Dry degradable delivery particles from mixed isocyanates comprising aromatic moieties and chitosan

Abstract

Improved dry delivery particles comprising a beneficial core material and a shell encapsulating the core material are described, along with methods and articles for forming such delivery particles. The shell is a polymer material, which is a reaction product of chitosan from an aqueous phase and a crosslinking agent comprising an isocyanate component. This isocyanate component comprises a mixture of two or more diisocyanates and / or polyisocyanates from an oil phase, each of which contains at least one aromatic moiety. The delivery particles of this invention exhibit improved release characteristics, lower free oil, lower leakage in the matrix and carrier, and enhanced degradation characteristics in OECD test method 301 B.

Description

Cross-reference of related applications

[0001] Encapsys, LLC and The Procter & Gamble executed a joint research agreement on or around July 29, 2021, and this invention is a result of activities carried out within the scope of the joint research agreement between the parties that was in effect on or before the date of this invention. Technical Field

[0002] This invention relates to a method for manufacturing capsules and biodegradable delivery particles produced by this method, the delivery particles comprising a core material and a shell encapsulating the core, the shell comprising a reaction product of a crosslinking agent and chitosan. The shell is made of chitosan and a crosslinking agent, wherein the crosslinking agent comprises an isocyanate component, the isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates from an oil phase, each of the diisocyanates and / or polyisocyanates containing an aromatic moiety. Background Technology

[0003] Encapsulation, also known as microencapsulation, is the process of encapsulating liquid droplets, solid particles, or gases within a solid shell, typically in the micrometer range. This shell isolates the core material from its surrounding environment. Encapsulation technology has wide commercial applications across various industries. Generally, capsules enable one or more of the following: (i) providing stability to formulations or materials through the mechanical separation of incompatible components; (ii) protecting the core material from the influence of the surrounding environment; (iii) masking or concealing undesirable properties of the active ingredient; and (iv) controlling or triggering the release of the active ingredient at a specific time or place. All these properties can extend the shelf life of a variety of products and stabilize active ingredients in liquid formulations.

[0004] Various encapsulation methods, as well as exemplary methods and materials, are described in the following patents: Schwantes (US Patent No. 6,592,990), Nagai et al. (US Patent No. 4,708,924), Baker et al. (US Patent No. 4,166,152), Wojciak (US Patent No. 4,093,556), Matsukawa et al. (US Patent No. 3,965,033), Ozono (US Patent No. 4,588,639), Irgarashi et al. (US Patent No. 4,610,927), Brown et al. (US Patent No. 4,552,811), Scher (US Patent No. 4,285,720), Jahns et al. (US Patent Nos. 5,596,051 and 5,292,835), Matson (US Patent No. 3,516,941), and Foris et al. (US Patent Nos. 4,001,140; 4,087,376; 4,089,802). The authors include: Greene et al. (US Patent Nos. 2,800,458; 2,800,457 and 2,730,456), Clark (US Patent No. 6,531,156), Hoshi et al. (US Patent No. 4,221,710), Hayford (US Patent No. 4,444,699), Hasler et al. (US Patent No. 5,105,823), Stevens (US Patent No. 4,197,346), Riecke (US Patent No. 4,622,267), Greiner et al. (US Patent No. 4,547,429), and Tice et al. (US Patent No. 5,407,609), as well as Herbig's teachings in the chapter entitled "Microencapsulation" on pages 438-463 of Volume 16 of the Kirk-Othmer Encyclopedia of Chemical Technology.

[0005] Core-shell encapsulation can be used to preserve active substances, such as probiotics, in harsh environments and release them at the desired time, which may be during or after use of articles incorporating delivery particles. Among the various mechanisms available for releasing probiotics from delivery particles, one commonly relied-upon mechanism is the mechanical rupture of the capsule shell through friction or pressure. Choosing mechanical rupture as the release mechanism presents another challenge for manufacturers, as rupture must occur at a specific, desired time, even if the capsule has undergone mechanical stress prior to the desired release time.

[0006] Industrial focus on encapsulation technology has led to the development of several polymer capsule chemistry programs that attempt to meet requirements for biodegradability, low shell permeability, high deposition, target mechanical properties, and rupture characteristics. Increased environmental concerns have brought polymer capsules under scrutiny, prompting manufacturers to begin researching sustainable solutions for encapsulating beneficial agents.

[0007] Biodegradable materials exist and can be formed into delivery particles through agglomeration, spray drying, or phase inversion precipitation. However, delivery particles formed using these materials and techniques are highly porous and unsuitable for aqueous compositions containing surfactants or other carrier materials because the beneficial agents are released into the composition prematurely.

[0008] There are leak-free and well-performing delivery particles in aqueous surfactant-based compositions; however, they are non-biodegradable due to their chemical properties and cross-linking.

[0009] Encapsulation is widely used in pharmaceuticals, personal care, textiles, food, coatings, and agriculture. However, a major challenge in encapsulation is maintaining the encapsulated active ingredient completely within the capsule throughout the supply chain until controlled or triggered release is applied to the core material. Microencapsulation technologies capable of meeting the stringent standards of long-term retention and activity protection required for commercial applications are very limited, especially for encapsulating small molecules.

[0010] Delivery particles having a shell made at least partially of a chitosan-based material are known. However, such particles may not provide the required performance levels. Furthermore, chitosan can be a challenging material to handle due to its thickening tendency.

[0011] U.S. Patent Publication No. 2020 / 0252469 discloses treating chitosan in an acidic medium, such as by adjusting the pH with hydrochloric acid (HCl), prior to microcapsule formation. However, challenges associated with such treatments exist. For example, under certain conditions, hydrochloric acid can be corrosive to manufacturing equipment typically made of steel. In addition, or alternatively, improving the performance of particle delivery remains desirable.

[0012] Biodegradable capsules are needed to minimize leakage or extend shelf life. During manufacturing and / or shelf storage, leakage into the carrier and matrix can depend on water content and may even be affected by surfactants and other additives present in many products, potentially leading to premature release or leakage of beneficial agents. Reducing leakage of beneficial agents in products such as fabric strengtheners, single-use unit formulations, laundry fragrance beads, spray-dried granules, liquid or dry cleaning detergents, and shampoos would be an advancement in the field, enabling more efficient manufacture of consumer and industrial products containing encapsulated beneficial agents such as fragrances.

[0013] There remains a need for improved processing compositions comprising delivery particles made from sustainable materials such as chitosan-based materials. There remains a need for improved processing compositions comprising delivery particles capable of successfully retaining the core contents to make them available at the desired point in the use cycle of the processing composition and releasing the contents when beneficial. There remains a need for processing compositions in which the beneficial agent is retained and stable during shelf storage, with reduced levels of leakage into the carrier and matrix. The compositions of the present invention achieve improved retention and stability of the core material of core-shell delivery particles in the presence of aqueous surfactants and other components of an aqueous carrier and matrix, while effectively releasing the core at the desired contact point and meeting degradation requirements for sustainability, representing an advancement in the art.

[0014] definition For ease of reference in this specification and claims, the term “monomer” as used herein with respect to structural materials of wall polymers forming delivery particles shall be understood as monomer, but also includes oligomers and / or prepolymers formed from specific monomers.

[0015] As used herein, the term "water-soluble material" refers to a material that has a solubility of at least 0.5% by weight in water at 60°C.

[0016] As used herein, the term "oil-soluble" refers to a material having a solubility of at least 0.1% by weight in the target core at 50°C.

[0017] As used herein, the term "oil dispersibility" refers to a material that can be dispersed in the target core at a rate of at least 0.1% by weight at 50°C without forming visible aggregates.

[0018] As used herein, unless otherwise stated, “delivery particle,” “particle,” “encapsulation,” “microcapsule,” and “capsule” are used interchangeably. As used herein, these terms generally refer to core / shell delivery particles. Summary of the Invention

[0019] This invention describes delivery particles comprising a core material and a shell encapsulating the core material. The core material may contain a beneficial agent. The shell comprises a polymer. More specifically, this invention discloses compositions comprising a core-shell encapsulation group, wherein the core contains a beneficial agent. The shell is a polymeric material comprising a crosslinking agent from an oil phase and a reaction product of chitosan from an aqueous phase. The crosslinking agent comprises a mixture of two or more diisocyanates and / or polyisocyanates from the oil phase, each diisocyanate and / or polyisocyanate containing an aromatic moiety. Surprisingly, leakage can be controlled by two isocyanates (each containing at least one aromatic moiety), which, when combined with chitosan, produce low-leakage delivery particles in different matrices and supports, achieving effects to a degree that have not been achieved to date using degradable structures. More specifically, the crosslinking agent comprises an isocyanate component, wherein the isocyanate component comprises a mixture of two or more diisocyanates and / or polyisocyanates from the oil phase, each diisocyanate and / or polyisocyanate comprising an aromatic moiety; and each isocyanate is independently selected from α-aromatic isocyanates and β-aromatic isocyanates. In embodiments, the mixture of diisocyanates and / or polyisocyanates may comprise at least one α-isocyanate and at least one β-isocyanate.

[0020] Surprisingly, enhanced performance in terms of lower leakage and retention of nuclear material in the carrier material is achieved, wherein the weighted % NCO of the aromatic isocyanate component is 15 to 32 wt%, or even 20 to 26 wt%, or even 20 to 25 wt%, or even 21 to 25 wt%.

[0021] The isocyanate component has a ratio of 20-50% by weight, preferably 25-40% by weight, and most preferably 30-35% by weight of α-aromatic isocyanate to β-aromatic isocyanate.

[0022] In addition to the composition, the present invention also discloses a method for preparing the composition, which is a group of core-shell delivery particles. The core contains a beneficial agent, and the shell contains a polymeric material, which is a reaction product of at least two isocyanate monomers, oligomers, or prepolymers with chitosan. The method for preparing the composition of the present invention includes the following steps: An aqueous phase in which chitosan is dissolved or dispersed in water is formed. Optionally, prior to capsule shell formation, the chitosan may be pretreated with one or more redox initiators such as persulfate or with one or more acids at a pH of 3 to 6.5, or even 4 to 6.5, at a temperature of at least 25°C for at least 1 hour, or to achieve a viscosity of less than 1500 centipoise (cp), preferably less than 500 cp, to form treated chitosan; and Forming an oil phase comprises dissolving together at least one beneficial agent and an isocyanate component comprising at least two isocyanates having aromatic moieties, wherein the weighted % NCO of the aromatic isocyanates in the isocyanate component is 15 to 32 wt%, or even 20 to 26 wt%, or even 20 to 25 wt%, or even 21 to 25 wt%; and An emulsion is formed by mixing the aqueous phase and the oil phase under high-shear stirring to an excess of aqueous phase, thereby forming oil phase droplets dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to pH 3 to pH 6; and The emulsion is cured by heating to at least 40°C for a duration sufficient to form a shell at the interface between the droplets and the aqueous phase. The shell comprises a crosslinking component and a reaction product of chitosan, and surrounds a core containing the oil-phase droplets. Optionally, the chitosan may be treated chitosan. The oil-phase droplets contain a beneficial agent, as the beneficial agent is itself an oil or soluble in added oil or a crosslinking agent.

[0023] In some embodiments, at least 21 wt% of the shell comprises chitosan. In some embodiments, the isocyanate component comprises methylene diphenyl isocyanate and phenyl diisocyanate in a weight ratio of 1:2 to 1:1.75. In some embodiments, the isocyanate component comprises 30 to 40 wt% methylene diphenyl isocyanate and 60 to 70 wt% phenyl diisocyanate.

