Treatment composition containing low concentrations of oligoamines

Abstract

A treatment composition comprising a relatively low concentration of an oligoamine, preferably diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, and related methods of use, preferably soiled fabric treatment and preparation.

Description

[Technical field]

[0001] The present disclosure relates to treatment compositions containing low concentrations of certain oligoamines. The present disclosure further relates to related methods of use and preparation of such compositions. [Background technology]

[0002] Many treatment processes, such as laundry cleaning processes, are designed to remove soil from surfaces, such as fabrics. Some soils can cause malodors on the fabrics that can persist or even form after the treatment process has ended. Thus, manufacturers of consumer and industrial cleaning products continue to seek to provide compositions and processes that provide improved malodor control.

[0003] Separately, certain polyamines or oligoamines are known to be used in detergent compositions. These polyamines or oligoamines may promote certain cleaning benefits, such as grease removal. However, at the concentrations typically required to provide such benefits, polyamines may cause discoloration, such as yellowing, on target surfaces, such as fabrics, due to the reactivity of polyamines or oligoamines with various molecular species on or around the fabric surface. Summary of the Invention [Problem to be solved by the invention]

[0004] What is needed is an improved treatment composition that preferably provides benefits against malodor without significant discoloration / yellowing problems. [Means for solving the problem]

[0005] The present disclosure relates to treatment compositions that include relatively low concentrations of certain oligoamines.

[0006] For example, the present disclosure provides a treatment composition comprising from about 0.01% to about 1.0% by weight of the treatment composition of an oligoamine having a structure according to Formula I and / or a salt thereof.

[0007] [ka] [In the formula, L is independently -(C m H 2m )-, the subscript m of each L is independently an integer from 2 to 6, n is an integer from 1 to 10, and R 1 ~R 5 are each independently selected from H and C1-C4 alkyl, preferably R 1 ~R 5 at least one of which is H], and additional processing aids.

[0008] The present disclosure also relates to a process for treating a surface, comprising the steps of providing a surface, preferably the surface is a fabric, more preferably the surface is a fabric soiled with sebum, and contacting the surface, optionally in the presence of water, with a composition described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present disclosure relates to treatment compositions comprising low concentrations of oligoamines of specific structures, which have been found to be capable of imparting surprising benefits against malodors, for example, on laundered fabrics.

[0010] Without being bound by theory, it is believed that the copper ions (e.g., Cu 2+ It is believed that metal ions such as copper ions, ...

[0011] Moreover, the oligoamines of the present disclosure have been found to be effective at surprisingly low concentrations. The low oligoamine concentrations are cost and formulation space efficient. In addition, with these low concentrations of oligoamines, the treated surfaces exhibit little or no discoloration or yellowing. As mentioned above, oligoamines are known to impart certain cleaning benefits, but generally, to see such benefits, oligoamines must be formulated at high concentrations. Thus, manufacturers have had little reason to expect any meaningful benefit from such low concentrations of oligoamines according to the present disclosure.

[0012] The compositions and methods of the present disclosure are described in more detail below.

[0013] 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 non-limiting. The compositions of the present disclosure can comprise, consist essentially of, or consist of the components of the present disclosure.

[0014] The terms "substantially free of" or "substantially free from" may be used herein. This means that the indicated material is in a minimal amount and has not been intentionally added to the composition to form part of the composition, or preferably is not present at a concentration detectable by analysis. This means that it includes compositions in which 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 concentration 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.

[0015] As used herein, the phrase "fabric care composition" includes compositions and formulations designed for fabric treatment. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric deodorizing compositions, laundry prewash, laundry pretreatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatments, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, dryer sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as laundry pretreatments, laundry posttreatments, or may be added during the rinse or wash cycle of laundry operations.

[0016] As used herein, "liquid" includes free-flowing liquids, as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light-duty and heavy-duty liquid detergent compositions, fabric softeners, detergent gels commonly used in laundry, bleaches, and laundry additives. Gas (e.g., suspended air bubbles) or solids (e.g., particles) may be included in the liquid. Liquid compositions can have from about 0% to about 90%, or from about 30% to about 90%, or from about 50% to about 80% water by weight of the composition, and can include non-aqueous liquid detergents.

[0017] As used herein, "solids" includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include granules, microcapsules, beads, flakes, noodles, and pearlescent balls.

[0018] Unless otherwise stated, all component or composition concentrations are in terms of the active portion of that component or composition and are exclusive of impurities, such as residual solvents or by-products, that may be present in commercially available sources of such component or composition.

[0019] All temperatures herein are in degrees Celsius (° C.) unless otherwise specified. All measurements herein are made at 20° C. and atmospheric pressure unless otherwise indicated.

[0020] In all embodiments of this disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless otherwise specified.

[0021] It is to be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation 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 is subsumed within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0022] Treatment Composition The present disclosure relates to a treatment composition suitable for treating a surface. The treatment composition can typically contain a relatively low concentration of an oligoamine and additional treatment aids. The treatment composition can be a fabric care composition, such as a laundry detergent composition.

[0023] The composition of the present disclosure can be a fabric care composition.Such compositions can be used as laundry pre-treatment, laundry post-treatment, or can be added during the rinse or wash cycle of laundry operation.Such compositions can also be used in dry cleaning environments.

[0024] The composition may be selected from the group consisting of a light duty liquid detergent composition, a heavy duty liquid detergent composition, a detergent gel commonly used in laundry, a bleaching composition, a laundry additive, a fabric strengthening composition, and combinations thereof. The composition may be a heavy duty liquid detergent composition or a fabric strengthening composition. The composition may be intended for use during the wash cycle and / or the rinse cycle of an automatic washing machine.

[0025] The treatment composition can be a hard surface cleaning composition suitable for treating hard surfaces such as tile, porcelain, countertops, and the like.

[0026] The composition may be in any suitable form. The composition may be in the form of a liquid composition, a granular composition, a single compartment pouch, a multi-compartment pouch, a dissolving sheet, a fragrance or bead, a fibrous article, a tablet, a bar, a flake, a dryer sheet, or a mixture thereof. The composition may be selected from a liquid, a solid, or a combination thereof.

[0027] The cleaning composition may be in the form of a unitized dose article, such as a tablet, pouch, sheet, or fibrous article. Such pouches typically include a water-soluble film, such as a polyvinyl alcohol water-soluble film, that at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition may be enclosed in a single compartment pouch or a multi-compartment pouch. A multi-compartment pouch may have at least two, at least three, or at least four compartments. A multi-compartment pouch may include side-by-side and / or stacked compartments. The composition contained in the pouch or its compartments may be liquid, solid (such as a powder), or a combination thereof. The pouch composition may have a relatively small amount of water, such as less than about 20% by weight of the detergent composition, or less than about 15% by weight, or less than about 12% by weight, or less than about 10% by weight, or less than about 8% by weight.

