Treatment composition having a pro-fragrance silicone polymer containing a heterocyclic moiety - Patents.com

Abstract

Treatment compositions comprising pro-fragrance silicone polymers, wherein the pro-fragrance silicone polymers comprise one or more heterocyclic moieties, the heterocyclic moieties comprising the residue of an aldehyde-containing perfume raw material, a ketone-containing perfume raw material, or a mixture thereof. Related premix compositions. Methods of making and using such pro-fragrance silicone polymers, related premix compositions, and treatment compositions. Related pro-fragrance silicone polymers and precursor silicone polymers.

Description

[Technical field]

[0001] The present disclosure relates to a treatment composition comprising a pro-fragrance silicone polymer comprising one or more heterocyclic moieties, the heterocyclic moieties comprising the residue of an aldehyde-containing perfume raw material, a ketone-containing perfume raw material, or a mixture thereof.The present disclosure also relates to related premix compositions, pro-fragrance silicone polymers, and precursor silicone polymers.The present disclosure also relates to related methods of making and using such silicone polymers, premix compositions, and treatment compositions. [Background technology]

[0002] Consumer product manufacturers and consumers alike desire treatment compositions that provide freshness benefits.To address this need, untreated perfume raw materials (PRMs) have been utilized as a means to deliver freshness to consumer products, such as in laundry treatment applications, where such delivery of freshness can be achieved during pretreatment, wash cycle, rinse cycle, tumble cycle, or combinations thereof.Such applications result in scented fabrics, but the scented fabrics do not exhibit sustained delivery or deposition of scent with high efficiency.Therefore, efforts are being made to develop compositions that can overcome these challenges.

[0003] Pro-fragrance compounds can be useful for manufacturers of various processing compounds, such as consumer products, such as liquid fabric enhancers, detergents, or dryer sheets. A "pro-fragrance compound" is a compound that may or may not be odorous itself, but produces an odor characteristic of one or more of its released fragrance materials upon external stimuli (e.g., light, temperature, or moisture). Such compounds typically release fragrance materials (i.e., perfume raw materials) upon hydrolysis of chemical bonds, which can result in a desirable release profile, for example by delaying the release of fragrance materials and with combined odor characteristics that may not be easily obtained from unprocessed perfume oils alone.

[0004] Various silicon-based compounds are known in the art to be useful as pro-fragrance carriers, but typically present certain problems.For example, silicic acid esters are known to be used as base molecules for pro-fragrance materials.However, silicic acid ester bonds are often hydrolytically unstable, leading to premature fragrance release.Amino-modified silicones are also known to be useful as the backbone of pro-fragrance materials, but such materials may form imine bonds with perfume raw materials, thereby leading to color and / or physical instability. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, there remains a need for improved silicone-based pro-fragrance materials, as well as stable and effective treatment compositions and related methods employing them. [Means for solving the problem]

[0006] The present disclosure relates to pro-fragrance silicone polymers. The polymers include one or more heterocyclic moieties that include the residue of a perfume raw material. For example, the pro-fragrance silicone polymers can include a silicone backbone, an organic linker group that includes a carbon atom bonded to the silicon atom of the silicone backbone, and a heterocyclic moiety bonded to the organic linker group, where the heterocyclic moiety includes 5-7 ring members, the ring members including a first ring member that is a nitrogen atom, a second ring member that is a carbon atom, the second ring member being part of the residue of a perfume raw material ("PRM"), the PRM forming the residue includes the second ring member including a moiety selected from an aldehyde moiety, a ketone moiety, and combinations thereof, and a third ring member selected from the group consisting of an oxygen atom or a sulfur atom, preferably an oxygen atom, and the second ring member is directly bonded to the first ring member and the third ring member. The present disclosure also relates to related precursor silicone polymers that can form such pro-fragrance silicone polymers.

[0007] The present disclosure also relates to a treatment composition having a processing aid and a pro-fragrance silicone polymer.

[0008] The present disclosure also relates to premix compositions, where the premix may comprise (a) a pro-fragrance silicone polymer and optionally one or more free perfume raw materials, and / or (b) a precursor silicone polymer and a perfume raw material comprising a moiety selected from an aldehyde moiety, a ketone moiety, or a combination thereof, where the precursor silicone polymer and the perfume raw material are capable of condensing to form the pro-fragrance silicone polymer.

[0009] The present disclosure further relates to methods of making such treatment compositions and liquid premix compositions.

[0010] The present disclosure further relates to methods of treating surfaces or articles with such treatment compositions, as well as surfaces or articles comprising the pro-fragrance silicone polymers.

[0011] The present disclosure also relates to the use of such pro-fragrance silicone polymers as fragrance agents. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present disclosure relates to pro-fragrance silicone polymers and certain precursor silicone polymers, as well as related premixes, treatment compositions, and methods of making and using such materials and compositions.

[0013] The pro-fragrance silicone polymers of the present disclosure contain heterocyclic moieties, such as oxazolidines, that contain the residues of perfume raw materials. Such polymers can be formed by combining certain nitrogen-containing precursor silicone polymers with certain perfume raw materials, for example in a premix, and then treating an article or surface with a composition containing the combination.

[0014] Without wishing to be bound by theory, it is believed that the heterocyclic moieties formed when perfume raw materials are condensed with certain silicone precursors tend to provide improved color and chemical stability compared to pro-fragrance materials formed from known amino-modified silicones or silicic esters. For example, compared to imine bonds derived from such amino-modified silicones, the heterocyclic pro-fragrance materials described herein are less likely to form conjugated systems resulting in undesirable color changes. Furthermore, it is believed that the heterocyclic moieties (e.g., Si-CR') covalently attached to the silicone polymer provide improved chemical stability during storage compared to, for example, silicic ester bonds (e.g., Si-OR'), resulting in a longer release profile and more perfume release at later touch points. Furthermore, the high hydrophobicity of the precursor silicone polymer and the resulting pro-fragrance silicone may improve the association and / or deposition of PRMs. In addition, it is believed that the perfume release profile can be tailored by the manufacturer by adjusting the polymer size and / or the substituents on the ring of the heterocyclic moiety. In addition, the heterocyclic moieties of the present disclosure are believed to be relatively stable under acidic conditions, for example at a pH of about 2 to about 4, such as those typical of liquid fabric softeners / conditioners.

[0015] The materials, compositions, and methods are described in more detail below.

[0016] As used herein, the articles "a" and "an" when used in a claim are understood to mean one or more of what is claimed or described. As used herein, the terms "include", "includes" and "including" are meant to be open-ended. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0017] The terms "substantially free of" or "substantially free from" may be used herein. This means that the indicated material is in minimal amounts and has not been intentionally added to the composition to form part of the composition, or preferably is not present at analytically detectable levels. It means that the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material may be present, if at all, at a level of less than 1% by weight of the composition, or less than 0.1% by weight, or less than 0.01% by weight, or even 0% by weight.

[0018] As used herein, "consumer product" means a baby care, personal care, fabric and home care, family care, feminine care, health care, snack and / or beverage product or device that is intended to be used or consumed in the form in which it is sold and not subsequently commercially manufactured or modified. Such products include diapers, bibs, wipes; products and / or related methods for treating hair (human, canine, and / or feline) including for bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other products applied topically for consumer use; and shaving products, products and / or related methods for treating fabrics, hard surfaces, and any other surface in the fabric and home care field including air care, auto care, dishwashing, fabric conditioning, hair care ... (including softening), laundry detergents, laundry and rinse additives and / or care, hard surface cleaning and / or treatments, and other cleaning for consumer or commercial use); products and / or methods related to toilet paper, tissue, paper handkerchiefs, and / or paper towels; tampons, feminine napkins; products and / or methods related to oral care, including toothpaste, tooth gel, tooth rinse, denture adhesives, tooth whitening products; over-the-counter health care products, including, but not limited to, cough and cold medicines, pain relievers, RX meds, pet health and nutrition, and water purification products.

[0019] As used herein, the phrase "fabric care composition" includes compositions and formulations designed to treat fabric.Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric deodorising compositions, laundry pre-cleaning agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein.Such compositions can be used as laundry pre-treatment agents, laundry post-treatment agents, or can be added during the rinse or wash cycle of laundry operations.

[0020] As used herein, "fragrance premix composition," "premix composition," and "premix" are used interchangeably unless otherwise indicated.

[0021] As used herein, "amine content," "amine number," and "amine content value" are used interchangeably unless otherwise indicated and may be determined according to the methods provided in the Test Methods section. Weight percent nitrogen may be determined from the total amine number as provided in the Test Methods section.

[0022] As used in this disclosure, the term "polymer" includes homopolymers, i.e., homopolymers obtained by polymerization of one type of monomer with appropriate end caps, and copolymers, i.e., copolymers obtained by polymerization of two or more types of monomers. In the present invention, the term "polymer" is understood to include higher order oligomers (e.g., trimers, tetramers, etc.). Unless otherwise noted, all component or composition levels refer to the active portion of that component or composition and are exclusive of impurities, e.g., residual solvents or by-products, that may be present in commercial sources of such components or compositions.

[0023] All temperatures herein are in degrees Celsius (° C.) unless otherwise indicated. All measurements herein are made at 20° C. and atmospheric pressure unless otherwise stated.

[0024] In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless otherwise specified.

[0025] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitation were expressly written herein. Every minimum numerical limit given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification includes every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0026] Pro Fragrance Silicone Polymer The present disclosure relates to a pro-fragrance silicone polymer. Such a polymer is useful, for example, for delivering fragrance to a target surface. In particular, the pro-fragrance silicone polymer of the present disclosure comprises a heterocyclic moiety, where the heterocyclic moiety comprises a fragment of a perfume raw material. The heterocyclic moiety can be formed, for example, by a condensation reaction between an aldehyde- or ketone-containing perfume raw material and a portion of a silicone precursor that comprises an alkanolamine or thiolamine moiety. The perfume raw material is then released by hydrolysis.

[0027] It has been found that by associating silicone polymer precursors with perfume raw materials in the manner described herein, desirable benefits related to color stability, perfume deposition, and / or perfume release profile can be achieved.

[0028] The present disclosure relates to pro-fragrance silicone polymers comprising a silicone backbone, an organic linker group, and a heterocyclic moiety bonded to the organic linker group. The organic linker group comprises a carbon atom bonded to a silicon atom of the silicone backbone. As described in more detail below, the heterocyclic moiety comprises a residue of a perfume raw material.

[0029] The pro-fragrance silicone polymer comprises a silicone backbone. Typically, the silicone backbone is a siloxane backbone. By "backbone" is meant the silicone polymer that provides the scaffold to which the organic linker groups are attached. The silicone backbone is typically formed from a precursor silicone polymer, which is described in more detail below. The silicone backbone may be functionalized, for example, with X groups and Y or Z groups, as described in more detail below. The silicone backbone may be linear or branched.

[0030] It may be preferred that the organic linker group and the heterocyclic moiety together form a pendant group attached to the silicone backbone. The pendant group, specifically the terminal carbon atom of the linker group, may be attached to a silicon atom located at a terminal position of the silicone backbone. Such a silicon atom is referred to herein as a "terminal silicon atom". The pendant group, specifically the terminal carbon atom of the linker group, may be attached to a silicon atom located at a non-terminal position of the silicone backbone. Such a silicon atom is referred to herein as a "non-terminal silicon atom". It may be preferred that the pro-fragrance silicone polymer comprises one or more pendant groups attached to one or more non-terminal silicon atoms. Given that in many silicone polymers there are more non-terminal silicon atoms than terminal silicon atoms, this configuration may be preferred as it may allow for greater PRM loading opportunities. The pro-fragrance silicone polymer may have pendant groups attached to terminal silicon atoms and pendant groups attached to non-terminal silicon atoms. One pendant group may be attached to another pendant group.

[0031] The pendant group may comprise one or more residues, for example at least two residues, of a perfume raw material. At least one of these residues, for example the first PRM residue, is a heterocyclic moiety, for example part of the first heterocyclic moiety. The second PRM residue may be part of a second heterocyclic moiety on the same pendant group. The second PRM residue may be located on the same pendant group, but not part of the second heterocyclic moiety. For example, the second PRM residue may be attached to the pendant group by an imine bond. The second PRM residue may be attached to an organic linker group. The second PRM residue may be located at a relatively terminal position on the pendant group relative to the first PRM residue. In other words, the second PRM residue may be located at a distal position relative to both the first PRM residue and the silicone backbone.

[0032] The organic linker group and the heterocyclic moiety may be connected to two or more silicone backbones. The organic linker group and the heterocyclic moiety may effectively bridge two silicone polymer fragments. In an alternative configuration, the organic linker group and the heterocyclic moiety may linearly link two silicone polymer fragments, as shown by the following synthesis example 18.

[0033] The heterocyclic moiety preferably contains 5 to 7 ring members. It is understood that the heterocyclic moiety may contain additional atoms, for example as substituents. The 5 to 7 ring members are only the atoms that form the "ring" of the heterocyclic moiety.

[0034] Some of the ring members, i.e., the first, second, and third ring members, have a particular identity, for example, the ring members include the first ring member, which is a nitrogen atom.

[0035] The second ring member is a carbon atom. Furthermore, the second ring member (i.e., the carbon atom) is part of the residue of a perfume raw material ("PRM", or parent PRM), where the PRM from which the residue is formed comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof. More specifically, the carbon atom is a carbon of an aldehyde moiety or a ketone moiety of the parent PRM. The heterocyclic ring moiety is formed when a condensation reaction occurs between an amine-containing moiety (e.g., an alkanolamine or a thiolamine) of the silicone precursor polymer and the parent PRM. Such PRMs are discussed in more detail below. During the formation of the described heterocyclic ring, open-chain tautomers may exist, although in small amounts and only temporarily.

[0036] The third ring member is an oxygen atom or a sulfur atom, preferably an oxygen atom. It may be preferred that the third ring member is an oxygen atom, as it is believed to have a faster rate of PRM hydrolysis, higher PRM loading, improved viscosity profile, and improved stability.

[0037] The second ring member is bonded towards the first ring member. The second ring member is also bonded directly to the third ring member. When the third ring member is an oxygen atom, when the heterocyclic moiety has five ring members, and when the fourth and fifth ring members are carbon atoms, the heterocyclic moiety is an oxazolidine type structure. When the third ring member is a sulfur atom, when the heterocyclic moiety has five ring members, and when the fourth and fifth ring members are carbon atoms, the heterocyclic moiety is a thiazolidine type structure. When the third ring member is an oxygen atom, when the heterocyclic moiety has six ring members, and when the fourth, fifth and sixth ring members are carbon atoms, the heterocyclic moiety can be an oxazinane or oxazine type structure. When the third ring member is a sulfur atom, when the heterocyclic moiety has six ring members, and when the fourth, fifth and sixth ring members are carbon atoms, the heterocyclic moiety can be a thiazinane or thiazine type structure.

[0038] The general structure of an oxazolidine ring is shown below. The structure has five ring members, each labeled with a number (1-5). In the present disclosure, it is understood that such rings are substituted with at least a second ring member, which is a residue of a PRM, as described above. Furthermore, such ring members are directly or indirectly bonded to an organic linker group, which is ultimately bonded to a silicone backbone.

[0039] [ka]

[0040] The pro-fragrance silicone polymer of the present disclosure may comprise at least one radical selected from the group consisting of Formula I, Formula II, and mixtures thereof, where the radicals of Formula I and Formula II have the following structure: (Si)-XZ Formula I; (Si)-X-(ZX) n -(Si) Formula II; having wherein "(Si)-" represents a bond to a Si atom, each X group is an organic linker group and is an independently selected divalent organic moiety containing 2 to 24 chain atoms, the Z group contains a heterocyclic moiety, and the index n in formula II is 1 or 2, preferably 1.

[0041] The pro-fragrance silicone polymer may have at least one radical, preferably two or more radicals, from the group consisting of formula I, formula II, and mixtures thereof. In some cases, the pro-fragrance silicone polymer may have one radical according to formula I, formula II, or mixtures thereof. The molar ratio of radicals (e.g., -XZ groups) to silicon atoms in the pro-fragrance silicone polymer may be, on average, about 1:1 to about 1:500, or about 1:2 to about 1:100, or about 1:2 to about 1:50, or about 1:2 to about 1:20, or about 1:2 to about 1:15, or about 1:2 to about 1:12, or about 1:5 to about 1:12. Relatively more radicals may be preferred so that a single pro-fragrance silicone polymer has a higher loading capacity with respect to PRM and can therefore more efficiently deliver a higher degree of freshness benefit. However, if the ratio is too high, stability and / or crosslinking issues may arise.

[0042] Preferably, at least one radical of the pro-fragrance silicone polymer has the structure of formula I. Such radicals may correspond to the pendant groups described above and may be located on terminal silicon atoms, non-terminal silicon atoms, or combinations thereof. Radicals according to formula I may be preferred for commercial viability and controllable physical properties, both in viscosity and formulation.

[0043] The structure of formula II shows the linkage of two polymeric silicone moieties. Such a structure can effectively crosslink two pendant silicone polymer fragments in an intramolecular or intermolecular manner (e.g., one or more X moieties are bonded to a non-terminal silicon atom). Additionally or alternatively, such a structure can effectively link two silicone polymer fragments in a linear fashion (e.g., the X moieties at the ends of the radicals are bonded to terminal silicon atoms). In such cases, "-X-(ZX) nThe "-" moiety may be substantially the central block of the silicone backbone. In addition, a mixture of pendant or terminal silicone polymer fragments may be crosslinked in an intramolecular or intermolecular manner. Preferably, n is equal to 1 due to ease of synthesis resulting in consistent viscosity and formulation properties. Radicals according to formula II may be preferred for improved perfume delivery and color benefits.

[0044] As noted above, "(Si)-" represents a covalent bond to a silicon atom of the silicon polymer. As discussed in more detail above, the silicon atom to which the X moiety is attached can be a terminal silicon atom or a non-terminal silicon atom.

[0045] The carbon atom of the X moiety is bonded to a silicon atom of the backbone, for example, via a "(Si)-" bond. This is believed to be a more stable configuration than if the oxygen of the linker group was bonded to the silicon atom. Preferably, the X group is bonded to a non-terminal silicon atom.

[0046] Each X group may independently be a divalent organic moiety having a molecular weight of from about 14 to about 1000 Da, preferably from about 28 to about 495 Da, more preferably from about 42 to about 98 Da. Such molecular weights may be preferred for a variety of reasons, including being readily commercially and / or affordably priced, to maintain a relatively high perfume loading by weight percent, to improve reactivity with the PRM, to improve the physical properties of the polymer, and / or for stability within a product or treatment composition.

[0047] As described above, each X group is an organic linker group. Each X group is an independently selected divalent organic moiety containing 2 to 24 chain atoms. By "chain atoms" is meant the number of atoms directly between the silicon atom and the Z group, counted in a linear chain. Although, the X group may contain substitutions along the chain. However, these substitution atoms should not be counted when determining the number of chain atoms. The majority of the chain atoms may be carbon atoms, but heteroatoms, preferably oxygen, may be present in the chain.