[0024] In another configuration, the delivery particles of the present invention can be incorporated into various articles to form new articles. Such articles can be selected from agricultural formulations, slurries encapsulating agricultural active substances, groups of dried encapsulated substances encapsulating agricultural active substances, agricultural formulations encapsulating insecticides, and agricultural formulations for delivering pre-germination herbicides. Agricultural active substances can be selected from agricultural herbicides, agricultural pheromones, agricultural insecticides, agricultural nutrients, insect control agents, and plant stimulants. Attached Figure Description

[0025] Figure 1 This is a description of free oil data for dried delivery particles of a combination of two isocyanates containing aromatic moieties. Figure 1 The free oil profiles of delivery particles containing different concentrations of α-aromatic isocyanate in combinations of α-isocyanate and β-isocyanate, as described in Table 3, were plotted. Detailed Implementation

[0026] This invention describes delivery particles comprising a core material and a shell encapsulating the core material. The core material may contain a beneficial agent. The shell comprises a polymer material, which is a reaction product of chitosan from an aqueous phase and a crosslinking agent from an oil phase. The crosslinking agent comprises an isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates, each of which contains an aromatic moiety. The isocyanate is a diisocyanate, a triisocyanate, or a mixture of diisocyanates and triisocyanates.

[0027] Controlling leakage into the matrix and carrier in the presence of water is challenging. The storage stability of a product in the presence of water with low leakage into the carrier or matrix is ​​important for maintaining the ability to deliver beneficial agents, such as fragrances, at desired contact points. Premature leakage of beneficial agents into the matrix or carrier reduces the amount available at desired subsequent contact points. Encapsulation is used to retain beneficial agents to increase product shelf life. In some articles, such as treatment compositions for fabrics and textiles, it is desirable to retain beneficial agents for release at later contact points (e.g., after washing, during drying cycles, or during wear). Leaked beneficial agents typically fail to achieve the desired release at such later stages, despite the high demand for such release. Surprisingly, leakage has been found to be controlled by a combination of two isocyanates, each containing an aromatic moiety, which, when combined with chitosan, produce low-leakage delivery particles in different matrices and carriers to an effect unattainable to date using degradable structures.

[0028] Low leakage can be achieved by carefully selecting mixtures of diisocyanates and / or polyisocyanates containing α or β isocyanates, particularly those combinations containing at least one α isocyanate and at least one β isocyanate. In embodiments, surprisingly low leakage into the carrier material is observed when the weighted % NCO of the aromatic isocyanate component of the isocyanate is 15 to 32 wt%, or even 20 to 26 wt%, or even 20 to 25 wt%, or even 21 to 25 wt%. In particular, the compositions of the present invention comprise an isocyanate component containing α and / or β aromatic isocyanates. The α aromatic isocyanate is selected from the group consisting of: III. , as well as IV Where R is a biuret, urea diketone, isocyanurate, a polyol having a carbamate side group, a polyamine having a urea side group, a polyacid having an anhydride group, a polyisocyanate containing a biuret, a polyisocyanate containing a urea diketone, or a polyisocyanate containing an isocyanurate.

[0029] R is bonded to the above structure through at least two reactive moieties (e.g., amino group, hydroxyl group, acid anhydride, etc.).

[0030] The R in structures I, II, III, and IV, and XII and XIII, for example, comprises a portion having at least two or more functional groups attached to the corresponding diisocyanate or triisocyanate. The R in structures I, II, III, and IV, and XII and XIII, for example, may comprise a polyol, or a polyol having one or more urethane side groups, or a polyamine, such as a polyamine having one or more urea side groups or other linking groups, a polyacid having an anhydride group, a polyisocyanate containing biuret, a polyisocyanate containing urea diketone, or a polyisocyanate containing isocyanurate. In structures I, II, III, and IV, and XII and XIII, for example, the R portion comprises at least two or more functional groups attached to the corresponding diisocyanate or triisocyanate.

[0031] The aromatic isocyanates of formulas I-XVI are based on derivative variants of commonly available isocyanates, such as phenyl dimethyl diisocyanate (XDI), toluene diisocyanate (TDI), and methylene diphenyl diisocyanate (MDI).

[0032] The aromatic isocyanates selected above are generally commercially available. For example, Covestro of Leverkusen, Germany, is a supplier of polyisocyanates and prepolymers under the Desmodur brand. Polyisocyanates conforming to structures I-XVI disclosed herein can be obtained from isocyanates and prepolymers under the Desmodur E brand, and / or can also be synthetically derived. Optionally, aromatic isocyanates are also commercially available from sources such as Mitsui Chemicals, Inc., Tokyo, Japan, such as isocyanates under the Takenate brand, for example, Takenate D-110N adducts based on phenylenedimethyl diisocyanate.

[0033] Specific examples of α-aromatic isocyanates that can be used in this invention can be selected from the following group: and Where n is an integer from 1 to 24, preferably from 1 to 18, or even from 1 to 12, or even from 1 to 8. .

[0034] The β-aromatic isocyanates that can be used in this invention are selected from the group consisting of: Where R is biuret, urea diketone, isocyanurate, polyol with urethane side group, polyamine with urea side group, polyacid with an anhydride group, polyisocyanate containing biuret, polyisocyanate containing urea diketone, or polyisocyanate containing isocyanurate.

[0035] The α-aromatic isocyanate may also be selected from the group consisting of toluene diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, naphthalene diisocyanate, phenyl diisocyanate, isomers thereof, adducts thereof, and combinations thereof; and preferably selected from methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, isomers thereof, adducts thereof, and combinations thereof.

[0036] Specific examples of β-aromatic isocyanates that can be used in this invention can be selected from the following group: , and .

[0037] The β-aromatic isocyanate may also be selected from the group consisting of: dimethyl phthalate, trimethylolpropane adduct of dimethyl phthalate, tetramethyl dimethyl phthalate, isomers thereof, adducts thereof, and combinations thereof.

[0038] This disclosure relates to a treatment composition comprising delivery particles having a shell at least partially made of a chitosan-based material. Specifically, the delivery particles comprise a shell containing a reaction product comprising chitosan and a crosslinking agent. The crosslinking agent comprises an isocyanate component from an oil phase, said isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates, each of said diisocyanates and / or polyisocyanates containing an aromatic moiety. The isocyanate component may comprise at least two diisocyanates and / or polyisocyanates selected from methylene diphenyl diisocyanate and phenyl diisocyanate. In embodiments, the phenyl diisocyanate comprises a trimethylolpropane adduct of phenyl diisocyanate, and the methylene diphenyl diisocyanate may be selected from 2,2'-methylene diphenyl diisocyanate and 4,4'-methylene diphenyl diisocyanate. Preferably, the weight ratio of the isocyanate components is from 1:2 to 1:1.75. Ideally, the isocyanate component comprises 30 to 40% by weight of methylene diphenyl diisocyanate and 60 to 70% by weight of phenyl diisocyanate. Usefully, the isocyanate component comprises about 34% by weight of methylene diphenyl diisocyanate and about 66% by weight of phenyl diisocyanate. Chitosan, combined with the isocyanate component within this isocyanate range or proportion, is surprisingly able to efficiently deliver the beneficial agent at the desired contact point. The combination of the two isocyanates and chitosan surprisingly reduces leakage into the matrix component and / or carrier. Mixtures of isocyanates having aromatic moieties may, for example, comprise trimers of phenyl diisocyanate (XDI) or oligomers or prepolymers of methylene diphenyl diisocyanate (MDI).

[0039] Optionally, prior to shell formation, the chitosan used to prepare the particulate shell can be treated with an acid or even a mixture of acids, such as those described in U.S. Serial No. 63429232, filed December 1, 2022, or with a redox initiator, preferably a persulfate, such as those described in U.S. Serial No. 63429240, filed December 1, 2022, which are incorporated herein by reference. The redox initiator is selected from any of persulfates or peroxides. Preferably, the redox initiator is selected from ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof.

[0040] Typically, when chitosan is dissolved in water, such as during the preparation of delivery particles, the resulting mixture tends to be very viscous. This can lead to flowability and processing challenges, and / or inhibit the adequate formation of the delivery particle shell. Acid treatment has been described in U.S. Serial No. 63429232 as potentially leading to a reduction in the viscosity of the mixture and an improvement in the shell structure. Furthermore, acid treatment of chitosan is believed to advantageously affect its molecular weight, thereby resulting in improved shell formation and / or delivery properties.

[0041] The delivery particles have a shell made at least partially of a chitosan-based material. In particular, the delivery particles include a shell containing a reaction product of chitosan and an isocyanate component.

[0042] Without being bound by theory, it is believed that careful selection of the chitosan and isocyanate combination within the weight ratios of the present invention is beneficial to achieving surprisingly long-shelf-life compositions containing delivery particles. For example, the selection of the isocyanate component according to the present invention results in delivery particles that perform better at certain contact points. It is believed that the combination of isocyanates of the present invention produces delivery particles with higher density. It is believed that the surprising reduction in leakage is attributable not only to the density of the polymer material but also to the combination of the presence of the aromatic moiety with the reactive sites of the isocyanate component.

[0043] Furthermore, chitosan often presents processing challenges in aqueous environments, particularly due to its viscosity. Viscosity affects solution flowability and / or inhibits adequate particle wall formation. Optional acid treatment can help reduce solution viscosity. Without being bound by theory, careful selection of the chitosan molecular weight is believed to be advantageous. For example, selecting chitosan with a molecular weight above a certain threshold can result in better particle delivery at certain contact points compared to particles made from lower molecular weight chitosan. Surprisingly, acid treatment yields a 3.5% concentration of chitosan, typically with an initial viscosity of around 4000 cP, showing a 60% or even greater viscosity reduction at the same concentration compared to untreated chitosan, reaching a viscosity of 1500 cP or even 1000 cP.

[0044] This invention teaches compositions comprising core-shell encapsulations (also known as delivery particles), including methods for preparing such encapsulations or delivery particles. The core contains a beneficial agent, preferably a fragrance, and the shell may contain, for example, a polyurea polymer material, which is a reaction product of a crosslinking agent comprising a mixture of two or more diisocyanates and / or polyisocyanates from an oil phase, each diisocyanate and / or polyisocyanate comprising an aromatic moiety. In forming the compositions of this invention, chitosan is dissolved or dispersed in an aqueous phase and optionally treated with acid, preferably at a pH of 3 to about 6.5. The chitosan is treated with acid for at least 1 hour at a pH of 6.5 or lower, or even below pH 6.0, or even at a pH of 3 to 6, or even at a pH of 3.5 to 6, or even at a pH of 4 to 6, and at a temperature of at least 25°C. Typically, this treatment step can be measured as the time to obtain a chitosan solution with a viscosity of 1500 centipoise or less (cp), preferably less than 500 cp.

[0045] Chitosan is characterized by a weight-average molecular weight of about 100 to about 80,000 kDa, or even 100 kDa to about 600 kDa. Preferably, chitosan is characterized by a weight-average molecular weight (Mw) of about 100 kDa to about 500 kDa, more preferably about 100 kDa to about 400 kDa, more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa. Methods for determining the molecular weight and related parameters of chitosan are provided in the Test Methods section below, using gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) technology. Selecting chitosan with a preferred weight-average molecular weight can result in capsules with suitable shell formation and / or desired processability. For clarity, the weight-average molecular weight of chitosan is measured prior to treatment with, for example, acid and / or redox initiators as described herein.

[0046] Based on weight, the ratio of isocyanate component crosslinking agent to chitosan is 79:21 to 10:90, or even 2:1 to 1:10, or even 1:1 to 1:7.

[0047] The shell can be 1 to 25% of the weight of the core-shell encapsulation.

[0048] In addition to the mixture of two or more diisocyanates or polyisocyanates, the crosslinking agent of the composition may optionally contain additional polyisocyanates. The additional crosslinking agent may be an aliphatic or aromatic monomer, oligomer, or prepolymer with two or more useful isocyanate functional groups. Other isocyanate-type crosslinking agents, for example, may be selected from aromatic toluene diisocyanates and their derivatives used for delivering the wall formation of particles, or aliphatic monomers, oligomers, or prepolymers, such as hexamethylene diisocyanate and its dimers or trimers, or 3,3,5-trimethyl-5-isocyanate methyl-1-isocyanate cyclohexane tetramethylene diisocyanate, polyisocyanurate of toluene diisocyanate, trimethylolpropane adduct of toluene diisocyanate, toluene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, phenylene diisocyanate, 1,3-diisocyanate 2-methylbenzene, hydrogenated MDI, bis(4-isocyanate cyclohexyl)methane, dicyclohexylmethane-4,4'-diisocyanate, and their oligomers and prepolymers. Other isocyanates that can be used in this invention include isocyanate monomers, oligomers or prepolymers, or dimers or trimers having at least two isocyanate groups. Optimal crosslinking can be achieved with isocyanates having at least three functional groups. This list is illustrative and not limiting.