[0028] The oligoamines and additional processing aids of the present disclosure are described in more detail below.

[0029] Oligoamines The treatment composition of the present disclosure includes an oligoamine or a salt thereof. The oligoamine according to the present disclosure includes amine functional groups, which can be primary, secondary, or tertiary amines, linked via specific alkylene groups. Without being bound by theory, it is believed that the oligoamine of the present disclosure is capable of reacting with copper (Cu 2+ It is believed that these compounds are well suited to chelating certain metals such as benzoquinone, benzotriazole ...

[0030] The treatment composition according to the present disclosure can include a relatively low concentration of oligoamine. As mentioned above, it has been surprisingly found that low concentrations of the oligoamine of the present invention can provide malodor control benefits with minimal undesirable events such as discoloration / yellowing. The treatment composition according to the present disclosure can include about 0.01% to about 1.0%, or about 0.75%, or about 0.5%, or about 0.4%, or about 0.3%, or about 0.2%, or about 0.15% of the oligoamine by weight of the treatment composition. For purposes of this disclosure, the weight percent of the linear oligoamine is calculated using the weight of the free base form.

[0031] The oligoamines of the present disclosure can be considered linear oligoamines. By "linear" we mean that there are no further amine-containing side chains grafted onto the oligoamine backbone represented by formula I. However, it is understood that linear oligoamines, at least in some cases, can have alkyl groups attached to the oligoamine backbone, such as methyl or ethyl groups.

[0032] The oligoamines of the present disclosure can have the structure set forth in Formula I.

[0033] [ka] [In the formula, Each L is independently -(C m H 2m)-, the subscript m of each L is independently an integer from 2 to 6, preferably m is 2 to 3, and most preferably m is 2 (e.g., an ethylene group); n is an integer of 1 to 10, preferably 1 to 5 (i.e., triamine, tetramine, pentamine, hexamine, heptamine, etc.), more preferably 1 to 3, even more preferably 1 to 2, and most preferably 1; R 1 ~R 5 each is independently selected from H and C1-C4 alkyl, preferably H and methyl (i.e., C1 alkyl). When n is greater than 1, each R 5 are independently selected from the groups shown, with each R 5 It is understood that they can be the same.

[0034] The subscript m of each L can independently be an integer from 2 to 6, where the subscript m is 2 or 3, preferably 2, for each of two L groups that are directly linked to a common N atom. It is believed that having two such L groups adjacent to a common N atom promotes improved metal sequestration, even when the other L group is relatively large (e.g., has m greater than 2).

[0035] R 1 ~R 5 Each of R may be H. 5 R may be methyl. 5 may be H. 1 and R 3 One or both of R may be methyl. 1 and R 3 may be methyl, R 2 and R 4 R may both be hydrogen. 1 ~R 5 Each of R may be methyl. 1 ~R 5 It may be preferred that at least one of R 1 ~R 4 It is even more preferred that at least one of R is H. 1~R 4 can be H, R 5 are independently H and C 1 It may be selected from alkyl.

[0036] The composition comprises a compound represented by formula I above, where L, m, n, and R 1 ~R 5 is defined as above, except that if n is equal to 1, then R 5 is selected from H and a moiety having 1-10 carbons, or 1-6 carbons, or 1-4 carbons.

[0037] Depending on the type of product desired and / or the overall benefit space, formulators can select oligoamines with primary, secondary, and / or tertiary nitrogens, especially in terminal positions. Without being bound by theory, it is believed that the presence of primary nitrogen in the oligoamines may provide improved malodor control benefits, which may be due to improved chelating efficiency and / or coordination to target surfaces such as fabrics. Also, without being bound by theory, it is believed that the tertiary nitrogen in the oligoamines may be less likely to interact with other materials in the treatment composition, such as with certain perfume materials that may discolor liquid products as a result of reaction (e.g., Schiff base reaction).

[0038] Treatment compositions containing mixtures of various oligoamines of formula I are also part of the scope of this disclosure.

[0039] Suitable oligoamines according to the present disclosure can include diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetraamine (TETA), 4-methyltriethylenetetraamine (4-MeTETA), 4,7-dimethyltriethylenetetraamine (4,7-Me2TETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), tripropylenetetraamine (TPTA), tetraethylenepentamine (TEPA), tetrapropylenepentamine (TPPA), pentaethylenehexamine (PEHA), pentapropylenehexamine (PPHA), hexaethyleneheptamine (HEHA), hexapropyleneheptamine (HPHA), N,N'-bis(3-aminopropyl)ethylenediamine, or mixtures thereof.

[0040] The oligoamine is preferably diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetramine (TETA), tripropylenetetraamine (TPTA), tetraethylenepentamine (TEPA), tetrapropylenepentamine (TPTA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, more preferably diethylenetriamine. The diamine may be selected from diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, even more preferably diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, most preferably diethylenetriamine (DETA). DETA may be preferred due to its low molecular weight and / or relatively low manufacturing costs.

[0041] The oligoamine is diethylenetriamine ("DETA"), where m is equal to 2, n is equal to 1, and R 1 ~R 5 each of R 1 ~R 5 wherein one or more of the groups are alkyl groups such as methyl. The oligoamine may comprise at least 80%, or even at least 90%, or even at least 95% by weight of the oligoamine in the form of diethylenetriamine (DETA), and even more preferably the oligoamine consists of the form of diethylenetriamine (DETA). The oligoamine may be selected from DETA, 4-methyldiethylenetriamine (DETA), and mixtures thereof, preferably DETA (non-alkylated diethylenetriamine).

[0042] Depending on the pH of the final product or the wash solution, the nitrogen atom is protonated, partially or completely, resulting in the salt form of the oligoamine of formula I. These (partially) protonated oligoamines are also considered as part of the scope of the present disclosure. When the oligoamine is in salt form, the salt may not be a salt of an anionic surfactant.

[0043] The oligoamines of the present disclosure may have a molecular weight of about 100 to about 1200 Da, or about 100 to about 900 Da, or about 100 to about 600 Da, or about 100 to about 400 Da, preferably about 100 Da to about 250 Da, and most preferably about 100 Da to about 175 Da, or even about 100 Da to about 150 Da. For purposes of the present disclosure, molecular weight is measured using the free base form of the oligoamine.