[0048] Each X group may independently contain 2 to 24 chain atoms, preferably 2 to 12 chain atoms, more preferably 2 to 9 chain atoms, even more preferably 2 to 6 chain atoms, even more preferably 3 to 5 chain atoms. Even more preferably, at least one of the chain atoms may be an oxygen atom. The X group may contain one or more oxygen atoms, preferably one oxygen atom, such as an alkoxy or ether group. The oxygen atom may be at a non-terminal position of the X group. The X group may be a four-carbon ether group. Preferably, the X group is -CH2-CH2-CH2-O-CH2- * and preferably where an asterisk ( * ) is the end of the X group that is attached to the Z group.

[0049] The organic linker groups are independently C2 to C 32 Substituted or unsubstituted hydrocarbons, C2-C 32 Substituted or unsubstituted alkoxy, C6-C 32 Substituted or unsubstituted aryloxy, C2-C 32 Substituted or unsubstituted acetoxy, C2-C 32 Saturated or unsaturated carbonyl, C2-C 32 Substituted or unsubstituted alkylamines, C2-C 32 Substituted or unsubstituted hydroxy, C5-C 32 Substituted arenes, C2-C 32 Substituted or unsubstituted epoxides, C2-C 32 Substituted or unsubstituted episulfides, or C2-C 32 A member of the group consisting of substituted or unsubstituted aziridines; preferably independently C2-C 32 Substituted or unsubstituted hydrocarbons, or C2-C 32 substituted or unsubstituted alkoxy; more preferably, a member selected from the group consisting of C2-C 32 Substituted or unsubstituted alkoxy; most preferably C2-C 32 unsubstituted alkoxy.

[0050] The organic linker group may be substituted or unsubstituted. The organic linker group may be linear or branched, preferably linear. As mentioned above, the organic linker group may have 2 to 24 chain atoms. In such a case, if the organic linker group has, for example, more than 24 carbons, this indicates that the organic linker group is substituted and / or branched.

[0051] In the radicals according to formula I and / or formula II, the Z group contains a heterocyclic moiety. More specifically, each Z group is selected from the group consisting of R 1 , one or more monovalent substituents of J, or a combination thereof, from formula III, where formula III has the structure:

[0052] [ka] wherein G is selected from the group consisting of oxygen or sulfur; In the formula, the index m is 2 to 4, preferably m is 2 to 3, and more preferably m is 2; In the formula, R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 495 Da, more preferably R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 101 Da, and even more preferably R 1 is H, wherein each J is independently C(R 2 )2, -O-, and -N(R 2 )-, In the formula, each R 2 are independently selected from H and a monovalent moiety having a molecular weight between 14 and 990 Da, more preferably R 2 is selected from H and a monovalent moiety having a molecular weight between 14 and 186 Da, and even more preferably R 2 is H, but provided that the first unit and the second unit may optionally be combined together as a divalent substituent, where the first unit is a first R 2group, and the second unit is a second R 2 Group, R 1 Groups and R 1 The monovalent substituents of the group are preferably selected from the group consisting of fused rings, spiro rings, unsaturated substituents, ═N(R 1 ), ═O, and ═S; In the formula, -C(R 3 )(R 4 The R )-moiety is a residue of a perfume raw material, preferably a perfume raw material containing 3 to 34 carbon atoms, where the perfume raw material from which the residue is derived contains an aldehyde moiety, a ketone moiety, or a combination thereof, preferably 3 are independently selected from monovalent organic moieties, preferably R 4 is independently selected from the group consisting of hydrogen and monovalent organic moieties, and optionally, R 1 , R 1 A second moiety selected from the substituent of X, one or more monovalent substituents of J, or a combination thereof, is replaced with a second linkage to the X group, preferably thereby forming a second ring structure, and in the Synthetic Examples section below, Synthetic Example 15 provides an example of such a structure in which a second ring structure is formed.

[0053] As stated above, each Z group is derivable by the removal of a moiety from formula III. However, it is important to note that "derivable" in this context does not necessarily mean that the moiety is actually derived from a compound according to formula III. In fact, it is expected that Z moieties are rarely, if ever, derived from such compounds. Instead, Z moieties are typically derived from a condensation reaction between a PRM and an alkanolamine or thiolamine moiety of a silicone polymer precursor, resulting in a heterocyclic moiety. Presenting formula III as an independent compound is intended only to illustrate the general formula of the Z group, as well as the various ways in which the Z group can be attached to the X group, and the site of removal of the (hypothetical) moiety from formula III indicates where the Z group is attached to the X group, typically to the terminal portion of the X group.

[0054] In other words, one of the substituents of formula III or even formula IV can be the point of attachment of the Z group to the X group (i.e., a covalent bond). More specifically, R 1 groups, and / or any R 2 The group may be the point of attachment of Z to the X group. Even more specifically, R 1 , any R 2 or a mixture thereof, at least one and not more than two may be preferred as the point of attachment of Z to the X group.

[0055] As above, the second moiety, e.g., R 1 , R 1 A substituent selected from Z, one or more monovalent substituents of J, or a combination thereof may be removed and replaced with a second linkage or a bond to an X group. The X group may be part of the same radical as the Z group in question or a different radical. When the X group is part of the same radical, the second bond may result in a second ring structure (e.g., in addition to the heterocyclic moiety containing the PRM residue). In the Synthetic Examples section below, Synthetic Example 13 and Synthetic Example 18 provide examples of such structures.

[0056] As shown above, -C(R 3 )(R 4 -C(R)-moiety is a residue of a perfume raw material (PRM), the parent PRM comprising an aldehyde moiety, a ketone moiety, or a combination thereof. 3 )(R 4 The "C" in the -moiety represents a carbon in an aldehyde or ketone portion of the PRM, e.g., an aldehyde or ketone portion that was part of the condensation reaction that resulted in the heterocyclic moiety. Thus, a parent PRM can be of the formula R 3 -C(O)-R 4 It can be characterized by R 4 When R is a monovalent organic moiety, the parent PRM includes a ketone that is fused to become part of the heterocyclic moiety. 4 is hydrogen, the parent PRM comprises an aldehyde that is fused to become part of a heterocyclic moiety. Suitable perfume raw materials are described in more detail below.

[0057] As noted above, the index m in formula III may be 2 to 4, preferably m may be 2 to 3, more preferably m may be 2. The lower ranges are preferred as 5- and 6-membered rings, preferably 5-membered rings, are believed to be more stable.

[0058] As above, each J is independently C(R 2 )2, -O-, and -N(R 2 Each J may be selected from the group consisting of C(R 2 ) independently selected from 2.

[0059] Each Z is preferably R 1 , J, or a combination thereof from formula IV, where formula IV has the following structure:

[0060] [ka] having In the formula, G, R 1 , R 3 , and R 4 is as defined above, preferably G is oxygen and each J is independently C(R 2 )2, and R 2 is as above. In this case, the index m in formula III is 2, thereby forming a 5-membered ring. Optionally, R 1 , R 1 A second moiety selected from a substituent of X, one or more monovalent substituents of J, or a combination thereof, is replaced with a second linkage to the X group, preferably thereby forming a second ring structure, more preferably this second ring structure comprises a second PRM residue, where the second ring structure may be in a distal position relative to both the first PRM residue and the silicone backbone, or form a bicyclic structure with a heterocyclic moiety.

[0061] The Z group is preferably an R 1 -R 2 -R 3 -R 4 -R 5 -R 6 -R 7 -R 8 -R 9 -R 10 -R 11 -R 12 -R 13 -R 14 -R 15 -R 16 -R 17 -R 18 -R 19 -R 20 -R 21 -R 22 -R 23 -R 24 -R 25 -R 26 - 1 It may be inducible by removal of

[0062] The Z group may preferably be derivable by removal of one or more monovalent substituents of J from formula III or formula IV, and preferably J is -C(R 2 )2- and R 2 One or more of the groups are removed, which means that the Z group is the removed R 2 This means that the X group is attached to the position where the R 1 is preferably H.

[0063] Each Z group may be a monovalent or divalent heterocyclic moiety according to formula III, where formula III has the following structure:

[0064] [ka] having wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen, wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2, wherein R 1 is selected from H, a monovalent moiety having a molecular weight of 15 to 495 Da, or the attachment point of Z to the X group, preferably R 1 is H or the point of attachment of Z to the X group, where R 1 When present as a monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted C1-C 35 alkyl group, more preferably a monovalent moiety having a molecular weight of 15 to 101 Da, even more preferably a substituted or unsubstituted C1 to C8 alkyl, wherein each J is independently C(R 2 )2, -O-, -N(R 2 )-, where each R 2 is independently selected from H, a monovalent moiety having a molecular weight of 14 to 990 Da, or the attachment point of Z to the X group, where R 2When present as a monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted, saturated or unsaturated C1-C 70 Alkyl, more preferably a monovalent moiety having a molecular weight of 14 to 186 Da, even more preferably a substituted or unsubstituted, saturated or unsaturated C1-C 12 alkyl, preferably R 2 is H or the point of attachment of Z to the X group, provided that the first unit and the second unit can optionally be joined together, if possible, as a divalent substituent, where the first unit is a first R 2 group, and the second unit is a second R 2 Group, R 1 Groups and R 1 The monovalent substituents of the group are preferably selected from the group consisting of fused rings, spiro rings, unsaturated substituents, ═N(R 1 ), ═O, and ═S, wherein -C(R 3 )(R 4 The R )-moiety is a residue of a perfume raw material (PRM), preferably a PRM containing 3 to 34 carbon atoms, where the perfume raw material from which the residue is derived contains an aldehyde moiety, a ketone moiety, or a combination thereof, preferably 3 are independently selected from monovalent organic moieties, preferably R 4 are independently selected from the group consisting of hydrogen and monovalent organic moieties, with the proviso that R 1 , any R 2 At least one, and no more than two of, or a mixture thereof, are points of attachment of Z to the X group.

[0065] Each Z may preferably be a monovalent or divalent five-membered heterocyclic moiety according to formula IV, where formula IV has the following structure:

[0066] [ka] having In the formula, G, R 1 , R 3 , and R 4 is as defined above, preferably G is oxygen and each J is independently C(R 2)2, and R 2 is as stated above.

[0067] R 1 , any R 2 or a combination of two thereof may be preferred as the point of attachment of Z to the X group, preferably forming a second ring structure.

[0068] Each Z is a monovalent or divalent heterocyclic moiety, preferably a 5-membered heterocyclic moiety, according to formula III or formula IV, where at least one R 2 is the point of attachment of Z to the X group, preferably in formula R 1 is preferably H.

[0069] The pro-fragrance silicone polymers of the present disclosure have a structure according to Formula V, shown below: [R 5 R 6 R 7 SiO 1 / 2 ] (q+2r+2) [R 8 R 9 SiO 2 / 2 ] p [R 10 SiO 3 / 2 ] q [SiO 4 / 2 ] r Formula V and In the formula, q is an integer from 0 to 150, p is an integer from 0 to 1500, and r is an integer from 0 to 150, in which q+p+r is equal to an integer equal to or greater than 1, and in which R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 Each of the moieties is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to formula I, or a radical according to formula II; R 5 ~R 10 At least one of the moieties is a radical according to formula I or a radical according to formula II, preferably a radical according to formula I.

[0070] R5 , R 6 , or R 7 When either R is a radical according to Formula I or Formula II, the radical is attached to a terminal silicon atom. 8 , R 9 , or R 10 is a radical according to Formula I or Formula II, then the radical is attached to a non-terminal silicon atom.

[0071] As mentioned above, R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 Each of the moieties may be independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula I, or a radical according to Formula II. The monovalent organic moiety, if present, is independently selected from the group consisting of C1-C 32 Alkyl, C2-C 32 Alkenyl, C2-C 32 Alkynyl, C1-C 32 Substituted alkyl, C6-C 32 Aryl, C5-C 32 Substituted Aryl, C6-C 32 Alkylaryl, C6-C 32 Substituted alkylaryl, C1-C 32 Alkoxy, C5-C 32 Aryloxy, C2-C 32 Acetoxy, C1-C 32 Carbonyl, C1-C 32 Carboxamide, C1-C 32 Alkylamines, C1-C 32 Thiolamine or C1-C 32 It may be selected from alkanolamines.

[0072] fragrance raw materials Certain perfume raw materials may be combined with silicone polymer precursors to form, for example, the pro-fragrance silicone polymers of the present disclosure. As noted above, the pro-fragrance silicone polymers may include heterocyclic moieties, which include, inter alia, residues of perfume raw materials. This section further describes perfume raw materials (and associated residues thereof) suitable for incorporation into such pro-fragrance silicone polymers.

[0073] The term "perfume raw material" (or "PRM"), as used herein, refers to a compound having a molecular weight of at least about 100 g / mole and useful for imparting odor, fragrance, essence, or scent, alone or together with other perfume raw materials. Typical PRMs include, among others, alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes such as terpenes. Lists of common PRMs can be found in various reference sources, such as, for example, "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).

[0074] The perfume raw material that reacts with the silicone precursor may comprise a moiety selected from an aldehyde moiety, a ketone moiety, or a combination thereof. It is believed that the PRM having one or more of these moieties can be effectively combined with the silicone polymer precursor described herein to form a heterocyclic moiety. Moreover, such PRM combined with the silicone precursor may provide an effective release and / or longevity profile. This is particularly advantageous, considering that PRMs having such moieties are common and desirable when formulating consumer-relevant olfactory experiences. The preferred PRM may comprise an aldehyde moiety or a ketone moiety that is unsaturated at the α,β position.

[0075] As noted above, the pro-fragrance silicone polymer, specifically the heterocyclic moiety, may comprise the residue of a perfume raw material that comprises an aldehyde moiety. Perfume raw materials that comprise an aldehyde moiety are set forth below in Table A. The materials set forth in Table A are believed to be illustrative (but non-limiting) examples of PRMs suitable for use according to the present disclosure.

[0076] [Table 1-1]

[0077] [Table 1-2]

[0078] The perfume raw materials from which the PRM residue of the heterocyclic moiety is formed may be selected from the group consisting of aldehyde-containing PRMs in Table A above. The PRM from which the PRM residue of the heterocyclic moiety is formed may comprise an aldehyde moiety and may preferably be selected from the group consisting of methyl nonyl acetaldehyde, benzaldehyde, florarozone, isocyclocitral, triplal (ligustral), precyclemon B, lilial, decyl aldehyde, undecylenic aldehyde, cyclamen homoaldehyde, cyclamen aldehyde, dupical, oncidal, adoxal, melonal, calypson, anisaldehyde, heliotropin, cumin aldehyde, centenal, 3,6-dimethylcyclohex-3-ene-1-carbaldehyde, satin aldehyde, canthoxal, vanillin, ethyl vanillin, cinnamaldehyde, and mixtures thereof.

[0079] As noted above, the pro-fragrance silicone polymer, specifically the heterocyclic moiety, may comprise the residue of a perfume raw material that comprises a ketone moiety. Perfume raw materials that comprise a ketone moiety are shown below in Table B. The materials shown in Table B are believed to be illustrative (but non-limiting) examples of PRMs suitable for use according to the present disclosure.

[0080] [Table 2-1]

[0081] [Table 2-2]

[0082] The perfume raw materials from which the PRM residue of the heterocyclic moiety is formed may be selected from the group consisting of ketone-containing PRMs in Table B above. The PRM from which the PRM residue of the heterocyclic moiety is formed may contain a ketone moiety and may preferably be selected from the group consisting of nerolion; 4-(4-methoxyphenyl)butan-2-one; 1-naphthalen-2-ylethanone nectaryl; Trimofix O; Fluramone; Delta damascone; Beta damascone; Alpha damascone; Methyl ionone; 2-hexylcyclopent-2-en-1-one; Galabascone; and mixtures thereof.

[0083] The pro-fragrance silicone polymer of the present disclosure may be used in combination with other perfume raw materials, even PRMs that do not contain aldehyde or ketone moieties. Other perfume raw materials, such as those that do not contain aldehyde or ketone moieties, may also be mixed with the silicone precursor, since it is believed that hydrophobic silicone droplets may promote the deposition of certain PMRs even if no condensation reaction occurs. Additionally or alternatively, it is possible that the PRM in question may react with other parts of the silicone precursor, even if the reaction does not result in a heterocyclic moiety as described herein. Additionally or alternatively, the PRM may react with other compounds, such as low molecular weight amines, and then react with the silicone precursor. Material suppliers may even want to provide reacted and unreacted PRMs in the same silicone emulsion, for example, to save on packaging, transportation, or storage costs. Additionally or alternatively, other PRMs may be provided as untreated or free oils in the premix composition and / or treatment composition according to the present disclosure, for example, to provide a more rounded olfactory experience.

[0084] Other perfume raw materials are provided in Table C below. The materials provided in Table C are believed to be illustrative (but non-limiting) examples of PRMs suitable for use according to the present disclosure. For example, these "other" PRMs may be co-formulated with the pro-fragrance silicone polymers of the present disclosure, for example, by addition as untreated perfume or encapsulated perfume. The pro-fragrance silicone polymers may further react / condense with one or more other perfumes, even if no heterocyclic moieties are formed during the process.

[0085] [Table 3-1]

[0086] [Table 3-2]

[0087] [Table 3-3]

[0088] [Table 3-4]

[0089] [Table 3-5]

[0090] The perfume raw materials herein, including those listed above, can be obtained from suppliers including International Flavors and Fragrances, New York, NY USA; Givaudan, Vernier Switzerland; Firmenich, Geneva, Switzerland; Symrise, Holzminden, Germany; Kao, Tokyo, Japan; Takasago, Tokyo, Japan; and Florasynth, Tel-Aviv, Israel.

[0091] Precursor Silicone Polymer The present disclosure also relates to certain silicone polymers that can serve as precursors of the pro-fragrance silicone polymers according to the present disclosure, for example. These precursor silicone polymers can be reacted with perfume raw materials, for example by condensation reaction, to form the pro-fragrance silicone polymers of the present disclosure. Thus, these precursors are stand-alone polymers that can act as raw material polymers or reactants that can be useful to form the pro-fragrance silicone polymers described herein.

[0092] Typically, the precursor silicone polymer has one or more moieties containing alkanolamine and / or thiolamine moieties that can be reacted with certain aldehyde or ketone-containing PRMs to form the heterocyclic moieties described herein. The one or more moieties containing alkanolamine and / or thiolamine moieties may be attached to the silicone polymer backbone via an organic linker group.