[0049] Other isocyanate-type crosslinking agents can be formed from polyisocyanate adducts. Adducts are products of a molecule with itself and / or with another molecule. In the case of polyisocyanates adducting with themselves, the isocyanate moieties of the polyisocyanate molecules can react with each other to form larger polyisocyanate products containing biuret, urea diketone, and / or isocyanurate moieties. In the case of polyisocyanate polyol adducts, the isocyanate moieties of the polyisocyanate molecules can react with the hydroxyl moieties of the polyol to form larger polyisocyanate products containing urethane moieties. In the case of polyisocyanate polyamine adducts, the isocyanate moieties of the polyisocyanate molecules can react with the amine moieties of the polyamine to form larger polyisocyanate products containing urea moieties. In the case of polyisocyanate polyacid adducts, the isocyanate moieties of the polyisocyanate molecules can react with the carboxyl moieties of the polyacid to form larger polyisocyanate products containing anhydride moieties. Here, a polyisocyanate is a molecule containing two or more isocyanate moieties.

[0050] When formulated according to the teachings of the present invention, and when tested according to test method OECD 301 B, the shell degrades by at least 40% or even at least 60% of its mass after at least 60 days.

[0051] The core-shell encapsulation has a core-to-shell ratio of at least 75:25, or 85:15, or 90:10, or even up to 99:1, or even at least 99.5:0.5 by weight.

[0052] Beneficial agents are selected from the following group: fragrances, flavorings, agricultural active substances, phase change materials, essential oils, lubricants, colorants, preservatives, antimicrobial active substances, antifungal active substances, herbicides, antiviral active substances, preservative active substances, antioxidants, bioactive substances, deodorants, emollients, moisturizers, exfoliants, ultraviolet absorbers, corrosion inhibitors, silicone oils, waxes, bleaching granules, fabric conditioners, odor reducers, dyes, optical brighteners, antiperspirant active substances, and mixtures thereof.

[0053] Unless otherwise stated, all component or composition levels refer to the active portion of the component or composition and do not include impurities that may be present in commercially available sources of such components or compositions, such as residual solvents or byproducts.

[0054] shell To produce the delivery particles of the present invention, an aqueous phase is prepared comprising an aqueous solution or dispersion of an amine-containing natural material having a free amino moiety. The amine-containing natural material is a bio-based material. Such materials include, for example, chitosan. The amine-containing natural material is dispersed in water. In the case of chitosan, in an embodiment, the material may even be hydrolyzed, thereby protonating at least a portion of the amine moiety and promoting dissolution in water. Hydrolysis is carried out for a period of time at an acidic pH, for example, from about 3 to about 6.5, or even about 5 or 5.5, under heating.

[0055] The oil phase is prepared by dissolving the isocyanate component in oil at 25°C. A diluent, such as isopropyl myristate, is used to adjust the hydrophilicity of the oil phase. The oil phase is then added to the aqueous phase and stirred at high speed to obtain the target size. The emulsion is then cured in one or more heating steps, for example, heating to 40°C over 30 minutes and holding at 40°C for 60 minutes. The time and temperature are approximate values. The temperature and time are selected to be sufficient for a shell to form and solidify at the interface between the droplets of the oil phase and the aqueous continuous phase. For example, the emulsion is heated to 85°C over 60 minutes and then held at 85°C for 360 minutes to solidify the capsule. The slurry is then cooled to room temperature.

[0056] The volume-weighted median particle size of the delivery particles according to the present invention can be from 5 micrometers to 150 micrometers, or even from 10 to 50 micrometers, preferably from 15 to 50 micrometers.

[0057] The crosslinking agents of this invention are mixtures of difunctional or polyfunctional isocyanates. When referring to useful crosslinking agents, for the purposes of this invention, reference to polyisocyanates should be understood to include isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. All such monomers, prepolymers, oligomers, dimers, or trimers of aliphatic or aromatic isocyanates are intended to be represented by the term "polyisocyanate" as used herein.

[0058] The capsule shell can also be reinforced using other co-crosslinking agents such as polyfunctional amines and / or polyamines such as diethylenetriamine (DETA), polyethyleneimine, and polyethyleneamine.

[0059] The shell can also be reinforced using other co-crosslinking agents such as polyfunctional amines and / or polyamines such as diethylenetriamine (DETA), polyethyleneimine, polyethyleneamine, or mixtures thereof. Acrylates can also be used as other co-crosslinking agents, for example, to reinforce the shell.

[0060] Polymer materials can be formed in a reaction in which the weight ratio of chitosan present in the reaction to the crosslinking agent present in the reaction is from about 1:10 to about 1:0.1. It is believed that selecting the desired ratio of biopolymer to crosslinking agent can provide the desired stretchability benefits and improved biodegradability. Preferably, at least 21 wt% of the shell is composed of a portion derived from chitosan, preferably derived from acid-treated chitosan. The weight percentage of chitosan as shell can be from about 21% to about 95% of the shell. Based on weight, the ratio of chitosan in the aqueous phase to isocyanate in the oil phase can be from 21:79 to 90:10, or even from 1:2 to 10:1, or even from 1:1 to 7:1. The shell may contain chitosan at a level of 21 wt% or even greater of the total shell, preferably from about 21 wt% to about 90 wt%, or even from 21 wt% to 85 wt%, or even from 21 wt% to 75 wt%, or 21 wt% to 55 wt% of chitosan. The chitosan in this section may optionally be acid-treated chitosan or chitosan treated with a redox initiator such as persulfate, or both.

[0061] Chitosan can be added to water in a jacketed reactor and pretreated at a pH of 3 to 6.5, optionally with one or two redox initiators or with one or more acids (e.g., HCl, formic acid, or acetic acid). An optional pretreatment step can be performed by heating to an elevated temperature, such as 85°C, over 60 minutes and then holding at that temperature for 1 minute to 1440 minutes or longer. The aqueous phase can then be cooled to 25°C. Optionally, a deacetylation step can be added to further promote or enhance the depolymerization or deacetylation of chitosan, for example, by enzymes. An oil phase is prepared by dissolving a mixture of isocyanates containing aromatic moieties in oil at 25°C. A diluent, such as isopropyl myristate, can be used to adjust the hydrophobicity of the oil phase. The oil phase can then be added to the aqueous phase and stirred at high speed to obtain the target size. The emulsion can then be cured in one or more heating steps, for example, heating to 40°C over 30 minutes and holding at 40°C for 60 minutes. The times and temperatures are approximate values. The temperature and time are selected to be sufficient for a shell to form and solidify at the interface between the oil phase droplets and the aqueous continuous phase. For example, the emulsion can be heated to 85°C for 60 minutes and then held at 85°C for 360 minutes to solidify the particles. The slurry can then be cooled to room temperature.

[0062] When tested according to OECD 301 B, the shell degrades by at least 50% after 20 days (or less). When tested according to OECD 301 B, the shell degrades by at least 60% of its mass after 60 days (or less). When tested according to OECD 301 B, the shell preferably degrades by at least 60% of its mass after 60 days (or less). The shell degrades by 30-100%, preferably 40-100%, 50-100%, 60-100%, or 60-95% within 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, and more preferably 14 days.

[0063] The delivery particles of this disclosure include a core. The core contains a beneficial agent. The core optionally contains a distributing modifier.

[0064] The core of the particle is surrounded by a shell. When the shell breaks, the beneficial agent in the core is released. Alternatively, the beneficial agent in the core may diffuse out of the particle, and / or it may be extruded. Suitable beneficial agents located in the core may include those that provide beneficial effects to the surface.

[0065] nuclear The kernel may contain about 5% to about 100% of beneficial agents by weight of the kernel, which may preferably contain fragrance. The kernel may also contain about 45% to about 95%, preferably about 50% to about 80%, more preferably about 50% to about 70% of beneficial agents by weight of the kernel, which may preferably contain fragrance.

[0066] Beneficial agents may include aldehyde-containing beneficial agents, ketone-containing beneficial agents, or combinations thereof. Such beneficial agents, such as aldehyde or ketone-containing flavoring ingredients, are known to provide preferred beneficial effects, such as freshness benefits. Beneficial agents may comprise at least about 20%, preferably at least about 25%, more preferably at least about 40%, and even more preferably at least about 50% by weight of the beneficial agent, aldehyde-containing beneficial agent, or combinations thereof.

[0067] The beneficial agent can be a hydrophobic beneficial agent. Such agents are compatible with the oil phase commonly used in the preparation of the delivery particles disclosed herein.

[0068] The beneficial agent in the core preferably comprises a flavoring material (or simply "flavoring"), which may include one or more flavoring ingredients. Flavoring is particularly suitable for encapsulation in the delivery particles described herein because flavoring-containing particles can provide freshness benefits at multiple points of contact.

[0069] As used herein, the term "fragrance ingredient" (or "PRM") refers to a compound with a molecular weight of at least about 100 g / mol that can be used alone or in combination with other fragrance ingredients to impart odor, flavor, essence, or aroma. Typical PRMs include, in particular, alcohols, ketones, aldehydes, esters, ethers, nitriles, and alkenes, such as terpenes. Lists of common PRMs can be found in various reference sources, such as "Perfume and Flavor Chemicals", Volumes I and II; Steffen Arctander Allured Pub. Co. (1994), and "Perfumes: Art, Science and Technology", Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0070] PRMs can be characterized by their boiling point (BP) measured at atmospheric pressure (760 mm Hg) and their octanol / water partition coefficient (P), which can be described by logP and determined according to the following test method. Based on these properties, PRMs can be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV flavorings, as described in more detail in U.S. Patent 6,869,923. Suitable Quadrant I, II, III, and IV flavoring raw materials are disclosed therein.

[0071] Flavoring raw materials with a boiling point (BP) below approximately 250°C and a logP below approximately 3 are designated as Quadrant I flavoring raw materials. Quadrant I flavoring raw materials are preferably limited to less than 30% of flavoring materials.

[0072] Flavorings may contain flavoring ingredients with a logP of about 2.5 to about 4. It should be understood that other flavoring ingredients may also be present in flavorings.

[0073] The delivery particles described in this teaching include a beneficial agent containing one or more ingredients intended to be encapsulated. The beneficial agent is selected from a variety of different materials, such as chromogens and dyes, flavorings, fragrances, sweeteners, spices, oils, fats, pigments, cleaning oils, pharmaceuticals, medicinal oils, essential oils, mold inhibitors, antimicrobial agents, fungicides, bactericides, disinfectants, adhesives, phase change materials, flavorings, fertilizers, nutrients, and herbicides: illustrative and not limiting. The beneficial agent and oil constitute the core. The core can be liquid or solid. For cores that are solid at ambient temperature, for certain applications where it is desirable, for example, to obtain an aggregated core, the wall material can effectively encapsulate a core smaller than the entire core. Such uses can include fragrance release, cleaning compositions, emollients, cosmetic delivery, etc. In the case where the encapsulating core is a phase change material, uses can include such encapsulating materials in mattresses, pillows, bedding, textiles, sports equipment, medical devices, building products, construction products, HVAC, renewable energy, clothing, sports surfaces, electronics, automotive, aerospace, footwear, beauty care, laundry, and solar energy applications.