[0044] Those skilled in the art will understand how to obtain the oligoamines according to the present disclosure. For example, oligoamines of formula I, where L has m equal to 2, can be obtained by reaction with ammonia and ethylene dichloride, followed by fractional distillation. Common oligoamines obtained are diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA). Through the use of suitable halogen disubstituted alkylenes, other oligoamines according to formula I with m equal to 2 to 6 can be formed.

[0045] Above the pentamines, i.e., hexanes, heptamines, octamines, and possibly nonamines, cogenerically derived mixtures are not expected to separate by distillation and may contain other substances such as cyclic amines, especially piperazines.

[0046] Suitable ethylenic oligoamines according to the present disclosure are commercially available from several chemical suppliers, including Dow, BASF, Huntsman, and Akzo Nobel Corporations.

[0047] Additional Processing Aids The treatment composition of the present disclosure can include additional treatment aids. The additional treatment aids can be suitable for delivering treatment effects to target surfaces, such as fabrics or other substrates. As used herein, treatment aids can also include agents that promote chemical or physical stability in the treatment composition, such as buffers, structuring / thickening agents, and / or carriers.

[0048] Processing aids may be present in the composition at a concentration suitable for the intended use of the composition.Typical use concentrations range from 0.001% by weight of the composition (for aids such as optical brighteners) to 50% by weight of the composition (for surfactants).

[0049] Processing aids can include surfactant systems, antioxidants, hueing agents, optical brighteners, additional chelating agents, enzymes, fatty acids and / or salts thereof, encapsulated benefit agents, soil release polymers, builders, dye transfer inhibitors, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersants, soil removal / anti-redeposition agents, polymeric grease cleaners, amphiphilic copolymers, defoamers, aesthetic dyes, fragrances (including encapsulated fragrances), structural elastomers, fabric softeners, carriers, fillers, hydrotropes, solvents, antimicrobials and / or preservatives, neutralizing agents and / or pH adjusters, processing aids, fillers, rheology modifiers or structuring agents, opacifiers, pearlescent agents, pigments, corrosion and / or color fastness agents, defoamers, chlorine scavengers, and mixtures thereof.

[0050] The processing aids may include surfactant systems, antioxidants, whitening or brightening agents such as hueing agents or optical brighteners, additional chelating agents, enzymes, or mixtures thereof. The additional aids may preferably include encapsulated benefit agents, which may be encapsulated perfumes, preferably encapsulated perfumes comprising a shell around a core, the shell comprising an amine compound and / or an acrylate polymer.

[0051] Some processing aids are discussed in more detail below.

[0052] Surfactant Systems The compositions according to the present disclosure can include a surfactant system. The surfactant system can consist of one type of surfactant. The surfactant system can include two or more types of surfactants. In particular, laundry detergents (such as heavy-duty liquid laundry detergents) can include surfactant systems, including systems including anionic surfactants.

[0053] The compositions of the present disclosure may comprise from about 1% to about 90% by weight of the composition, or from about 1% to about 80% by weight, or from 1% to about 70% by weight, or from about 2% to about 60% by weight, or from about 5% to about 50% by weight of the surfactant system. Liquid compositions may comprise from about 5% to about 40% by weight of the composition. Compact formulations, including compact liquids, gels, and / or compositions suitable for unit dosage forms, may comprise from about 25% to about 90% by weight of the composition, or from about 25% to about 70% by weight, or from about 30% to about 50% by weight of the composition.

[0054] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include linear alkylbenzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, alkyl ethoxylated carboxylates, nonionic surfactants (such as ethoxylated alcohols), amine oxides, or mixtures thereof. The surfactants may be derived, at least in part, from natural sources, such as natural feedstock alcohols.

[0055] The surfactant system can include an anionic surfactant. The molar ratio of the anionic surfactant to the protonatable amine in the oligoamine can be less than about 15:1. In such a case, the oligoamine can have a structure according to formula I, where the subscript n is an integer from 2 to 5.

[0056] Suitable anionic surfactants can include any conventional anionic surfactant. It may include, for example, sulfate detergent surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid detergent surfactants, such as alkylbenzene sulfonates. The anionic surfactants can be linear, branched, or combinations thereof. Preferred surfactants include linear alkylbenzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactants can be in acid form, salt form, or mixtures thereof. The anionic surfactants may be partially or fully neutralized, for example, with an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine). The anionic surfactant may be pre-neutralized, preferably with an alkali metal, alkaline earth metal, amine such as ethanolamine, or mixtures thereof. The anionic surfactant is preferably not (pre-)neutralized with the oligoamines of the present disclosure.

[0057] 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, alkoxypolysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(oxyalkylated) alcohol surfactants, and combinations 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. Specific 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.

[0058] Suitable zwitterionic surfactants include alkyl dimethyl betaines and coco dimethyl amidopropyl betaines, C8-C 18 (For example, C 12 ~C 18 ) amine oxides (e.g., C 12 ~C 14 dimethylamine oxide), and / or sulfo and betaine, e.g., alkyl groups having C8-C 18 , or C 10 ~C 14 The zwitterionic surfactant may include any conventional zwitterionic surfactant, such as betaines, including N-alkyl-N,N-dimethylamino-1-propanesulfonates, which may be: Zwitterionic surfactants may include amine oxides.

[0059] Fabric conditioning active agent The treatment composition of the present disclosure can include fabric conditioning actives (FCA). Such actives-containing compositions, such as liquid fabric enhancing compositions, can be useful for providing various benefits to target fabrics, including softness, wrinkle prevention, static prevention, conditioning, stretch prevention, color and / or appearance benefits. Suitable fabric conditioning actives (FCA) for the composition of the present disclosure can include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty acid esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening oils or conditioning oils, polymer latexes, or combinations thereof.

[0060] Antioxidants The composition of the present disclosure can include an antioxidant. Without being bound by theory, it is believed that the antioxidant can be useful for improving the malodor control and / or cleaning performance of the composition, especially in combination with the oligoamine of the present disclosure. The antioxidant can also be useful for reducing the yellowing that may be associated with amines, thus allowing the amines to be formulated at relatively high concentrations. The antioxidant is a material as described in Kirk-Othmer (vol. 3, p. 424) and Ullmann's Encyclopedia (vol. 3, p. 91).

[0061] The compositions of the present disclosure may include an antioxidant, preferably a hindered phenol antioxidant, in an amount of from about 0.001% to about 2%, preferably from about 0.01% to about 0.5% by weight of the composition.

