, the average value of n preferably falls between 0.5 and 1.5.

[0043] In some embodiments, the aromatic polyisocyanate has the structural formula shown below, and includes structural isomers thereof

[0044]

[0045] Where R can be C1-C 10 Alkyl, C1-C 10 Ester, or isocyanurate. Representative polyisocyanates with this structure are known under the trademark D-110N (Mitsui Co., Ltd.), L75 (Covestro) and IL (Covestro) sales.

[0046] The trimethylolpropane adduct of xylylene diisocyanate has the structural formula shown below:

[0047]

[0048] In some embodiments, the aromatic polyisocyanate is selected from the group consisting of: 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), xylylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, dialkyl diphenylmethane diisocyanate and tetraalkyl diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of tolylene diisocyanate (TDI), 4,4'-diisocyanatophenylperfluoroethane, diisocyanatoethyl phthalate, 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.

[0049] In some embodiments, the polyisocyanate is an aliphatic polyisocyanate.In some embodiments, the aliphatic polyisocyanate is 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, which can be obtained, for example, 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, dimerized fatty acid diisocyanate, and mixtures thereof.

[0050] In some embodiments, the weight average molecular weight of polyisocyanate ranges from 250Da to 1000Da or 275Da to 500Da. In some embodiments, the polyisocyanate for preparing 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 aliphatic polyisocyanates and aromatic polyisocyanates. In some embodiments, polyisocyanate is a mixture of trimethylolpropane adducts of the biuret of hexamethylene diisocyanate and xylylene diisocyanate. In some embodiments, polyisocyanate is a combination of aliphatic polyisocyanates or aliphatic polyisocyanates, without any aromatic polyisocyanates. In some embodiments, polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate, and the shell of the microcapsule includes the trimethylolpropane adducts of the xylylene diisocyanate of self-condensation.

[0051] Active Materials

[0052] The core of microcapsule comprises active material encapsulated therein. In some aspects, active material has the logP value (partition coefficient) less than 2. In some aspects, microcapsule comprises at least two, three, four or more active materials in core. The active material that can be encapsulated in the core-shell microcapsule of the present disclosure includes but is not limited to spices, flavoring agents, agricultural active substances, pesticides, insecticides, herbicides, fungicides, pharmaceutical active substances, nutrient preparation active substances, animal nutrition active substances, food active substances, microbial active substances, malodor counteractants (malodor counteractant), and / or cosmetic active substances. In certain embodiments, active material is selected from the group consisting of: spices, spice precursors, malodor counteractants (malodor counteractive agent), and combinations thereof. In certain embodiments, active material includes spices, preferably comprising at least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine or at least ten selected from the spices of the high performance spices of the group consisting of the super high impact spices listed in Table 1 and the high impact spices listed in Table 2.

[0053] Table 1 - High Impact Fragrance Ingredients

[0054]

[0055]

[0056] 1 Available from International Flavors & Fragrances.

[0057] Table 2 - High Impact Fragrance Ingredients

[0058]

[0059]

[0060]

[0061]

[0062] 1 Available from International Flavors & Fragrances, New York.

[0063] 2 Available from TRIPPER PTE Ltd. (Indonesia).

[0064] 3 Available from TREATT & CO. Ltd. (UK).

[0065] In addition to the fragrance ingredients listed in Table 1 and Table 2, the fragrance may further include at least one additional fragrance ingredient. Preferably, the fragrance may further include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40 or more additional fragrance ingredients not listed in Table 1 and Table 2. Non-limiting examples of such additional fragrance ingredients include those described in US2018 / 0325786A1, US 4,534,891, US 5,112,688 and US 5,145,842. Other suitable active materials that can be encapsulated include active materials listed on pages 38-50 of WO 2016 / 049456.

[0066] In some embodiments, the additional perfume ingredients make up the total perfume composition when combined with one or more perfume ingredients of Table 1 and Table 2. In this aspect, the balance of 100 wt % relative to the total weight of the perfume component consists of one or more super high impact perfume ingredients of Table 1 and high impact perfume ingredients of Table 2 and one or more additional perfume ingredients.

[0067] It has been unexpectedly discovered that perfumes containing certain types of ultra-high impact and high impact perfume ingredients produce high-performance perfume ingredients for fabric care compositions, preferably fabric conditioners, thereby improving the performance of the fragrance characteristics and / or system. As used herein, the term "fragrance characteristics" means the description of the perceived fragrance by the nose of a person at any time. The fragrance characteristics may change over time. The fragrance characteristics are the result of a combination of the base notes, middle notes and top notes (if present) of the fragrance. The base notes are characterized by providing animal, woody, sweet, amber or musky characteristics and are not prone to volatility. The middle notes are related to the desired characteristics (such as floral characteristics (e.g., jasmine, rose), fruity, marine, aromatic or spicy characteristics). "Top notes (top note / head note)" provide citrus, green, light or fresh characteristics and tend to evaporate quickly due to their high volatility. The fragrance characteristics consist of two characteristics: "intensity" and "characteristics". "Intensity" relates to perceived intensity, while "characteristics" refers to the odor impression or quality of the fragrance, i.e., fresh, clean, etc.

[0068] In some embodiments, the active material component (e.g., fragrance) of the core-shell microcapsule is present at a level between 1 wt% and 35 wt%, preferably between 15 wt% and 35 wt%, or more preferably between 20 wt% and 35 wt% relative to the weight of the microcapsule slurry. When the fragrance comprises a combination of the super high impact fragrance ingredients listed in Table 1 and the high impact fragrance ingredients listed in Table 2, the fragrance can be used at a significantly reduced dosage (e.g., at least 2, 5 to 10 times lower) compared to a standard fragrance that does not contain the super high impact fragrance ingredients listed in Table 1 and the high impact fragrance ingredients listed in Table 2. In particular, fragrances comprising at least five high performance fragrance ingredients (including super high impact fragrances) can be used at a dosage level of ≤1 wt% (e.g., 0.01 wt% to 1 wt%) relative to the total weight of the microcapsule slurry. In certain aspects, when the fragrance is a neat fragrance, an encapsulated fragrance, or a combination thereof, the weight ratio of the super high impact fragrance ingredient to the high impact fragrance ingredient is in the range of 1:0 to 1:19.

[0069] In some embodiments, the active material includes agricultural active substances, pesticides, insecticides, herbicides, and / or fungicides. Encapsulating agricultural active substances, pesticides, insecticides, herbicides, and / or fungicides can increase their efficacy, extend their shelf life and protect the environment. In some embodiments, the insecticide is an organophosphate insecticide. In some embodiments, the insecticide can be an organophosphate insecticide selected from the group consisting of: acephate, methyl azinphos-methyl, chlorpyrifos, chloroxyfos, methyl chlorpyrifos, diazinon, dimethoate, ethoxychlor, cypermethrin, fenthion, fenamiphos, thiamethoxam, malathion, methamidophos, methidathion, oxydemeton, sulfone, parathion, methyl parathion, phorate, phosmet, propylbromophos, trichlorfon, and mixtures thereof. In some embodiments, the insecticide is selected from the group consisting of: cypermethrin, bifenthrin, lambda-cyhalothrin, and mixtures thereof. In some embodiments, the herbicide is selected from the group consisting of clomazone, acetochlor, pendimethalin, and mixtures thereof. In some embodiments, the fungicide is tebuconazole.

[0070] Denatured protein

[0071] Denatured proteins are used in the methods of the present disclosure to produce core-shell microcapsule slurries, and the denatured proteins include denatured pea proteins and / or denatured whey proteins. 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 contain legumin, vicilin, and convicilin protein. The term "pea protein" is also intended to include partially or completely modified pea proteins. Individual pea protein components (such as legumin, vicilin, or convicilin) ​​may also be used to prepare microcapsules of the present disclosure.

[0072] The term "whey protein" refers to the protein fraction of milk that does not precipitate at pH 4.6. The term "whey" encompasses whey derived from cheese making or casein manufacture and whey obtained from various membrane filtrations of milk such as microfiltration, ultrafiltration, nanofiltration, reverse osmosis, diafiltration, chromatography, crystallization, or a combination thereof. "Whey protein" is intended to include whey protein isolate, whey protein concentrate, or a combination thereof.