[0093] The precursor silicone polymer may include at least one radical selected from the group consisting of Formula VI, Formula VII, and mixtures thereof, where the radicals of Formula VI and Formula VII have the following structure: (Si)-XY Formula VI; (Si)-X-(YX) n -(Si) Formula VII; and In the formula, "(Si)-" is a bond to a silicon atom, for example, a silicon atom of a silicone backbone; In the formula, the index n is 1 to 2, preferably 1; wherein each X group is an organic linker group, an independently selected divalent organic group containing 2 to 24 chain atoms, including a carbon atom bonded to a silicon atom of the silicone backbone (i.e., each X group is covalently bonded to “(Si)” via a Si—C bond); and wherein each Y group is independently a monovalent or divalent moiety comprising a nitrogen atom and a second atom, where the second atom is selected from the group consisting of oxygen atoms and sulfur atoms, and where the nitrogen atom is separated from two atoms by a second atom, three atoms, or four atoms.

[0094] Suitable organic linkers / X groups are described in more detail above with respect to the pro-fragrance silicone polymer. The above related disclosures are substantially equally applicable to the precursor silicone polymer. For example, the carbon atom of the X moiety is bonded to the silicon atom of the backbone, for example, via a "(Si)-" bond. It is believed that the configuration is more stable than when the oxygen of the linker group is bonded to the silicon atom. Preferably, the X group is bonded to a non-terminal silicon atom.

[0095] In the radicals according to Formula VI and / or Formula VII, the Y group comprises an alkanolamine and / or a thiolamine moiety. The Y group may be selected such that it is capable of forming a Z group when reacted with an aldehyde- or ketone-containing perfume raw material, as described above.

[0096] For example, the Y group can be R 1 , J, or a combination thereof, from formula VIII, where formula VIII has the following structure:

[0097] [ka] having wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen; In the formula, the index m is 2 to 4, preferably m is 2 to 3, and more preferably m is 2; In the formula, R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 495 Da, more preferably R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 101 Da, and even more preferably R 1is H, where each J is independently C(R 2 )2, -O-, and -N(R 2 )-, wherein each R 2 are independently selected from H and a monovalent moiety having a molecular weight between 14 and 990 Da, more preferably R 2 is selected from H and a monovalent moiety having a molecular weight between 14 and 186 Da, and even more preferably R 2 is H, but provided that the first unit and the second unit may optionally be combined together as a divalent substituent, where the first unit is a first R 2 group, and the second unit is a second R 2 Group, R 1 Groups and R 1 The monovalent substituents of the group are preferably selected from the group consisting of fused rings, spiro rings, unsaturated substituents, ═N(R 2 ), -C(O)-, and -C(S)-, and optionally R 1 , R 1 A second moiety selected from a substituent of X, one or more monovalent substituents of J, or a combination thereof, is replaced with a second linkage to the X group, preferably thereby forming a ring structure.

[0098] In other words, each Y can be independently a monovalent or divalent moiety according to formula VIII, which has the following structure:

[0099] [ka] having wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen, wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2, wherein R 1 is selected from H, a monovalent moiety having a molecular weight between 15 and 500 Da, or the attachment point of Y to the X group, preferably R 1 is H or the point of attachment of Y to the X group, where R, when present as a monovalent moiety, is preferably a substituted or unsubstituted C-C35 an alkyl group, more preferably a monovalent moiety having a molecular weight of 15 to 101 Da, even more preferably a substituted or unsubstituted C1 to C 8 alkyl, preferably R is H, where each J is independently C(R 2 )2, -O-, -N(R 2 )-, where each R 2 is independently selected from the group consisting of H, a monovalent moiety having a molecular weight of 14 to 990 Da, or the attachment point of Y to the X group, where R 2 When present as a monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted, saturated or unsaturated C1-C 70 Alkyl, more preferably a monovalent moiety having a molecular weight of 14 to 186 Da, even more preferably a substituted or unsubstituted, saturated or unsaturated C1-C 12 alkyl, preferably each R 2 is H, provided that the first unit and the second unit may optionally be joined together, if possible, as a divalent substituent, where the first unit is a first R 2 group, and the second unit is a second R 2 Group, R 1 Groups and R 1 The monovalent substituents of the group are preferably selected from the group consisting of fused rings, spiro rings, unsaturated substituents, ═N(R 2 ), ═O, and ═S, where R 1 , any R 2 At least one, and no more than two of, or a combination thereof, are points of attachment of Y to the X group.

[0100] G is oxygen and Y is R 1 It may be preferred that m is not 2 or 3, since if it is derivable from the removal of m, then such compounds are believed to be novel and useful in making the pre-mix and pro-fragrance silicone compounds described herein.

[0101] As with the discussion of the Z group above, the term "derivable" in this context does not necessarily mean that the moiety is actually derived from the compound of formula VIII. Similarly, the (hypothetical) "removal" site indicates where the Y moiety is attached to the X moiety.

[0102] Any of the precursor silicone polymers described above are believed to be suitable for use in forming the pro-fragrance silicone polymers of the present disclosure, or in any of the related processes, premixes, or treatment compositions described herein. However, for purposes of patentability of the precursor silicone polymer itself, when G is an oxygen atom, preferably the Y group is R 1 When derivable from removal of a group (e.g., the Y group is R 1 In some cases it may be preferred that m is not 2 or 3, where the group is connected to the X group via the nitrogen group of formula VIII as shown.

[0103] The precursor silicone polymer of the present disclosure has a structure according to Formula IX, shown below: [R 5 R 6 R 7 SiO 1 / 2 ] (q+2r+2) [R 8 R 9 SiO 2 / 2 ] p [R 10 SiO 3 / 2 ] q [SiO 4 / 2 ] r Formula IX and In the formula, q is an integer from 0 to 150, p is an integer from 0 to 1500, and r is an integer from 0 to 150, in which q+p+r is equal to an integer equal to or greater than 1, and in which R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 Each of the moieties is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula VI, or a radical according to Formula VII; R 5 ~R10 At least one of the moieties is a radical according to formula VI or a radical according to formula VII, preferably a radical according to formula VI.

[0104] The precursor silicone polymer may be characterized by a weight average molecular weight of about 450 Da to about 200,000 Da, and / or the pro-fragrance silicone polymer may have a molecular weight of about 0.004 (Pa * s)~100(Pa * The silicone polymer may be characterized by a viscosity falling within the range of 0.1 to 1.5 wt. s. Methods for determining the weight average molecular weight and viscosity of the silicone polymer are provided in the Test Methods section below. Such molecular weights and / or viscosities may be preferred as they are believed to provide improved surface deposition, formulation stability, and compatibility with perfume raw materials.

[0105] The precursor silicone polymer comprises nitrogen atoms. The precursor silicone polymer may be characterized by a total amine content of about 0.05 to about 2.2, preferably about 0.071 to about 2.14, or about 0.071 to about 1.78, or about 0.71 to about 1.43, or about 0.14 to about 1.07, or about 0.14 to about 0.71, or about 0.21 to about 0.71, or about 0.36 to about 0.71. The precursor silicone polymer may be characterized by a nitrogen content, reported as weight percent of functional group equivalent, of about 0.1% to about 3%, or about 0.1% to about 2%, or about 0.2% to about 1.5%, or about 0.2% to about 1.0%, or about 0.3% to about 0.8%, or about 0.3% to about 0.75%. The weight percent of amine content and functional group equivalent can be determined according to the methods provided in the Test Methods section. Too low a nitrogen concentration may result in insufficient PRM loading, whereas too high a nitrogen concentration may lead to increased water solubility and / or reduced performance.

[0106] Precursor silicone polymers can be obtained from the combination of appropriately functionalized homopolymer, copolymer, or higher oligomeric silicones with appropriate corresponding small molecule additives (e.g., amines, oxiranes, alkanolamines, thiiranes, etc.), with or without co-solvent catalysts (alcohols, diols, acids, bases), with or without external stimuli (e.g., pressure, heat, mechanical agitation), with or without catalysts, and with or without purification.

[0107] In the present disclosure, the silicone polymer precursors may be obtained from the polymerization of individual silane compounds to arrive at a silicone polymer described in formula IX of appropriate composition and functionality.

[0108] Methods for making pro-fragrance silicone polymers and related premixes - Patents.com The present disclosure also relates to methods of making the pro-fragrance silicone polymers and associated premixes according to the present disclosure.

[0109] The present disclosure relates to a method of making a pro-fragrance silicone polymer, which may include combining a precursor silicone polymer as described above with a suitable perfume raw material, i.e., one that contains an aldehyde moiety, a ketone moiety, or a combination thereof.

[0110] The combining step may occur at any suitable time, for example in a premix, in a base composition, or on a surface or article, such as a fabric article, which may even involve removal of water (e.g., via a drying process).

[0111] The precursor silicone polymer and one or more perfume raw materials can be combined in the treatment composition, for example, by adding each as a separate input to the base composition.

[0112] The precursor silicone polymer and perfume raw materials may be combined in a liquid premix composition. Accordingly, the present disclosure relates to such liquid premix compositions and methods of making such liquid premix compositions.

[0113] The liquid premix compositions of the present disclosure (also referred to herein as "premix compositions" or simply "premixes" or "premix") may be useful components of treatment compositions and may help improve perfume delivery and performance of these compositions compared to products in which such premixes are not used. Furthermore, it is believed that combining ingredients in a premix provides more efficient perfume delivery and performance in treatments compared to adding the ingredients separately (e.g., not as a premix) to consumer products, especially aqueous consumer products. In addition, the premix compositions may be conveniently prepared in advance and stored and / or transported between locations as desired, or may be prepared by a third party prior to incorporation into the treatment composition.

[0114] The present disclosure relates to a method for making a premix composition, preferably the premix composition described herein. The method includes the steps of providing a precursor silicone polymer, which may comprise one or more radicals according to formula VI, formula VII, or a mixture thereof, as described in more detail above, and combining the precursor silicone polymer with a perfume raw material comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof.As described in more detail below, the precursor silicone polymer may be combined with an emulsifier, preferably a non-ionic surfactant, to form an oil-in-water emulsion, to which a PRM may be added.

[0115] The liquid premix composition comprises (a) a pro-fragrance silicone polymer as described herein, for example, a pro-fragrance silicone polymer comprising at least one radical selected from the group consisting of Formula I, Formula II, and mixtures thereof, as described in more detail above, and optionally further comprising one or more free perfume raw materials; or (b) a precursor silicone polymer, which may comprise one or more radicals according to Formula VI, Formula VII, or combinations thereof, as described in more detail above, and a perfume raw material comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof, wherein the precursor silicone polymer and the perfume raw material can condense to form the pro-fragrance silicone polymer; or (c) a mixture thereof, may include.

[0116] The liquid premix composition may include a precursor silicone polymer present at a concentration of about 1% to about 99%, preferably about 80% to about 10%, or about 75% to about 20%, or about 60% to 40% by weight of the liquid premix composition, and a perfume raw material present at a concentration of about 1% to about 50%, preferably about 5% to about 50%, or about 5% to about 30%, or about 5% to about 20%, or about 5% to about 15%, or about 5% to about 10% by weight of the liquid premix composition. The PRM may be present at about 10% to about 40%, or about 15% to about 30%, or about 15% to about 25% by weight of the liquid premix composition. Any amount of emulsifier may be present at a concentration of about 0% to about 10%, preferably about 1% to about 5%, or about 2% to 4%. The weight ratio of the precursor silicone polymer to the perfume raw material can be from about 99:1 to about 1:1, preferably from about 50:1 to about 2:1, and more preferably from about 10:1 to about 5:1. The preferred amounts and / or ratios are desirable to achieve convenient and efficient payload delivery.

[0117] The premix composition is typically a liquid. The liquid premix composition may be characterized by a viscosity, measured for example at 0.1 rad / s and 25° C., of about 10 to about 10,000 Pa·s, preferably about 10 to about 5,000 Pa·s, preferably about 10 to about 1,000 Pa·s, preferably about 10 to about 500 Pa·s, preferably about 20 to about 400 Pa·s, more preferably about 25 to about 300 Pa·s, and even more preferably about 100 to about 300 Pa·s. For processing reasons, it may be desirable to obtain a liquid premix composition with a target viscosity, especially since premixes with very high viscosities may be difficult to formulate into products.

[0118] Liquid premix compositions may be substantially free of water. Premix compositions may contain less than 10% by weight, or less than 5% by weight, or less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or even 0% by weight of the premix composition. Such low-water premixes may be desirable, for example, when the premix is ​​formulated into a low-water consumer product, such as a solid composition (especially if water-soluble) or a composition encapsulated by a water-soluble film. In such cases, silicone polymer may be the fluid that is the majority of the premix.

[0119] The fragrance premix composition may include water. The fragrance premix composition may include about 1% to about 90% by weight of the composition, or about 1% to about 75% by weight, or about 1% to about 60% by weight, or about 1% to about 50% by weight, or about 5% to about 50% by weight, or about 5% to about 25% by weight, or about 5% to about 15% by weight, or about 5% to about 10% by weight of water. The fragrance premix composition may include about 10% to about 50% by weight of the composition, or about 25% to about 50% by weight of water. The presence of water can promote the formation of droplets, and in view of the relatively hydrophobic nature of silicone polymers, this can promote more convenient dispersion of the premix in treatment compositions, especially aqueous ones.

[0120] The liquid premix composition may be in the form of an emulsion. The emulsion may preferably be an oil-in-water emulsion. The emulsion may preferably include a plurality of droplets, including droplets characterized by a volume weighted average particle size of about 100 nm to about 100 μm, more preferably 1 μm to 10 μm, and even more preferably 1 μm to 5 μm. Without wishing to be bound by theory, it is believed that droplets of a certain minimum size are desirable for deposition efficiency on a target surface, while droplets exceeding a certain size may cause performance and / or stability issues, such as spotting on the target surface.

[0121] The liquid premix composition may include one or more emulsifiers. As used herein, "emulsifier" and "emulsion agent" are used interchangeably. Selecting an appropriate emulsifier can facilitate the formation of droplets of a desired size and / or stable incorporation of the premix into the final product. The emulsifier may also be selected so as not to have an undesirable effect on the viscosity of the emulsion, for example, by increasing the viscosity to an undesirable level.

[0122] The emulsifier may be present in a concentration of about 0.5% to about 40%, preferably about 1% to about 30%, more preferably about 1% to about 20%, more preferably about 2% to about 20%, more preferably about 2% to about 10% by weight of the liquid premix composition. The emulsifier may be present in an amount of about 1% to about 10% by weight, more preferably 1% to about 5% by weight of the liquid premix composition. The weight ratio of the precursor silicone polymer to the emulsifier may be about 99:1 to about 1:1, preferably about 50:1 to about 2:1, more preferably about 15:1 to about 5:1. The liquid premix composition may contain about 20% to about 40% by weight of water and about 1% to about 5% by weight of the liquid premix composition.

[0123] The one or more emulsifiers may include a non-ionic surfactant. Suitable non-ionic surfactants may include alkoxylated fatty alcohols. The non-ionic surfactant may be represented by the formula R(OC2H4) nOH ethoxylated alcohols and ethoxylated alkylphenols, where R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkylphenyl radicals in which the alkyl group contains from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.

[0124] The one or more emulsifiers may comprise linear emulsifiers, branched emulsifiers, or mixtures thereof, preferably linear nonionic surfactants, branched nonionic surfactants, or mixtures thereof. In particular, linear emulsifiers may be useful for emulsifying perfume raw materials, and branched emulsifiers may be useful for emulsifying silicone polymers, in particular amino-modified silicone polymers.

[0125] The one or more emulsifiers may be substantially hydrophobic. The one or more emulsifiers may be characterized by an HLB value of about 5 to about 20, or about 8 to about 16. The HLB value of the nonionic surfactants may be determined according to the method provided below.

[0126] The liquid premix compositions of the present disclosure may further comprise as an additional ingredient an amino-functional material which is believed to be capable of associating with the perfume raw materials, and possibly the silicone materials described herein, to facilitate perfume deposition and release when used as part of a treatment composition.

[0127] The liquid premix composition may comprise from about 1% to about 20%, or from about 2% to about 15%, or from about 3% to about 12%, or from about 4% to about 10%, or from about 5% to about 10% amino-functional material by weight of the fragrance premix composition.

[0128] The amino-functional material may be characterized by a relatively low molecular weight. For mass efficiency reasons (e.g., favorable / high ratio of amine groups to molecular weight), a relatively low molecular weight may be preferred. For example, the amino-functional material may be characterized by a molecular weight of about 17 to about 1000 daltons, more preferably about 30 to about 1000 daltons, about 40 to about 1000 daltons, preferably about 50 to 800 daltons, more preferably about 60 to about 600 daltons, and even more preferably about 60 to about 500 daltons.

[0129] The amino-functional material may contain one, two or three amine moieties per molecule, preferably one or two amine moieties. The amine moieties may be selected from the group consisting of primary amine moieties, secondary amine moieties, or combinations thereof. It is believed that primary and / or secondary amine moieties may better associate with PRMs compared to tertiary and / or quaternary amine moieties. Furthermore, two or even three amine moieties may provide improved association / loading in combination with perfume raw materials compared to compounds with only one amine group. However, as described in more detail below, it may be desirable to limit the number of amine groups.

[0130] It is believed that certain amino-functional materials are likely to perform better than others in the compositions of the present disclosure due to the type and / or structure of their amine moieties. For example, the amino-functional materials may be characterized by one of the following: (a) containing a total of one primary amine moiety and no secondary amine moiety, or (b) containing a total of two primary amine moieties and no secondary amine moiety, or (c) containing one primary amine moiety and one secondary amine moiety, preferably the primary amine moiety and the secondary amine moiety are separated by two carbon atoms, or (d) containing one primary amine moiety or one secondary amine moiety separated by two carbon atoms from the hydroxyl group.

[0131] The amino-functional materials include linear aliphatic amino-functional materials such as octylamine, nonylamine, and / or decylamine; branched aliphatic amino-functional materials such as 2-ethylhexylamine, branched tridecylamine, t-butylamine, 2-(diethylamino)ethylamine, neopentanediamine (2,2-dimethylpropane-1,3-diamine), 3-methoxyethylamine, trimethyl-1,6-hexanediamine, 2-aminoheptane, and / or 2-butyloctylamine; alicyclic amines including methylcyclohexanediamines such as 2-methylcyclohexane-1,3-diamine and / or 4-methylcyclohexane-1,3-diamine; trialkoxy(aminoethylaminopropyl)silanes. , amino-functional silanes such as alkyldialkoxy(aminoethylaminopropyl)silanes, dialkylalkoxy(aminoethylaminopropyl)silanes, trialkoxy(aminopropyl)silanes, alkyldialkoxy(aminopropyl)silanes, and / or dialkylalkoxy(aminopropyl)silanes; aminoalcohols such as 2-(butylamino)ethanol, 1-(cyclohexylamino)2-propanol, 1-(dodecyloxy)-3-[(2-hydroxyethyl)amino]-2-propanol, and / or 3-(dodecylamino)-1,2-propanediol; 1,3-bis(3-aminopropyl)tetramethyldisiloxane; or mixtures thereof.

[0132] The amino-functional material may be substantially free of aromatic amines (e.g., amino-functional moieties directly attached to aromatic rings), or even substantially free of aromatic moieties altogether, since such moieties may tend to increase the solubility of the amino-functional material and thus reduce the likelihood of association with the hydrophobic silicone.