[0062] Suitable antioxidants include those having the general formula:

[0063] [ka] wherein R is each a C1-C aryl group which (1) optionally has one or more ester (-CO2-) or ether (-O-) linkages therein, and (2) is optionally substituted with an organic group containing an alkyleneoxy or polyalkyleneoxy group selected from EO (ethoxy), PO (propoxy), BO (butoxy), and mixtures thereof, more preferably EO alone or EO / PO mixtures. 22 Straight chain alkyl or C3-C 22 branched alkyl, R is preferably methyl, branched C3-C6 alkyl, or C1-C6 alkoxy, preferably methoxy, R1 is C3-C6 branched alkyl, preferably tert-butyl, and x is 1 or 2.

[0064] A preferred class of alkylated phenols having this formula includes hindered phenol compounds. As used herein, the term "hindered phenol" refers to a phenol having (a) at least one C3 or higher branched alkyl, preferably a C3-C6 branched alkyl, preferably tert-butyl, bonded in an ortho position relative to at least one phenolic -OH group, or (b) independently a C1-C6 alkoxy, preferably methoxy, ... 22 Straight chain alkyl or C3-C 22It is used to refer to a compound containing a phenol group having any of the substituents selected from the group consisting of branched alkyl, preferably methyl or branched C3-C6 alkyl, or mixtures thereof. If the phenyl ring contains multiple -OH groups, the compound is a hindered phenol as long as at least one such -OH group is substituted as described immediately above. If any R group in the above structure contains three or more consecutive monomers, the antioxidant is defined herein as a "polymeric hindered phenol antioxidant." The compositions according to the present disclosure may include a hindered phenol antioxidant. A preferred hindered phenol antioxidant includes 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

[0065] A further class of hindered phenol antioxidants that may be suitable for use in the compositions is represented by the following formula:

[0066] [ka] [wherein R1 and R2 are each independently alkyl, or R1 and R2 together may form a C5-C6 cyclic hydrocarbyl moiety; B is absent or CH2; R4 is a C1-C6 alkyl; R5 is hydrogen or -C(O)R3; and R3 is hydrogen or a C1-C6 alkyl group. 19 R is an alkyl, R is a C1-C6 alkyl, R is hydrogen or a C1-C6 alkyl, X is -CH2OH or -CH2A, and A is a nitrogen-containing unit, phenyl, or substituted phenyl. Preferred nitrogen-containing A units include amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.

[0067] Suitable hindered phenol antioxidants can include 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, methyl ester, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, octadecyl ester, or mixtures thereof.

[0068] Commercially available antioxidants that may be suitable include BHT, RALOX 35™, and / or TINOGARD TS™.

[0069] Additional antioxidants may be used. Examples of antioxidants suitable for use in the composition include, but are not limited to, the group consisting of α-, β-, γ-, δ-tocopherol, ethoxyquin, 2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and its salts, and mixtures thereof. It is noted that ethoxyquin (1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is sold under the name Raluquin™ by Raschig™. Other types of antioxidants that may be used in the composition are 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox™) and 1,2-benzisothiazolin-3-one (Proxel GXL™). Antioxidants such as tocopherol sorbate, butylated hydroxylbenzoic acid and its salts, gallic acid and its alkyl esters, uric acid and its salts, sorbic acid and its salts, and dihydroxyfumaric acid and its salts may also be useful. Other useful antioxidants may include tannins, such as tannins selected from the group consisting of gallotannins, ellagitannins, complex tannins, condensed tannins, and combinations thereof.

[0070] In some cases, it may be preferable to use a non-yellowing antioxidant, such as a non-yellowing hindered phenol antioxidant. Antioxidants that form such yellow by-products may be avoided if they lead to perceived negative attributes in the consumer experience (e.g., deposition of yellow by-products on fabrics, etc.). Those skilled in the art can make an informed decision regarding the selection of antioxidants to use.

[0071] Whitening Agent / Brightener Additional processing aids of the present disclosure may include whitening or brightening agents. Such agents may be selected from hueing agents, optical brighteners, or mixtures thereof. The use of such agents may further reduce the effect of discoloration or yellowing and may allow the incorporation of higher concentrations of oligoamines.

[0072] The composition of the present disclosure can include a hueing agent. Surprisingly, it has been discovered that the grafted polymer according to the present disclosure can inhibit the migration of easily migrating dyes without significantly affecting the adhesion and / or performance of the hueing agent on the target fabric.

[0073] Hueing agents (sometimes called hue dyes, fabric shading dyes, or bluing or whitening agents) typically impart a blue or purple hue to a fabric. Such agents are well known in the art and can be used either alone or in combination to create particular shades of hue and / or shade various types of fabrics. The hueing agent may be selected from any suitable chemical class of dyes known in the art, including, but not limited to, acridines, anthraquinones (including polycyclic quinones), azines, azos (e.g., monoazos, disazos, triazos, tetrakisazos, polyazos), benzodifurans, benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethanes, formazans, hemicyanines, indigoids, methanes, naphthalimides, naphthoquinones, nitros, nitroso, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof. The hueing agent may be selected from azo agents, triarylmethane agents, triphenylmethane agents, or mixtures thereof.

[0074] Suitable hueing agents include fabric shading dyes such as small molecule dyes, polymeric dyes, and dye-clay conjugates. Preferred fabric shading dyes are selected from small molecule dyes and polymeric dyes. Suitable small molecule dyes can be selected from the group consisting of dyes that fall under the Colour Index (CI, Society of Dyers and Colourists, (Bradford, UK)) classification of acid dyes, direct dyes, basic dyes, reactive dyes, solvent dyes, or disperse dyes.

[0075] Suitable polymeric dyes include dyes selected from the group consisting of polymers containing covalently bound (sometimes referred to as conjugated) chromogens (also known as dye-polymer conjugates), such as polymers having chromogen monomers copolymerized in the polymer backbone, and mixtures thereof. Preferred polymeric dyes include optionally substituted alkoxylated dyes such as alkoxylated triphenylmethane polymeric colorants, alkoxylated carbocyclic azo colorants, and alkoxylated thiophene polymeric colorants, including alkoxylated heterocyclic azo colorants, and mixtures thereof, such as the mordant-free fabric dye sold under the name Liquitint® (Milliken, Spartanburg, (South Carolina, USA)).

[0076] Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic dye / basic dye and smectite clay, preferred clays may be selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof.

[0077] Pigments are well known in the art and may also be used as hueing agents in the fabric care compositions disclosed herein. Suitable pigments include CI Pigment Blues 15-20, particularly 15 and / or 16, CI Pigment Blue 29, CI Pigment Violet 15, Monastral Blue, and mixtures thereof.