[0074] The core constitutes the material encapsulated by the delivery particles. Typically, especially when the core material is a liquid, it is combined with one or more compositions forming the inner wall of the delivery particles or a solvent used for the beneficial agent or dispensing modifier. If the core material can act as an oil solvent in the capsule, for example, as a solvent or carrier for the wall-forming material or beneficial agent, the core material can be the primary encapsulating material, or if the carrier itself is a beneficial agent, it can be the total encapsulating material. However, the beneficial agent is typically 0.01 to 99% by weight of the capsule contents, preferably 0.01 to 65% by weight, more preferably 0.1 to 45% by weight. For some applications, the core material can be effective even in trace amounts.

[0075] Where the beneficial agent itself is insufficient to serve as an oil phase or solvent, particularly for wall-forming materials, the oil phase may comprise a suitable carrier and / or solvent, i.e., added oil. In this sense, the oil is optional, as the beneficial agent itself can sometimes be oil. These carriers or solvents are typically oils, preferably oils with a boiling point greater than about 80°C, low volatility, and being non-flammable. While not limited thereto, they preferably comprise one or more esters, preferably esters with a chain length of up to 18 carbon atoms or even up to 42 carbon atoms, and / or triglycerides, such as esters of C6 to C12 fatty acids and glycerol. Exemplary carriers and solvents include, but are not limited to: ethyl diphenylmethane; isopropyl diphenyl ethane; butyl biphenyl ethane; benzyl xylene; alkyl biphenyls, such as propyl biphenyl and butyl biphenyl; dialkyl phthalates, such as dibutyl phthalate, dioctyl phthalate, dinonyl phthalate and ditridecyl phthalate; 2,2,4-trimethyl-1,3-pentanediol diisobutyrate; alkylbenzenes, such as dodecylbenzene; alkyl or aralkyl benzoates, such as benzyl benzoate; diaryl ethers; di(aralkyl) ethers and arylaralkyl ethers; ethers, such as diphenyl ethers, Dibenzyl ethers and phenylbenzyl ethers; liquid higher alkyl ketones (having at least 9 carbon atoms); alkyl benzoates or aralkyl benzoates, such as benzyl benzoate; alkylated naphthalenes, such as dipropylnaphthalene; partially hydrogenated terphenyls; high-boiling straight-chain or branched hydrocarbons; alkylaryl hydrocarbons, such as toluene; vegetable and other crop oils, such as rapeseed oil, soybean oil, corn oil, sunflower oil, cottonseed oil, lemon oil, olive oil, and pine oil; transesterified fatty acid methyl esters, methyl oleate, esters of vegetable oils such as soybean methyl ester, straight-chain alkanes, aliphatic hydrocarbons, and mixtures thereof.

[0076] Available beneficial agents include fragrance ingredients such as alcohols, ketones, aldehydes, esters, ethers, nitriles, olefins, fragrances, fragrance solubilizers, essential oils, phase change materials, lubricants, colorants, cooling agents, preservatives, antimicrobial or antifungal active substances, herbicides, antiviral active substances, disinfectant active substances, antioxidants, bioactive substances, deodorants, emollients, humectants, exfoliants, UV absorbers, self-healing compositions, corrosion inhibitors, sunscreens, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lipids, skin cooling agents, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleaching particles, silica particles, odor reducers, dyes, whitening agents, bacterial active substances, antiperspirant active substances, cationic polymers, and mixtures thereof. By way of example and not limitation, phase change materials that can be used as beneficial agents may include alkanes having 13 to 28 carbon atoms, various hydrocarbons such as n-octadecane, n-heptadecane, n-hexadecane, n-pentane, n-tetradecane, n-tridecane, n-docosahexadecane, n-undecanane, n-eicosane, n-eicosane, n-nonadecanane, octadecane, n-heptadecane, n-pentadecanane, n-tetradecane, and n-tridecane. Phase change materials may alternatively and optionally also include crystalline materials such as 2,2-dimethyl-1,3-propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, acids of straight-chain or branched hydrocarbons such as eicosanoic acid and esters such as methyl palmitate, fatty alcohols, and mixtures thereof.

[0077] Preferably, in the case of fragrances, essential oils act as both beneficial agents and solvents for wall-forming materials, as illustrated in the embodiments herein.

[0078] Optionally, the aqueous phase may contain an emulsifier. Non-limiting examples of emulsifiers include alkyl sulfates, alkyl ether sulfates, alkyl isothiosulfates, alkyl carboxylates, alkyl sulfosuccinates, water-soluble salts of alkyl succinates, alkyl sulfates such as sodium dodecyl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolysates, acyl aspartate salts, alkyl or alkyl ether or alkyl aryl ether phosphates, sodium dodecyl sulfate, phospholipids or lecithin, or soaps, sodium stearate, potassium stearate or ammonium stearate, oleate or palmitate esters, alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, sodium dialkyl sulfosuccinate, dioctyl sulfosuccinate, sodium dilauryl sulfosuccinate, sodium poly(styrene sulfonate), isobutylene-maleic anhydride copolymers, gum arabic, sodium alginate, carboxymethyl cellulose, cellulose sulfates and pectin, and poly(styrene sulfonate). Isobutylene-maleic anhydride copolymers, carrageenan, sodium alginate, pectic acid, tragacanth gum, almond gum, and agar; semi-synthetic polymers, such as carboxymethyl cellulose, sulfated cellulose, sulfated methyl cellulose, carboxymethyl starch, phosphorylated starch, lignin sulfonic acid; and synthetic polymers such as maleic anhydride copolymers (including their hydrolysis products), polyacrylic acid, polymethacrylic acid, butyl acrylate copolymers or crotonic acid homopolymers and copolymers, vinylbenzene sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid homopolymers and copolymers, 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 ethoxylates, palmitamide propyltrimethylammonium chloride (Varisoft PATC). TMPurchased from Degussa Evonik, Essen, Germany; distearate dimethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, quaternary ammonium compounds, aliphatic amines, aliphatic ammonium halides, alkyl dimethyl benzyl ammonium halides, alkyl dimethyl ethyl ammonium halides, polyethyleneimine, poly(2-dimethylamino)ethyl methacrylate) methyl chloride quaternary ammonium salt, poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), poly(acrylamide-co-diallyl dimethyl ammonium chloride), poly(allylamine), poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea] quaternized polymer and poly(dimethylamine-co-epimylchlorohydrin-co-ethylenediamine), condensation products of aliphatic amines and epoxides; possessing Quaternary ammonium compounds with long-chain aliphatic groups, such as distearate diammonium chloride; and aliphatic amines, alkyl dimethyl benzyl ammonium halides, alkyl dimethyl ethyl ammonium halides; polyalkylene glycol ethers; condensation products of alkylphenols, fatty alcohols or fatty acids with epoxides, ethoxylated alkylphenols, ethoxylated arylphenols, ethoxylated polyarylphenols, carboxylic acid esters dissolved in polyols, polyvinyl alcohol, polyvinyl acetate or copolymers of polyvinyl alcohol and polyvinyl acetate, polyacrylamide, poly(N-isopropylacrylamide), poly(2-hydroxypropyl methacrylate), poly(-ethyl-2-oxazoline), poly(2-isopropenyl-2-oxazoline-co-methyl methacrylate), poly(methyl vinyl ether), and polyvinyl alcohol-co-ethylene, and cocamidopropyl betaine. If an emulsifier is used, the emulsifier is typically from about 0.1 to 40% by weight, preferably from 0.2 to about 15% by weight, and more typically from 0.5 to 10% by weight, based on the total weight of the formulation.

[0079] In addition to beneficial agents, delivery particles may also encapsulate partitioning modifiers. Non-limiting examples of partitioning modifiers include isopropyl myristate, C4-C... 24 Monoesters, diesters, and triesters of fatty acids, castor oil, mineral oil, soybean oil, methyl hexadecanoate, isododecane, isoparaffin oil, polydimethylsiloxane, brominated vegetable oils, and combinations thereof. Delivery particles may also have different ratios of partition modifiers to beneficial agents to prepare different groups of delivery particles that may have different release modes. Such groups may also be infused with different essential oils to prepare groups of delivery particles exhibiting different release modes and different aroma experiences. Patent publication US 2011-0268802 discloses other non-limiting examples of delivery particles and partition modifiers, which are incorporated herein by reference.

[0080] Optionally, if desired, the delivery particles can be dehydrated, for example, by decantation, filtration, centrifugation, or other separation techniques. Alternatively, the aqueous slurry delivery particles can be spray-dried.

[0081] In some examples of methods and compositions, the delivery particles may consist of one or more distinct groups. The composition may have at least two distinct groups of delivery particles that vary in the exact composition and median particle size of the essential oil and / or the weight ratio of the partition modifier to the essential oil (PM:PO). In some examples, the composition comprises more than two distinct groups that differ in the exact composition and breaking strength of the essential oil. In some further examples, the delivery particle groups may differ in the weight ratio of the partition modifier to the essential oil. In some examples, the composition may comprise a first group of delivery particles having a first ratio of 2:3 to 3:2 and a second group of delivery particles having a second ratio of less than 2:3 but greater than 0.

[0082] In some embodiments, each different delivery particle group can be prepared in a different slurry. For example, a first delivery particle group can be contained in a first slurry, and a second delivery particle group can be contained in a second slurry. It should be understood that there is no limitation on the number of different slurries used for combination, and the formulator's choice allows for the combination of 3, 10, or 15 different slurries. The first and second delivery particle groups can differ in the exact composition of the beneficial agent, such as the essential oil, as well as in the median particle size and / or PM:PO weight ratio.

[0083] In some embodiments, the composition may be prepared by combining a first slurry and a second slurry with at least one auxiliary ingredient and optionally packaged in a container. In some instances, the first and second delivery particle groups may be prepared in different slurries and then spray-dried to form particles. The different slurries may be combined prior to spray drying or spray-dried separately and then combined together in powder form. Once in powder form, the first and second delivery particle groups may be combined with auxiliary ingredients to form a composition that can be used as a raw material for manufacturing consumer goods, industrial goods, medical supplies, or other commodities. In some instances, at least one delivery particle group is spray-dried and combined with a slurry of the second delivery particle group. In some instances, the at least one delivery particle group is dried and prepared by preferably spray drying, or by fluidized bed drying, disc drying, or other such drying processes available.

[0084] In some instances, the slurry or dried particles may include one or more auxiliary materials, such as processing aids selected from carriers, aggregation inhibitors, deposition aids, particulate suspension polymers, and mixtures thereof. Non-limiting examples of aggregation inhibitors include salts that can have a charge-shielding effect around the particles, such as magnesium chloride, calcium chloride, magnesium bromide, magnesium sulfate, and mixtures thereof. Non-limiting examples of particulate suspension polymers include polymers such as xanthan gum, carrageenan, guar gum, shellac, alginate, chitosan; cellulose materials such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, cationic cellulose materials; polyacrylic acid; polyvinyl alcohol; hydrogenated castor oil; ethylene glycol distearate; and mixtures thereof.

[0085] In some embodiments, the slurry may contain one or more processing aids selected from water, aggregation inhibitors such as divalent salts, and particulate suspension polymers such as xanthan gum, guar gum, and carboxymethyl cellulose.

[0086] In other embodiments of the present invention, the slurry may include one or more carriers selected from polar solvents, including but not limited to water, ethylene glycol, propylene glycol, polyethylene glycol, and glycerin; and non-polar solvents, including but not limited to mineral oil, fragrance raw materials, silicone oil, hydrocarbon paraffin oil, and mixtures thereof.

[0087] In some instances, the slurry may include a deposition aid comprising a polymer selected from the group consisting of: polysaccharides, in one aspect, cationic modified starch and / or cationic modified guar gum; polysiloxanes; polydiallyl dimethyl ammonium halide; copolymers of polydiallyl dimethyl ammonium chloride and polyvinylpyrrolidone; compositions comprising polyethylene glycol and polyvinylpyrrolidone; acrylamide; imidazole; imidazoline halides; polyvinylamine; copolymers of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; polyglycerol ether siloxane crosslinked polymers; copolymers of polyacrylic acid, polyacrylate, polyvinylamine, and polyol oligomers of amines, in... In one aspect, the amine is diethylenetriamine, ethylenediamine, bis(3-aminopropyl)piperazine, N,N-bis-(3-aminopropyl)methylamine, tri(2-aminoethyl)amine, and mixtures thereof; polyethyleneimine, derived polyethyleneimine, and in one aspect, ethoxylated polyethyleneimine; a polymeric compound comprising at least two moieties selected from the group consisting of a carboxylic acid moiety, an amine moiety, a hydroxyl moiety, and a nitrile moiety on the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile, or combinations thereof; a pre-formed condensed layer of an anionic surfactant in combination with a cationic polymer; polyamines and mixtures thereof.