[0133] Liquid premix composition can be made according to any suitable process.For example, the present disclosure provides a process for making premix composition such as those described herein, which includes (preferably in this order) providing silicone polymer precursor, adding amino-functional material if present, and adding perfume raw material, each being provided in the above relative amount.Mixing can be provided throughout or intermittently.The resulting mixture can be mixed with sufficient mixing energy to combine the materials.

[0134] If it is desired that the fragrance premix composition be in the form of an emulsion, the process may include (preferably in this order) providing a silicone polymer precursor, adding an amino-functional material, if present, adding an emulsifier, adding water, and adding a perfume raw material, each provided in the relative amounts described above. Mixing may be provided throughout or intermittently. The resulting mixture may be mixed with sufficient mixing energy to combine and emulsify the materials, for example to form droplets as described above.

[0135] The process may include (preferably in that order) providing a silicone polymer precursor, adding an emulsifier, adding water, if present, adding an amino-functional material, and adding a perfume raw material, each provided in the relative amounts described above. Mixing may be provided throughout or intermittently. The resulting mixture may be mixed with sufficient mixing energy to combine and emulsify the materials, for example to form droplets as described above.

[0136] Certain components may be premixed, for example, the silicone polymer precursor and emulsifier, and / or the fragrance material and emulsifier. The emulsifier for each ingredient may be the same or different.

[0137] Treatment Composition The present disclosure also relates to treatment compositions comprising the pro-fragrance silicone polymers as described above, and methods of making and using such treatment compositions. The treatment compositions may further comprise processing aids.

[0138] The treatment composition can be a consumer product composition. The consumer product composition can be useful for treating surfaces, such as fabric, hair, or skin, for example, to freshen and / or condition the surface. Suitable consumer product compositions are described above. Preferred consumer product compositions can include baby care compositions, personal care compositions, fabric care compositions, home care compositions, family care compositions, and / or feminine care compositions, preferably fabric care compositions and / or home care compositions, more preferably fabric care compositions.

[0139] The treatment composition may include a liquid premix composition according to the present disclosure, for example in the form of an emulsion, and a processing aid. The treatment composition may be made by providing a premix composition according to the present disclosure and combining the premix with a processing aid. The processing aid may be part of the base composition.

[0140] The treatment composition may comprise a pro-fragrance silicone polymer according to the present disclosure in a concentration of from about 0.01% to about 99.9% by weight of the treatment composition, preferably from about 0.01% to about 50% by weight, more preferably from about 0.01% to about 25% by weight, more preferably from about 0.1% to about 10% by weight, more preferably from about 0.1% to about 5% by weight, more preferably from about 0.2% to about 5% by weight of the treatment composition. The concentration may be determined by the intended end use and form of the treatment composition.

[0141] The treatment compositions described herein may comprise from about 0.1% to about 20%, or from about 0.1% to about 15%, or from about 0.1% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 3% by weight of the treatment composition of a liquid premix composition according to the present disclosure.

[0142] The treatment composition may include one or more of the following ingredients at one or more of the following levels, where the ingredients are provided by a liquid premix and the weight percentages are by weight of the treatment composition: from about 0.1% to about 20% of a silicone polymer, and / or from about 0% to about 10% of an amino-functional material (if present), and / or from about 0.05% to about 20% of one or more perfume ingredients.

[0143] The present disclosure also provides a treatment composition comprising a treatment aid and a plurality of droplets, the droplets comprising the silicone polymer precursor described above, optionally the amino-functional material described above, optionally the emulsifier described above, and the perfume raw material described above, where the components are present in the droplets in the relative amounts described above. Additionally or alternatively, the droplets may comprise a pro-fragrance silicone polymer according to the present disclosure. The droplets may be present in the treatment composition as a result of combining a liquid premix composition described herein with a treatment aid. The plurality of droplets may be characterized as having a volume weighted average diameter of about 1 micrometer to about 10 micrometers, preferably about 1 micrometer to about 5 micrometers.

[0144] The treatment composition according to the present disclosure may be in the form of a liquid composition, a granular composition, a single compartment pouch, a multi-compartment pouch, a dissolving sheet, a particulate form in which the individual particles have a mass of from about 1 mg to about 1 gram (such as a pastille or bead, which may preferably be water soluble), a fibrous article, a tablet, a bar, a flake, a nonwoven sheet, or a mixture thereof.

[0145] The treatment composition of the present disclosure may be a household care composition, preferably a household care composition selected from the group consisting of fabric and home care products, beauty care products, or mixtures thereof.

[0146] When the treatment composition is a fabric and home care product, the fabric and home care product may preferably be selected from a laundry detergent composition, a fabric conditioning composition, a fabric pretreatment composition, a fabric refresher composition, or a mixture thereof. The fabric conditioning composition may preferably be a liquid fabric conditioning composition.

[0147] When the treatment composition is a beauty care product, the beauty care product may preferably be selected from a hair treatment product, a skin care product, a shaving care product, a personal cleansing product, a deodorant and / or an antiperspirant, or a mixture thereof. Preferably, the hair treatment composition may be a shampoo, a conditioner, or a combination thereof.

[0148] The treatment composition may include, in addition to the fragrance premix composition and / or droplets, a processing aid. The processing aid may be any adjunct ingredient in any amount suitable for the intended product and / or intended end use of the product. The treatment composition may be made by a process that includes combining the fragrance premix composition with the processing aid.

[0149] The processing aid may be part of a base composition that is combined with a liquid premix composition. For example, the present disclosure relates to a method of making a processing composition that includes combining a premix composition with a base composition, the base composition including a processing aid. The premix composition may be added to the base composition. The processing aid may be added to the base composition before and / or after the premix composition is added to the base composition. As used herein, a "base composition" is understood to be an intermediate composition to which other ingredients can be added to form a finished or final processing composition.

[0150] The processing aids may be useful as performance aids, stability or processing aids, or both. For example, the processing aids may be selected from amines, surfactant systems, water binding agents, sulfites, fatty acids and / or their salts, enzymes, encapsulated benefit agents, soil release polymers, hueing agents, builders, chelating agents, dye transfer inhibitors, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersants, soil removal / anti-redeposition agents, polymeric dispersants, polymeric grease cleaners, brighteners, suds suppressors, dyes, hueing agents, free fragrances, structural elastifiers, conditioning agents or softeners, carriers, fillers, hydrotropes, organic solvents, antimicrobials and / or preservatives, neutralizing agents and / or pH adjusters, processing aids, fillers, rheology modifiers or structurants, opacifiers, pearlescent agents, pigments, corrosion and / or colorfastness agents, malodor agents, and mixtures thereof. Those skilled in the art are generally familiar with these adjuvants, some of which are described in more detail below.

[0151] The treatment composition may include a surfactant. The surfactant may be useful, for example, to provide cleaning benefits. The composition may include a surfactant system, which may contain one or more surfactants.

[0152] The compositions of the present disclosure may comprise from about 1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50% of the surfactant system by weight of the composition. Liquid compositions may comprise from about 5% to about 40% of the surfactant system by weight of the composition. Compositions suitable for dense formulations, e.g., dense, liquid, gel, and / or unit dose forms, may comprise from about 25% to about 70%, or from about 30% to about 50% of the surfactant system by weight of the composition.

[0153] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include nonionic surfactants such as linear alkyl benzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactants may be derived, at least in part, from natural sources, such as natural feedstock alcohols.

[0154] Suitable anionic surfactants may include any conventional anionic surfactant. This may include, for example, sulfate detergent surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid detergent surfactants, such as alkyl benzene sulfonates. The anionic surfactant may be linear, branched, or a combination thereof. Preferred surfactants include linear alkyl benzene sulfonate (LAS), alkyl ethoxylated sulfate (AES), alkyl sulfate (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkyl benzene sulfonate (MLAS), methyl ester sulfonate (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylate (AEC). The anionic surfactant may be present in acid form, salt form, or mixtures thereof. The anionic surfactants may be partially or totally neutralized, for example, with an alkali metal (eg, sodium) or an amine (eg, monoethanolamine).

[0155] The surfactant system may include a nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(oxyalkylated) alcohol surfactants, and mixtures thereof. The alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof. The nonionic surfactants may be linear, branched (e.g., mid-chain branched), or combinations thereof. Particular nonionic surfactants may include alcohols having an average of about 12 to about 16 carbons and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactants.

[0156] Suitable zwitterionic surfactants include betaines, C8-C9 alkyl dimethyl betaines, including alkyl dimethyl betaines and cocodimethylamidopropyl betaines. 18 (For example, C 12 ~C 18 ) amine oxides (e.g., C 12 ~ 14 dimethylamine oxide), and / or N-alkyl-N,N-dimethylamino-1-propanesulfonate (wherein the alkyl group is C8 to C 18 Or C 10 ~C 14 The zwitterionic surfactant may include any conventional zwitterionic surfactant, such as sulfo and hydroxybetaines, such as (which may be

[0157] Depending on the formulation and / or intended end use, the composition may be substantially free of certain surfactants. For example, a liquid fabric enhancing composition, such as a fabric softener, may be substantially free of anionic surfactants, since such surfactants may negatively interact with cationic components.

[0158] The treatment composition may include a conditioning active. Compositions containing conditioning actives may provide benefits related to softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color, and / or appearance.

[0159] The conditioning active may be present at a level of about 1% to about 99% by weight of the composition, or about 1% to about 35% by weight, or about 1% to about 20% by weight, or about 1% to about 15% by weight, or about 1% to about 10% by weight, or about 1% to about 6% by weight. The composition may comprise from about 1% by weight, or from about 2% by weight, or from about 3% by weight, to about 99% by weight, or to about 75% by weight, or to about 50% by weight, or to about 40% by weight, or to about 35% by weight, or to about 30% by weight, or to about 25% by weight, or to about 20% by weight, or to about 15% by weight, or to about 10% by weight of the composition. The composition may comprise from about 5% to about 30% by weight of the composition of conditioning active.

[0160] Suitable conditioning actives for the compositions of the present disclosure can include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty esters, sucrose esters, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof, preferably at least quaternary ammonium ester compounds; such materials are also known to be relatively environmentally friendly while providing useful conditioning benefits.

[0161] The composition may contain a quaternary ammonium ester compound, a silicone, or a combination of a plurality of pairs thereof, preferably a combination of a plurality of pairs thereof. The total amount of the quaternary ammonium ester compound and the silicone may be about 5% by weight to about 70% by weight, or about 6% by weight to about 50% by weight, or about 7% by weight to about 40% by weight, or about 10% by weight to about 30% by weight, or about 15% by weight to about 25% by weight of the composition. The composition may contain the quaternary ammonium ester compound and the silicone in a weight ratio of about 1:10 to about 10:1, or about 1:5 to about 5:1, or about 1:3 to about 1:3, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.

[0162] The composition may contain a mixture of different types of conditioning actives. The composition of the present disclosure may contain a particular conditioning active but may be substantially free of other conditioning actives. For example, the composition may be free of quaternary ammonium ester compounds, silicones, or both. The composition may include quaternary ammonium ester compounds but may be substantially free of silicones. The composition may include silicones but may be substantially free of quaternary ammonium ester compounds.

[0163] The compositions of the present disclosure may include rheology modifiers and / or structurants. Rheology modifiers may be used to "thicken" or "thin" the liquid composition to a desired viscosity. Structurants may be used to promote phase stability and / or to suspend or inhibit aggregation of particle or droplet aggregates in the liquid composition, such as droplets of the emulsions described herein. Suitable rheology modifiers and / or structurants may include non-polymeric crystalline hydroxyl functional structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulose fibers (e.g., microfibrillated cellulose, which may be derived from bacterial, fungal, or plant sources, including wood), diamide gelling agents, or combinations thereof.

[0164] The treatment composition made by the method described herein may include free perfume. In order to provide a broader and more diverse scent profile, it may be desirable to include in the free perfume of the treatment composition perfume raw materials that are not present in the pro-fragrance silicone, and / or vice versa. For example, if the pro-fragrance silicone polymer includes one or more perfume raw materials that include an aldehyde moiety, the free perfume of the treatment composition may include one or more fragment or residue perfume raw materials that do not include an aldehyde moiety. Similarly, if the pro-fragrance silicone polymer includes one or more perfume raw materials that include a ketone moiety, the free perfume of the treatment composition may include one or more fragment or residue perfume raw materials that do not include a ketone moiety. The free perfume may include perfume raw materials that include an aldehyde moiety, perfume raw materials that do not include an aldehyde moiety, perfume raw materials that include a ketone moiety, perfume raw materials that do not include a ketone moiety, or mixtures thereof.

[0165] The treatment composition may include a carrier material. The carrier material may be selected from the group consisting of water, silica, zeolite, carbonate, polyvinyl alcohol, polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxoalkylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, sodium sulfate, starch, and mixtures thereof. The carrier material may be selected based on the desired final form of the consumer product, for example, for liquid products, water may be used as a carrier, while for powder or particulate products, carbonate or polyethylene glycol (PEG) may be used.

[0166] The base composition may be in the form of a liquid. The base composition may contain water. The base composition may contain water in an amount of about 1% to about 99% by weight, preferably about 5% to about 98% by weight, or about 10% to about 95% by weight, or about 50% to about 95% by weight, or about 60% to about 95% by weight, or about 75% to about 95% by weight of the base composition.

[0167] The treatment composition may be in liquid form. The treatment composition may include water. The treatment composition may include about 1% to about 99% by weight of the treatment composition, preferably about 5% to about 98% by weight, or about 10% to about 95% by weight, or about 50% to about 95% by weight, or about 60% to about 95% by weight, or about 75% to about 95% by weight. Certain unit dose formulations may have a relatively small amount of water so as not to dissolve the water-soluble film, for example, the composition may include about 20% or less, or about 15% or less, or about 12% or less, or about 10% or less by weight of the composition. The fragrance premix of the present disclosure may be particularly useful in liquid compositions that include a relatively large amount of water, since it is believed that the hydrophobicity of the silicone allows the silicone, amino-functional material, emulsifier, and fragrance material to partition out of the water and associate with the high water matrix.

[0168] The liquid treatment composition may have a viscosity of about 20 cps to about 1000 cps (about 20-1000 mPa·s), preferably about 25 cps to about 500 cps (about 25-500 mPa·s), and more preferably about 50 cps to about 300 cps (about 50 mPa·s to about 300 mPa·s). Viscosity is determined using a Brookfield viscometer, No. 2 spindle, at 60 RPM / s and about 22°C.

[0169] The treatment composition may be in particulate form, such as a plurality of microparticles. Each individual microparticle may have a mass of about 1 mg to about 1 g. The emulsion may be dispersed in a water-soluble carrier. The water-soluble carrier may be selected from the group consisting of polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxoalkylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, sodium sulfate, starch, and mixtures thereof. The water-soluble carrier may be a water-soluble polymer. When the treatment composition is in particulate form, it may comprise about 25% to about 99.99% by weight of a water-soluble carrier, and about 0.01% to about 50% by weight of a silicone premix. The particulate form may be in the form of beads or pastilles.

[0170] The treatment composition may be characterized by a pH level of from about 2 to about 12, or from about 2 to about 8.5, or from about 2 to about 7, or from about 2 to about 5, preferably from about 2 to about 4, preferably from about 2 to about 3.7, more preferably from about 2 to about 3.5, where the pH is determined by dissolving / dispersing the treatment composition in deionized water to form a 10% concentration solution at about 20° C.

[0171] Method of Making a Treatment Composition The present disclosure relates to a process for making any of the treatment compositions described herein.

[0172] The method may include providing a base composition, the base composition including a processing aid, and combining the base composition with one or more of the following: (a) a pro-fragrance silicone polymer as described herein, such as one comprising one or more radicals according to Formula I, Formula II, or a mixture thereof; (b) a precursor silicone polymer as described herein, such as one comprising one or more radicals according to Formula VI, Formula VII, or a combination thereof, and a perfume raw material comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof, preferably wherein the precursor silicone polymer and the perfume raw material are provided as a liquid premix composition, preferably in emulsion form; and / or (c) a mixture thereof. The above compositions may optionally be combined with an amino-functional compound.

[0173] The precursor silicone polymer and the perfume raw material may be provided to the base composition preferably as a premix composition, preferably as a liquid premix composition, more preferably as a liquid premix in emulsion form.The precursor silicone polymer and the perfume raw material may be provided to the base composition preferably as separate additions.The separate additions may be performed simultaneously or sequentially.When performed sequentially, the precursor silicone polymer, which may preferably be emulsified, is preferably added before the addition of the perfume raw material.The mixture may be mixed to homogenize the resulting composition.

[0174] The processing composition of the present disclosure can be formulated in any suitable form and can be dispensed by any process selected by the formulator. The materials may be combined in a batch process, a circulation loop process, and / or an in-line mixing process. Suitable equipment for use in the processes disclosed herein can include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, high shear mixers, static mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, where available, in continuous process configurations), spray dryers, and extruders.

[0175] Methods of using the treatment composition The present disclosure also relates to a method of treating a surface, comprising contacting the surface with the treatment composition described herein, optionally in the presence of water. Preferably, the surface is fabric, hair, or skin, more preferably fabric, even more preferably clothing.

[0176] The process of the present disclosure may include diluting the composition with water to form a treatment liquid that can be contacted with the surface to be treated. The composition may be diluted 100 to 1000 times with water, or 200 to 900 times, or 300 to 800 times.

[0177] The contacting step may occur in the drum of an automatic washing machine. The contacting step may occur as part of a wash cycle or immediately prior to a wash cycle, e.g., the consumer product may be a detergent composition or may be added substantially simultaneously with the detergent composition. The contacting step may occur as part of a rinse cycle that may occur following a wash cycle, e.g., the consumer product may be a fabric enhancer product, such as a liquid fabric enhancer product, and may contact the surface subsequent to the surface being treated with the detergent product.

[0178] The contacting step may be carried out, for example, as a pretreatment step prior to a wash cycle.

[0179] use The present disclosure relates to the use of the pro-fragrance silicone polymer according to the present disclosure as a fragrance.The pro-fragrance silicone polymer can be used as a surface, preferably fabric, fragrance.For such use, the pro-fragrance silicone polymer can be optionally incorporated into a treatment composition, as described in more detail above.

[0180] Articles and / or Surfaces The present disclosure relates to an article, preferably a fabric article, comprising a surface, wherein the surface comprises a pro-fragrance silicone polymer according to the present disclosure. The present disclosure also relates to an article, preferably a fabric article or dryer sheet, or an absorbent article (such as a diaper or incontinence product), treated with a treatment composition according to the present disclosure, preferably according to the treatment method described herein.

[0181] The present disclosure also relates to surfaces, such as hard surfaces, comprising the pro-fragrance silicone polymer according to the present disclosure. The present disclosure also relates to surfaces, preferably hard surfaces, treated with a treatment composition according to the present disclosure, preferably according to the treatment methods described herein.