[0073] In some embodiments, pea protein and / or whey protein are separated and optionally purified to homogeneity or near homogeneity, for example, at least about 80%, about 85%, about 90%, about 92%, about 95%, about 97%, about 98%, or about 99% pure for pea and / or whey protein. Preferably, pea protein and / or whey protein are denatured, preferably without causing gelation of the protein. Exemplary conditions for protein denaturation include, but are not limited to, exposure to heat or cold, pH changes, exposure to denaturants (such as detergents, urea or other chaotropic agents) or mechanical stress (including shear forces). In some aspects, pea protein and / or whey protein are partially denatured, for example, at least 50%, 60%, 70%, 80% or 85% of the pea protein and / or whey protein is denatured based on the total weight of the pea protein and / or whey protein. In other aspects, the pea protein and / or whey protein is substantially or completely denatured, for example, at least 90%, 95%, or 98% of the pea protein and / or whey protein is denatured based on the total weight of the pea protein and / or whey protein. For example, when 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 produce substantially denatured pea protein.

[0074] In particular, it has been found that chaotropes are particularly useful in providing denatured proteins for preparing microcapsules of the present disclosure. As is conventional in the art, chaotropes are compounds that destroy hydrogen bonds in aqueous solutions, thereby causing an increase in entropy. Typically, this reduces the hydrophobic effect necessary for the three-dimensional structure of proteins. Chaotropes can be obtained by having a positive chaotropic value (i.e., kJ kg on the Hallsworth scale). -1 An example of a value for the chaotropic property is, for example, CaCl2+92.2 kJ kg -1 MgCl2+54.0kJ kg -1 , butanol +37.4 kJ kg -1 、Guanidine hydrochloride +31.9 kJ kg -1 and urea +16.6kJ kg -1 In certain aspects, the chaotropic agent is a guanidine salt, such as guanidine sulfate, guanidine carbonate, guanidine nitrate or guanidine chloride. In specific aspects, the pea protein and / or whey protein is partially or completely denatured with guanidine carbonate.

[0075] β-1-4 nonionic polysaccharide

[0076] The β-1-4 nonionic polysaccharide used to prepare the microcapsules of the present disclosure is a nonionic polysaccharide having a linear backbone of β-(1→4)-linked glucosyl residues, preferably modified with a regular pattern of α-(1→6)-linked xylosyl residues, which are optionally extended with galactosyl, fucosyl and / or arabinosyl residues. In certain aspects, the β-1-4 nonionic polysaccharide is hydrophilic. In specific aspects, the β-1-4 nonionic polysaccharide is xyloglucan. The β-1-4 nonionic polysaccharide used in the present disclosure is known in the art and can be easily obtained from commercial sources.

[0077] Microcapsule Forming Aids

[0078] Most microcapsule forming aids are used as dispersants (i.e., emulsifiers or surfactants). They promote the formation of stable emulsions containing nano- or micron-sized oil droplets to be encapsulated. In addition, microcapsule forming aids improve the performance of the microcapsules by stabilizing the capsules and / or their deposition to the target area or release to the environment. The amount of these microcapsule forming aids is from about 0.1% to about 40% by weight of the microcapsule, more preferably from about 0.1% to about 10%, more preferably from about 0.1% to about 5% by weight of the microcapsule.

[0079] Examples of microcapsule-forming aids are polyvinyl pyrrolidone, 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 acrylamidopropyltrimethylammonium chloride, terpolymers (i.e., terpolymers of acrylic acid, acrylamide, and acrylamidopropyltrimethylammonium chloride), partially or fully hydrolyzed polyvinyl acetate polymers (i.e., polyvinyl alcohol), or combinations thereof.

[0080] Other microcapsule forming aids include alkyl sulfates, alkyl ether sulfates, alkyl isosulfates, alkyl carboxylates, alkyl sulfosuccinates, water-soluble salts of alkyl succinates, alkyl sulfates such as sodium lauryl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolysates, acyl aspartates, alkyl or alkyl ether or alkyl aryl ether phosphates, sodium lauryl sulfate, phospholipids or lecithin, or soaps, sodium, potassium or ammonium stearate, oleates or palmitates, alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, sodium dialkyl sulfosuccinate, dioctyl sulfosuccinate, sodium dilauryl sulfosuccinate, poly(styrene sulfonate) sodium salt, isobutylene-maleic anhydride copolymers, sodium alginate, cellulose sulfate and pectin. , isobutylene-maleic anhydride copolymer, gum arabic, carrageenan, sodium alginate, pectic acid, tragacanth gum, almond gum and agar; semi-synthetic polymers such as sulfated cellulose, sulfated methyl cellulose, carboxymethyl starch, phosphorylated starch, lignin sulfonic acid; and synthetic polymers such as maleic anhydride copolymer (including its hydrolyzate), polyacrylic acid, polymethacrylic acid, acrylic acid-butyl acrylate copolymer or crotonic acid homopolymer and copolymer, vinylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid homopolymer and copolymer, and partial amides or partial esters of such polymers and copolymers, carboxyl-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and phosphoric acid-modified polyvinyl alcohol, phosphorylated or sulfated tristyrylphenol polyoxyethylene ether.

[0081] Commercially available surfactants include, but are not limited to, those sold under the trade names Sulfonated naphthalene formaldehyde condensates sold under the trade names D425 (sodium salt of alkylnaphthalene sulfonate formaldehyde condensate, AkzoNobel, Fort Worth, TX); (For example 3-83)(Air Products), or Partially hydrolyzed polyvinyl alcohol sold under the trade names 203 (Sekisui), or polyvinyl alcohols such as Ultalux FP, Ultalux FA, Ultalux AD, OKS-8089 (Sourus); or Materials (BASF Corporation) marketed as ethylene oxide-propylene oxide block copolymers or poloxamers; Sulfonated polystyrene sold under the trade name Ethylene-maleic anhydride polymers sold by Vertellus Specialties Inc.; SC 60 (BASF), a copolymer of acrylamide and acrylamidopropyltrimethylammonium chloride; 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). Surfactants 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 aspects, the surfactant or emulsifier is a sulfonated polystyrene, for example, available under the trade name II high molecular weight polystyrene sulfonate sodium salt sold.

[0082] In other aspects, the capsule forming aid is a processing aid such as a hydrocolloid, which improves the colloidal stability of the slurry, preventing coagulation, sedimentation and creaming. The term "hydrocolloid" refers to a large class of water-soluble or water-dispersible polymers having anionic, cationic, zwitterionic or nonionic character. Hydrocolloids useful in the present disclosure include, but are not limited to, polysaccharides such as starch, modified starch, dextrin, maltodextrin and cellulose derivatives, and quaternized forms thereof; natural gums such as alginates, carrageenan, xanthan gum, agar, pectin, pectic acid, gum arabic, tragacanth and gum karaya, guar gum and quaternized guar gum; gelatin, protein hydrolysates, and quaternized forms thereof; synthetic polymers and copolymers such as poly(vinyl pyrrolidone-co-vinyl acetate), poly(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) copolymers, polyalkylene oxides, poly(vinyl methyl ether), poly(vinyl ether-co-maleic anhydride), and the like, as well as poly(ethylene imine), poly((meth)acrylamide), poly(alkylene oxide-co-dimethylsiloxane), poly(aminodimethylsiloxane), Ultrez 20 (Acrylates / C10-30 Alkyl Acrylate Crosspolymer), sold under the trade name Ultrez 30 is a crosslinked homopolymer of acrylic acid polymerized in a cosolvent system of cyclohexane and ethyl acetate and sold under the trade name Excel (acrylate copolymer) is sold under the trade name 981 (carbomer), and the like, and quaternized forms thereof. In certain aspects, the microcapsule composition is prepared in the presence of gum arabic as the hydrocolloid.

[0083] During processing, the capsule forming aid may also be used in combination with carboxymethyl cellulose ("CMC"), polyvinyl pyrrolidone, polyvinyl alcohol, alkyl naphthalene sulfonate formaldehyde condensate, and / or a surfactant to facilitate capsule formation. Examples of surfactants that may be used in combination with the capsule forming aid include, but are not limited to, cetyl trimethyl ammonium chloride (CTAC), (For example F127), (For example F127), or poloxamers sold under the trade name Q- (National Starch Food Innovation); or gum arabic, such as Seyal or Senegal. In some aspects, the CMC polymer has a molecular weight range of between about 90,000 Daltons and 1,500,000 Daltons, preferably between about 250,000 Daltons and 750,000 Daltons, and more preferably between 400,000 Daltons and 750,000 Daltons. The CMC polymer has a degree of substitution between about 0.1 and about 3, preferably between about 0.65 and about 1.4, and more preferably between about 0.8 and about 1.0. The CMC polymer is present in the capsule slurry at a level of about 0.1% to about 2%, and preferably about 0.3% to about 0.7%. In other aspects, the polyvinyl pyrrolidone used in the present invention is a water-soluble polymer and has a molecular weight of 1,000 to 10,000,000. Suitable polyvinyl pyrrolidone is polyvinyl pyrrolidone K12, K15, K17, K25, K30, K60, K90, or a combination thereof. The amount of polyvinyl pyrrolidone is 2%-50%, 5%-30% or 10%-25% by weight of the capsule delivery system. Commercially available alkyl naphthalene sulfonate formaldehyde condensates include D-425, a sodium salt of a naphthalenesulfonate condensate, is available from Akzo Nobel, Fort Worth, Texas.