[0078] The amount of auxiliary hueing agent present in the laundry care composition of the present invention can be from 0.0001 to 0.05% by weight of the total cleaning composition, preferably from 0.0001 to 0.005% by weight. Based on the wash liquor, the concentration of the hueing agent can typically be from 1 ppb to 5 ppm, preferably from 10 ppb to 500 ppb.

[0079] The compositions of the present disclosure can include optical brighteners. Optical brighteners, sometimes called fluorescent whitening agents, are capable of emitting at least some visible light.

[0080] Commercially available optical brighteners that may be used herein can be classified into subgroups that include, but are not necessarily limited to, derivatives of stilbenes, pyrazolines, coumarins, carboxylic acids, methinecyanines, dibenzothiphene-5,5-dioxides, azoles, 5- and 6-membered heterocycles, and various other agents. The brighteners may be added in particulate form or as a premix with a suitable solvent, such as a nonionic surfactant, monoethanolamine, and / or propanediol.

[0081] Suitable optical brighteners include disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenzyl sulfonate (brightener 15 available from BASF under the trade name Tinopal AMS-GX); disodium 4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbenzyl disulfonate (available from BASF under the trade name Tinopal UNPA-GX); disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenzyl sulfonate (available from BASF under the trade name Tinopal UNPA-GX); and / or disodium 4,4'-bis((4-amino-6-anilino-1,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfonate (brightener 49). The brightener can be brightener 49, brightener 15, brightener 3, or a mixture thereof.

[0082] Additional Chelating Agents The additional processing aids of the present disclosure can include additional chelating agents (also known as chelant or chelating agents). The additional chelating agents can be selected to have affinity for metal ions different from those for which the oligoamine has affinity. For example, the oligoamine DETA of the present disclosure has a particular affinity for copper ions, while another chelating agent DTPA has a particular affinity for calcium ions. Thus, a composition with a combination of chelating agents can provide broad spectrum metal ion sequestration and therefore improved performance. For example, it may be preferred to combine a copper chelating agent such as the oligoamine of the present disclosure with a calcium chelating agent such as DTPA and / or HEDP to optimize cleaning performance by improving / maximizing chelating agent usage in the composition formulation while maintaining enzyme stability.

[0083] The additional chelating agent may be present in a concentration of about 0.1% to about 10% by weight of the composition, or about 5% by weight, or about 2% by weight. The oligoamine and the additional chelating agent may be present in the treatment composition in a combined concentration of about 0.1% to about 10% by weight of the treatment composition, preferably about 5% by weight. The weight ratio of the oligoamine to the additional chelating agent may be about 10:1 to about 1:50, or about 1:1 to about 1:25, or about 1:2 to about 1:20. The amount of the oligoamine present by weight may be less than the amount of the additional chelating agent present by weight.

[0084] Suitable additional chelating agents may include phosphonates, aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, or mixtures thereof, preferably aminocarboxylates. As used herein, additional chelating agents is not intended to include traditional builders such as citric acid, although such builders may be present in the compositions of the present disclosure.

[0085] Aminocarboxylates useful as chelating agents include, but are not limited to, ethylenediaminetetraacetate, N-(hydroxyethyl)ethylenediaminetriacetate, nitrotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanoldiglycine, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.Aminophosphonates are also suitable for use with chelating agents in the compositions of the present invention when low concentrations of total phosphorus are acceptable, and include ethylenediaminetetrakis(methylenephosphonate).Polyfunctionally substituted aromatic chelating agents can include catechols, such as sulfonated catechols.

[0086] Additional chelating agents may include DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethanediphosphonic acid), EDDS (ethylenediaminedisuccinate (EDDS)), DTPMP (diethylenetriaminepenta(methylenephosphonic acid)), EDTMP (ethylenediaminetetra(methylenephosphonic acid)), Tiron® (1,2-dihydroxybenzene-3,5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycinediacetic acid), GLDA (glutamine-N,N-diacetic acid), any suitable derivatives thereof, salts thereof, and mixtures thereof.

[0087] enzyme The treatment composition of the present disclosure may comprise one or more enzymes that provide cleaning performance and / or fabric care benefits.Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, mannanase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, amylase, nuclease (such as deoxyribonuclease and / or ribonuclease), phosphodiesterase, or mixtures thereof.Mixtures of protease, amylase, lipase, cellulase, phosphodiesterase, and / or pectate lyase may be particularly preferred. The compositions of the present disclosure can include an oligoamine of the present disclosure, a calcium-binding chelator such as DTPA, and an amylase.

[0088] Other agents The treatment composition of the present disclosure may include a solvent, preferably an organic solvent such as a non-amino functional organic solvent. Suitable organic solvents include glycerol, ethylene glycol, 1,3 propanediol, 1,2 propanediol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, 2,3-butanediol, 1,3 butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol formal dipropylene glycol, polypropylene glycol, dipropylene glycol n-butyl ether, and mixtures thereof.

[0089] The treatment composition of the present disclosure may include a chlorine scavenger. It is believed that chloride ions in the treatment solution, for example from hypochlorite bleach or naturally present in water resources, may contribute to fading or other discoloration. The chlorine scavenger may be incorporated at a concentration sufficient to neutralize at least about 1 ppm, or at least about 2 ppm, or at least about 5 ppm, or at least about 10 ppm of chlorine in the treatment solution. The chlorine scavenger may include an amine (other than the oligoamines listed above) and / or an ammonium salt. Preferred amines may include those that include primary and / or secondary amines, and may include alkanolamines such as monoethanolamine (MEA), diethanolamine (DEA), and / or triethanolamine (TEA).

[0090] The treatment compositions of the present disclosure may contain cleaning and / or dispersion polymers, which may impart cleaning and / or whitening benefits. Suitable cleaning and / or dispersion polymers may include: soil release polymeric agents, which may be anionic or nonionic and / or may contain terephthalate moieties; alkoxylated polyamines, such as ethoxylated and / or propoxylated polyethyleneimines (such as PEI600 EO20 and / or PEI EO24 PO16), ethoxylated hexamethylenediamines, and sulfates thereof; alkoxylated polycarboxylates, including those derived from polyacrylates; amphiphilic graft copolymers, such as those derived from a polyethylene glycol backbone and having at least one pendant moiety selected from polyvinyl acetate, polyvinyl alcohol, or mixtures thereof (such as Sokalan HP22); cellulose polymers, such as carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof; carboxylate polymers, maleate / acrylate random copolymers, or polyacrylate homopolymers; or mixtures thereof. Cellulosic and / or carboxylate polymers may be particularly useful in dry or powder compositions since they can be more difficult to formulate in liquid and gel forms.