[0182] combination Specifically contemplated combinations of the present disclosure are described herein in the alphabetical sections below, and are intended to be exemplary in nature and not limiting.

[0183] A. A treatment composition comprising a processing adjunct and a pro-fragrance silicone polymer, the pro-fragrance silicone polymer comprising a silicone backbone, an organic linker group comprising a carbon atom bonded to a silicon atom of the silicone backbone, and a heterocyclic moiety bonded to the organic linker group, the heterocyclic moiety comprising 5-7 ring members, the ring members comprising a first ring member which is a nitrogen atom and a second ring member which is a carbon atom, the second ring member being part of a residue of a perfume raw material ("PRM"), the PRM forming the residue comprising the second ring member comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof, and a third ring member selected from the group consisting of an oxygen atom or a sulfur atom, preferably an oxygen atom, the second ring member being directly bonded to the first ring member and the third ring member.

[0184] B. The pro-fragrance silicone polymer comprises at least one radical selected from the group consisting of Formula I, Formula II, and mixtures thereof, wherein the radicals of Formula I and Formula II have the following structure: (Si)-XZ Formula I (Si)-X-(ZX) n -(Si) Formula II having The treating composition of paragraph A, wherein "(Si)-" represents a bond to a Si atom, each X group is an organic linker group and is an independently selected divalent organic moiety containing 2 to 24 chain atoms, the Z group comprises a heterocyclic moiety, and the index n is 1 or 2, preferably 1.

[0185] C. The treatment composition of any one of paragraphs A or B, wherein at least one radical has the structure of formula I.

[0186] D. The PRM from which the residue is formed contains an aldehyde moiety, preferably the PRM is: methylnonylacetaldehyde; benzaldehyde; floralozone; isocyclocitral; tripral (ligustral); precylcemone B B); lilial; decyl aldehyde; undecylenic aldehyde; cyclamen homoaldehyde; cyclamen aldehyde; dupical; oncidal; adoxal; melonal; calypsone; anisaldehyde; heliotropin; cumin aldehyde; scentenal; 3,6-dimethylcyclohex-3-ene-1-carbaldehyde; satinaldehyde; canthoxal; vanillin, ethyl vanillin, cinnamaldehyde; and mixtures thereof, the treatment composition of any one of paragraphs A-C.

[0187] E. The treatment composition of any of paragraphs A-D, wherein the PRM from which the residue is formed comprises a ketone moiety, preferably the PRM is selected from the group consisting of: nerolione; 4-(4-methoxyphenyl)butan-2-one; 1-naphthalen-2-ylethanone; nectaryl; trimofix O; fleuramone; delta damascone; beta damascone; alpha damascone; methyl ionone; 2-hexylcyclopent-2-en-1-one; galbascone; and mixtures thereof.

[0188] F. The treatment composition of any one of paragraphs A through E, wherein each X group can independently be a divalent organic group having a molecular weight from about 14 to about 1000 Da, preferably from about 28 to about 495 Da, and more preferably from about 42 to about 98 Da.

[0189] G. The treatment composition of any one of paragraphs A-F, wherein each X group independently contains 2 to 12 chain atoms, preferably 2 to 12 chain atoms, more preferably 2 to 9 chain atoms, more preferably 2 to 6 chain atoms, even more preferably at least one of the chain atoms is an oxygen atom, even more preferably the X group is a four-carbon ether group, and most preferably the X group is -CH2-CH2-CH2-O-CH2-.

[0190] H. The treatment composition of any of paragraphs A through G, wherein the X group is bonded to a non-terminal silicon atom.

[0191] I. Each Z group is R 1 a monovalent or divalent heterocyclic moiety derivable from formula III by removal of a moiety selected from the group consisting of one or more monovalent substituents of J, J, or a combination thereof, wherein formula III has the following structure:

[0192] [ka] having wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen, wherein the index m is 2 to 4, preferably m is 2 to 3, more preferably m is 2, and wherein R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 495 Da, more preferably R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 101 Da, and even more preferably R 1 is H, where each J is independently C(R 2 )2, -O-, and -N(R 2 )-, wherein each R 2 are independently selected from H, a monovalent moiety having a molecular weight between 14 and 990 Da, more preferably R 2 is selected from H, a monovalent moiety having a molecular weight between 14 and 186 Da, and even more preferably R 2is H, provided that the first unit and the second unit may optionally be joined together, if possible, as a divalent substituent, where the first unit is a first R 2 group, and the second unit is a second R 2 Group, R 1 Groups and R 1 The monovalent substituents of the group are preferably selected from the group consisting of fused rings, spiro rings, unsaturated substituents, ═N(R 1 ), -C(O)-, and -C(S)-, wherein -C(R 3 )(R 4 and wherein the R )-moiety is a residue of a perfume raw material (PRM), preferably a PRM containing 3 to 34 carbon atoms, wherein the perfume raw material from which the residue is derived contains an aldehyde moiety, a ketone moiety, or a combination thereof, preferably 3 is independently selected from monovalent organic moieties, preferably R 4 , hydrogen, and a monovalent organic moiety; and optionally, R 1 The treating composition of any of paragraphs A-H, wherein a second moiety selected from the group consisting of one or more monovalent substituents of J, or a combination thereof, is replaced with a second linkage to the X group, preferably forming a second ring structure.

[0193] J. Each Z group is R 1 a monovalent or divalent five-membered heterocyclic moiety derivable from formula IV by removal of a moiety selected from one or more monovalent substituents of J, J, or a combination thereof, wherein formula IV has the following structure:

[0194] [ka] having In the formula, G, R 1 , R 3 , and R 4 is as defined above, preferably wherein G is oxygen, and wherein each J is independently C(R 2 )2, wherein R 2 is as above, and optionally, in which R 1, one or more monovalent substituents of J, or a combination thereof is replaced with a second linkage to the X group, preferably forming a second ring structure.

[0195] K. each is a monovalent or divalent heterocyclic moiety, preferably a 5-membered heterocyclic moiety, derivable from formula III or formula IV by removal of a moiety selected from one or more monovalent substituents of J, preferably R 1 The treatment composition of any one of paragraphs I or J, wherein

[0196] L. The pro-fragrance silicone polymer has the following structure: [R 5 R 6 R 7 SiO 1 / 2 ] (q+2r+2) [R 8 R 9 SiO 2 / 2 ] p [R 10 SiO 3 / 2 ] q [SiO 4 / 2 ] r Formula V having In the formula, q is an integer from 0 to 150, p is an integer from 0 to 1500, and r is an integer from 0 to 150, in which q+p+r is equal to an integer of 1 or more, and R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 Each of the moieties is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula I, or a radical according to Formula II; R 5 ~R 10 The treatment composition of any of paragraphs A-K, wherein at least one of the moieties is a radical according to formula I or a radical according to formula II, preferably a radical according to formula I.

[0197] M. The treatment composition of any one of paragraphs A-L, wherein the pro-fragrance silicone polymer is present in a concentration of from about 0.01% to about 99.9% by weight of the treatment composition, preferably from about 0.01% to about 50% by weight, more preferably from about 0.01% to about 25% by weight, more preferably from about 0.1% to about 10% by weight, more preferably from about 0.1% to about 5% by weight, more preferably from about 1% to about 5% by weight, based on the weight of the treatment composition.

[0198] N. The processing aid is an amine, a surfactant system, a water binding agent, a sulfite, a fatty acid and / or its salt, an enzyme, an encapsulated benefit agent, a soil release polymer, a color toner, a builder, a chelating agent, a dye transfer inhibitor, a dispersant, an enzyme stabilizer, a catalytic material, a bleaching agent, a bleach catalyst, a bleach activator, a polymeric dispersant, a soil removal / anti-redeposition agent, a polymeric dispersant, a polymeric grease cleaner, a whitening agent, a foam suppressor, a dye, a free fragrance, a structural elastomer, a conditioning agent or softener, a carrier, a filler, a hydrotrope, an organic solvent, an odor control agent, an antimicrobial agent and / or a preservative, a neutralizing agent and / or a pH adjuster, a processing aid, a filler, a rheology modifier or structurant, an opacifier, a peroxide, a fluoride ... The treatment composition of any one of paragraphs A-M, wherein the treatment aid is selected from the group consisting of a lubricant, a pigment, an anti-corrosion and / or anti-discoloration agent, and mixtures thereof, preferably the treatment aid comprises a surfactant system, a conditioning agent or softener, or mixtures thereof, more preferably the surfactant system, if present, comprises an anionic surfactant, a nonionic surfactant, a cationic surfactant, and / or a zwitterionic surfactant, and / or more preferably the conditioning agent or softener, if present, comprises a quaternary ammonium compound, a silicone compound, or both.

[0199] O. The treatment composition of any one of paragraphs A-N, wherein the treatment composition is characterized by a pH level of from about 2 to about 12, preferably from about 2 to about 8.5, more preferably from about 2 to about 7, more preferably from about 2 to about 5, more preferably from about 2 to about 4, and even more preferably from about 2 to about 3.5, wherein the pH is determined by dissolving / dispersing the treatment composition in deionized water to form a 10% concentration solution at about 20°C.

[0200] P. The treatment composition of any one of paragraphs A-O, wherein the treatment composition further comprises water, preferably from about 1% to about 99%, preferably from about 5% to about 98%, or from about 10% to about 95%, or from about 50% to about 95%, or from about 60% to about 95%, or from about 75% to about 95% by weight of the treatment composition.

[0201] Q. The treatment composition of any of paragraphs A-P, wherein the treatment composition is in the form of a liquid composition, a granular composition, a single compartment pouch, a multi-compartment pouch, a dissolvable sheet, a particulate form wherein the individual particles have a mass of from about 1 mg to about 1 gram, a fibrous article, a tablet, a bar, a flake, a nonwoven sheet, or a mixture thereof, preferably in the form of a liquid composition and in the form of a particulate form wherein the individual particles have a mass of from about 1 mg to about 1 gram, or a mixture thereof.

[0202] R. The treatment composition is a liquid, preferably 1 to 1500 centipoise (1 to 1500 mPa * s), 100-1000 centipoise (100-1000mPa * s), or 200-500 centipoise (200-500mPa * s) viscosity for 20 seconds -1 and the treatment composition of any of paragraphs A-Q is in the form of a liquid having a temperature of 21° C.

[0203] S. A liquid premix composition comprising: (a) a pro-fragrance silicone polymer described in any one of paragraphs A-L, optionally further comprising one or more free perfume raw materials; or (b) a precursor silicone polymer, and a perfume raw material comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof, wherein the precursor silicone polymer and the perfume raw material are capable of condensing to form the pro-fragrance silicone polymer described in any one of paragraphs A-L; or (c) a mixture thereof.

[0204] T. The liquid premix composition of paragraph S, wherein the liquid premix composition further comprises from about 1% to about 90%, or from about 1% to about 75%, or from about 1% to about 60%, or from about 1% to about 50%, or from about 5% to about 50%, or from about 5% to about 25%, or from about 5% to about 15%, or from about 5% to about 10% water, by weight of the composition.

[0205] U. The liquid premix composition of any one of paragraphs S or T, wherein the liquid premix composition is in the form of an oil-in-water emulsion, preferably comprising droplets characterized by a volume weighted average particle size of from about 100 nm to about 100 μm, more preferably from 1 μm to 10 μm, and even more preferably from 1 μm to 5 μm.

[0206] V. The liquid premix composition of any one of paragraphs S to U, wherein the precursor silicone polymer is present in a concentration of about 1% to about 99% by weight, preferably about 80% to about 10% by weight, or about 75% to about 20% by weight, or about 60% to 40% by weight of the liquid premix composition, and the fragrance raw material is present in a concentration of about 1% to 50% by weight, preferably about 5% to about 50% by weight, or about 5% to about 40% by weight, or about 5% to about 30% by weight, or about 5% to about 20% by weight, or about 5% to about 15% by weight, or about 5% to about 10% by weight of the liquid premix composition, and preferably the weight ratio of the precursor silicone polymer to the fragrance raw material is about 99:1 to about 1:1, preferably about 50:1 to about 2:1, and more preferably about 10:1 to about 5:1.

[0207] W. The liquid premix composition of any of paragraphs S-V, wherein the liquid premix composition further comprises an emulsifier, preferably an emulsifier selected from a linear nonionic surfactant, or a branched nonionic surfactant, or a mixture thereof, more preferably an emulsifier present in an amount from about 1% to about 10% by weight of the liquid premix composition.

[0208] X. The pro-fragrance silicone polymer comprises at least one radical selected from the group consisting of Formula VI, Formula VII, and mixtures thereof, wherein the radicals of Formula VI and Formula VII have the following structure: (Si)-XY Formula VI; (Si)-X-(YX) n -(Si) Formula VII; having wherein "(Si)-" is a bond to a Si atom, wherein the index n is 1 to 2, preferably 1, wherein each X group is an independently selected divalent organic group covalently bonded to "(Si)" through a Si-C bond and containing 2 to 24 chain atoms, wherein each Y is independently selected from the group consisting of R 1 a monovalent or divalent moiety derivable by removal of a moiety selected from one or more monovalent substituents from J, or a combination thereof from formula VIII, which has the following structure:

[0209] [ka] having wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen, wherein the index m is 2 to 4, preferably m is 2 to 3, more preferably m is 2, and wherein R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 500 Da, more preferably R 1 is selected from H or a monovalent moiety having a molecular weight between 15 and 101 Da, and even more preferably R 1 is H, where each J is independently C(R 2 )2, -O-, -N(R 2 )-, wherein each R 2 is independently selected from the group consisting of H, and a monovalent moiety having a molecular weight of 14 to 990 Da, more preferably each R 2 is independently selected from the group consisting of H, and a monovalent moiety having a molecular weight between 14 and 186 Da, and even more preferably each R 2 is H, provided that, where possible, the first unit and the second unit may be taken together optionally as a divalent substituent, where the first unit is a first R 2 group, and the second unit is a second R 2 Group, R 1 Groups and R 1 Monovalent substituents of the group, preferably the divalent substituents are selected from the group consisting of fused rings, spiro rings, unsaturated substituents, ═N(R 1 ), -C(O)-, and -C(S)-, and optionally R 1 The liquid premix composition of any of paragraphs S-W, wherein a second moiety selected from one or more monovalent substituents of J, or combinations thereof, is replaced with a second linkage to the X group, preferably forming a second ring structure.

[0210] Y. The precursor silicone polymer has a viscosity of 0.004 (Pa * s)~100(Pa *The liquid premix composition of any of paragraphs S-X, characterized by at least one of: (a) a viscosity ranging from about 450 Da to about 200,000 Da; and / or (b) a weight average molecular weight ranging from about 450 Da to about 200,000 Da.

[0211] Z. The liquid premix composition of any one of paragraphs S through Y, wherein the liquid premix composition further comprises an amino-functional material, or the amino-functional material is characterized by a molecular weight of from about 40 to about 1000 daltons, more preferably from about 50 to 800 daltons, even more preferably from about 60 to about 600 daltons, and even more preferably from about 60 to about 500 daltons.

[0212] AA. A method of making a treatment composition, the method comprising the steps of providing a base composition, the base composition comprising a processing aid, and combining the base composition with one or more of the following: a) a pro-fragrance silicone polymer described in any one of paragraphs A-L; b) a precursor silicone polymer described in any one of paragraphs S-Z, and a perfume raw material comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof, preferably wherein the precursor silicone polymer and the perfume raw material are provided together as a liquid premix composition, preferably in the form of an emulsion; or (c) a mixture thereof.

[0213] BB. A method of treating a surface or article comprising contacting the surface or article with a treatment composition of any one of paragraphs A-R, optionally in the presence of water.

[0214] CC. An article, preferably a fabric article, comprising a surface, the surface comprising a pro-fragrance silicone polymer of any one of paragraphs A-L.

[0215] DD. The pro-fragrance silicone of any one of paragraphs A-L.

[0216] EE. Use of the pro-fragrance silicone polymer described in paragraph DD as a fragrance, optionally on a surface, preferably on a fabric, optionally incorporated in a treatment composition, which may be a treatment composition described in any one of claims A-R.

[0217] FF. Preferably, G is oxygen and Y is R 1 The precursor silicone polymer of any one of claims S-Z, wherein m is not 2 or 3 when derivable from the removal of

[0218] Test Method Preparation of Pro-Fragrance Silicone Polymer Premix Emulsion The pro-fragrance silicone polymer premix emulsion can be prepared as follows.

[0219] Starting with 60.0 parts by weight of the siloxane precursor compound, add Surfonic L24-9 (2.0 parts by weight; ex. Huntsman Holland BV) and Tergitol™ 15-S-40 (2.5 parts; ex. The Dow Chemical Company). The mixture is mixed for 1 minute with an IKA RW 20 at 800 rpm. Water (35.5 parts total) is added separately in two portions, and after each water addition the mixture is mixed with the IKA RW 20 for approximately 10-15 minutes.

[0220] Perfume raw materials, added in molar equivalents approximately equal to the molar amount of radicals present according to formula VI and / or VII in the precursor silicone polymer, are added to the emulsion and stirred for 15 minutes on an IKA RW 20 at 275 rpm.

[0221] As a specific example, 93.5 parts by weight of the silicone fluid disclosed in Synthesis Example 1 below, emulsified as described above, is combined with 6.5 parts of a perfume raw material (eg, cinnamaldehyde).

[0222] Preparation of test fabric enhancer / softener compositions To the 7.5 wt% N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride in water mixture, add the Profragrance Silicone Polymer Premix Emulsion (or untreated perfume oil) in an amount such that the concentration of perfume raw material or perfume raw material fragments in the fabric softener is about 0.3 wt% after fabric softener preparation. The mixture is stirred for 5 minutes at 350 rpm using an IKA RW 20 D Sl mixer, model RW20DS1, and an IKA Rl 342 impeller blade. The structurant and deposition aid are added and the mixture is stirred for 10 minutes. Water is added as necessary to standardize the concentration of N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride between the test legs to 7.3 wt% and the mixture is stirred for 5 minutes. If necessary, the pH is adjusted to 2-3 with HCl.

[0223] Preparation of test pastille compositions Add 6.12% of the Pro-Fragrance Silicone Premix Emulsion of Synthesis Example 6 to the 93.88% by weight molten PEG-8000 material in the Speedmixer cup. Quickly place the Speedmixer cup into a Flacktek DA150.FVZ-K Speedmixer at 3,500 rpm for 1 minute. Sample pastilles were immediately made from the mixture by pouring into a blue siliconized rubber mold that had been pre-equilibrated to 4°C and opened with a 10-inch plastic taping knife. The pastilles were cooled at room temperature for approximately 30 minutes, and then the pastilles were removed from the mold and stored under ambient conditions.