[0084] The present disclosure provides a core-shell microcapsule slurry. The core-shell microcapsule slurry comprises: (a) a core-shell microcapsule, wherein the core-shell microcapsule has a microcapsule core and a microcapsule shell encapsulating the microcapsule core, the microcapsule core comprises an active material, and the microcapsule shell comprises a self-condensing polyisocyanate and a β-1-4 nonionic polysaccharide; (b) a dispersant comprising a denatured protein, wherein the denatured protein comprises a denatured pea protein and / or a denatured whey protein; and (c) a hydrocolloid comprising gum arabic; wherein the microcapsule shell is characterized by a rupture force of at least 100 μN. In some embodiments, the β-1-4 nonionic polysaccharide comprises or is xyloglucan. In some embodiments, the polyisocyanate comprises or is an aromatic polyisocyanate. In some embodiments, the polyisocyanate comprises or is a trimethylolpropane adduct of xylylene diisocyanate. In some embodiments, the denatured protein comprises or is a denatured pea protein. In some embodiments, the denatured protein comprises or is a denatured whey protein.

[0085] The microcapsule shell comprises, consists essentially of, or consists of a self-condensing polyisocyanate and a β-1-4 nonionic polysaccharide (e.g., xyloglucan). In some embodiments, the amount of self-condensing polyisocyanate present in the microcapsule shell is in the range of 0.1% to 10%, preferably 0.1% to 8%, more preferably 0.2% to 5%, and even more preferably 1.5% to 3.5% or 0.1% to 5%, all based on the weight of the core-shell microcapsule slurry by weight. In some embodiments, the amount of self-condensing polyisocyanate is no more than 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, or 0.2% by weight based on the weight of the core-shell microcapsule slurry. In some embodiments, the amount of β-1-4 nonionic polysaccharide (e.g., xyloglucan) present in the microcapsule shell is in the range of about 0.1 wt% to about 5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 0.5 wt%, based on the weight of the microcapsule slurry. In some embodiments, the amount of β-1-4 nonionic polysaccharide (e.g., xyloglucan) present in the microcapsule shell is at least about 0.01 wt%, or at least about 0.02 wt%, or at least about 0.05 wt%, or at least about 0.1 wt%, or at least about 0.15 wt%, or at least about 0.2 wt%, based on the weight of the microcapsule slurry. In some embodiments, the amount of β-1-4 nonionic polysaccharide (e.g., xyloglucan) present in the microcapsule shell is no more than about 5 wt%, or no more than about 4 wt%, or no more than about 3 wt%, or no more than about 2 wt%, or no more than about 1 wt%, or no more than about 0.5 wt% based on the weight of the microcapsule slurry. In some embodiments, the weight ratio of β-1-4 nonionic polysaccharide (e.g., xyloglucan) to denatured protein (e.g., denatured pea protein and / or denatured whey protein) is in the range of 1:6 to 1:7.5. In some embodiments, the weight ratio of β-1-4 nonionic polysaccharide (e.g., xyloglucan) to microcapsule shell is in the range of 1:3 to 1:5.

[0086] It has been found that polyisocyanates (such as trimethylolpropane adducts of xylylene diisocyanate) can self-polymerize in the presence of denatured proteins (as dispersants) and form wall materials suitable for encapsulating active materials when reacting with water to form amine groups. In some embodiments, the polyisocyanates do not crosslink or form covalent bonds with the denatured proteins. On the contrary, the denatured proteins appear to act as a scaffold to promote the self-polymerization reaction of the polyisocyanates to form wall polymers that encapsulate the active materials. In addition, the addition of gum arabic prior to emulsification facilitates the dissolution of the denatured proteins in the aqueous phase, thereby preventing their aggregation. In some embodiments, the self-condensing polyisocyanates are formed in the absence of exogenous (i.e., added) crosslinking agents (such as polyamines and polyols). In some embodiments, the self-condensing polyisocyanates are not crosslinked or covalently bonded to the β-1-4 nonionic polysaccharide.

[0087] In some embodiments, in addition to the β-1-4 nonionic polysaccharide, the microcapsule shell is substantially free of or free of biopolymers (e.g., denatured proteins and gum arabic) and / or polyelectrolytes. In some embodiments, in addition to the β-1-4 nonionic polysaccharide, the microcapsule shell contains 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 contains no more than 15%, 10%, 5%, 3%, 1%, 0.5%, 0.2%, or 0.1% of polyelectrolytes relative to the total weight of the microcapsule shell. As used herein, the term "biopolymer" means a polymer obtained from a natural source (e.g., a plant, fungus, bacteria, or animal) or a modified biopolymer thereof. The biopolymer can be a polypeptide (e.g., a protein) or a polysaccharide. In some embodiments, the biopolymer is selected from the group consisting of gelatin, collagen, chitosan, guar gum, gum arabic (gum arabic), xanthan gum, proteins (e.g., pea protein), hydrophobins, enzymes, alginates, carrageenans, pectins, modified starches, and mixtures thereof.

[0088] In some embodiments, the microcapsule shell is substantially free of or free of silicon-based materials. In some embodiments, the microcapsule shell comprises no more than 2%, 1%, 0.5%, 0.2%, 0.1%, 0.05%, or 0.01% of silicon-based materials relative to the total weight of the microcapsule shell. In some embodiments, the microcapsule shell is substantially free of or free of salts (e.g., inorganic salts). In some embodiments, the microcapsule shell comprises no more than 1%, 0.5%, 0.2%, 0.1%, 0.05%, 0.01%, 0.005%, or 0.002% of salt relative to the total weight of the microcapsule shell. In some embodiments, the microcapsule shell consists essentially of or consists of a self-condensing polyisocyanate and a β-1-4 non-ionic polysaccharide (e.g., xyloglucan), i.e., the total weight of the self-condensing polyisocyanate and the β-1-4 non-ionic polysaccharide present in the microcapsule shell is at least 90%, 95%, 98%, 99%, 99.5%, 99.8%, or 99.9% relative to the total weight of the microcapsule shell.

[0089] The microcapsule shells of the present disclosure exhibit improved wall strength, thereby providing a lower percentage of microcapsule rupture after spraying onto a powder. Advantageously, the microcapsules of the present disclosure can achieve a perfume load of up to 35% and show improved drying performance in powder detergent applications compared to similar microcapsules without β-1-4 nonionic polysaccharides (e.g., xyloglucan). The microcapsules can also advantageously exhibit the same performance as commercial melamine formaldehyde capsules. Notably, denatured protein is necessary in the process of producing the microcapsules of the present disclosure because replacing the denatured protein with another biopolymer dispersant (e.g., modified starch) reduces the wall strength. In addition, it was found that adding the β-1-4 nonionic polysaccharide to the emulsion within 5 minutes after the start of the emulsification step (c) was crucial to achieving the observed improvements in wall strength and low capsule rupture upon spraying. The microcapsules of the present disclosure are used for the encapsulation of fragrances, pro-fragrances, malodor counteractants, cosmetics, colorants, vitamins, antioxidants, etc. and the delivery of these in consumer products such as powder detergents, liquid detergents, fabric conditioners, antiperspirants, deodorants, fine perfumes and hair care products.

[0090] Advantageously, the microcapsule shells of the present disclosure are characterized by a rupture force of at least 100 μN. In some embodiments, the microcapsule shells are characterized by a rupture force of at least 110 μN, at least 120 μN, at least 130 μN, or at least 140 μN.

[0091] The microcapsule core comprises an active material. In some embodiments, the active material is a fragrance present at a level of 1 wt% to 35 wt% relative to the weight of the microcapsule slurry. In some embodiments, the active material is a fragrance present at an amount of 0.01 wt% to 1 wt% relative to the weight of the core-shell microcapsule slurry, and the fragrance comprises at least five high-performance fragrance ingredients, including ultra-high impact fragrance ingredients as listed in Table 1, high impact fragrance ingredients as listed in Table 2, or combinations thereof. In some embodiments, the weight ratio of ultra-high impact fragrance ingredients to high impact fragrance ingredients is in the range of 1:0 to 1:19.