[0091] In particular, when a detergent that is primarily derived from natural or sustainable resources is desired, it may be desirable to limit or even eliminate certain adjuvants.The detergent composition of the present disclosure may be free of silicones, dyes, brighteners, or combinations thereof.The detergent composition of the present disclosure may contain less than 5% by weight, or less than 3% by weight, or less than 1% by weight of the composition of amine-containing compounds, provided that amine oxide surfactants (if present) are not included in the total amount of amine-containing compounds.

[0092] The compositions of the present disclosure may be substantially free of selenium compounds.The detergent compositions of the present disclosure may be substantially free of halopropargyl compounds.

[0093] Method for making the composition The present disclosure relates to a method of making a fabric care composition comprising the oligoamines described herein. The method may include combining the components of the compositions described herein in the proportions described. For example, the oligoamines of the present disclosure may be provided and combined with at least one additional processing adjunct to form a treatment composition.

[0094] The liquid compositions of the present disclosure may be manufactured according to conventional methods, for example, in a batch process or a continuous loop process.

[0095] The solid compositions of the present disclosure can be made by conventional methods, such as by a spray drying process or in an agglomeration process.

[0096] The detergent composition described herein can be enclosed in a pouch, preferably a pouch made of water-soluble film, to form a unit dose article that can be used to treat fabric.The pouch can include one compartment, or can have multiple compartments, which can be side-by-side and / or stacked.Such compositions may preferably have a relatively small amount of water, for example, less than about 20% by weight of the detergent composition, or less than about 15% by weight, or less than about 12% by weight, or less than about 10% by weight, or less than about 8% by weight.

[0097] Methods of using the composition The present disclosure relates to methods of using the compositions described herein. The detergent compositions can be fabric care compositions and can be used to treat surfaces such as fabrics or other substrates.

[0098] A method for treating a surface can include providing a surface, preferably a fabric, and contacting the surface with a composition of the present disclosure, as described above. The method can include agitating the fabric in the presence of water. The method can further include performing a washing or cleaning operation. Water can be added before, during, or after the contacting step to form a treatment solution. The water and / or treatment solution can contain copper ions (Cu), for example at a concentration of 0.1 ppm to about 25 ppm. 2+ ).

[0099] The present disclosure further relates to a process for treating fabrics, preferably soiled fabrics, using a composition of the present disclosure, e.g., by machine, comprising placing a composition of the present disclosure in contact with the fabric to be treated and performing a treatment operation, e.g., a washing, cleaning, or fabric strengthening operation. The contacting step can occur during the wash cycle or during the rinse cycle of an automatic washing machine.

[0100] Any suitable washing machine can be used, for example, a top-loading or front-loading automatic washing machine. Those skilled in the art will recognize suitable machines for the relevant processing operations. The articles of the present disclosure may be used in combination with other compositions, such as fabric additives, fabric softeners, rinse aids, etc. Furthermore, the detergent compositions of the present disclosure may be used in known hand washing methods.

[0101] The present disclosure may also be directed to a method of treating fabrics, comprising contacting the fabrics with a detergent composition as described herein, performing a washing step, and then contacting the fabrics with a fabric softening composition. The entire method, or at least the washing step, may be performed manually, machine assisted, or in an automatic washing machine. The step of contacting the fabrics with the fabric softening composition may be performed in the presence of water, for example, during the rinse cycle of an automatic washing machine.

[0102] combination Specifically contemplated combinations of the present disclosure are set forth herein in the alphabetized paragraphs below, and are intended to be exemplary in nature and not limiting.

[0103] A. From about 0.01% to about 1.0% by weight of the treatment composition of an oligoamine and / or salt thereof having a structure according to Formula I:

[0104] [ka] [In the formula, L is independently -(C m H 2m )-, the subscript m of each L is independently an integer from 2 to 6, n is an integer from 1 to 10, and R 1 ~R 5 are each independently selected from H and C1-C4 alkyl, and an additional processing adjuvant. B. The treatment composition of paragraph A, wherein the treatment composition comprises from about 0.01% to about 0.75%, or to about 0.5%, or to about 0.4%, or to about 0.3%, or to about 0.2%, or to about 0.15% by weight of the treatment composition of an oligoamine. C. The treatment composition of any one of paragraphs A or B, wherein the subscript m is 2 or 3, preferably the subscript m is 2. The treatment composition of any one of paragraphs A to C, wherein Dn is an integer from 1 to 5, preferably 1 to 3, more preferably 1 or 2, or even more preferably 1. ER 1 ~R 5 is independently selected from H and C alkyl, preferably R 1 ~R 5 At least one of R is H, more preferably 1 ~R 4 The treatment composition of any one of paragraphs AD, wherein at least one of is H, or even more preferably, all are H. F. The treatment composition of any one of paragraphs A-E, wherein the oligoamine is characterized by a molecular weight of from about 100 to about 1200 Da, or from about 100 to about 900 Da, or from about 100 to about 600 Da, or from about 100 to about 400 Da, or preferably, from about 100 Da to about 250 Da, more preferably from about 100 Da to about 200 Da, and even more preferably, from about 100 Da to about 150 Da. G. Oligoamines include diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetraamine (TETA), 4-methyltriethylenetetraamine (4-MeTETA), 4,7-dimethyltriethylenetetraamine (4,7-Me2TETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA) , tripropylenetetraamine (TPTA), tetraethylenepentamine (TEPA), tetrapropylenepentamine (TPPA), pentaethylenehexamine (PEHA), pentapropylenehexamine (PPHA), hexaethyleneheptamine (HEHA), hexapropyleneheptamine (HPHA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof. H. The treatment composition of any one of paragraphs A-G, wherein the oligoamine is selected from the group consisting of diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, preferably diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof. I. The treatment composition of any one of paragraphs AH, wherein the oligoamine comprises diethylenetriamine (DETA). J. The treatment composition of any one of paragraphs A-I, wherein the additional processing aid is selected from surfactant systems, fabric conditioning actives (FCAs), antioxidants, hueing agents, optical brighteners, additional chelating agents, enzymes, fatty acids and / or salts thereof, encapsulated benefit agents, soil release polymers, builders, dye transfer inhibitors, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersants, soil removal / anti-redeposition agents, polymeric grease cleaners, amphiphilic copolymers, suds suppressors, aesthetic dyes, fragrances, structural elastifiers, fabric softeners, carriers, fillers, hydrotropes, solvents, antimicrobials and / or preservatives, pH adjusters, processing aids, fillers, rheology modifiers, structurants, opacifiers, pearlescent agents, pigments, corrosion inhibitors, color retarders, defoamers, chlorine scavengers, and mixtures thereof. K. The treatment composition of any one of paragraphs A-J, wherein the additional treatment adjunct comprises a surfactant system, preferably, the surfactant system comprises an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, a cationic surfactant, or a combination thereof, more preferably, the surfactant system comprises an anionic surfactant. L. The treatment composition of paragraph K, wherein the anionic surfactant is pre-neutralized, preferably with an alkali metal, alkaline earth metal, amine, or mixtures thereof. M. The treating composition of any one of paragraphs K or L, wherein the molar ratio of anionic surfactant to protonatable amine in the oligoamine is less than about 15:1, preferably wherein in the oligoamine of formula I, the subscript n is an integer from 2 to 5. N. The processing composition of any one of paragraphs A through M, wherein the additional processing aid comprises an antioxidant, preferably an antioxidant that comprises a hindered phenol. O. The treatment composition of any one of paragraphs A-N, wherein the additional processing aid comprises a whitening or brightening agent, preferably a whitening or brightening agent selected from a hueing agent, an optical brightener, or mixtures thereof. P. The processing composition of any one of paragraphs A-O, wherein the additional processing adjunct comprises an additional chelating agent, preferably selected from a phosphonate, an aminocarboxylate, an aminophosphonate, a polyfunctionally substituted aromatic chelating agent, or mixtures thereof, more preferably an additional chelating agent selected from DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethanediphosphonic acid), EDDS (ethylenediaminedisuccinic acid (EDDS), DTPMP (diethylenetriaminepenta(methylenephosphonic acid)), EDTMP (ethylenediaminetetra(methylenephosphonic acid)), Tiron® (1,2-dihydroxybenzene-3,5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycinediacetic acid), GLDA (glutamic acid-N,N-diacetic acid), any suitable derivatives thereof, salts thereof, and mixtures thereof. Q. The treatment composition of any one of paragraphs A-P, wherein the weight ratio of oligoamine to additional chelating agent is from about 10:1 to about 1:50, or from about 1:1 to about 1:25, or from about 1:2 to about 1:20. R. The treatment composition of any one of paragraphs A-Q, wherein the oligoamine and the additional chelating agent are present in the treatment composition in a combined concentration of from about 0.1% to about 10%, preferably from about 0.5% to about 5%, by weight of the treatment composition. S. The treatment composition of any one of paragraphs A-R, wherein the additional processing aid comprises an enzyme, preferably the enzyme is selected from proteases, amylases, lipases, cellulases, phosphodiesterases, pectate lyases, and mixtures thereof. T. The treatment composition of any one of paragraphs A-S, wherein the treatment composition is a laundry detergent composition. U. The treatment composition of any one of paragraphs A-T, 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 fragrance or bead, a fibrous article, a tablet, a bar, a flake, a dryer sheet, or a mixture thereof, preferably in the form of a liquid composition. V. A process for treating a surface, preferably a fabric, providing a surface, preferably the surface is a fabric, more preferably the surface is a fabric soiled with oil; contacting the surface with a composition of any one of paragraphs A through U, optionally in the presence of water; The process includes:

[0105] Test Method Test method for odor reduction The following method is used to test the malodor reducing effectiveness of the compositions.

[0106] A. Preparation of 75 grams of odor marker The fatty acids and malodor markers are placed in a 100 mL glass jar with a Teflon-lined cap as described in Table A and mixed thoroughly using a vortex.

[0107] [Table 1]

[0108] B. Preparation of Body Soil Malodor Compositions A 200 mL glass jar with a Teflon-lined cap was filled with the specific amount of each material listed in Table B. Artificial body soil (ABS) is commercially available from Accurate Product Development; 2028 Bohlke Blvd, Fairfield, Ohio 45014.

[0109] [Table 2]

[0110] C. Preparation of Fabrics for Odor Testing Prepare 16 malodor test fabrics per wash load by applying 300 μL of the body soil malodor composition described in Table B to a desized 2×5 inch white polycotton 50 / 50 (PCW50 / 50) swatch. Place 48 grams of liquid detergent to be tested (see, for example, Example 1, Table 1 below) in a Duet 9200 washing machine set for a normal cycle; 77° F. wash cycle followed by a 60° F. rinse cycle. Use tap water containing an appropriate amount of copper, for example, via a copper piping system. Wash the malodor test fabrics with 7 gpg of wash water together with 3.9 kg of clean cotton and polycotton ballast, 50×50 cm, then dry in a Maytag double stack tumble dryer set at low temperature for 20 minutes. Place the dried fabrics in a Mylar bag and seal for 24 hours.

[0111] D. Analytical detection of malodours on fabrics Malodor reduction is quantitatively measured using the ABS / squalene malodor sensor by gas chromatography mass spectrometry using an Agilent gas chromatograph 7890B equipped with a mass selective detector (5977B), a Chemstation quantitation package, and a Gerstel multipurpose sampler equipped with a solid phase microextraction (SPME) probe. Calibration standards 6-methyl-5-hepten-2-one (CAS 110-93-0), trans-2-heptenal (18829-55-5), and 3-methyl-2-butenal (107-86-8) are prepared by dissolving known weights of these materials in light mineral oil (CAS 8020-83-5) (each material is commercially available from Sigma Aldrich). Fabrics are cut into 2" x 2.5" test pieces and placed in 10 mL headspace crimp vials. Vials are allowed to equilibrate for over 12 hours before analysis. The following settings are used for the autosampler: incubation temperature of 80C, incubation time of 90 minutes, sample tray type of VT32-10, vial penetration of 22 mm, extraction time of 20 minutes, injection penetration of 54 mm, and desorption time of 300 seconds. For the Front Split / Splitless inlet helium, the following settings are used: split mode, temperature of 250C, pressure of 12 psi, total flow rate of 79.5 mL / min, septum purge flow rate of 3 mL / min, split ratio of 50:1, and GC run time of 22.5 minutes. The following settings are used for the oven: initial temperature of 40C, heating program of 12°C / min, temperature of 250C, and hold time of 5 minutes. Based on the partition coefficients (K at 80° C.) of each component, calculate the total nmol / L for 6-methyl-5-hepten-2-one (K=3353), trans-2-heptenal (K=3434), and 3-methyl-2-butenal (K=1119).