[0088] In some other embodiments used to illustrate the invention, at least one group of delivery particles may be contained in an agglomerate, which is then combined with different groups of delivery particles and at least one auxiliary material. The agglomerate may contain materials selected from silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride, and binders such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0089] Suitable equipment used in the methods disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow-shear mixers, belt mixers, vertical shaft pelletizers, and drum mixers, in both batch and (if applicable) continuous process configurations, as well as spray dryers and extruders. Such equipment is available from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., USA), and Arde Barinco (New Jersey, USA).

[0090] Spray-dried delivery particles Several technologies are known for drying core-shell type beneficial agent delivery particles. Spray drying is the most common method for removing excess moisture from particulate materials. Variations of spray drying can include batch or continuous processes, or the use of pulse combustion dryers, convection or radiation ovens, direct-heated ovens, hot air or combustion air evaporators, indirect heating (e.g., through heated container walls, pipes, or jackets), whether by steam, gas, hot air, solar energy, or other energy sources. Heaters can be radiant heaters or rely on hot air flows, such as disc dryers, or continuous co-current atomization, counter-current atomization, rotary atomization, or even fluidized bed processes. If the packaged material needs to be transported to different locations before use, moisture removal eliminates the costs and quality associated with transporting water. Spray drying is a preferred technology.

[0091] The problem with current drying methods is that, despite advancements in the process of heating particulate materials, encapsulations remain prone to excessive leakage. There remains a need for such dried encapsulations that retain the core contents of beneficial agents, even when the encapsulation has a high core-shell ratio. To reduce the amount of shell material used and minimize and reduce foreign residual material, the proportion of shell wall material needs to be reduced to an extremely low level. Determining a method for drying encapsulations in a manner that yields robust encapsulations with a high core-shell ratio, which successfully retain beneficial agents while releasing them at the desired contact point, and simultaneously reducing the amount of shell material used, remains extremely challenging. The competing requirements of robust encapsulation while minimizing the amount of shell and releasing beneficial agents at the desired contact point have been difficult to achieve prior to the combination and process of this invention.

[0092] Current methods for removing moisture in microencapsulation processes have several problems: either the process consumes extremely high energy, or the process involves high shear at the atomization point, high pressure, or the shell material is incompatible with the effective encapsulation.

[0093] High shear and high pressure are problematic for pressure-sensitive microcapsules, causing many to rupture prematurely and undesirably. This is particularly problematic for microcapsules with non-solid core materials such as oils or fragrances, as these materials cannot provide structural support during drying. Premature rupture of microcapsules during drying reduces the commercial quality of the collected microcapsules and the efficiency of the drying process itself, as prematurely released core contents can, in some cases, interfere with the drying process, contaminate processing equipment, or produce poorly performing delivery particles. The compositions and processes of the present invention surprisingly overcome these problems.

[0094] Water-soluble unit dose products Water-soluble single-dose products (commonly referred to as single-use unit doses "SUD") comprise a water-soluble film, preferably a polyvinyl alcohol film, and a laundry detergent composition, wherein the water-soluble film encapsulates the laundry detergent composition. The laundry detergent composition comprises capsules. The term "capsule" is inclusive or interchangeable with terms such as "delivery particles," "particles," "encapsulation," and "microcapsules." It has been found that when formulated into water-soluble single-dose products comprising a detergent composition encapsulated in a water-soluble film, the consumer-perceived freshness benefit on fabrics after a washing operation is less than expected. It has been found that the encapsulation in single-dose products and / or laundry detergent compositions, when formulated in formulations containing surfactants (particularly in low-water formulations containing surfactants), can leak fragrance. Fragrance leakage can impair freshness delivery on fabrics and may also cause discoloration in some products when fragrance ingredients react with other components formulated in the detergent formulation, such as amines. This invention provides fragrance encapsulants with reduced petrochemical content that are less susceptible to leakage when formulated in low-water detergent formulations containing surfactants, and that provide improved freshness benefits to fabrics during and after washing when formulated in water-soluble unit-dose detergent compositions encapsulated in a water-soluble film. Furthermore, this invention also achieves lower leakage when the encapsulants are dispersed in laundry detergent compositions and / or unit-dose articles. A dried encapsulant is also described in an embodiment.

[0095] The water-soluble unit-dose article includes a water-soluble membrane, preferably a water-soluble polyvinyl alcohol membrane, which is shaped such that the unit-dose article includes at least one internal compartment surrounded by the water-soluble membrane. The unit-dose article may include a first water-soluble membrane and a second water-soluble membrane sealed to each other to define the internal compartment. The water-soluble unit-dose article is configured such that the detergent composition does not leak from the compartment during storage. However, when the water-soluble unit-dose article is added to water, the water-soluble membrane dissolves and releases the contents of the internal compartment into the detergent solution.

[0096] A compartment should be understood as an enclosed internal space within a unit dose of the product that contains the detergent composition. During manufacturing, a first water-soluble membrane may be formed to include an open compartment into which the detergent composition is added. A second water-soluble membrane is then laid on top of the first membrane in a direction that closes the opening of the compartment. The first and second membranes are then sealed together along a sealing region.

[0097] The membrane of the water-soluble unit dose product is soluble in or dispersible in water. The thickness of the water-soluble membrane is preferably 20-150 micrometers, more preferably 35-125 micrometers, even more preferably 50-110 micrometers, and most preferably about 76 micrometers.

[0098] Preferably, the membrane has a water solubility of at least 50%, preferably at least 75%, or even at least 95%, as measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers. Add 5 g ± 0.1 g of membrane material to a pre-weighed 3 L beaker, then add 2 L ± 5 mL of distilled water. Stir vigorously at 600 rpm for 30 minutes at 30 °C using a 5 cm magnetic stir bar on a magnetic stirrer (Labline Model 1250 or equivalent). Then, filter the mixture through a pleated qualitative sintered glass filter with the pore size (maximum 20 μm) defined above. Remove water from the collected filtrate using any conventional method and determine the weight of the remaining material (i.e., the dissolved or dispersed portion). The percentage of solubility or dispersion can then be calculated.

[0099] Laundry detergent composition The laundry detergent composition can be any suitable composition. The composition can be in the form of a solid, a liquid, or a mixture thereof.

[0100] Solids can be in the form of free-flowing particles, compacted solids, or mixtures thereof. It should be understood that solids may contain some water, but are essentially water-free. In other words, no water is intentionally added except for additions from the various raw materials.

[0101] Regarding the laundry detergent compositions of the present invention, the term "liquid" includes forms such as dispersions, gels, pastes, etc. Liquid compositions may also include gases in appropriately subdivided forms. The term "liquid laundry detergent composition" refers to any laundry detergent composition containing a liquid capable of wetting and treating fabrics, for example, for cleaning clothes in a household washing machine. Dispersions are, for example, liquids containing solids or containing particulate matter.

[0102] Laundry detergent compositions can be used as fully formulated consumer products, or can be added to one or more other ingredients to form fully formulated consumer products. Laundry detergent compositions can be pretreatment compositions, which are added to the fabric, preferably to the fabric stains, before the fabric is added to the detergent solution.

[0103] The laundry detergent composition comprises capsules or encapsulations, and the capsules are described in more detail in this specification.

[0104] Preferably, the laundry detergent composition comprises a non-soap surfactant. The non-soap surfactant is preferably selected from non-soap anionic surfactants, nonionic surfactants, or mixtures thereof. Preferably, the laundry detergent composition comprises 10% to 60%, more preferably 20% to 55% of the non-soap surfactant by weight of the laundry detergent composition.

[0105] Preferably, the anionic non-soap surfactant comprises a linear alkylbenzene sulfonate, an alkyl sulfate, an alkoxylated alkyl sulfate, or a mixture thereof. Preferably, the alkoxylated alkyl sulfate is an ethoxylated alkyl sulfate.

[0106] Preferably, the laundry detergent composition comprises 5% to 60%, more preferably 15% to 55%, more preferably 25% to 50%, and most preferably 30% to 45% of a non-soap anionic surfactant by weight of the detergent composition.

[0107] Preferably, the non-soap anionic surfactant comprises a linear alkylbenzene sulfonate and an alkoxylated alkyl sulfate, wherein the weight ratio of the linear alkylbenzene sulfonate to the alkoxylated alkyl sulfate is preferably 1:10 to 10:1, preferably 6:1 to 1:6, more preferably 4:1 to 1:4, and even more preferably 4:1 to 1:1. Alternatively, the weight ratio of the linear alkylbenzene sulfonate to the alkoxylated alkyl sulfate is 1:2 to 1:4. The alkoxylated alkyl sulfate can be derived from synthetic alcohols or natural alcohols, or blends thereof, depending on the desired average alkyl carbon chain length and average degree of branching. Preferably, the synthetic alcohol is prepared according to the Ziegler process, OXO process, modified OXO process, Fischer-Tropsch process, Guerbet process, or mixtures thereof. Preferably, the naturally derived alcohol is derived from natural oils, preferably coconut oil, palm kernel oil, or mixtures thereof.

[0108] Preferably, the laundry detergent composition comprises 0% to 30%, more preferably 1% to 25%, more preferably 3% to 20%, and most preferably 5% to 20% of a nonionic surfactant by weight of the laundry detergent composition. Preferably, the weight ratio of the non-soap anionic surfactant to the nonionic surfactant is 1:2 to 20:1, 1:1.5 to 15:1, 1:1 to 10:1, or 1.5:1 to 5:1. The nonionic surfactant is preferably selected from alcohol alkoxylated nonionic surfactants, including alcohol alkoxylated nonionic surfactants based on naturally derived alcohols, synthetically derived alcohols, and mixtures thereof, depending on the desired average alkyl carbon chain length and average degree of branching. The alcohol alkoxylated nonionic surfactant can be a primary alcohol alkoxylated nonionic surfactant or a secondary alcohol alkoxylated nonionic surfactant, preferably a primary alcohol alkoxylated nonionic surfactant. Synthetic alcohol alkoxylated nonionic surfactants include Ziegler-synthesized alcohol alkoxylated compounds, carbonyl-synthesized alcohol alkoxylated compounds, modified carbonyl-synthesized alcohol alkoxylated compounds, Fischer-Tropsch-synthesized alcohol alkoxylated compounds, Gelbert alcohol alkoxylated compounds, alkylphenol alcohol alkoxylated compounds, or mixtures thereof. The alkoxylated chain can be a mixed alkoxylated chain containing ethoxy, propoxy, and / or butoxy units, or it can be a pure ethoxylated alkyl chain, preferably a pure ethoxylated alkyl chain.

[0109] Preferably, the laundry detergent composition contains 1% to 20% by weight of the laundry detergent composition, more preferably 2% to 15%, even more preferably 3% to 10%, and most preferably 4% to 8% of soap, preferably a fatty acid salt, more preferably an amine-neutralized fatty acid salt, wherein the amine is preferably an alkanolamine, more preferably selected from monoethanolamine, diethanolamine, triethanolamine or mixtures thereof, and more preferably monoethanolamine.

[0110] Preferably, the laundry detergent composition contains a non-aqueous solvent, preferably selected from ethanol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, glycerin, sorbitol, ethylene glycol, polyethylene glycol, polypropylene glycol, or mixtures thereof, preferably wherein the polypropylene glycol has a molecular weight of 400. Preferably, the liquid laundry detergent composition contains 10% to 40%, preferably 15% to 30% of a non-aqueous solvent by weight of the liquid laundry detergent composition. It is not desirable to be bound by theory, but the non-aqueous solvent ensures an appropriate level of membrane plasticization, so that the membrane is neither too brittle nor too soft. It is not desirable to be bound by theory, but having the correct degree of plasticization will also promote membrane dissolution when exposed to water during washing.