[0092] In some embodiments, the microcapsule core further comprises auxiliary core materials, such as solvents, emollients, and / or core regulator materials. The example of auxiliary core materials includes nano-scale solid granular materials, polymer core regulators, solubility regulators, density regulators, stabilizers, wetting agents, viscosity regulators, pH regulators, or combinations thereof. The example of suitable auxiliary core materials also includes those described in WO 2016 / 049456 and US2016 / 0158121. In some embodiments, the solvent includes caprylic acid triglyceride. In some embodiments, the solvent includes benzyl benzoate. In some embodiments, the auxiliary core material may also be present in the wall of the capsule in the slurry or outside the capsule. In some embodiments, the auxiliary core material may be present in the core in an amount of 0.01% to 25% (e.g., 0.5% to 10%) by weight of the capsule.

[0093] In certain embodiments, core-shell microcapsules have a diameter ranging from 0.1 micron to 1000 microns (e.g., 0.5 micron to 500 microns, 1 micron to 200 microns, 1 micron to 100 microns, or 1 micron to 50 microns). In certain embodiments, core-shell microcapsules have a diameter of at least 0.1 micron, 0.5 micron, 1 micron, 2 microns, 5 microns, or 20 microns. In certain embodiments, core-shell microcapsules have a diameter no greater than 1000 microns, 500 microns, 200 microns, 100 microns, 75 microns, 50 microns, 30 microns, 20 microns, 10 microns, or 5 microns. Microcapsules in the present disclosure need not be perfectly spherical. As used herein, the term "diameter" with respect to microcapsules means the diameter of a ball having the same volume as the microcapsule.

[0094] In some embodiments, the hydrocolloid comprises gum arabic added to the aqueous phase prior to the emulsification step during the slurry formation. In some embodiments, the microcapsule slurry is an aqueous suspension of microcapsules. In some embodiments, the microcapsule slurry is white. In some embodiments, the core-shell microcapsule slurry comprises a microcapsule formation aid. The microcapsule slurry can be directly used in consumer products. The microcapsule slurry can also be washed, coated, dried (e.g., spray dried) and / or combined with one or more other microcapsules, active materials, and / or carrier materials.

[0095] In some embodiments, the microcapsule shell is biodegradable. As used herein, the term "biodegradable" with respect to a material (such as a microcapsule shell as a whole or a polymer of a microcapsule shell) means that the material has no actual or perceived health and / or environmental issues and is capable of and / or does undergo physical, chemical, thermal, microbiological, biological and / or UV or light degradation. Ideally, the microcapsule shell and / or polymer is considered "biodegradable" when it passes one or more of the following tests, including: Respirometric biodegradation in aquatic media, available from the Organization for Economic Co-operation and Development (OECD), the International Organization for Standardization (ISO), and the American Society for Testing and Materials (ASTM), including but not limited to OECD 301F or 310 (ready biodegradation), OECD 302 (intrinsic biodegradation), ISO 17556 (solid irritation study), ISO 14851 (fresh water irritation study), ISO 18830 (marine sediment irritation study), OECD 307 (soil irritation study), OECD 308 (sediment irritation study), and OECD 309 (water irritation study). Preferably, the microcapsule is readily biodegradable as determined using the respirometric biodegradation method, OECD 301F or OECD 310 test in an aquatic medium. More preferably, the microcapsule shell and / or polymer is biodegradable if it has a biodegradation rate of at least 20%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% 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 has a biodegradation rate of at least 20% within 60 days according to the OECD 301F test.

[0096] In some embodiments, the shell of the microcapsule has a biodegradation rate of at least 20%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% based on the weight of the shell within 60 days according to OECD301F or OECD310. In some embodiments, the shell of the microcapsule has a biodegradation rate of at least 20% based on the weight of the shell within 60 days according to OECD301F or OECD310.

[0097] The present disclosure also provides a method for producing a core-shell microcapsule slurry. The present disclosure also provides a core-shell microcapsule slurry obtainable by the method described in the present disclosure. The method comprises: (a) providing an aqueous phase comprising a denatured protein and gum arabic, wherein the denatured protein comprises a denatured pea protein and / or a denatured whey protein; (b) providing an oil phase comprising an active material and a polyisocyanate; (c) emulsifying the oil phase with the aqueous phase to form an emulsion; (d) adding all of the β-1-4 nonionic polysaccharide to the emulsion within 5 minutes after the start of the emulsification step (c) to form a microcapsule slurry comprising core-shell microcapsules; and (e) curing the shell of the microcapsule at a temperature in the range of 40°C to 90°C.

[0098] In step (a), prepare and provide aqueous phase. In certain embodiments, aqueous phase is homogeneous. In certain embodiments, aqueous phase has a pH lower than 6 or 5.5. In certain embodiments, aqueous phase has a pH within the range of 2 to 6, or 3 to 5.5, or 3.5 to 4.5, or 3.8 to 4.2. Aqueous phase comprises denatured protein and gum arabic. Adding gum arabic before emulsification is conducive to the dissolution of denatured protein in aqueous phase, thereby preventing its aggregation. In certain embodiments, denatured protein includes or is denatured pea protein. In certain embodiments, denatured protein includes or is denatured whey protein. In certain embodiments, aqueous phase further comprises xanthan gum. In certain embodiments, aqueous phase further comprises tannic acid.

[0099] In some embodiments, step (a) further comprises denaturing the protein (pea protein and / or whey protein) in the aqueous solution. In some embodiments, the pea protein is denatured by heating the pea protein aqueous solution to a temperature of 80°C to 170°C, or 80°C to 140°C, or 80°C to 120°C, or 80°C to 105°C, or 80°C to 90°C. In some embodiments, pea protein and / or whey protein are denatured by a denaturant. In some embodiments, pea protein and / or whey protein are denatured by a chaotropic agent. In some embodiments, the chaotropic agent includes or is a guanidine salt. In some embodiments, the guanidine salt is selected from the group consisting of guanidine sulfate, guanidinium carbonate, guanidinium nitrate, guanidine chloride, and mixtures thereof. In some embodiments, the chaotropic agent includes or is guanidine carbonate. In some embodiments, the denaturing step includes mixing guanidine carbonate with pea protein and / or whey protein in an aqueous solution (e.g., an aqueous phase). In some embodiments, the denaturation step comprises: (i) mixing pea protein with water to form an aqueous mixture, (ii) adjusting the pH of the aqueous mixture to above 9, (iii) adding gum arabic to the aqueous mixture, and (iv) adding guanidine carbonate to the aqueous mixture and adjusting the pH to below 6. In some embodiments, xanthan gum and / or tannic acid are added to the aqueous phase during or after the denaturation step.

[0100] In step (b), an oil phase is prepared and provided. The oil phase comprises an active material and a polyisocyanate. In some embodiments, the polyisocyanate comprises or is an aromatic polyisocyanate. In some embodiments, the polyisocyanate comprises or is a trimethylolpropane adduct of xylylene diisocyanate. In some embodiments, the amount of polyisocyanate present in the oil phase is in the range of 0.1% to 10%, 0.1% to 8%, 0.2% to 5%, 1.5% to 3.5%, 0.1% to 5%, 0.1% to 4%, or 0.1% to 2% based on the weight of the microcapsule slurry. In some embodiments, the amount of polyisocyanate present in the oil phase is less than 1%, less than 0.95%, less than 0.9%, less than 0.85%, less than 0.8%, less than 0.7%, less than 0.6%, less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1% based on the weight of the microcapsule slurry. In certain embodiments, oil phase further comprises auxiliary core material, such as solvent, emollient and / or core regulator material.In certain embodiments, solvent is selected from the group consisting of: caprylic acid triglyceride, benzyl benzoate, 3-methoxybutyl acetate, phenylethyl benzoate and mixture thereof.Oil phase can be prepared by mixing active material with polyisocyanate.In certain embodiments, auxiliary core material (for example, solvent) is also mixed with active material and polyisocyanate.In certain embodiments, polyisocyanate is dissolved in the solution comprising solvent (for example, caprylic acid triglyceride) and active material.

[0101] In step (c), the oil phase is emulsified with the aqueous phase to form an emulsion. In some embodiments, an emulsifier is used in step (c), that is, the emulsion comprises an emulsifier (e.g., sulfonated polystyrene). The emulsification process can be performed using techniques known in the art. For example, a stirrer, agitator, or a homogenizer (e.g., a high shear homogenizer) can be used for emulsification.