[0224] How to prepare the fabric To prepare fabric for headspace analysis testing, fabric samples (100% cotton terry cloth, item number ITL 1022-15PGP, Calderon Textiles, Inc. 6131 W. 80tA St., Indianapolis, Ind. 46278, desized and conditioned with three wash cycles of detergent and fabric softener) are run through a clothes mini washer, a full scale machine, and a clothes dryer with the fabric softener formulation in a manner consistent with North American consumers. Prior to headspace GCMS analysis, the fabrics are equilibrated at 21.1°C and 50% relative humidity for 24 hours (see method below). Ballast loads consist of swatches of cotton and polycotton knits approximately 20 x 20 inches (50 x 50 cm) in size.

[0225] Cleaning treatment conditions In the following pastilles composition performance tests, fabrics are treated with the following wash process conditions: A North America Kenmore 600 series top-loading washing machine is used. Each machine is set to run a normal single cycle with a 12 minute wash agitation period and one 3 minute rinse. The water used has a hardness of 137 ppm and is at 30.6°C for each wash and 15.5°C for the rinse. The volume of water in each step is 64 liters. The total fabric load weight is 3.6 kg (which included 32 test fabric hand towel terry cloths, 9 100% cotton ballasts, and approximately 5 50 / 50 polycotton ballasts). The detergent used is unscented liquid TIDE Original Scent (manufactured by The Procter & Gamble Company). While the wash water is being filled, 81 g of detergent is added to the wash water. After the detergent is added, 25 g of the pastilles to be evaluated are also added, followed by the fabrics. After the water load is complete, the machine is allowed to soak for a period. This is followed by a wash agitation (normal setting), and a rinse step (with the corresponding spin cycle). After the wash process is complete, the fabric is removed. The test fabric is machine dried for 50 minutes in a Kenmore dryer at Cotton / High setting. The test fabric is then equilibrated for 24 hours in a controlled room at 21.1°C / 50% relative humidity.

[0226] In the following fabric strengthener / softener composition performance test, fabrics are treated with the following wash process conditions: Wash: 12 minutes agitation, 30.6°C. Rinse: 2 minutes agitation, 15.5°C. Water hardness: 137 ppm. Water: 7.6 pH. Fabric load weight: 290 g. Tumble dry setting: High 50 minutes, cotton. Detergent dosage: 9.65 g. Fabric softener dosage: 5.71 g.

[0227] Fabric Headspace Analysis The following procedure determines the level of perfume ingredients in the headspace on the fabric.

[0228] Gas chromatograph 7890B with mass selective detector (5977B) (MSD) and ChemStation quantitation package, Gerstel multipurpose sampler with solid phase microextraction (SPME) probe or similar system, divinylbenzene / carboxene / polydimethylsiloxane SPME fiber (or similar fiber) from Supleco part #57298-U, nominal diameter 30 mm x 0.25 mm, film thickness 0.25 m, J&W 122-5532UI DB-5, 20 mL headspace vials.

[0229] To prepare the fabric for analysis, cut three 2.54 cm x 5.08 cm cotton swatches from the cotton terry prepared and treated as described above. Place each piece into a 20 mL headspace vial and cap.

[0230] The parameters of the Gerstel autosampler are as follows: SPME-derived from incubator, incubation temperature: 65 °C., incubation time: 10.00 min. Sample parameters, vial penetration volume: 22.00 mm, extraction time: 5. 00 min, initial penetration volume: 54.00 mm, desorption time: 300 s. The parameters of the GC oven are as follows: for front SS inlet He, mode - splitless, heater: 270 °C., GC runtime: 14.28 min. For oven, initial temperature: 40 °C., hold time: 0.5 min, heating program: speed 17 °C / min, temperature 270 °C, hold time 0.25 min. The MSD parameters are as follows: run in scan mode with a minimum range of 35-350 m / z.

[0231] A calibration curve is prepared from standard fragrance materials. In the ChemStation software (or similar quantitative software), the calibration curve for each fragrance ingredient is used to calculate the headspace mass.

[0232] Color change of the composition A premix (e.g., a premix emulsion) or treatment composition can be tested for a color change according to the following procedure. * , a * , and b * Reflectance spectra and color measurements, including those shown in Table 1, were made using a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, VA; D65 light source, 10 degree observer, UV excluded). * , a * , and b * Values ​​are measured at time t=0 and 14 days after mixing in the PRM. The total color change (ΔE) of the premix emulsion or treatment composition is calculated based on the data collected at each time point t using the following formula: ΔE t =[(L * cL * s) 2 +(a * ca * s) 2 +(b *cb * s) 2 ] 1 / 2 where the subscripts c and s refer to the control, i.e., the premix emulsion or treatment composition having zero PRM, and the sample, i.e., the premix emulsion or treatment composition having the respective aldehyde / ketone PRM, respectively, where ΔE t The values ​​used to calculate are those at the corresponding time points t (0 days, 14 days). The desired PRM is slowly added (e.g., in sufficient relative amounts to provide 1:1 molar equivalent of amine groups in the silicone to aldehyde or ketone groups in the perfume) to a sample of the noted functionalized silicone in a jar that is overhead mixed with a 4-blade IKA RW 20 impeller and mixed gently for 15 minutes. The premix emulsion mixture or treatment composition is poured into a standard screw-capped 50 mL (25 cm 2 ) into a CELLSTAR® cell culture flask. After t=0 and 14 days at room temperature, the color appearance of each premix emulsion or treatment composition sample was measured using a LabScan XE 10 reflectance spectrophotometer (HunterLabs, Reston, VA; D65 light source, 10 degree observer, UV light excluded).

[0233] Determination of amine content and % nitrogen The following method is used to determine the total amine content, primary amine content, and / or % nitrogen of aminofunctional silicones. More specifically, this method is used to determine the primary, secondary, and tertiary amine values ​​(meq / g), which are defined as the milliequivalents of amine functional groups (primary, secondary, and tertiary) present in one gram of sample.

[0234] This method is based on the official method ASTM D2074-07, which should be used to supplement this method if necessary. With a wide stoke, the sample is dissolved in isopropyl alcohol and titrated to the bromophenol blue end point using a standardized HCl solution.

[0235] The following materials are used: 0.1 N hydrochloric acid in isopropyl alcohol (CAS7647-01-1, 67-63-0; 99.5%; ex. Fisher Scientific); isopropyl alcohol (CAS#67-63-0; 99%; ex. EMD); phenyl isothiocyanate (CAS#103-72-0; 98%; ex. Sigma Aldrich); salicylaldehyde (CAS#90-02-8; 98%; ex. Sigma Aldrich); bromophenol blue indicator (0.1 wt% solution in ethanol or isopropyl alcohol; ex. Fisher Scientific).

[0236] Each of the following titrations must be repeated a total of three times. Additionally, the titration volume must be determined experimentally. The titration volume must be between 1 and 20 mL. If the titration volume is less than 1 mL, weigh out more sample. If the sample is greater than 20 mL, weigh out less sample. A burette such as a Metrohm Dosimat 775 or equivalent can be used for the titration. Regarding the yellow endpoint of the titration, the yellow may fade to green, but if it is a bright, clear yellow, adding 0.1 N HCl does not change the original color and should be ignored.

[0237] A. Titration of total amine content If not already liquid, melt the sample (typically 100% active) in a water bath. Mix thoroughly and weigh accurately 0.5 to 1.0 grams into a 250 mL Erlenmeyer flask (wide-mouth; alkaline-resistant). Record the weight to four decimal places. Add 50 mL of isopropyl alcohol to the flask. Add 0.5 mL of bromophenol blue indicator. Titrate with 0.1 N HCl solution while swirling until a yellow end point is reached. The volume of HCl used is V. 1,2,3 Record as.

[0238] B. Titration of secondary and tertiary amine content Melt the sample (typically 100% active) in a water bath if not already liquid. Mix thoroughly and weigh exactly 1.0 gram into two 250 Erlenmeyer flasks. Record the weight to four decimal places. Mark the flasks as S and T, respectively. Add 50 mL of isopropyl alcohol to each flask. Add 1 mL of salicylaldehyde to flask S. Stir the solution (using a magnetic stir bar) for 30 minutes. Add 0.5 mL of bromophenol blue indicator solution and titrate with 0.1 N HCl to a yellow endpoint while stirring. The volume of HCl used is V. 2及び3 Record as. To Flask T, add 1 mL of phenylisothiocyanate. Stir the solution for 30 minutes (using a magnetic stir bar). Add 0.5 mL of bromophenol blue indicator solution and titrate with 0.1 N HCl to a yellow endpoint while stirring. Record the volume of HCl used as V3.

[0239] C. Calculation of Amine Content The variables in the calculations below correspond to the following: V: HCl required to titrate the sample (mL) Normality of N:HCl solution S: weight of sample (g) meq / g: milliequivalent per gram Total: Total amine value AS: Amine number of secondary and tertiary amine groups TA: Tertiary amine value Based on the measurements obtained in connection with the titrations above, the following calculations are used to determine the various amine contents.

[0240]

number

[0241] D. Calculation of Nitrogen Weight Percentage To determine the weight percent of nitrogen in the amino functional silicone based on the amine content, the following calculation is used: The weight percent of nitrogen in a compound can be calculated from the amine number (meq / g) as follows: (Amine number / 1000) x (MW of nitrogen) x 100 = weight percent nitrogen As an example, dimethylethanolamine has an amine number of 11.2 (meq / g). Its weight percent of nitrogen (15.7 wt%) is: (11.2 / 1000) x (14.01) x 100 = 15.7% by weight of nitrogen The table below (Table D) shows the weight percent nitrogen and the equivalent amine number.

[0242] [Table 4] When the amino-functional material contains nitrogen atoms that are not in the form of primary, secondary, and / or tertiary amines, the nitrogen content (as weight percent) can be determined according to methods known to those skilled in the art.

[0243] E. Standard material To check the quality control of the method, one may test with a suitable standard, for example, dimethylethanolamine (tertiary amine, 99.5%; available from Sigma-Aldrich). For this particular amine, the total amine and tertiary amine content should be 11.2±0.2 meq / g. Primary and secondary amine content should be <0.1 meq / g.

[0244] Particle / Droplet Size The droplet size of the siloxane compounds as premix emulsions and in the fabric softeners is analyzed using a Horiba, Partica, Laser Scattering, Particle Size Distribution Analyzer LA-950V2 equipped with a static quartz cell and operated according to the manufacturer's instructions.

[0245] HLB value of nonionic surfactants Nonionic surfactants can be classified by the balance between the hydrophilic and lipophilic moieties in the surfactant molecule. The hydrophilic-lipophilic balance (HLB) scale, devised by Griffin in 1949, is a scale of 0 to 20 (20 being hydrophilic) used to characterize the properties of surfactants. The HLB of a surfactant can be calculated as follows: HLB=20 * Mh / M where Mh is the molecular weight of the hydrophilic portion of the molecule, M is the molecular weight of the entire molecule, and the results are given on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic / hydrophobic molecule, and a value of 20 corresponds to a completely hydrophilic / lipophobic molecule. See Griffin, WC Calculation of HLB values ​​of Nonionic Surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249-256. HLB values ​​of commonly used surfactants are readily available from the literature (e.g., HLB index in McCutcheon's Emulsifiers and Detergents, MC Publishing Co., 2004). The HLB value of a mixture of surfactants can be calculated as a weighted average of the HLB values ​​of the surfactants.

[0246] Viscosity test method for silicone A preliminary estimate of the sample viscosity at 25°C is used to select an appropriate instrument configuration for use in the final viscosity measurement analysis, which is performed on a Model AR-G2 Rheometer (TA Instrument Corp., New Castle, Del., USA). A preliminary estimate of the sample viscosity can also be obtained using a Brookfield Viscometer (Brookfield Engineering Laboratories Inc., Middleboro, Massachusetts, USA). The selection of the configuration for use with the AR-G2 Rheometer is determined based on Table E below.

[0247] [Table 5]

[0248] The configuration is mounted in the instrument, the instrument is mapped, the gap distance is set to 0, and the instrument temperature is set to 25°C. Select the measurement mode as rigid mode if using parallel plates, or flexible mode if using the Couette cup and bob configuration. The sample material is mounted in a sample holding mechanism, such as a base plate. The minimum gap distance allowed between the base plate and the selected configuration is 10 times the diameter of the largest common particle present in the sample. If there are common particles in the sample with a diameter larger than 100 μm (measured by microscope), the gap value is set to 10 times the diameter of the largest common particle, otherwise the gap distance is set to an initial value of 1000 μm (i.e., 1 mm). The selected configuration is lowered to the appropriate gap and any excess sample material is removed using a plastic tool. The sample material is allowed to equilibrate to the instrument temperature. Three rheological measurement analyses are performed using the following selections and settings: flow curve, stress sweep, and frequency sweep.

[0249] Flow curve: Select step flow rate from 0.01 to 100; points / decade=10; shear stress; constant time=20; take the average of the last 10.

[0250] Stress sweep: set the stress range to 0.01~100 Pa; set the frequency to 1 rad / s.

[0251] Frequency sweep: Set the angular frequency range from 0.1 to 100.

[0252] The stress value is set to 1 / 3 of the stress value that existed at the time G' began to drop during the previous stress sweep analysis so that the analysis is performed within the linear viscoelastic region.

[0253] Molecular weight of silicone samples The molecular weight of the silicone samples can be determined by size exclusion chromatography with multi-angle light scattering detection (SEC-MALS), as presented below.

[0254] The following equipment is used: Waters Alliance 2695 Separations Module (pump and autosampler) with Wyatt SN C055M791M; rEX refractive index detector SN 874-REX, Waters external column heater, and Wyatt Technology DAWN; Heleos II laser photometer SN 286-H2.

[0255] The following chromatographic conditions were followed: 0.025 M tetrabutylammonium benzoate (TBAB) in toluene solution at a flow rate of 1 mL / min; columns: Waters Styragel guard column and two Waters Styragel HR5 linear columns; refractive index detector at 25° C.; all other components at ambient room temperature.

[0256] To prepare the samples, accurately weigh the samples into a polyseal cap vial. The samples are then diluted with 3 mL of eluent (TBAB in toluene) to achieve a concentration of 8.0 mg / mL. The samples are swirled by hand, mixed gently, and left overnight to ensure complete dissolution of the samples. They are then filtered through a syringe filter (PALL Acrodisc 13 mm syringe filter with 0.2 mm nylon membrane) into an autosampler vial. A poly(dimethyl)siloxane (PDMS) reference material is prepared in the same manner.

[0257] Data collection and post-processing are performed using Astra 5.3.4.19 software (Wyatt Technology, Santa Barbara, Calif.) The dn / dc values ​​of the silicone samples are calculated from the peak data using the Astra software. EXAMPLES

[0258] The examples provided below are intended to be illustrative and not limiting in nature.

[0259] Synthesis Example The following Synthesis Examples 1-20 show the synthesis of exemplary pro-fragrance silicone polymers and their silicone precursors according to the present disclosure. Comparative Synthesis Example A shows a comparative silicone polymer that does not include the heterocyclic moieties provided by the present disclosure.

[0260] For consistency and illustrative / comparative purposes, each example reacts an untreated silicone precursor with the same perfume raw material, cinnamaldehyde, or isocyclocitral, having the following structures:

[0261] [ka]

[0262] However, it is understood that other aldehyde- or ketone-containing PRMs according to the present disclosure can also result in the formation of suitable pro-fragrance silicone polymers, some of which are illustrated and tested in the performance examples below. It is also understood that the synthetic examples may be formulated directly into the treatment composition, however, for the performance and stability examples reported below, all synthetic examples are formulated into the treatment composition as liquid premix emulsions as described above.

[0263] For each synthetic example, the silicone precursor (e.g., with reported XY groups) and the resulting pro-fragrance heterocyclic moiety (e.g., with reported XZ groups) are provided below in Table F. Comparative synthetic example A is also provided, but it does not contain a -Y moiety according to the present disclosure, and the resulting material also does not contain a -Z moiety according to the present disclosure.

[0264] Comparative synthesis example A. Cinnamaldehyde (0.35 g; available from Symrise, Holzminden, Germany) is added to amino-modified silicone (A) KF-8003 (5 g, available from Shin-Etsu Silicones of America Inc., Akron, Ohio). The mixture is stirred for 12 hours. The resulting clear fluid (A') is 1 Analyze by 1 H NMR.

[0265] As shown in Table F below, the resulting material of Comparative Synthesis Example A' does not contain a heterocyclic moiety according to the present disclosure.

[0266] Synthesis example 1. Method A: An epoxy functionalized silicone, EMS-622 fluid (60 g; available from Gelest, Morrisville, PA) is stirred with isopropyl alcohol (3 g; Sigma-Aldrich, St. Louis, MO) in a three-neck round bottom flask. To this fluid is added butylamine (28 g; Sigma-Aldrich, St. Louis, MO). The flask is sealed and placed under a N2 atmosphere for 48 hours. Excess amine is removed under reduced pressure to give a clear fluid. Independent Silicone Fluid 1 was prepared by: 1 Appeared stable for several months by 1 H NMR. Method B: Epoxy-functionalized silicone, EMS-622 fluid (5 g; available from Gelest, Morrisville, PA) was combined with 2-methyl-2,4-pentanediol (0.25 g; Sigma-Aldrich, St. Louis, MO) and butylamine (2.3 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24 h. Excess amine was removed under reduced pressure to give 1 as a clear fluid. Method C: Epoxy-functionalized silicone, EMS-622 fluid (5 g; available from Gelest, Morrisville, PA) was combined with butylamine (2.3 g; Sigma-Aldrich, St. Louis, MO) and stirred for 48 h. Excess amine was removed under reduced pressure to give 1 as a clear fluid. Regardless of the method, cinnamaldehyde (0.5 g; available from Symrise, Holzminden, Germany) is added to a separate 5 g fraction of Fluid 1 and stirred for 12 hours. The resulting clear Fluid 1' is 1 Analyze by 1 H NMR.

[0267] Synthesis example 2. An epoxy functionalized silicone, EMS-622 fluid (60 g; available from Gelest, Morrisville, PA) was combined with isopropyl alcohol (3 g; Sigma-Aldrich, St. Louis, MO) and isopropylamine (23 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24 hours. Excess amine was removed under reduced pressure to give a clear fluid. Separate silicone fluid 2 was 1 Appeared stable for several months by 1 H NMR. To a stirred fluid of 2 (5 g) was added cinnamaldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 2' was 1 Analyze by 1 H NMR.

[0268] Synthesis Example 3. An epoxy functionalized silicone, EMS-622 fluid (60 g; available from Gelest, Morrisville, PA) was combined with isopropyl alcohol (3 g; Sigma-Aldrich, St. Louis, MO) and cyclopropylamine (38 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24 hours. Excess amine was removed under reduced pressure to give a pale yellow fluid. Separate silicone fluid 3 was prepared by: 1 Appeared stable for several months by 1 H NMR. To a stirred fluid of 3 (5 g) was added cinnamaldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 3' was 1 Analyze by 1 H NMR.