[0111] Preferably, the liquid laundry detergent composition contains 1% to 20%, preferably 5% to 15% water by weight of the liquid laundry detergent composition.

[0112] Preferably, the laundry detergent composition comprises an ingredient selected from: cationic polymers, polyester terephthalate polymers, amphiphilic graft copolymers, alkoxylated, preferably ethoxylated polyethylimide polymers, carboxymethyl cellulose, enzymes, bleaching agents, or mixtures thereof.

[0113] Laundry detergent compositions may contain encapsulated ingredients and may contain unencapsulated fragrances.

[0114] Laundry detergent compositions may include auxiliary ingredients selected from tinting dyes, aesthetic dyes, detergent builders (preferably citric acid), chelating agents, cleaning polymers, dispersants, dye transfer inhibitor polymers, optical brighteners, opacifiers, defoamers, preservatives, antioxidants, or mixtures thereof. Preferably, the chelating agent is selected from aminocarboxylate chelating agents, aminophosphonate chelating agents, or mixtures thereof.

[0115] Preferably, the pH of the laundry detergent composition is 6 to 10, more preferably 6.5 to 8.9, and most preferably 7 to 8, wherein the pH of the laundry detergent composition is measured at a 10% dilution in softened water at 20°C.

[0116] Liquid laundry detergent compositions can be Newtonian or non-Newtonian fluids. Preferably, the liquid laundry detergent composition is a non-Newtonian fluid. Not wishing to be bound by theory, the properties of non-Newtonian fluids differ from those of Newtonian fluids; more specifically, the viscosity of a non-Newtonian fluid depends on the shear rate, while the viscosity of a Newtonian fluid is constant and independent of the applied shear rate. The decrease in viscosity of a non-Newtonian fluid upon application of shear is considered to further promote the dissolution of the liquid detergent. The liquid laundry detergent compositions described herein can have any suitable viscosity depending on factors such as the formulation composition and the intended use of the composition. When a Newtonian fluid is used, according to the method described herein, the viscosity at 20 s... -1 At a shear rate and a temperature of 20°C, the composition can have a viscosity value of 100 to 3,000 cP, or 200 to 2,000 cP, or 300 to 1,000 cP. When it is a non-Newtonian fluid, the composition can be produced within 20 seconds according to the method described herein. -1 The shear rate and high shear viscosity values ​​of 100 to 3,000 cP, or 300 to 2,000 cP, or 500 to 1,000 cP at 20°C, and at 1s -1 The viscosity has a low shear viscosity value of 500 to 100,000 cP, or 1,000 to 10,000 cP, or 1,300 to 5,000 cP at a shear rate and a temperature of 20°C. Methods for measuring viscosity are known in the art. According to this disclosure, viscosity is measured using a rotational rheometer, such as the TA Instruments AR550. This instrument includes a 40 mm 2° or 1° conical clamp with a gap of approximately 50-60 μm for isotropic liquids, or a 40 mm flat steel plate with a gap of 1000 μm for liquids containing particles. The measurement is performed using a flow procedure that includes a conditioning step, a peak holding step, and a continuous ramp step. The conditioning step includes setting the measurement temperature to 20°C and, at 10 s... -1 Pre-shear at a certain shear rate for 10 seconds, and then equilibrate at a selected temperature for 60 seconds. The peak hold step includes applying a shear rate of 20°C for 0.05 seconds. -1 The shear rate was maintained for 3 minutes, with sampling every 10 seconds. Continuous ramp steps were performed at 20°C at rates ranging from 0.1 to 1200 s. -1 The shear rate was set for 3 minutes to obtain a complete flow profile.

[0117] Preferred membrane materials are preferably polymeric materials. As is known in the art, membrane materials can be obtained, for example, by casting, blow molding, extrusion, or blown film extrusion of polymeric materials.

[0118] The water-soluble film preferably contains polyvinyl alcohol. Preferably, the water-soluble film contains at least 50%, preferably at least 60%, of polyvinyl alcohol by weight of the water-soluble film. The water-soluble film may contain 50% to 100%, or even 60% to 99% of polyvinyl alcohol by weight of the water-soluble film.

[0119] Preferably, the water-soluble film comprises polyvinyl alcohol selected from polyvinyl alcohol homopolymers or polyvinyl alcohol copolymers or blends thereof, more preferably a blend of polyvinyl alcohol homopolymers and / or polyvinyl alcohol copolymers, preferably wherein the polyvinyl alcohol copolymer is selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly carboxylated anionic polyvinyl alcohol copolymers, and most preferably wherein the polyvinyl alcohol comprises a blend of polyvinyl alcohol homopolymers and carboxylated anionic polyvinyl alcohol copolymers, or a blend of polyvinyl alcohol homopolymers. Alternatively, the water-soluble film comprises a single carboxylated polyvinyl alcohol copolymer.

[0120] The preferred membrane exhibits good solubility in cold water (meaning unheated distilled water). Preferably, such membranes dissolve well in 24... o C, or even better, 10 o Good solubility is defined as the membrane exhibiting at least 50%, preferably at least 75%, or even at least 95% water solubility, as measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers as described above.

[0121] The preferred membranes are those supplied by Monosol under the trade names M8630, M8900, M8779, and M8310.

[0122] The film can be opaque, transparent, or translucent. The film may include printed areas.

[0123] Delivery Particles The laundry detergent composition comprises a capsule (delivery particle) having a core and a shell, wherein the shell surrounds the core.

[0124] The laundry detergent composition preferably contains capsules in an amount of 0.05% to 20%, more preferably 0.05% to 10%, even more preferably 0.1% to 5%, and most preferably 0.2% to 3% by weight of the laundry detergent composition.

[0125] The core material contains a fragrance. The shell contains a polymer. More specifically, the present invention discloses compositions comprising a group of core-shell encapsulants (capsules), wherein the core contains a fragrance. The shell is a polymeric material comprising a reaction product of chitosan, preferably from an oil phase and preferably from an aqueous phase. The crosslinking agent comprises a mixture of two or more diisocyanates and / or polyisocyanates, preferably from an oil phase, each containing an aromatic moiety. Surprisingly, leakage has been found to be controlled by two isocyanates, each containing at least one aromatic moiety, which, when combined with chitosan, produce low-leakage capsules in different matrices and carriers to an effect unseen to date in biodegradable constructions. More specifically, the crosslinking agent comprises an isocyanate component, wherein the isocyanate component comprises a mixture of two or more diisocyanates and / or polyisocyanates from the oil phase, each diisocyanate and / or polyisocyanate comprising an aromatic moiety; and each isocyanate is independently selected from α-aromatic isocyanates and β-aromatic isocyanates. The mixture of diisocyanates and / or polyisocyanates comprises at least one α-isocyanate and at least one β-isocyanate as described herein.

[0126] Test methods It should be understood that the test methods disclosed in the test methods section of this application are used to determine the corresponding values ​​of the parameters of the subject matter claimed by the applicant as claimed and described herein.

[0127] Determination of polymer molecular weight and related parameters The following describes a gel permeation chromatography method with multi-angle light scattering and refractive index detection (GPC-MALS / RI) for determining the molecular weight distribution measurements and correlation values ​​of the polymers described herein.

[0128] Gel permeation chromatography (GPC) with multi-angle light scattering (MALS) and refractive index (RI) detection (GPC-MALS / RI) allows for the measurement of the absolute molecular weight of polymers without the need for column calibration methods or standards. GPC systems allow molecules to be separated according to their molecular size. MALS and RI provide information on number-average (Mn) and weight-average (Mw) molecular weights.

[0129] The molecular weight distribution (Mw) of water-soluble polymers such as chitosan is typically measured using a liquid chromatography system (e.g., an Agilent 1260 Infinity pump system with OpenLabChemstation software, Agilent Technology, Santa Clara, CA, USA) and a column array operating at 40 °C (e.g., two Tosoh TSKgel G6000WP 7.8 × 300 mm 13 μm pore sizes, and a guard column A0022 6 mm × 40 mm PW xl-cp, King of Prussia, PA). The mobile phase is 0.1 M sodium nitrate in water containing 0.02% sodium azide and 0.2% acetic acid. The mobile phase solvent is isocratically pumped at a flow rate of 1 mL / min. A multi-angle light scattering (18-Angle MALS) detector (DAWN®) and a differential refractive index (RI) detector controlled by WyattAstra® software v8.0 (Wyatt Technology of Santa Barbara, CA, USA) are used.

[0130] Samples are typically prepared by dissolving chitosan material at ~1 mg / ml in the mobile phase and hydrating the mixed solution overnight at room temperature. Prior to GPC analysis, samples are filtered through a 0.8 μm Versapor membrane filter (PALL, Life Sciences, NY, USA) into LC autosampler vials using a 3 ml syringe.

[0131] The number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz), peak molecular weight (Mp), and polydispersity (Mw / Mn) were determined using Astra detector software using the dn / dc value (the differential change of refractive index with concentration, 0.15).

[0132] Figure 1 The diagram shows illustrative examples of these points on a hypothetical graph of polymer molecular weight distribution, where: Mn is represented by structure number 1; Mp by structure number 2; Mw by structure number 3; and Mz by structure number 4.

[0133] Viscosity The viscosity of the liquid product was measured using an AR 550 rheometer / viscometer from TA Instruments (New Castle, DE, USA) with a parallel steel plate of 40 mm diameter and 500 μm gap size. (20s) -1 High shear viscosity and 0.05s -1 The low shear viscosity decreased from 0.01 s⁻¹ in 3 minutes at 21°C. -1 up to 25s-1 The logarithmic shear rate was obtained by scanning.

[0134] Test methods for determining logP The log value (logP) of the octanol / water partition coefficient is calculated for each material tested (e.g., each PRM in the flavor blend). The logP for individual materials (e.g., PRMs) is calculated using the Consensus logP calculation model version 14.02 (Linux), available from Advanced Chemistry Development Inc. (ACD / Labs) (Toronto, Canada), to provide unitless logP values. The Consensus logP calculation model from ACD / Labs is part of the ACD / Labs model suite.

[0135] Volume-weighted granularity and granularity distribution Volume-weighted particle size distribution was determined using an AccuSizer 780 AD instrument and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent via single-particle optical sensing (SPOS) (also known as optical particle counting (OPC)). The instrument was configured with the following conditions and selections: flow rate = 1 ml / s; lower particle size threshold = 0.50 μm; sensor model = LE400-05 or equivalent; autodilution = on; collection time = 60 s; number of channels = 512; container fluid volume = 50 ml; maximum overlap = 9200. Measurements were initiated by rinsing the sensor with water until the background count was less than 100, allowing it to cool. The delivery capsule sample was introduced into a suspension, and its capsule density was adjusted with DI water via autodilution as needed to produce a capsule count of at least 9200 / ml. The suspension was analyzed over a 60-second period. Plot and record the resulting volume-weighted PSD data, and determine the desired volume-weighted granularity value (e.g., median / 50). th percentile, 5 th percentiles and / or 90 th percentile).

[0136] Procedure for determining % degradation The percentage degradation is determined by the OECD Guideline 301B for the Testing of Chemicals, adopted on July 17, 1992, for CO2 release (modified Sturm test). For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0137] spray drying process This method removes water from the microcapsule slurry by spray drying, converting it into powder. The slurry is diluted with RO water to a solids content of 19-21%. Then, the slurry is spray-dried using a Buchi miniature spray dryer B-290 at an inlet temperature of 180°C, a getter setting of 90%, a pump setting of 20-65%, and a target outlet temperature of 90°C. The resulting spray-dried microcapsule powder is collected from a collection container.