[0102] In step (d), all of the β-1-4 nonionic polysaccharide is added to the emulsion within 5 minutes after the start of emulsification (i.e., after the start of the emulsification step (c)) to form a microcapsule slurry containing core-shell microcapsules. In some embodiments, the β-1-4 nonionic polysaccharide comprises or is xyloglucan. In some embodiments, all of the β-1-4 nonionic polysaccharide is added to the emulsion within 14 minutes, or within 13 minutes, or within 12 minutes, or within 11 minutes, or within 10 minutes, or within 9 minutes, or within 8 minutes, or within 7 minutes, or within 6 minutes, or within 5 minutes, or within 4.5 minutes, or within 4 minutes, or within 3.5 minutes, or within 3 minutes, or within 2.5 minutes, or within 2 minutes, or within 1.5 minutes, or within 1 minute after the start of emulsification. In some embodiments, the amount of β-1-4 nonionic polysaccharide (e.g., xyloglucan) added to the emulsion in step (d) is in the range of about 0.1 wt% to about 5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 0.5 wt%, based on the weight of the microcapsule slurry. In some embodiments, the amount of β-1-4 nonionic polysaccharide (e.g., xyloglucan) added to the emulsion in step (d) is at least about 0.05 wt%, or at least about 0.1 wt%, or at least about 0.15 wt%, or at least about 0.2 wt%, based on the weight of the microcapsule slurry. In some embodiments, the amount of β-1-4 nonionic polysaccharide (e.g., xyloglucan) added to the emulsion in step (d) is no more than about 5 wt%, or no more than about 4 wt%, or no more than about 3 wt%, or no more than about 2 wt%, or no more than about 1 wt%, or no more than about 0.5 wt%, based on the weight of the microcapsule slurry.

[0103] In step (e), the microcapsule shell is cured at a temperature in the range of 40°C to 90°C. In some embodiments, the curing step (e) is performed after step (d) (adding β-1-4 nonionic polysaccharide (e.g., xyloglucan) to the emulsion). As used herein, the term "curing" means a process of toughening or hardening a polymer by heat, chemical additives, and / or light radiation. In some embodiments, the microcapsule shell is cured at a temperature in the range of 50°C to 80°C, or 55°C to 80°C, or 55°C to 75°C, or 55°C to 70°C, or 60°C to 70°C, or 60°C to 68°C, or 63°C to 67°C. In some embodiments, the microcapsule shell is cured at a temperature below 90°C, 80°C, or 70°C. In some embodiments, the microcapsule shell is cured for about 30 minutes to 24 hours, or 1 hour to 8 hours, or 2 hours to 6 hours, or 1 minute to 10 hours, or 0.1 hours to 5 hours, or 0.2 hours to 4 hours, or 0.5 hours to 3 hours.

[0104] In some embodiments, the method may further include the step of drying the core-shell microcapsules to remove water. The microcapsules may be dried at a temperature of 20° C. to 250° C., or at room temperature. In some embodiments, the microcapsules are dried by a dehumidifier configured to supply dry air to the microcapsules, a radiant heat source for promoting the drying of the microcapsules, or subjecting the microcapsules to an air flow to obtain dry, free-flowing microcapsules. It should be understood that any standard method known to those skilled in the art for such drying is also applicable.

[0105] Advantageously, including denatured protein and beta-1-4 nonionic polysaccharide (eg, xyloglucan) in the process of producing microcapsules provides desirable microcapsule properties such as reduced percentage of microcapsule breakage after spraying onto powders and improved drying properties in powder detergent applications.

[0106] One or more rheology modifiers or viscosity control agents can be added to the microcapsule slurry to realize the desired slurry viscosity so that the microcapsules are dispersed in the slurry for an extended period of time. During capsule preparation, the rheology modifier is preferably added before the aqueous phase and the oil phase emulsification, and is typically evenly dispersed in the microcapsule slurry and outside the microcapsule wall. Suitable rheology modifiers include acrylate copolymers, cationic acrylamide copolymers, polysaccharides or their combinations. In some aspects, the polysaccharide used as rheology modifier includes starch, pectin and vegetable gum, such as alginate, guar gum, locust bean gum and xanthan gum. Preferably, at least one rheology modifier is xanthan gum.

[0107] One or more preservatives can be added to the microcapsule slurry to prevent microbial damage or unintentional growth within a specific time period, 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, propylene glycol materials, isothiazolinones, quaternary compounds, benzoates, and combinations thereof. Exemplary preservatives include low molecular weight alcohols, dehydroacetic acid, phenyl and phenoxy compounds, and combinations thereof. 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 antibacterial preservatives include a combination of methylchloroisothiazolinone and methylisothiazolinone, sold under the trade name CG is available; 5-bromo-5-nitro-1,3-dioxane, sold under the trade name Available; 2-bromo-2-nitro-1,3-propanediol, under the trade name Available; 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 Available: glutaraldehyde; ICI polyaminopropyl biguanide; dehydroacetic acid; and 1,2-benzisothiazolin-3-one, under the trade name GXL Sales.

[0108] The microcapsule slurry can be formulated into a capsule delivery system for a consumer product. The capsule delivery system can be a microcapsule slurry suspended in an external solvent (e.g., water, ethanol, or a combination thereof), wherein the capsules are present at a level of about 0.1% to about 80% (e.g., 70%-75%, 40%-55%, 50%-90%, 1% to 65%, or 5% to 45%) by weight of the capsule delivery system.

[0109] In some embodiments, the microcapsules and slurries thereof prepared according to the present disclosure are subsequently purified. In some embodiments, purification can be achieved by washing the microcapsule slurry with water until a neutral pH is obtained.

[0110] application

[0111] The microcapsules and microcapsule slurries of the present disclosure are very suitable for use in fabric softeners, fabric refreshers, or laundry detergents. Liquid or powder laundry detergents in which the microcapsules and microcapsule slurries of the present disclosure can be used include those disclosed in U.S. Pat. Nos. 5,929,022, 5,916,862, 5,731,278, 5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809, 5,288,431, 5,194,639, 4,968,451, 4,597,898, 4,561,998, 4,550,862, 4,537,707, 4,537,706, 4,515,705, 4,446,042, and 4,570,708. 4,318,818 described in those systems. Unit dose bags, tablets and capsules are included in those described in EP 1431382A1, US2013 / 0219996 A1, US2013 / 0284637 A1 and US 6,492,315. These unit dose formulations can contain high concentrations of functional materials (e.g., about 5%-100% fabric softener or detergent actives), spices (e.g., 0.5%-100%, 0.5%-40% and 0.5%-15%) and flavors (e.g., 0.1%-100%, 0.1%-40% and 1%-20%). In addition, they can be free of water to limit the water content to less than 30% (e.g., less than 20%, less than 10% and less than 5%). Fabric care products such as rinse conditioners (containing 1 to 30 wt. % fabric conditioning actives), fabric liquid conditioners (containing 1 to 30 wt. % fabric conditioning actives), fabric refreshers, fabric refresher sprays, ironing liquids and fabric softener systems such as those described in US 6,335,315, US 5,674,832, US 5,759,990, US 5,877,145, US 5,574,179, US 5,562,849, US 5,545,350, US 5,545,340, US 5,411,671, US 5,403,499, US 5,288,417, US 4,767,547 and US 4,424,134.

[0112] The liquid fabric softener / refresher contains at least one fabric softener, which is preferably present in a concentration of 1% to 30% (e.g., 4% to 20%, 4% to 10% and 8% to 15%). The ratio between the active material and the fabric softener can be 1:500 to 1:2 (e.g., 1:250 to 1:4 and 1:100 to 1:8). As an illustration, when the fabric softener is 5% by weight of the fabric softener, the active material is 0.01% to 2.5%, preferably 0.02% to 1.25% and more preferably 0.1% to 0.63%. As another example, when the fabric softener is 20% by weight of the fabric softener, the active material is 0.04% to 10%, preferably 0.08% to 5% and more preferably 0.4% to 2.5%. The active material is a fragrance, a malodor counteractant or a combination thereof. Liquid fabric softeners can have 0.15% to 15% capsules (e.g., 0.5% to 10%, 0.7% to 5%, and 1% to 3%). When capsules are included at these levels, the net 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%).

[0113] Suitable fabric softeners include cationic surfactants. Non-limiting examples are quaternary ammonium compounds, 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. Fabric softening compositions and components thereof are generally described in US 2004 / 0204337 and US 2003 / 0060390. Suitable softeners include commercially available softeners from Evonik Industries under the trade name Esterquats sold as WE 18 and commercially available from Stepan Corporation SP-90.