[0269] Synthesis Example 4. C: Epoxy functionalized silicone, EMS-622 fluid (10 g; available from Gelest, Morrisville, PA) was combined with isopropyl alcohol (0.5 g; Sigma-Aldrich, St. Louis, MO) and tert-butylamine (4.6 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24 hours. Excess amine was removed under reduced pressure to give a clear fluid. Separate silicone fluid 4 was 1 Appeared stable for several months by 1 H NMR. To a stirred fluid of 4 (5 g) was added cinnamaldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 4' was 1 Analyze by 1 H NMR.

[0270] Synthesis Example 5. Epoxy-functionalized silicone, EMS-622 fluid (10 g; available from Gelest, Morrisville, PA) was combined with isopropyl alcohol (0.5 g; Sigma-Aldrich, St. Louis, MO) and methylamine (2.0 g; Sigma-Aldrich, St. Louis, MO), the flask was sealed and stirred for 24 h. Excess amine was removed under reduced pressure to give 5 as a clear fluid. To a stirred fluid of 5 (5 g) was added cinnamaldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 5' was 1 Analyze by H-NMR.

[0271] Synthesis Example 6. Method A: Epoxy functionalized silicone, EMS-622 fluid (45 g; available from Gelest, Morrisville, PA) is combined with NH3 (50 mL, 2 M in IPA, Sigma-Aldrich, St. Louis, MO) in a round bottom flask. The flask is sealed and stirred at room temperature for 72 hours. Excess amine is removed under reduced pressure to give a clear fluid. Separate silicone fluid 6 was prepared by: 1Appeared stable for several months by 1 H NMR. Method B: Epoxy functionalized silicone, EMS-622 fluid (10 g; available from Gelest, Morrisville, PA) was combined with isopropyl alcohol (0.5 g; Sigma-Aldrich, St. Louis, MO) and NH3 was bubbled through the fluid for 12 h (2.0 g; Sigma-Aldrich, St. Louis, MO), the flask was sealed and stirred for an additional 24 h. Excess amine was removed under reduced pressure to give 6 as a clear fluid. To the stirred fluid of 6 (5 g) was added cinnamaldehyde (0.55 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 6’ is analyzed by 1H NMR.

[0272] Synthesis Example 7. An epoxy functionalized silicone, X-22-343 (15 g; available from Shin-Etsu Silicones of America Inc., Akron, Ohio) was combined with 2-methyl-2,4-pentanediol (0.95 g; Sigma-Aldrich, St. Louis, Mo.) and octylamine (4.0 g; Sigma-Aldrich, St. Louis, Mo.) and stirred via an overhead stirrer at 800 rpm for 16 hours. 1 Appeared stable for several months by 1 H NMR. To a stirred fluid of 7 (5 g) was added cinnamaldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 7' was 1 Analyze by 1 H NMR.

[0273] Synthesis Example 8. Amino-modified silicone, KF-8003 (500 g; available from Shin-Etsu Silicones of America Inc., Akron, OH) is combined with 2-methyl-2,4-pentanediol (26 g; Sigma-Aldrich, St. Louis, MO) in a three-neck round-bottom flask. The solution is stirred until homogeneous and placed under a N2 atmosphere. To this solution, 1,2-propylene oxide (18.15 g; Sigma-Aldrich, St. Louis, MO) is added and the mixture is stirred at 80° C. for 48 hours. Independent Fluid 8 is 1 By 1 H NMR it appears to be stable for several months. Cinnamaldehyde (0.32 g; available from Symrise, Holzminden, Germany) is added to a separate 5 g fraction of Fluid 8 and stirred for 12 hours. The resulting clear Fluid 8' is 1 Analyze by 1 H NMR.

[0274] Synthesis Example 9. Amino-modified silicone, KF-8003 (500 g; available from Shin-Etsu Silicones of America Inc., Akron, OH) is combined with 2-methyl-2,4-pentanediol (27 g; Sigma-Aldrich, St. Louis, MO) in a three-neck round-bottom flask. The solution is stirred until homogeneous and placed under a N2 atmosphere. To this solution, butyl glycidyl ether (40.7 g; Sigma-Aldrich, St. Louis, MO) is added and the mixture is stirred at 80° C. for 48 hours. Independent Fluid 9 is 1 By 1 H NMR it appears to be stable for several months. To a separate 5 g portion of Fluid 9, 2,4,6-trimethylcyclohex-3-ene-1-carbaldehyde (0.35 g; available from IFF, New York, NY) is added and stirred for 12 hours. The resulting clear Fluid 9' is 1 Analyze by 1 H NMR.

[0275] Synthesis Example 10. Amino-modified silicone, KF-8003 (100 g; available from Shin-Etsu Silicones of America Inc., Akron, Ohio) is combined with 2-methyl-2,4-pentanediol (5.5 g; Sigma-Aldrich, St. Louis, Mo.) in a three-neck round-bottom flask. The solution is stirred until homogeneous and placed under a N2 atmosphere. To this solution, cyclohexene sulfide (8.9 g; Sigma-Aldrich, St. Louis, Mo.) is added and the mixture is stirred at 80° C. for 48 hours. Independent Fluid 10 is 1 H NMR indicates it appears to be stable for several months in a sealed container. Cinnamaldehyde (0.31 g; available from Symrise, Holzminden, Germany) is added to a 5 g fraction of the above-mentioned independent fluid 10 and stirred for 12 hours. The resulting pale yellow fluid 10' is 1 Analyze by 1 H NMR.

[0276] Synthesis Example 11. Amino-modified silicone, AMS-152 (100 g; available from Shin-Etsu Silicones of America Inc., Akron, OH) is combined with 2-methyl-2,4-pentanediol (10.5 g; Sigma-Aldrich, St. Louis, MO) in a three-neck round-bottom flask. The solution is stirred until homogeneous and placed under a N2 atmosphere. To this solution, ethylene sulfide (4.25 g; Sigma-Aldrich, St. Louis, MO) is added and the mixture is stirred at 50° C. for 48 hours. Independent Fluid 11 is 1 H NMR indicates it appears to be stable for several months in a sealed container. Cinnamaldehyde (0.35 g; available from Symrise, Holzminden, Germany) was added to a separate 5 g fraction of fluid 11 and stirred for 12 hours. The resulting pale yellow fluid 11' was 1 Analyze by 1 H NMR.

[0277] Synthesis Example 12. Epoxy-functionalized silicone, XF-22-343 (50 g; available from Shin-Etsu Silicones of America Inc., Akron, OH) is stirred with 1,2-hexanediol (7 g; Sigma-Aldrich, St. Louis, MO) in a three-neck round-bottom flask. To this fluid is added an isomeric mixture of cyclic diamine Baxxodur® (98 g; BASF, Ludwigshafen, Germany). The flask is sealed and placed under a N2 atmosphere for 24 hours. Excess amine is removed under reduced pressure to give a pale yellow fluid. Independent silicone fluid 12 darkened upon standing for several months. Cinnamaldehyde (2.15 g; available from Symrise, Holzminden, Germany) was added to a 5 g fraction of freshly prepared independent fluid 12 and stirred for 12 hours. The resulting pale yellow fluid 12' was 1 Analyze by 1 H NMR.

[0278] Synthesis Example 13. An epoxy functionalized silicone, XF-22-343 (50 g; available from Shin-Etsu Silicones of America Inc., Akron, Ohio) is stirred with 1,2-hexanediol (2.8 g; Sigma-Aldrich, St. Louis, Mo.) in a three-neck round-bottom flask. To this fluid is added an isomeric mixture of cyclic diamine Baxxodur® (6.7 g; BASF, Ludwigshafen, Germany). The flask is sealed and placed under a N2 atmosphere for 24 hours. Independent Fluid 13 is 1 H NMR indicates it appears to be stable for several months in a sealed container. Cinnamaldehyde (2.15 g; available from Symrise, Holzminden, Germany) is added to a 5 g fraction of freshly prepared independent fluid 13 and stirred for 12 hours. The resulting fluid 13' is 1 Analyze by 1 H NMR.

[0279] Synthesis Example 14. Epoxy functionalized silicone, XF-22-343 (100 g; available from Shin-Etsu Silicones of America Inc., Akron, OH) is stirred with 1,2-hexanediol (8.5 g; Sigma-Aldrich, St. Louis, MO) in a three-neck round bottom flask. To this fluid is added ethylenediamine (71 g; Sigma-Aldrich, St. Louis, MO). The flask is placed under a N2 atmosphere and heated to 30° C. for 24 hours. Excess amine is removed under reduced pressure to give 14 as a pale yellow fluid. Crosslinking is easy with ethylenediamine, therefore, excess amine is important in the preparation of 14. To a separate 5 g portion of fluid 14, 2,4,6-trimethylcyclohex-3-ene-1-carbaldehyde (0.35 g; available from IFF, New York, NY) is added and stirred for 12 hours. The resulting clear fluid 14' is 1 Analyze by 1 H NMR. The predominant structural motif is the oxazolidine, however, traces of imine were observed.

[0280] Synthesis Example 15. Epoxy-functionalized silicone, KF-102 (50 g; available from Shin-Etsu Silicones of America Inc., Akron, Ohio) is combined with isopropyl alcohol (5 g; Sigma-Aldrich, St. Louis, Mo.) and butylamine (5 g; Sigma-Aldrich, St. Louis, Mo.), then the flask is placed under a N2 atmosphere. Once homogeneous, the flask is heated to 30° C. and stirred for 72 hours. The progress of the reaction is monitored. 1 The reaction was monitored by H NMR. Excess amine was removed under reduced pressure to give a clear fluid. 1 Appeared stable for several months by 1 H NMR. To a stirred fluid of 15 (5 g) was added cinnamaldehyde (0.2 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 15' was 1 Analyze by 1 H NMR.

[0281] Synthesis Example 16. Amino-modified silicone, KF-8003 (10 g; available from Shin-Etsu Silicones of America Inc., Akron, Ohio) is combined with 2-methyl-2,4-pentanediol (0.5 g; Sigma-Aldrich, St. Louis, Mo.) in a three-neck round-bottom flask. The solution is stirred until homogeneous and placed under a N2 atmosphere. To this solution is added methyl glycolate (0.6 g; Sigma-Aldrich, St. Louis, Mo.) and the mixture is stirred at 120° C. for 48 hours. The resulting Fluid 16 is 1 By 1 H NMR it appears to be stable for several months. Cinnamaldehyde (0.34 g; available from Symrise, Holzminden, Germany) is added to a 5 g fraction of Fluid 16, which is stirred at 50° C. for 12 hours. The resulting Fluid 16′ is 1 Analyze by 1 H NMR.

[0282] Synthesis Example 17. An acrylate-functionalized silicone, UMS-182 fluid (50 g; available from Gelest, Morrisville, PA), is combined with ethanolamine (6.25 g; Sigma-Aldrich, St. Louis, MO) and placed under a N2 atmosphere. The mixture is stirred at room temperature until the reaction is complete. 1 The independent fluid 17 is monitored by H NMR. 1 H NMR indicates it appears to be stable for several months in a sealed container. Cinnamaldehyde (1.25 g; available from Symrise, Holzminden, Germany) was added to a separate 5 g fraction of fluid 17 and stirred for 12 hours. The resulting clear fluid 17' was 1 Analyzed by 1 H NMR.

[0283] Synthesis Example 18. Amino-modified silicone, DMS-A15 (10 g; available from Gelest, Morrisville, PA) is combined with isopropyl alcohol (5 g; Sigma-Aldrich, St. Louis, MO) and 1,4-butanediol diglycidyl ether (10 g; Sigma-Aldrich, St. Louis, MO), then the flask is placed under a N2 atmosphere. Once homogeneous, the flask is heated to 30° C. and stirred for 72 hours. The progress of the reaction is monitored. 1 The reaction was monitored by H NMR. Excess oxirane was removed under reduced pressure to give a clear fluid. Independent silicone fluid 18 was 1 Appeared stable for several months by 1 H NMR. To a stirred fluid of 18 (5 g) was added cinnamaldehyde (0.4 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 18' was 1 Analyze by 1 H NMR.

[0284] Synthesis Example 19. A halogenated modified silicone, LMS-152 fluid (10 g; available from Gelest, Morrisville, PA), is combined with ethanolamine (6.25 g; Sigma-Aldrich, St. Louis, MO) and placed under a N2 atmosphere. The mixture is stirred at 30° C. until the reaction is complete. 1 The isolated fluid 19 was monitored by H NMR. 1 H NMR indicates it appears to be stable for several months in a sealed container. Cinnamaldehyde (1.25 g; available from Symrise, Holzminden, Germany) is added to a separate 5 g fraction of Fluid 19 and stirred for 12 hours. The resulting Fluid 19' is 1 Analyze by 1 H NMR.

[0285] Synthesis Example 20. An epoxy functionalized silicone, EMS-622 fluid (10 g; available from Gelest, Morrisville, PA) was combined with isopropyl alcohol (0.5 g; Sigma-Aldrich, St. Louis, MO), butylamine (2.5 g; Sigma-Aldrich, St. Louis, MO), propylamine (2.2 g; Sigma-Aldrich, St. Louis, MO) and stirred for 48 hours. Excess amine was removed under reduced pressure to give a clear fluid. Independent silicone fluid 20 was 1 Appeared stable for several months by 1 H NMR. To a stirred fluid of 20 (5 g) was added cinnamaldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12 hours, the resulting clear fluid 20' was 1 Analyze by 1 H NMR.

[0286] Structure of a synthetic example. Table F below shows the XY and XZ structures of the above synthetic examples. The XY column shows radicals such as, for example, the (Si)-XY moieties of the precursor silicone polymer, according to formula VI or formula VII, which in the above synthetic examples are labeled with a number, for example, 1. The XZ column shows radicals such as, for example, the (Si)-XZ moieties of the pro-fragrance silicone polymer, according to formula I or formula II, which in the above synthetic examples are labeled with a number with a "prime" notation, for example, 1'.

[0287] Table F also includes comparative synthetic examples A (and A') that do not contain the (Si)-XY or (Si)-XZ radicals described in this disclosure (e.g., no heterocyclic ring is formed), but are included in the table for convenience / comparison purposes. * ) is attached.

[0288] [Table 6-1]

[0289] [Table 6-2]

[0290] [Table 6-3]

[0291] [Table 6-4]

[0292] [Table 6-5]

[0293] In the above synthesis examples, the precursor silicone polymer (or comparative silicone such as KF-8003) and the indicated perfume raw materials are combined / reacted to form a fluid comprising a pro-fragrance silicone polymer according to the present disclosure.

[0294] In the following performance and stability examples, the precursor silicone polymer (or comparative silicone such as KF-8003) and the indicated perfume raw materials are made into an emulsion substantially following a procedure similar to that found in the Test Methods section above ("Preparation of Pro-Fragrance Silicone Polymer Premix Emulsion"). Despite the differences in the preparation methods between the synthesis, performance, and stability examples, the inputs and outputs for the pro-fragrance silicone polymer are substantially the same.

[0295] Performance Examples In the following Performance Examples 1-5, untreated perfume oil, a liquid premix emulsion containing a precursor silicone polymer according to the present disclosure (e.g., based on alkanolamine or thiolamine silicone precursors as described above), and a treatment composition containing a PRM as indicated, or a premix emulsion containing a comparative silicone polymer are compared through a treatment cycle in an automatic washing machine according to the fabric treatment method provided above. After treatment, the fabric is tested for headspace analysis according to the test method provided above. The following data demonstrate the advantages offered by heterocyclic moieties such as oxazolidine and thiazolidine motifs in the delivery of benefit agents.

[0296] Performance Examples 1. Benefits of Pro-Fragrance Silicone Polymers First, two silicone scaffolds are selected to investigate the fragrance benefits. The first benefit comes from traditional amino-modified silicones, which can then be reacted with oxiranes to give alkanolamines (Synthesis Example 8). The second benefit comes from epoxy silicones, which form alkanolamines after nucleophilic attack from amines (Synthesis Example 1). A wide range of fragrance raw materials are being explored to evaluate these materials.

[0297] In the following examples, equal molar concentrations of four aldehyde perfume raw materials are provided in the premix emulsion of each test leg, and then incorporated into the test fabric enhancer / softener composition prepared as provided in the test method above. According to the test method above, the fabric is prepared, washed, and tested for fabric headspace analysis.

[0298] In both Table 1 and subsequent tables, for a row referencing "Synthetic Example 1," etc., it is understood that a sample was prepared substantially according to the methods and silicone precursors provided in the recited Synthetic Example, but using the perfume raw materials recited in the example (at equal molar concentrations) rather than just cinnamaldehyde or isocyclocitral, and formulated as a premix emulsion as detailed above.

[0299] The results of the headspace analysis testing of the fabrics are presented in Table 1 below.

[0300] [Table 7] a All aldehyde sources were combined in equimolar concentrations. b The silicone used in Comparative Synthesis Example A (KF-8003) is a product of Shin-Etsu Silicones of America Inc., Akron, OH. Comparative Silicone Premix Emulsion Solution. Synthesis Sample A is prepared using substantially the same method as the premix emulsions of Synthesis Examples 1 and 8.

[0301] As shown in Table 1, alkanolamine silicone 1, alkanolamine silicone 8, and comparative amino modified Comparative Synthetic Example A showed improved total headspace over the untreated raw material. Additionally, alkanolamine silicone 1 and alkanolamine silicone 8 showed increased total headspace over the amino modified Comparative Synthetic Example A. Example Fluid 8, synthetically derived from KF-8003, had affinity for the untreated raw material, which is sterically unhindered, relative to the parent KF-8003 silicone (see Comparative Synthetic Example A). Fluid 1 had the highest total headspace and a more balanced reactivity towards non-allylic aldehydes.

[0302] Performance Example 2. Effect of steric hindrance This example illustrates the effect of stearic hinderance at the nitrogen atom of the heterocyclic ring portion of a pro-fragrance silicone polymer. Testing is carried out substantially similarly to Performance Example 1, using the PRMs and synthesis examples provided in Table 2 below. As with Performance Example 1, it is understood that the pro-fragrance silicone polymer is made using the listed PRMs, rather than just cinnamaldehyde or isocyclocitral, and reacted in the form of a premix emulsion as described above.

[0303] The results of the headspace analysis of the fabrics are presented in Table 2.

[0304] [Table 8] a The matching formulation is as follows: 10% by weight methylnonylacetaldehyde, 40% by weight PT Bucinal, 20% by weight Precyclemon B, and 30% by weight Floralozone.

[0305] As shown in Table 2, each of the exemplary pro-fragrance silicones delivered a higher total headspace than the untreated raw material. The total headspace concentrations of the synthetic example silicones are 1>3>2>4. Without wishing to be bound by theory, this trend is believed to be rationalized on a steric basis, where less steric bulk at the nitrogen improves the total headspace (e.g., n-butylamine>cyclohexylamine>iso-propylamine>tert-butylamine). The steric influence is highlighted when considering synthetic examples 2 and 3. The α-carbon to nitrogen atom in both synthetic examples 2 and 3 is secondary substituted with respect to the carbon atom, however, in synthetic example 3, the α-carbon is a ring structure, resulting in less steric influence. This subtle difference resulted in a noticeable difference in the total amount of perfume raw material delivered.