[0138] Free oil determination procedure This method determines the "free oil" in microcapsule powders. Weigh 200-250 mg of powder into a 20 mL scintillation vial. Add 10 mL of hexane. Cap the vial and vortex at 3000 RPM for 5 seconds, then allow to settle for 2 minutes. Extract at least 2 mL of the solvent solution using a syringe, filter through a 0.45 μm syringe filter, and inject into a gas chromatography (GC) vial. Inject the solution into the GC instrument and determine the concentration of fragrance in the solvent using a standard curve prepared with a series of fragrance dilutions dissolved in hexane. The "free oil" is then calculated as the mass fraction of fragrance in 10 mL of hexane relative to the powder mass. Repeat the procedure twice for each powder sample, and average the results. Calculate the standard deviation from the two points and provide the average.

[0139] Delivery particles exhibiting a positive zeta potential can be prepared. These capsules offer improved deposition efficiency, for example, on fabrics.

[0140] Sample preparation for biodegradability measurements Water-soluble or water-dispersible materials are purified by crystallization until a purity of over 95% is achieved, and then dried before biodegradability measurements.

[0141] It is necessary to extract the oily medium containing the beneficial agent from the delivery particle slurry in order to analyze only the polymer wall. Therefore, the delivery particle slurry is freeze-dried to obtain a powder. Then, it is further washed with an organic solvent by Soxhlet extraction to extract the oily medium containing the beneficial agent until the weight percentage of the oily medium, based on the total delivery particle polymer wall, is less than 5%. Finally, the polymer wall is dried and analyzed.

[0142] The weight ratio of delivery particles to solvent is 1:3. Residual oily medium is determined by thermogravimetric analysis (60-minute isotherm at 100°C and another 60-minute isotherm at 250°C). The determined weight loss must be less than 5%.

[0143] leakage The amount of beneficial agent leakage from delivery particles containing beneficial agents was determined using the following method: i) Obtain two 1g samples containing delivery particles of the beneficial agent.

[0144] ii) Add 1g of the delivery particles containing the beneficial agent to 99g of the consumer product matrix in which the particles will be used, and label the mixture as Sample 1. In step d, immediately use a second 1g sample of the delivery particles containing the beneficial agent in its pure form without contacting the consumer product matrix, and label it as Sample 2.

[0145] iii) The product matrix containing the delivery particles (sample 1) was aged in a sealed glass jar at 35°C for 1 week.

[0146] iv) Use filtration to recover particles from both samples. Recover particles from Sample 1 (in a consumer product matrix) after the aging step. Recover particles from Sample 2 (pure raw material slurry) at the same time as the aging step of Sample 1 begins.

[0147] v) Treat the recovered particles with a solvent to extract beneficial agent materials from the particles.

[0148] vi) Analyze the solvents containing the extracted beneficial agents from each sample by chromatography.

[0149] vii) Integrate the area of ​​the obtained beneficial agent peaks under the curve and sum these areas to determine the total amount of beneficial agent extracted from each sample.

[0150] viii) The percentage of beneficial agent leakage is determined by subtracting the total amount of beneficial agent extracted from sample 1 (S1) from the total amount of beneficial agent extracted from sample 2 (S2), expressed as a percentage of the total amount of beneficial agent extracted from sample 2 (S2), as shown in the following equation: 0 For powder samples, repeat the procedure twice and average the results. Calculate the standard deviation from the two points and provide the average.

[0151] Olfactory evaluation methods After treatment, professional perfumers assess the fragrance intensity of the dry fabric using both direct contact (dry fabric scent = DFO) and rubbing contact (rubbing fabric scent = RFO; the fabric is dried for one day, then smelled for DFO, and then manually rubbed to create RFO). The scores are averaged. The score is based on a fragrance intensity scale of 0 to 100, where 0 = no fragrance, 25 = slight fragrance, 50 = medium fragrance, 75 = strong fragrance, and 100 = very strong fragrance. This can be reported as "Delta RFO," the difference between RFO and DFO.

[0152] The breadth index can be calculated by determining the particle size at which the cumulative particle volume exceeds 95% (95% particle size), the particle size at which the cumulative particle volume exceeds 5% (5% particle size), and the median particle size (50% particle size—that is, 50% of the particle volume is greater than this particle size and 50% is less than this particle size). Broadness index = ((95% particle size) - (5% particle size)) / (50% particle size).

[0153] Method for determining the headspace concentration above the treated dry fabric.

[0154] Cotton tracer fabric samples were analyzed using a rapid headspace GC / MS (gas chromatography-mass spectrometry) method. Four × 4 cm aliquots of the cotton tracer fabric samples were transferred to 25 mL headspace vials. The fabric samples were equilibrated at 65 °C for 10 min. The headspace above the fabric was sampled for 5 min using SPME (50 / 30 μm DVB / Carboxen / PDMS). The SPME fibers were then thermally desorbed into the GC. Analytes were analyzed by rapid GC / MS in full scan mode. The total headspace response and fragrance headspace composition above the test group were calculated using ion extraction at specific mass numbers of the PRM.

[0155] %NCO The %NCO of isocyanate compounds is calculated using the following formula: in It is the count of isocyanate groups present in the compound. It is a single The molecular weight of the group, It is the molecular weight of the entire isocyanate compound, excluding any solvents or other substances that can be mixed with the isocyanate.

[0156] When isocyanates are used as a mixture of multiple isocyanates, The report is a weighted sum of the mass percentage of each individual isocyanate in the mixture.

[0157] Unless otherwise stated, all temperatures in this article are in degrees Celsius (°C). Unless otherwise stated, all measurements in this article were performed at 20°C and atmospheric pressure.

[0158] Unless otherwise stated, all percentages and ratios are by weight. Unless otherwise specified, all percentages and ratios are calculated based on the total composition.

[0159] It should be understood that each maximum numerical limit given throughout this specification includes each lower numerical limit as if such lower numerical limit were explicitly stated herein. Each minimum numerical limit given throughout this specification will include each higher numerical limit as if such higher numerical limit were explicitly stated herein. Each numerical range given throughout this specification will include each narrower numerical range falling within such a wider numerical range as if such narrower numerical ranges were explicitly stated herein.

[0160] In the following embodiments, abbreviations, materials, or trade names correspond to the materials listed in Table 1. These embodiments are illustrative in nature and not restrictive.

[0161] Table 1. Materials - Chitosan

[0162] Diisocyanates and / or polyisocyanates contain an aromatic moiety. The isocyanates used have two functional groups: an isocyanate group and an aromatic moiety. For ease of reference, isocyanate molecules can be further subdivided into several classes.

[0163] The first category can be based on the presence or absence of the aromatic moiety throughout the molecule; therefore, the following two categories are defined: 1- An isocyanate containing at least one aromatic moiety.

[0164] 2- Isocyanates that do not contain any aromatic moieties.

[0165] For convenience, based on carbon atom nomenclature, the presence of aromatic moieties can be further classified as α or β. Therefore, isocyanates containing aromatic moieties can be further subdivided.

[0166] 1.i) Isocyanates containing an α-aromatic moiety; and 1. ii) Isocyanates containing a β-aromatic moiety.

[0167] For ease of reference, categories 1, i), and ii) in Category 1 are referred to as: 1.i) aFang ethnic group 1.ii) β-Aromatics, And category 2 is called: 2. "Non-fragrant tribe" This naming convention is reflected in Table 2 below: Table 2. Materials - Isocyanates

[0168] Theoretically, the aromatic ring can influence reactivity. Surprisingly, isocyanates containing α-aromatic moieties are found to be more reactive than those containing β-aromatic moieties. This is thought to be due to the nature of the electron-withdrawing aromatic ring, which enhances the electrophilic properties of the isocyanate group (NCO). Isocyanates containing one or more α-aromatic moieties have a benzene ring attached to the NCO group, which is theoretically thought to enhance reactivity. The delocalization of electrons in the aromatic ring is thought to make the α-carbon even more electron-deficient, making it a stronger electrophile and thus more readily engaging in nucleophilic interactions with amines (e.g., chitosan amino groups). On the other hand, isocyanates containing one or more β-aromatic moieties have a smaller electron-withdrawing aromatic ring effect and are attached to the β-carbon. While they are still reactive, their reactivity is generally lower than that of their α-aromatic counterparts. This can lead to faster reaction rates, making α-aromatics (e.g., class I.i) more efficient in certain applications. However, their high reactivity can also make them more challenging to handle and may require additional precautions, such as against the potentially undesirable reactivity with PRM. Unexpectedly, an improvement was found when the isocyanate component was selected as a mixture comprising two or more isocyanates, each containing an aromatic moiety, and each isocyanate being independently selected from α-aromatic isocyanates and β-aromatic isocyanates. It should be understood that the isocyanate can be a diisocyanate or a polyisocyanate.

[0169] Example The embodiments provided below are illustrative in nature and not restrictive.

[0170] Comparative Example 1, Schemes 1A, 1B, and 1C The comparative examples and embodiments were prepared according to the following procedure: A chitosan solution treated with acid and potassium persulfate was prepared by dispersing 134.79 g of chitosan in 2875 g of water and mixing simultaneously in a jacketed reactor at 60 °C. If desired, potassium persulfate (“KPS”) was then added to the chitosan dispersion under mixing to a level such that the viscosity of the chitosan solution was 50 cP–2000 cP after the hydrolysis and depolymerization steps. The pH of the chitosan solution was then adjusted to 5.9 under mixing using 36.8 g of 32% hydrochloric acid and 4.2 g of 90% formic acid. The temperature of the chitosan solution was then raised to 85 °C over 60 minutes and maintained at 85 °C for a period of time to hydrolyze and depolymerize the chitosan. The temperature was then lowered to 25 °C over 90 minutes after the hydrolysis step to obtain the chitosan solution treated with acid and potassium persulfate. The resulting chitosan stock solution was used to prepare capsules for the comparative examples and embodiments described below.

[0171] The aqueous phase was prepared by mixing 435.07 g of chitosan stock solution in a jacketed reactor. The oil phase was prepared by mixing 127.25 g of fragrance and 31.82 g of isopropyl myristate with isocyanate at room temperature, according to the weights listed in Tables 2 and 3. The oil phase was added to the aqueous phase, preferably within 20 minutes, under high-shear milling to obtain an emulsion with the desired particle size. The emulsion was heated to 60°C over 45 minutes, then to 85°C over 60 minutes and held at this temperature for 6 hours while mixing, and then cooled to 25°C over 90 minutes.

[0172] Spray-dried slurry.

[0173] Schemes 1D and 1E A chitosan solution treated with acid and potassium persulfate was prepared by dispersing 42.03 g of chitosan in 893 g of water and mixing in a jacketed reactor at 60 °C. If desired, potassium persulfate (“KPS”) was then added to the chitosan dispersion under mixing at a level such that the viscosity of the chitosan solution was 50 cP–2000 cP after the hydrolysis and depolymerization steps. 10.04 g of 32% hydrochloric acid and 1.92 g of 90% formic acid were added under mixing. The temperature of the chitosan solution was then raised to 85 °C over 60 minutes and maintained at 85 °C for a period of time to hydrolyze and depolymerize the chitosan. The temperature was then lowered to 25 °C over 90 minutes after the hydrolysis step to obtain the chitosan solution treated with acid and potassium persulfate. The resulting chitosan stock solution was used to prepare the capsules in the following examples.

[0174] The aqueous phase was prepared by mixing 440.6 g of chitosan stock solution in a jacketed reactor. The oil phase was prepared by mixing 128.9 g of fragrance and 32.23 g of isopropyl myristate with isocyanate at room temperature, according to the weights listed in Tables 2 and 3. The oil phase was added to the aqueous phase under high-shear milling to obtain an emulsion with the desired particle size. The emulsion was heated to 60 °C over 45 minutes, then to 85 °C over 60 minutes and held at this temperature for 6 hours while mixing, and then cooled to 25 °C over 90 minutes.

[0175] Spray-dried slurry.