[0114] In a specific aspect, the microcapsule slurry is used in a consumer product (such as a fabric softener, a fabric refresher, or a laundry detergent), preferably in the form of a spray-dried powder. Therefore, the disclosure also provides a consumer product (e.g., a fabric softener, a fabric refresher, or a laundry detergent) comprising the core-shell microcapsule slurry of the disclosure. In some aspects, the consumer product further comprises one or more detersive enzymes. Ideally, the microcapsule slurry is present at a level between 0.1wt% and 10wt% relative to the weight of the consumer product.

[0115] It has been demonstrated that inclusion of a beta-1-4 nonionic polysaccharide improves the performance of microcapsules, and the present disclosure further provides a method for improving the performance of core-shell microcapsules in powder applications by adding a beta-1-4 nonionic polysaccharide (such as xyloglucan) to an emulsion in the presence of denatured pea protein and / or denatured whey protein and within 5 minutes after the start of emulsification. In particular, it was found that including a beta-1-4 nonionic polysaccharide in the preparation of microcapsules provides a higher rupture force, improves tolerance to applied stress, improves sensory properties, enhances deposition of microcapsules on surfaces, and / or increases the stability of microcapsule slurries.

[0116] Many aspects and embodiments have been described above and are exemplary and non-limiting only. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

[0117] Examples

[0118] The following non-limiting examples are provided to further illustrate the present invention but should not be construed as limitations of the present invention as many variations of the invention are possible without departing from the spirit or scope of the invention.

[0119] Methods for measuring rupture force

[0120] The rupture force of the microcapsules was measured using a micromanipulation technique based on parallel plate compression of a single microcapsule. Two drops (about 75 μL / drop) of microcapsule slurry slightly diluted with water were pipetted onto a high tempered glass slide (19.76 cm 2) with a smooth polished flat surface. 2 ; length 7.6 cm; width 2.6 cm; thickness 0.3 cm) and allowed to air dry for 2 hours. The slide was fixed to a metal stage and placed under a borosilicate glass probe with a 60 μm tip. The tip was glued longitudinally to the selected force sensor head (Series 403A, Model 1568, maximum force scale 5.0 mN, sensitivity 0.459 mN·V) using super glue (Loctite cyanoacrylate super glue, Henkel, Germany, EU). -1; Aurora Scientific Inc., Ontario, Canada) on the output borosilicate glass tube, the force sensor head is paired with an electric control box (Signal Interface 604A, Aurora Scientific Inc., Ontario, Canada). The force sensor is mounted on a three-dimensional fine stage (300-P, Newport Corporation, Irvine, CA, USA) controlled by a servo motor (821A-MC1000e, Siskiyou Corporation, Grants Pass, OR, USA). A high-resolution (± 0.2 μm) micromanipulator is operated to move the glass probe up / down. The descent speed (e.g., 1.33 μm·s -1 ), to allow the probe tip to contact and gradually compress each single microcapsule. The microcapsules were digitally observed with the help of a camera (high-sensitivity color, 1280x1024 pixel C-mount camera, DCC1240C, Thorlabs, Newton, NJ, USA) with a high-intensity fiber-coupled illuminator (OSL2, Thorlabs, Newton, NJ, USA). Ten single randomly selected microcapsules were crushed to produce statistically significant results. The measurement of rupture force in the present disclosure is based on a technique known as micromanipulation in the art. See, for example, Baiocco et al., Microplastic-Free Microcapsules to Encapsulate Health-Promoting Limonene Oil, Molecules 2022, 27, 7215, which is incorporated herein by reference in its entirety for all purposes.

[0121] Example 1: Microcapsules prepared in the presence of denatured pea protein and by adding xyloglucan (XG) to the emulsion within 1 minute after the start of emulsification

[0122] The oil phase is prepared by mixing the fragrance, caprylic / capric triglyceride ( M-5) and trimethylolpropane adduct of xylylene diisocyanate ( D-110N). Separately, the aqueous phase was prepared by dispersing pea protein powder in water and adjusting the pH to 9.5 with NaOH (37 wt % aqueous solution). Then, gum arabic was mixed with high molecular weight polystyrene sulfonate sodium salt ( II) was added to the aqueous phase and the resulting mixture was mixed until uniform. Guanidine carbonate (denaturant) and citric acid solution were mixed and added to the aqueous phase. The reaction was allowed to proceed under acidic conditions for 15 minutes to denature the pea protein. Xanthan gum (1% solution) was added to the aqueous phase along with tannic acid (Tanal-02, 30% solution). The oil phase was then added to the aqueous phase and the mixture was mixed by IKA ULTRA- The homogenizer was emulsified at 6000 rpm (revolutions per minute) to form an oil-in-water emulsion. All of the xyloglucan (2% solution) was added to the emulsion within 1 minute after the start of emulsification. The curing of the microcapsule shell was carried out at 65°C for 3 hours and 15 minutes. The microcapsule slurry was cooled to room temperature and a preservative (1,2-benzisothiazolin-3-one, sold under the trade name GXL sold) to form the final microcapsule slurry (microcapsule 1). The ingredients and their amounts used to prepare the slurry are shown in Table 3. Microcapsule 1 contained a fragrance load of 27.1%.

[0123] Table 3 - Microcapsules 1

[0124]

[0125]

[0126] Example 2 (comparative): Microcapsules prepared in the presence of denatured pea protein and by adding XG to the aqueous phase about 15 minutes before the start of emulsification

[0127] Microcapsules 2 (microcapsule slurry) were prepared as described in Example 1, except that all of the xyloglucan (XG) was added to the water phase approximately 15 minutes before the start of emulsification (before the oil and water phases were mixed).

[0128] Example 3 (comparative): Microcapsules prepared in the presence of denatured pea protein and by adding XG to the emulsion about 15 minutes after the start of emulsification

[0129] Microcapsules 3 (microcapsule slurry) were prepared as described in Example 1, except that all of the xyloglucan (XG) was added to the emulsion approximately 15 minutes after the start of emulsification.

[0130] Example 4 (comparative): Microcapsules prepared in the presence of denatured pea protein and by adding XG to the emulsion about 45 minutes after the start of emulsification

[0131] Microcapsules 4 (microcapsule slurry) were prepared as described in Example 1, except that all of the xyloglucan (XG) was added to the emulsion approximately 45 minutes after the start of emulsification.

[0132] Example 5: Microcapsules prepared with additional amounts of tannic acid

[0133] Microcapsule 5 (microcapsule slurry) was prepared as described in Example 1, except that the amount of tannic acid was doubled. The ingredients and their amounts used to prepare the slurry are shown in Table 4. Microcapsule 5 contained a fragrance load of 26.7%.

[0134] Table 4 - Microcapsules 5

[0135]

[0136]

[0137] Example 6 (Comparative): Microcapsules prepared without xyloglucan (XG)

[0138] Microcapsule 6 (microcapsule slurry) was prepared as described in Example 5, except that no xyloglucan was used in the preparation of the microcapsule slurry. The ingredients and their amounts used to prepare the slurry are shown in Table 5. Microcapsule 6 contained a fragrance load of 30.7%.

[0139] Table 5 - Microcapsules 6

[0140]

[0141] Example 7: Microcapsules prepared with reduced amounts of XG

[0142] Microcapsule 7 (microcapsule slurry) was prepared as described in Example 1, except that the amount of xyloglucan (XG) was reduced by 50%. The ingredients and their amounts used to prepare the slurry are shown in Table 6. Microcapsule 7 contained a fragrance load of 29.0%.

[0143] Table 6-Microcapsules 7

[0144]

[0145] Example 8: Microcapsules prepared with reduced fragrance loading

[0146] Microcapsule 8 (microcapsule slurry) was prepared as described in Example 1, except that the amount of fragrance was reduced. The ingredients and their amounts used to prepare the slurry are shown in Table 7. Microcapsule 8 contained 21.7% fragrance loading.

[0147] Table 7-Microcapsule 8

[0148]

[0149]

[0150] Example 9: Microcapsules prepared with additional amounts of trimethylolpropane adduct of xylylene diisocyanate

[0151] Microcapsules 9 (microcapsule slurry) were prepared as described in Example 1, except that an additional amount of trimethylolpropane adduct of xylylene diisocyanate ( D-110N). The ingredients and their amounts used to prepare the slurry are shown in Table 8. Microcapsule 9 contained a fragrance load of 26.9%.