[0306] Example 3. Effect of amine substitution This example shows the effect of primary versus secondary substitution at the nitrogen atom of the heterocyclic moiety of the pro-fragrance silicone polymer. Testing is carried out substantially similarly to Performance Example 1, using the PRMs and synthesis examples provided in Table 3 below. As with the previous examples, it is understood that the pro-fragrance silicone polymer is made using the listed PRMs, rather than just cinnamaldehyde or isocyclocitral, and reacted in the form of a premix emulsion as described above.

[0307] The results of the headspace analysis of the fabrics are presented in Table 3.

[0308] [Table 9] a The matching formulation is as follows: 10% by weight methylnonylacetaldehyde, 40% by weight PT Bucinal, 20% by weight Precyclemon B, and 30% by weight Floralozone.

[0309] As shown in Table 3, the alkanolamine silicones of Synthesis Example 1 and Synthesis Example 6 had increased total headspace over the untreated raw material. Additionally, Synthesis Example 1, which has a secondary amine, provided higher total headspace than the primary amine of Synthesis Example 6. Thus, alkyl substitution of the amine may be more preferred in certain applications.

[0310] Example 4. Additional Examples of Pro-Fragrance Silicone Polymers This example shows additional examples of pro-fragrance silicone polymers. Synthesis Example 11 contains a thiolamine in the precursor, which forms a thiazolidine ring when reacted with a perfume raw material. Synthesis Example 12 forms an oxazolidine ring, but the precursor also contains a cyclic amine in the pendant group that can react with a perfume raw material, so that the pendant group can ultimately carry two PRM residues.

[0311] Testing is carried out substantially in the same manner as Performance Example 1, using the PRMs and synthesis examples provided below in Table 4. As with the previous examples, it is understood that the pro-fragrance silicone polymers are made using the PRMs listed, rather than just cinnamaldehyde or isocyclocitral, and reacted in the form of a premixed emulsion as described above.

[0312] The results of the headspace analysis of the fabrics are presented in Table 4.

[0313] [Table 10] aAll aldehyde sources were combined in equimolar concentrations.

[0314] Synthesis Example 11, which forms a thiazolidine ring in the presence of the raw materials, increased the total headspace through washing compared to the untreated raw material (see Table 4). Fluid 11 had strong interactions with sterically hindered aldehydes and ketones. Oxazolidine-forming silicone 12 reacted strongly with each raw material.

[0315] Example 5. Use in particulate laundry additives In this example, the material blend is prepared with a dry formed particle coating. (e.g., pastilles with polyethylene glycol as a carrier; similar in size and shape to those sold by The Procter & Gamble Company under the trademark DOWNY UNSTOPABLES). The formulation of the particles for each leg, incorporating Synthesis Example 6 as a premix emulsion as above, is presented in Table 5A. The amounts are given as weight % of the composition.

[0316] [Table 11] a The cumulative feedstock was equal to 0.66 wt% in both legs.

[0317] In the following examples, equimolar perfume raw materials are provided in the pastille composition of the test fabric prepared as provided in the above test method. According to the above test method, the fabric is prepared, washed, and tested for headspace analysis on the fabric. The performance test results are presented in Table 5B.

[0318] [Table 12] a All aldehyde sources were combined in equimolar concentrations.

[0319] As shown in Table 5B, Synthesis Example 6 in a dry particle formulation demonstrated an advantage over the untreated raw material through washing.

[0320] Stability example In Stability Example 1, the silicone premix emulsion and treatment composition are tested for color stability upon storage.

[0321] Stability Example 1. Color stability in silicone premixes Prepare post-perfume silicone premixes, particularly premixes in the form of emulsions, and related fabric softener products formed from such premix emulsions. The color measurements of silicone premix emulsions of Synthesis Example 1 and Synthesis Example 8 are presented and measured as described in the above test method. Aldehyde-containing perfume raw materials (cymal, isocyclocitral, cinnamaldehyde, and florarozone) are combined with silicone at equimolar concentrations. As with the previous examples, it is understood that pro-fragrance silicone polymers are made with the listed PRMs, rather than just cinnamaldehyde or isocyclocitral, and react with the PRMs in the form of premix emulsions as described above. Comparative compositions are made with KF-8003 silicone premix emulsions and the same PRMs.

[0322] The color stability of the premix emulsion and fabric softener product upon two weeks of storage is evaluated by color change as per the Composition Test Method above. The results are presented in Table 6 below.

[0323] [Table 13] a ΔE t is calculated as defined in the test method. b KF-8003, a product of Shin-Etsu Silicones of America Inc., Akron, OH. Comparative silicone premix emulsion solution. Synthetic Sample A is prepared using substantially the same method as the premix emulsions of Synthetic Example 1 and Synthetic Example 8.

[0324] As shown in Table 6, Synthesis Examples 1 and 8, each of which combines with a PRM residue to form a heterocyclic moiety, exhibited lower ΔE in both the premix emulsion and treatment composition compared to solutions formed from the imine-forming silicone KF-8003. t Without wishing to be bound by theory, it is believed that π-bonds are likely the source of the color intensity of the imine represented by Comparative Synthesis Example A. The effect of π-bond conjugation is further accentuated using cinnamaldehyde, where extended conjugation upon imine formation results in significant coloration. Additionally or alternatively, it is believed that the nature of the bond in the heterocycle eliminates static π-bonds, resulting in Synthesis Example 1 and Synthesis Example 8 having improved color stability over time due to reduced conjugation and reduced gelation.

[0325] Exemplary Formulations This section provides exemplary, non-limiting formulations of premixes and treatment compositions.

[0326] Formulation Example 1. Exemplary Premix Table 7 provides exemplary fragrance premix formulations that can be incorporated into consumer products. Amounts are provided as weight % by weight of the premix.

[0327] [Table 14] 1 Precursor silicone polymer of synthesis example 1 2 Methylcyclohexanediamine (Baxxodur EC210, manufactured by BASF) 3 Each PRM contains ethyl vanillin, vanillin, heliotropin, and lilial, each selected to be present in an amount to provide equimolar aldehyde moieties.

[0328] Formulation Example 2. Fabric treatment composition Particulate treatment compositions can be made according to the following procedures, and such compositions can be useful as laundry additive consumer products.

[0329] A pro-fragrance silicone polymer premix emulsion made according to the method provided in the Test Methods section and made according to Synthesis Example 1, made with equimolar amounts of the following PRMs: cymal, cinnamaldehyde, acetophenone, and benzaldehyde, (113.3 grams) is combined with 1756.6 grams of molten polyethylene glycol (Pluriol E 8000 Prill supplied by BASF Corporation) and 119.8 grams of free fragrance. The blend is mixed and solidified into consumer product particles having an average diameter of about 0.3 cm to about 1.5 cm and / or an average mass of about 1 mg to about 1 g.

[0330] The resulting consumer product is a plurality of particles suitable for addition to the wash cycle of an automatic fabric washing machine, optionally in combination with a laundry detergent.

[0331] Formulation example 3. Liquid fabric strengthener Table 8 shows exemplary formulations of compositions according to the present disclosure. Specifically, the following compositions are liquid fabric enhancer products:

[0332] [Table 15] 1 Ester Quat 1: A mixture of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid esters, (2-hydroxypropyl)-(1-methyl-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid esters and bis-(1-methyl-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid esters, where the fatty acid esters are made from a C12-C18 fatty acid mixture (REWOQUAT DIP V 20 M Conc, e.g., Evonik). 2Ester Quat 2: N,N-bis(hydroxyethyl)-N,N-dimethylammonium chloride fatty acid ester (REWOQUAT CI-DEEDMAC, e.g., Evonik), produced from a mixture of C12 to C18 fatty acids 3 Ester Quat 3: Esterification products of (C16-18 and C18 unsaturated) fatty acids with triethanolamine, quaternized with dimethyl sulfate (REWOQUAT WE 18, e.g., Evonik) * A pro-fragrance silicone polymer premix emulsion according to Synthesis Example 1 was made using equal amounts of the following PRMs: cymar, cinnamaldehyde, acetophenone, and benzaldehyde.

[0333] Formulation example 4. Liquid laundry detergent Table 9 shows exemplary formulations of heavy duty liquid laundry detergent compositions that can be made according to the present disclosure. Amounts provided are by weight % of actives unless otherwise indicated.

[0334] [Table 16] AE1.85 is C1215 alkyl ethoxy (1.8) sulfate AE3S is C1215 alkyl ethoxy (3) sulfate AE7 is a C1213 alcohol ethoxylate with an average degree of ethoxylation of 7 AE8 is a C1213 alcohol ethoxylate with an average degree of ethoxylation of 8 AE9 is a C1213 alcohol ethoxylate with an average degree of ethoxylation of 9 Alkoxylated polyaryls are, for example, EMULSOGEN® T5160, HOSTAPAL® BV concentrate, SAPOGENAT® T11O, and / or SAPOGENAT® T139, all from Clariant. Amylase 1 is STAINZYME®, 15 mg activity / g Amylase 2 is NATALASE®, 29 mg activity / g Amylase 3 is STAINZYME PLUS®, 20 mg activity / g Isoamylase has glycogen debranching activity AS is C1214 alkyl sulfate Cellulase 2 is CELLUCLEAN™, 15.6 mg activity / g Xyloglucanase is WHITEZYME®, 20 mg activity / g Chelating agent 1 is diethylenetriaminepentaacetic acid (DTPA) Chelating agent 2 is l-hydroxyethane 1,1-diphosphonic acid (HEDP) Chelating agent 3 is the sodium salt of ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS). Dispersin B is a glycoside hydrolase, reported as 1000 mg activity / g DTI1 is poly(4-vinylpyridine-l-oxide), such as CHROMABOND S-403E® · DTI2 is poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as SOKALAN HP56®). Dye control agents, such as SUPAREX® O.IN (M1), NYLOFIXAN® P (M2), NYLOFIXAN® PM (M3), or NYLOFIXAN® HF (M4). HSAS is a medium branched alkyl sulfate, as disclosed in U.S. Patents 6,020,303 and 6,060,443. · LAS is a linear alkylbenzene sulfonate with an average aliphatic carbon chain length of C9-C15 (HLAS is the acid form). Lipase is LIPEX®, 18mg activity / g Mannanase is MANNAWAY®, 25 mg activity / g Optical brightener 1 is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,-2'-stilbenedisulfonate Optical brightener 2 is disodium 4,4'-bis-(2-sulfostyryl)biphenyl (sodium salt) Optical Brightener 3 is OPTIBLANC SPL1O® manufactured by 3V Sigma The photobleaching agent is a sulfonated zinc phthalocyanine. The polishing enzyme is para-nitrobenzyl esterase, reported as 1000 mg activity / g. Polymer 1 is bis((C2H5O)(C2H4O)n)(CH3)-N-CH----N'----(CH3)-bis((C2H50)(C2H40)n), where n=20-30 and x=3-8, or sulfurized or sulfonated variants thereof. Polymer 2 is an ethoxylated (EO15) tetraethylenepentamine Polymer 3 is an ethoxylated polyethyleneimine (PEI600 EO20) Polymer 4 is an ethoxylated hexamethylenediamine Polymer 5 is ACUSOL® 305 provided by Rohm & Haas Polymer 6 is a polyethylene glycol polymer grafted with vinyl acetate side chains provided by BASF A Pro-Fragrance Silicone Polymer Premix Emulsion was made using equal amounts of the following PRMs: Cymal, cinnamaldehyde, acetophenone, and benzaldehyde, Synthesis Example 6. Protease is PURAFECT PRIME®, 40.6 mg activity / g Protease 2 is SAVINASE®, 32.89 mg activity / g Protease 3, PURAFECT®, 84 mg activity / g · The quaternary ammonium is C1214 dimethylhydroxyethyl ammonium chloride S-ACMC is Reactive Blue 19 Azo-CM-Cellulose provided by Megazyme The soil release agent is REPEL-O-TEX® SF2 The structurant is hydrogenated castor oil. Violet DD is a thiophene azo dye offered by Milliken Water-insoluble plant material is, for example, Herbacel AQ+ type N supplied by Herbafood Ingredients GmbH, Werder, Germany

[0335] Formulation Example 5. Unit dose product Table 10 shows the formulations of various unit dose detergent articles in the form of a pouch. A multi-compartment pouch can contain multiple benefit agents. As a non-limiting example, a two-component or three-component pouch may contain the formulations presented in Table 10 in separate enclosures, where the dose is the amount of formulation in each enclosure. The pouch can be formed from a water-soluble film, such as a polyvinyl alcohol film available from MonoSol, LLC (Indiana, USA).

[0336] [Table 17] 1 Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl] ester as described in U.S. Pat. No. 7,169,744 2 PAP = phthaloyl-amino-peroxycaproic acid, as 70% active wet cake 3Polyethylenimine (MW=600) with 20 ethoxylate groups per -NH. 4 Ethoxylated thiophene, EO(R1+R2)=5 5 RA = Reserve alkalinity (g NaOH / dose) * A silicone / PRM premix emulsion according to the present disclosure. * The weight percentages provided in the table are the amount of fragrance premix provided, not the amount of perfume delivered by the premix, and the premix is ​​substantially free of water. The premixes are made with about 20% by weight of perfume raw materials, based on the weight of the premix.

[0337] Dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0338] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or the benefit thereof, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest or disclose such invention, either alone or in combination with any other reference(s). Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0339] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. 1. A treatment composition comprising a processing aid and a pro-fragrance silicone polymer, the pro-fragrance silicone polymer comprises a silicone backbone, an organic linker group comprising a carbon atom bonded to a silicon atom of the silicone backbone, and a heterocyclic moiety bonded to the organic linker group; The pro-fragrance silicone polymer comprises at least one radical selected from the group consisting of Formula I, Formula II, and mixtures thereof; The radicals of formula I and formula II have the following structure: (Si)-X-Z formula I (Si)-X-(Z-X) n-(Si) Formula II having In the formula, "(Si)-" represents a bond to a Si atom, wherein each X group is an organic linker group, and is an independently selected divalent organic moiety containing from 2 to 24 chain atoms; where the index n is from 1 to 2, and each Z is a mono- or divalent heterocyclic moiety according to formula III; Formula III has the following structure: 【Chemistry 1】 having wherein G is selected from the group consisting of oxygen or sulfur; wherein the index m is from 2 to 4; wherein R 1 is selected from H, a monovalent moiety having a molecular weight of 15-495 Da, or the attachment point of Z to the X group; wherein each J is independently selected from the group consisting of C(R 2 ) 2 , —O—, —N(R 2 )—; wherein each R 2 is independently selected from H, a monovalent moiety having a molecular weight of 14 to 990 Da, or the attachment point of Z to the X group; The treatment composition, wherein the -C(R 3 )(R 4 )- moiety is a residue of a perfume raw material (PRM), the perfume raw material from which the residue is derived comprises an aldehyde moiety, a ketone moiety, or a combination thereof.

2. The treatment composition of claim 1 , wherein the PRM forming the residue comprises an aldehyde moiety.

3. The processing composition of claim 1 or 2, wherein the PRM forming the residue comprises a ketone moiety.

4. The treatment composition of any one of claims 1 to 3, wherein each X group independently contains from 2 to 12 chain atoms.

5. The treating composition of any one of claims 1 to 4, wherein the X group is attached to a non-terminal silicon atom.

6. each Z is a monovalent or divalent 5-membered heterocyclic moiety according to formula IV; Formula IV has the following structure: 【Chemistry 2】 having In the formula, G, R １ , R ３ , and R ４ But as stated above, wherein each J is independently C(R ２ ) ２ Wherein R ２ The treatment composition according to any one of claims 1 to 5, wherein:

7. R １ , any R ２ or a combination of two of these are points of attachment of Z to the X group.

8. At least one R ２ The treatment composition of any one of claims 1 to 7, wherein is the point of attachment of Z to the X group.

9. The pro-fragrance silicone polymer has the following structure: [R ５ R ６ R ７ SiO １／２ （ｑ＋２ｒ＋２） [R ８ R ９ SiO ２／２ ｐ [R １０ SiO ３／２ ｑ [SiO ４／２ ｒ Formula V​​​​ having During the ceremony, q is an integer from 0 to 150; p is an integer from 0 to 1500; r is an integer from 0 to 150; where q+p+r is equal to an integer greater than or equal to 1; R ５ , R ６ , R ７ , R ８ , R ９ , and R １０ each of the moieties is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula I, or a radical according to Formula II; In the formula, R ５ ~R １０ The treatment composition of any one of claims 1 to 8, wherein at least one of the moieties is a radical according to formula I or a radical according to formula II.

10. 1. A liquid premix composition comprising: (a) a pro-fragrance silicone polymer according to any one of claims 1 to 9; or (b) a precursor silicone polymer and a perfume raw material comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof; The precursor silicone polymer and the perfume raw material are capable of condensing to form a pro-fragrance silicone polymer according to any one of claims 1 to 9; or (c) mixtures thereof; 1. A liquid premix composition comprising:

11. 11. The liquid premix composition of claim 10, wherein the liquid premix composition is in the form of an oil-in-water emulsion.

12. based on the weight of said liquid premix composition, the precursor silicone polymer is present in a concentration of 1% to 99%; 12. A liquid premix composition according to claim 10 or 11, wherein the perfume raw material is present at a concentration of from 1% to 50%.

13. The precursor silicone polymer comprises at least one radical selected from the group consisting of Formula VI, Formula VII, and mixtures thereof; The radicals of formula VI and formula VII have the following structure: (Si)-XY formula VI; (Si)-X-(Y-X) ｎ - (Si) formula VII; having In the formula, "(Si)-" is a bond to a Si atom. where the index n is from 1 to 2, wherein each X group is covalently bonded to “(Si)” via a Si—C bond and is an independently selected divalent organic group containing 2 to 24 chain atoms; wherein each Y is independently a monovalent or divalent moiety according to formula VIII: Formula VIII has the following structure: 【Chemistry 3】 having wherein G is selected from the group consisting of oxygen or sulfur; wherein the index m is from 2 to 4; In the formula, each R １ is selected from H, a monovalent moiety having a molecular weight of 15-500 Da, or the point of attachment of Y to the X group; wherein each J is independently C(R ２ ) ２ , -O-, -N(R ２ )- selected from the group consisting of In the formula, each R ２ is independently selected from the group consisting of H, a monovalent moiety having a molecular weight of 14 to 990 Da, or the point of attachment of Y to the X group.

14. 1. A method of making a treatment composition, the method comprising: providing a base composition, the base composition including a processing aid; The base composition comprises: a) a pro-fragrance silicone polymer according to any one of claims 1 to 9; b) a precursor silicone polymer according to any one of claims 10 to 13 and a perfume raw material comprising a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof; or c) mixtures thereof, and combining the A method comprising:

15. Use of a pro-fragrance silicone polymer according to any one of claims 1 to 9 as a fragrance.

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