[0176] Scheme of Example 1F: A chitosan solution treated with acid and potassium persulfate was prepared by dispersing 42.03 g of chitosan in 893 g of water and mixing in a jacketed reactor at 60 °C. If desired, potassium persulfate (“KPS”) was then added to the chitosan dispersion under mixing to a level such that the viscosity of the chitosan solution was 50 cP–2000 cP after the hydrolysis and depolymerization steps. 11.48 g of 32% hydrochloric acid and 1.28 g of 90% formic acid were added under mixing. The temperature of the chitosan solution was then raised to 85 °C over 60 minutes and maintained at 85 °C for a period of time to hydrolyze and depolymerize the chitosan. The temperature was then lowered to 25 °C over 90 minutes after the hydrolysis step to obtain the chitosan solution treated with acid and potassium persulfate. The resulting chitosan stock solution was used to prepare capsules in the following examples.

[0177] The aqueous phase was prepared by mixing 440.8 g of chitosan stock solution in a jacketed reactor. The oil phase was prepared by mixing 100.62 g of fragrance and 25.15 g of isopropyl myristate with isocyanate at room temperature, according to the weights listed in Tables 2 and 3. The oil phase was added to the aqueous phase under high-shear milling to obtain an emulsion with the desired particle size. The emulsion was heated to 60 °C over 45 minutes, then to 85 °C over 60 minutes and held at this temperature for 6 hours while mixing, and then cooled to 25 °C over 90 minutes.

[0178] Spray-dried slurry.

[0179] Table 3:

[0180] The capsules according to the invention can have a core-to-wall ratio as high as 95% core to 1% wall. In applications where enhanced degradability is desired, even higher core-to-wall ratios can be used, such as 99% core to 1% wall, or even 99.5% by weight to 0.5% by weight or higher. By appropriately selecting the core-to-wall ratio, the shell of the composition according to the invention can be selected to achieve at least 40% degradation after 28 days and at least 60% degradation after at least 60 days when tested according to test method OECD 301 B.

[0181] Detergent composition in unit dose products The following are exemplary water-soluble unit-dose base formulations prepared by mixing individual starting materials in a batch process. The following compositions can be encapsulated in water-soluble films, preferably polyvinyl alcohol-based water-soluble films, more specifically, water-soluble films comprising blends of polyvinyl alcohol homopolymers and carboxylated anionic polyvinyl alcohol copolymers, or water-soluble films comprising blends of polyvinyl alcohol homopolymers, or water-soluble films comprising carboxylated anionic polyvinyl alcohol copolymers, such as MonoSol's M8630 or M8310, or combinations thereof.

[0182] Table 4: Liquid Detergent Compositions

[0183] *Nucleases, such as those claimed for protection in the co-pending European application 19219568.3 **Lutensol FP620 ex BASF-Ethoxylated Polyethyleneimine (PEI600 EO20) ***A polyethylene glycol grafted polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, comprising a polymer system of 40% by weight of the polyethylene glycol backbone and a polymer system of 60% by weight of the grafted vinyl acetate side chains. ****Lutent Z96 (Zwitterionic Polyamine ex BASF - zwitterionic hexamethylenediamine according to the following formula: 100% quaternized and approximately 40% of polyethoxy (EO24) groups are sulfonated).

[0184] The use of the singular "a" and "an" is intended to cover both singular and plural unless otherwise stated herein or clearly contradicted by the context. The terms "comprising," "having," "including," and "containing" should be interpreted as open-ended terms. All references cited herein, including publications, patent applications, and patents, are incorporated herein by reference. Descriptions of certain embodiments as "preferred" embodiments, and descriptions of embodiments, features, or scopes as preferred, or suggestions that they are preferred, are not considered limiting. The invention is considered to include embodiments that are currently considered less preferred and may be so described herein. All methods described herein may be performed in any suitable order unless otherwise stated herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended to illustrate the invention and does not constitute a limitation on the scope of the invention. Any statement in this document regarding the nature or benefits of the invention or preferred embodiments is not intended to be limiting. The invention includes all modifications and equivalents of the subject matter described herein permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, the invention covers any combination of the foregoing elements in all possible variations. Descriptions of any references or patents herein, even those marked "previously," are not intended to constitute a concession by such references or patents to the prior art of this invention. No unclaimed language should be construed as limiting the scope of the invention. Unless reflected in the appended claims, any statement or suggestion herein that constitutes a component of the claimed invention is not intended to be limiting.

Claims

1. A drying composition comprising a group of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, wherein the shell comprises a polymeric material, the polymeric material being a reaction product of chitosan from an aqueous phase and a crosslinking agent, wherein the crosslinking agent comprises an isocyanate component, the isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates from an oil phase, each of the diisocyanates and / or polyisocyanates comprising an aromatic moiety; and wherein the mixture of diisocyanates and / or polyisocyanates comprises at least one α-isocyanate and at least one β-isocyanate, and wherein the drying composition has less than 20% free oil.

2. The dried composition according to claim 1, wherein the weighted % NCO of the aromatic isocyanate component of the isocyanate component is 15-32 wt%, or even 20-26 wt%, or even 20-25 wt%, or even 21-25 wt%.

3. A method for forming a population of dry delivery particles according to claim 1, the method comprising the following steps: Forming an aqueous phase containing chitosan; Forming an oil phase comprises dissolving at least one beneficial agent together with an isocyanate component, said isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates, each of said diisocyanates and / or polyisocyanates comprising an aromatic moiety, wherein the weighted % NCO of said aromatic isocyanate component is 15 to 32 wt%, or even 20 to 26 wt%, or even 20 to 25 wt%, or even 21 to 25 wt%; An emulsion is formed by mixing the aqueous phase and the oil phase under high shear stirring to form an excess of aqueous phase, thereby forming droplets of oil phase and beneficial agent dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to pH 2 to pH 6. The emulsion is cured by heating to at least 40°C for a duration sufficient to form a shell at the interface between the droplets and the aqueous phase. The shell contains a reaction product of a polyisocyanate component and chitosan. The shell surrounds the core, which contains droplets of the oil phase and a beneficial agent, thereby forming an aqueous slurry containing a group of delivery particles dispersed in an excess aqueous phase. The slurry is converted into dry delivery particles by removing water through heating.

4. The method of claim 3, wherein the microcapsules are dried to a moisture content of 0 to 14%.

5. The method of claim 3, wherein the aqueous slurry comprises a group of delivery particles dispersed in an aqueous carrier solution, which encapsulates a non-solid core material; and wherein the method further comprises the following steps: a) Provides a spray drying apparatus for generating a hot airflow, the spray drying apparatus including a hot airflow in contact with the aqueous slurry, the spray drying apparatus having an outlet device for discharging the hot airflow and the dried material, and a material feed introduction device; b) Input the microcapsule slurry into the material feeding and introduction device; c) In the spray drying apparatus, the microcapsule slurry is converted into dry delivery particles, the spray drying apparatus receiving the slurry fed into the material feed inlet and in contact with the hot gas flow; d) Collect the dried delivery particles in a collection assembly associated with the spray drying apparatus; e) The dried delivery particles are separated using the provided separator device, which separates the hot gas stream from the dried microcapsules, thereby separating the dried delivery particles substantially without breaking them.

6. The method according to claim 3, wherein the mass percentage of α-aromatic isocyanate in the isocyanate component is 1-99% by weight, preferably 5-90% by weight, and most preferably 30-60% by weight.

7. The method of claim 3, wherein the α-aromatic isocyanate is selected from the group consisting of: ， ， ， as well as Where R is a biuret, urea diketone, isocyanurate, a polyol having a carbamate side group, a polyamine having a urea side group, a polyacid having an anhydride group, a polyisocyanate containing a biuret, a polyisocyanate containing a urea diketone, or a polyisocyanate containing an isocyanurate.

8. The method of claim 3, wherein the α-aromatic isocyanate is selected from the group consisting of: ， Where n is an integer from 1 to 24, , , , , as well as, 。 9. The method of claim 3, wherein the β-aromatic isocyanate is selected from the group consisting of: as well as Where R is a biuret, urea diketone, isocyanurate, a polyol having a carbamate side group, a polyamine having a urea side group, a polyacid having an anhydride group, a polyisocyanate containing a biuret, a polyisocyanate containing a urea diketone, or a polyisocyanate containing an isocyanurate.

10. The method of claim 3, wherein the β-aromatic isocyanate is selected from the group consisting of: ,and 。 11. The method of claim 3, wherein the chitosan is pretreated at a pH of 6.5 or lower and a temperature of at least 25°C, or pretreated with a redox initiator, or both.

12. The method of claim 3, wherein the isocyanate component comprises at least two diisocyanates and / or polyisocyanates, the α-isocyanate being selected from methylene diphenyl diisocyanate and polymeric methylene diphenyl isocyanate, and the β-isocyanate comprising a trimethylolpropane adduct of diphenylmethylene diisocyanate.

13. The composition according to claim 1, wherein the β-aromatic isocyanate is selected from phthalimide diisocyanate, trimethylolpropane adduct of phthalimide diisocyanate, tetramethylphthalimide diisocyanate, its isomers, its adducts, and combinations thereof. The composition according to claim 1, wherein the α-aromatic isocyanate is selected from toluene diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, its isomers, its adducts, and combinations thereof.

14. The method of claim 3, wherein the isocyanate component comprises a trimethylolpropane adduct of methylene diphenyl isocyanate, polymeric methylene diphenyl isocyanate, and diphenylmethylene diisocyanate in a weight ratio of 1:2 to 1:1.

75.

15. The method of claim 3, wherein the isocyanate component comprises 30 to 55% by weight, preferably 34% by weight, a combination of methylene diphenyl isocyanate and polymeric methylene diphenyl isocyanate, and 45 to 70%, preferably 66%, of a trimethylolpropane adduct of diphenylmethylene diisocyanate.

16. The method of claim 3, wherein the chitosan is characterized by a weight-average molecular weight of about 100 kDa to about 80,000 kDa, or even 100 kDa to about 600 kDa, preferably about 100 kDa to about 500 kDa, more preferably about 100 kDa to about 400 kDa, more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa.

17. The method of claim 3, wherein the desired isocyanates are each present in at least 20 mol% of the total isocyanate component.

18. The method according to claim 3, wherein the weight ratio of chitosan to the crosslinking agent is 79:21-10:90, or even 67:33-11:89, or even 50:50-13:

87.

19. The method of claim 3, wherein when tested according to test method OECD 301 B, the shell has biodegradability of more than 30% CO2, preferably more than 40% CO2, more preferably more than 50% CO2, and even more preferably more than 60% CO2 (maximum 95%) within 60 days.

20. The method of claim 3, wherein at least 21 wt% of the shell is composed of a portion derived from the chitosan.

21. The method of claim 3, wherein the core-shell encapsulation has a core-to-shell ratio of at least 75:25, or at least 99:1, or even at least 99.5:0.5, the ratio being based on weight.

22. The method of claim 3, wherein the beneficial agent is selected from the group consisting of: fragrances, flavorings, agricultural active substances, phase change materials, essential oils, lubricants, colorants, preservatives, antimicrobial active substances, antifungal active substances, herbicides, antiviral active substances, preservative active substances, antioxidants, bioactive substances, deodorants, emollients, moisturizers, exfoliants, ultraviolet absorbers, corrosion inhibitors, silicone oils, waxes, bleaching particles, fabric conditioners, odor reducers, dyes, optical brighteners, antiperspirant active substances, and mixtures thereof.

23. The method according to claim 3, wherein the beneficial agent is a fragrance, preferably a fragrance containing a fragrance ingredient, wherein the fragrance ingredient is characterized by a logP of about 2.5 to about 4.

5.

24. The method of claim 3, wherein the core further comprises a distribution regulator selected from the group consisting of isopropyl myristate, vegetable oils, modified vegetable oils, monoesters, diesters and triesters of C4-C24 fatty acids, dodecyl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, preferably isopropyl myristate.

25. The method of claim 3, wherein the delivery particles have a median particle size of 1 to 200 micrometers, preferably 1 to 50 micrometers, and even more preferably 1 to 20 micrometers.

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