[0152] Table 8-Microcapsules 9

[0153]

[0154] Example 10 (Comparative): Microcapsules prepared in the presence of modified starch

[0155] The oil phase is prepared by mixing the fragrance, caprylic / capric triglyceride ( M-5) and a mixture of two polyisocyanates (trimethylolpropane adduct of xylylene diisocyanate ( D-110N) and hexamethylene diisocyanate biuret ( Separately, the aqueous phase was prepared by mixing the The modified starch powder sold by Ingredion (Ingredion, Westchester, IL) was dispersed in water. II, 10% solution) was added to the aqueous phase along with carboxymethylcellulose (1% solution) and 1,4-diazabicyclo[2.2.2]octane (DABCO, 20% solution), and the resulting mixture was mixed until homogeneous. Tannic acid (Tanal-01, 30% solution) was added to the aqueous phase. The oil phase was then added to the aqueous phase and the mixture was mixed by IKA ULTRA- The homogenizer was emulsified at 6000 rpm (revolutions per minute) to form an oil-in-water emulsion. The curing of the microcapsule shell was carried out at 80°C for 4 hours and 15 minutes. After curing for 1 hour, xyloglucan (2% solution) was added to the microcapsule slurry, followed by a second dose of hexamethylene diisocyanate biuret ( N100A). The microcapsule slurry was cooled to room temperature and a preservative (1,2-benzisothiazolin-3-one, trade name GXL sold) to form the final microcapsule slurry (microcapsule 10). The ingredients and their amounts used to prepare the slurry are shown in Table 9. Microcapsule 10 contained 30.0% fragrance loading.

[0156] Table 9-Microcapsules 10

[0157]

[0158] Example 11 (Comparative): Microcapsules prepared in the presence of modified starch

[0159] Microcapsules 11 (microcapsule slurry) were prepared as described in Example 10, except that the biuret of hexamethylene diisocyanate ( N100A) was reduced and the amount of tannic acid (Tanal-01) was increased. The ingredients used to prepare the slurries and their amounts are shown in Table 10. Microcapsule 11 contained a fragrance load of 30.0%.

[0160] Table 10 - Microcapsules 11

[0161]

[0162] Example 12 (Comparative): Microcapsules prepared in the presence of modified starch

[0163] Microcapsule 12 (microcapsule slurry) was prepared as described in Example 11, except that the amount of xyloglucan was reduced. The ingredients and their amounts used to prepare the slurry are shown in Table 11. Microcapsule 12 contained a fragrance load of 30.0%.

[0164] Table 11 - Microcapsules 12

[0165]

[0166]

[0167] Example 13 (Comparative): Melamine Formaldehyde Microcapsules Prepared Using Xyloglucan Deposition Aid

[0168] The oil phase was prepared by mixing the fragrance and caprylic / capric triglyceride ( Separately, the aqueous phase was prepared by mixing a copolymer of acrylamide and acrylic acid (available under the trade name 200) and methylated melamine formaldehyde resin (sold under the trade name The two components were allowed to react under acidic conditions for at least one hour. The oil phase was then added to the aqueous phase and the mixture was stirred by IKA ULTRA- Homogenizer was used to emulsify to form an oil-in-water emulsion. Xyloglucan (1% solution) was added to the emulsion as a deposition aid. The microcapsule shell was cured at 125°C. Then, the microcapsule slurry was cooled to room temperature and ethylene urea was added to the microcapsule slurry. In addition, a rheology modifier ( 33) and preservatives were added to the microcapsule slurry, and the pH was adjusted using NaOH to form the final microcapsule slurry (microcapsule 13). The ingredients used to prepare the slurry and their amounts are shown in Table 12. Microcapsule 13 contained a fragrance load of 24.37%.

[0169] Table 12 - Comparative Microcapsules 13

[0170]

[0171] Example 14 (Comparative): Microcapsules prepared without xyloglucan (XG)

[0172] Microcapsules 14 (microcapsule slurry) were prepared as described in Example 1, except that no xyloglucan was used in the preparation of the microcapsule slurry. The ingredients and their amounts used to prepare the slurry are shown in Table 13. Microcapsules 14 contained a fragrance load of 31.2%.

[0173] Table 13 - Comparative Microcapsules 14

[0174]

[0175] Example 15: Preparation of powdered detergent samples containing microcapsules

[0176] A fragrance-free biodetergent powder was used. Microcapsules 1-14 were diluted with water respectively and added to the powder detergent and mixed. The fragrance loading in the prepared powder detergent samples was 0.043% net oil equivalent (NOE). The samples were prepared one day before the washing experiment.

[0177] Example 16: Hand-washing protocol of prepared powder detergent samples containing microcapsules

[0178] The amount of powder detergent sample used in the hand wash experiment is determined by the amount of the wash load. Two small towel fabrics require five grams of powder detergent and 1L of water. The stainless steel wash basin is filled with water at 20°C. An appropriate amount of powder detergent sample is added to the water and stirred to dissolve. The wash load contains only cotton towel fabric. The towels are soaked, and then each towel is folded twice and passed through a mangle. Subsequently, the wash basin is filled with clean water and the towels are rinsed. Some towels are retained for wet evaluation, and the remaining towels are air-dried at room temperature for dry evaluation.

[0179] Example 17: Sensory performance evaluation of microcapsules 1-14 in powder detergents according to the hand wash regimen

[0180] Fragrance intensity was evaluated by performing a laundry experiment following the hand wash protocol described in Example 16. Randomly selected towel samples were evaluated by several experts using an intensity scale of 0-5, where 0 = "no performance" and 5 = "strong performance". The evaluation was performed "blind" so that each towel sample had a randomly assigned number. The dry sensory performance evaluation was performed the day after the wet evaluation and was performed by the same experts using the same intensity scale of 0-5. When evaluating "before drying treatment" and "after drying treatment", the sensory scores were recorded before and after gentle handling of each randomly selected dry towel (packed in an individual polyethylene bag).

[0181] The fragrance intensity of the samples was evaluated at different stages (contact points) of the consumer's laundry experience. "Pop" simulates the point of purchase. It simulates the moment when a consumer opens a bottle of powder detergent product in a store and smells the fragrance. "Pop" refers to the evaluation conducted by opening and sniffing a container containing a prepared powder detergent sample (containing microcapsules). "Soak" refers to the evaluation conducted by soaking a towel fabric in a wash basin containing a powder detergent sample dissolved in water for a few minutes, and then evaluating (sniffing) the fragrance intensity accumulated at the head space of the wash basin. "Wet" refers to the evaluation of wet towels after washing. "Before drying treatment" refers to the evaluation of towels after the towels are dried, but before "treatment". "After drying treatment" refers to the evaluation of towels after the towels are dried and "treated". The towels are "treated" by gently shaking them in the air 3 times, simulating the way consumers shake clothes after picking them up from the clothesline and before folding them. "Floating" refers to the evaluation of the fragrance intensity in the room where the towels are dried. In other words, it refers to the evaluation of the fragrance release when the towels are drying in the room.

[0182] Example 18: Analytical and sensory performance data of microcapsules 1-14

[0183] The fragrance loading, PS mode and viscosity of microcapsules 1-14 are listed in Table 14. "PS" means particle size. The dry sensory performance of microcapsules 1-14 was evaluated. The dry sensory performance of microcapsules 1-12 was compared with the dry sensory performance of microcapsules 13 and 14, respectively. "Dry sensory performance" means the sensory performance at the "before drying treatment" stage and the "after drying treatment" stage. "++" means that the performance is much better than the benchmark (microcapsule 13 or 14); "+" means that the performance is better than the benchmark; "=" means that the performance is about the same as the benchmark; "-" means that the performance is worse than the benchmark; and "--" means that the performance is much worse than the benchmark.

[0184] As shown in Table 14, microcapsules 1 and 7 exhibited better performance compared to microcapsule 14, demonstrating the advantage of including xyloglucan in the microcapsule preparation. Furthermore, the best performance was observed for those microcapsules prepared by adding xyloglucan to the emulsion within 5 minutes after the start of emulsification (microcapsules 1, 5, 7, 8, and 9 compared to microcapsules 2, 3, and 4), demonstrating that the timing of xyloglucan addition is critical to the performance of the produced microcapsules.

[0185] Table 14 - Drying sensory properties

[0186]

[0187] 1 NA, not applicable.

[0188] Example 19: Timing of XG addition is important for good dry sensory properties

[0189] Figure 1 It is shown that microcapsule 1 outperforms microcapsules 2, 3 and 4 in the drying stage, demonstrating that the timing of xyloglucan (XG) addition is critical to the performance of the produced microcapsules and that adding xyloglucan to the emulsion within 5 minutes after the start of emulsification has advantages. Figure 1 It is also shown that microcapsule 1 performs significantly better than comparative microcapsule 14 during the drying phase, demonstrating the advantage of including xyloglucan in the microcapsule preparation.

[0190] Example 20: The amount of XG is important for good dry sensory properties

[0191] Figure 2 It is shown that the amount of xyloglucan used to prepare the microcapsules is important for the good dry sensory properties of the resulting microcapsules. Compared to microcapsules 7 (prepared with half the amount of xyloglucan used in microcapsules 1), microcapsules 1 exhibited improved dry sensory properties, demonstrating that xyloglucan improves the wall strength of the resulting microcapsules.

[0192] Example 21: Sensory properties of different microcapsules

[0193] Figure 3 Shown are the sensory performance of different kinds of microcapsules sprayed onto powder detergent and then used in laundry experiments according to the hand wash protocol described in Example 16. Microcapsule 1 (prepared using denatured pea protein as dispersant) showed significantly better sensory performance at the drying stage compared to microcapsules 10-12 (prepared using modified starch as dispersant), and showed similar sensory performance compared to microcapsule 13 (commercial melamine formaldehyde microcapsules).

[0194] Example 22: Sensory properties of different microcapsules

[0195] Figure 4 Shown are the sensory performance of different kinds of microcapsules sprayed to powder detergent and then used in laundry experiments according to the hand wash protocol described in Example 16. Microcapsules 8 and 9 (containing xyloglucan) showed better sensory performance in the drying stage compared to comparative microcapsule 14 (without xyloglucan).

[0196] Example 23: Microcapsule spray rupture test

[0197] The microcapsule slurry was sprayed into a commercial fragrance-free OMO Red Core PWD VN powder detergent base at a dosage of 0.05% NOE using a pressure of 1 bar. The resulting detergent was mixed for 5 minutes. The percentage of rupture was measured and is shown in Table 15. It was found that by including xyloglucan in the preparation of the microcapsules (microcapsules 8 and 9), the percentage of rupture after spraying was reduced when compared to the comparative microcapsules 14 (without xyloglucan). In addition, reducing the fragrance load (microcapsule 8) can further reduce the percentage of rupture.

[0198] Table 15 - Microcapsule rupture

[0199]

[0200] Example 24: Mechanical strength of capsules

[0201] The mechanical strength of the capsules was characterized by the micromanipulation technique described in the section "Methods for measuring rupture force" of this disclosure. A microcapsule slurry was diluted in water at 0.2% NOE, a drop of which was placed on a glass slide and air-dried. The dried microcapsules were aligned with a compression probe and compressed at a rate of 2 μm / sec. The rupture force, deformation, and applied stress are presented in Table 16.

[0202] Table 16 - Mechanical strength of capsules

[0203] Microcapsules Rupture force (μN) Deformation % Stress(MPa) Microcapsule 1 147.7±37.7 48.4±3.8 0.7±0.2 Comparison of microcapsules 14 89.9±17.3 48.9±3.6 0.4±0.1 Comparison of microcapsules 13 109.9±28.5 32.2±3.9 0.6±0.2

[0204] The capsules of microcapsule 1 exhibited the highest strength in terms of rupture force. Notably, the rupture force of the capsules of microcapsule 1 was almost twice that of the capsules of comparative microcapsule 14 (without xyloglucan) with the same deformation. The capsules of microcapsule 1 also showed improved wall strength compared to the melamine formaldehyde microcapsules (microcapsule 13).

[0205] Each document cited herein, including any cross-referenced or related patent or application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety for all purposes unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, nor is it an admission that it alone or in any combination with any other reference or references teaches, suggests, or discloses any such invention. In addition, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0206] It should be noted that not all of the activities described above in the general description or examples are required, a portion of a specific activity may not be required, and one or more additional activities may be performed in addition to those described. Furthermore, the order in which the activities are listed is not necessarily the order in which they are performed.

[0207] In the foregoing description, concepts have been described with reference to specific embodiments. However, it will be appreciated by those skilled in the art that various modifications and changes may be made without departing from the scope of the invention as set forth in the following claims. Therefore, this description should be considered illustrative rather than restrictive, and all such modifications are intended to be included within the scope of the invention.

[0208] Benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, benefits, advantages, solutions to problems, and any one or more features that may cause any benefit, advantage, or solution to occur or make it more obvious are not to be construed as key, necessary, or essential features of any or all claims.

[0209] It is to be understood that, for clarity, certain features described herein in the context of separate embodiments may also be provided in a single embodiment in combination. Conversely, for brevity, the various features described in the context of a single embodiment may also be provided individually or in any sub-combination.

Claims

1. A core-shell microcapsule slurry comprising: (a) a core-shell microcapsule, wherein the core-shell microcapsule has a microcapsule core and a microcapsule shell encapsulating the microcapsule core, the microcapsule core comprises an active material, and the microcapsule shell comprises a self-condensed polyisocyanate and a β-1-4 nonionic polysaccharide; (b) a dispersant comprising a denatured protein, wherein the denatured protein comprises denatured pea protein and / or denatured whey protein; and (c) hydrocolloids comprising gum arabic; The microcapsule shell is characterized by a rupture force of at least 100 μN.

2. The core-shell microcapsule slurry according to claim 1, wherein The active material includes a fragrance, a pro-fragrance, a malodor counteractant, or a combination thereof.

3. The core-shell microcapsule slurry according to claim 1 or 2, wherein: The beta-1-4 nonionic polysaccharide is xyloglucan.

4. The core-shell microcapsule slurry according to claim 3, wherein The xyloglucan is present in an amount of 0.1 wt% to 5 wt%, or preferably 0.1 wt% to 1 wt%, or preferably 0.1 wt% to 0.5 wt%, relative to the weight of the core-shell microcapsule slurry.

5. A core-shell microcapsule slurry as claimed in any one of the preceding claims, wherein The weight ratio of the β-1-4 nonionic polysaccharide to the denatured pea protein and / or the denatured whey protein is in the range of 1:6 to 1:7.

5.

6. A core-shell microcapsule slurry as claimed in any one of the preceding claims, wherein The weight ratio of the beta-1-4 nonionic polysaccharide to the microcapsule shell is in the range of 1:3 to 1:

5.

7. A core-shell microcapsule slurry as claimed in any one of the preceding claims, wherein The active material is a fragrance present at a level of 1 wt% to 35 wt% relative to the weight of the core-shell microcapsule slurry.

8. The core-shell microcapsule slurry according to any one of claims 1 to 6, wherein The active material is a fragrance present in an amount of 0.01 wt% to 1 wt% relative to the weight of the core-shell microcapsule slurry, and the fragrance comprises at least five high-performance fragrance ingredients, the high-performance fragrance ingredients including super high-impact fragrance ingredients as listed in Table 1, high-impact fragrance ingredients as listed in Table 2, or combinations thereof.

9. A core-shell microcapsule slurry as claimed in any one of the preceding claims, wherein The polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

10. A method for producing a core-shell microcapsule slurry, the method comprising: (a) providing an aqueous phase comprising a denatured protein and gum arabic, wherein the denatured protein comprises denatured pea protein and / or denatured whey protein; (b) providing an oil phase comprising an active material and a polyisocyanate; (c) emulsifying the oil phase with the water phase to form an emulsion; (d) adding all of the β-1-4 nonionic polysaccharide to the emulsion within 5 minutes after the start of the emulsification step (c) to form a microcapsule slurry comprising core-shell microcapsules; and (e) curing the shell of the microcapsule at a temperature in the range of 40°C to 90°C.

11. The method of claim 10, wherein: The beta-1-4 nonionic polysaccharide is xyloglucan.

12. The method according to claim 10 or 11, wherein: The amount of beta-1-4 nonionic polysaccharide added to the emulsion in step (d) is in the range of about 0.1 wt% to about 5 wt% based on the weight of the microcapsule slurry.

13. The method according to any one of claims 10 to 12, wherein: The aqueous phase further comprises tannic acid.

14. A core-shell microcapsule slurry obtainable by the method according to any one of claims 10 to 13.

15. A consumer product comprising the core-shell microcapsule slurry according to any one of claims 1 to 9, wherein: The consumer product is a fabric softener, a fabric refresher, or a laundry detergent, preferably wherein the consumer product is in the form of a spray-dried powder.

Images