[0112] These values ​​for these three measurements (nmol / L) are combined to provide the total ABS / squalene marker (nmol / L) for a given study group.

[0113] E. Calculation of odor reduction rate (%) of oxidation products The % reduction in malodor of oxidation products provides the reduction in the amount of a selected malodor marker caused by the test composition as a percentage compared to that of a reference composition (containing no oligoamines). The values ​​are measured as follows: Reduction rate of oxidation products (%) = (marker ref -marker test ) x 100 / marker ref

[0114] marker ref and marker test Define the values ​​of as follows: marker ref = Total ABS / Squalene marker (nmol / L) for fabrics washed with formulations not containing oligoamines (e.g., reference or control formulations). marker test = Total ABS / squalene marker (nmol / L) for fabrics washed with formulations containing test oligoamines

[0115] Since the oxidation products measured are typically considered to be malodorous, it is believed that the higher the reduction of oxidation products provided by the composition, the less likely the treated fabric will be malodorous.Therefore, a higher value of the reduction of malodorous oxidation products is typically preferred.The composition and process of the present disclosure can provide a value of the reduction of malodorous oxidation products (%) of at least about 10%, or at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%.

[0116] Testing the whiteness degradation test method The following procedure is used to test for brightness loss (eg, ΔWI).

[0117] A. Preparation of fabric for whiteness test Desized cotton, polycotton, and polyester whiteness test fabrics can be ordered from WFK (WFK Testgewebe GmbH, Christenfeld 10, D-41379 Bruggen, Germany). Four of each type of fabric (12 fabrics in total) are prepared for whiteness testing by washing four times with 48 grams (750 ppm) Tide Free and Clear and 25 grams (390 ppm) Downy Free rinse in a Kenmore Top Loader set at normal wash cycle, 77F wash, 60F wash, 7 gpg. An initial whiteness reference measurement is made using a Konica Minolta spectrophotometer and reported as an Initial Whiteness Index CIE. The Whiteness Index CIE value is a common index for whiteness and refers to measurements made under D65 illumination, which is a standard reproduction of outdoor daylight. A completely reflective, non-fluorescent white material has a CIE whiteness of 100. In technical terms, whiteness is a single index that refers to the relative degree of whiteness of a near-white material under certain lighting conditions. The index is designed so that most people would agree that the higher the whiteness index, the whiter the material.

[0118] B. Whiteness test The fabrics are placed in a 7.57 liter custom washing tub under the conditions summarized in Table 3 below. The fabrics are washed with 5.65 grams (746 ppm) of detergent (Liquid TIDE®) in the wash cycle along with background soil, followed by 3 grams (396 ppm) of liquid fabric softener (DOWNY® Free) in the rinse cycle. After the rinse cycle, all fabrics are removed and placed in a tumble dryer. This is repeated for 10 wash, rinse, and dry cycles. After 10 cycles, the whiteness loss of the fabrics is measured using a Konica Minolta spectrophotometer, and the measurement is reported as the Final Whiteness Index. The average delta WI (or ΔWI), which represents the difference between the initial and post-treatment whiteness index measurements, is calculated for each fabric tested and expressed as the following formula: ΔWI=Initial Whiteness Index after Preparation-Post-treatment Whiteness Index after 10-20 cycles. Typically, whiteness tends to decrease after washing with background soil, so ΔWI is a negative value. The whiteness index is reported in the table as ΔΔWI=ΔWI test with oligoamine-ΔWI REF (without oligoamine). If whiteness tends not to decrease after washing with the test liquid detergent composition containing oligoamine compared with the reference liquid detergent composition without oligoamine, ΔΔW is a negative value. A number close to zero indicates that oligoamine has little effect on the yellowing of fabric.

[0119] [Table 3] EXAMPLES

[0120] The examples provided below are intended to be illustrative and not limiting in nature.

[0121] Example 1. Representative Formulation (Heavy Duty Liquid Laundry Detergent) The following heavy duty liquid laundry detergent compositions can be prepared by conventional methods known to those skilled in the art by mixing the ingredients listed in Table 1. Composition 1A is a conventional premium laundry detergent that does not contain the linear oligoamines of the present disclosure. Composition 1B is a comparative example that includes an EDDS chelating agent.

[0122] [Table 4] 1. Linear alkylbenzene sulfonate having an average aliphatic carbon chain length of C11-C12, supplied by Stepan, Northfield, Illinois, USA. 2. AE9 is a C12-14 alcohol ethoxylate with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA. 3. Diethylenetetraaminepentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA; hydroxyethane diphosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark may also be used. 4. Polyethylenimine (MW=600) with 20 ethoxylate groups per -NH. 5. The amphiphilic alkoxylated grease-cleaning polymer is a polyethyleneimine (MW=600) with 24 ethoxylate groups per -NH and 16 propoxylate groups per -NH. 6. Proteases may be those supplied by Genencor International (Palo Alto, California, USA) (e.g., Purafect Prime®) or those supplied by Novozymes (Bagsvaerd, Denmark) (e.g., Liquanase®, Coronase®). 7. Natalase®, Mannaway® are all products of Novozymes, Bagsvaerd, Denmark. 8. Suitable optical brighteners are, for example, Tinopal® AMS, Tinopal® CBS-X. 9. Diethylenetriamine (DETA) 10. N,N'-bis(3-aminopropyl)ethylenediamine 11. Tetraethylenepentamine (TEPA)

[0123] Example 2. Comparison of Oligoamines and Known Chelating Agents for Malodor Control To demonstrate the malodor control effectiveness of the oligoamines of the present disclosure, various liquid detergent compositions are prepared according to Example 1A above, Table 1. Some have one or more conventional chelating agents and some contain the linear oligoamines of the present disclosure.

[0124] Example 2A is a premium laundry detergent containing a conventional chelating agent (diethylenetetraaminepentaacetic acid (DTPA)). Additional amines are added to Examples 2B, 2C, 2D, and 2E. Example 2B contains an additional amino chelating agent, ethylenediaminedisuccinic acid (EDDS). Examples 2C, 2D, and 2E contain oligoamines of the present disclosure, as detailed in Table 2 below. The compositions are tested for percent reduction in oxidation products according to the test method provided above. The results are shown in Table 2.

[0125] [Table 5] 1 N,N'-bis(3-aminopropyl)ethylenediamine has the following structure:

[0126] [ka]

[0127] The results in Table 2 show the malodor control effectiveness of the linear oligoamines of Examples 2C, 2D, and 2E compared to the composition of 2A containing no additional amine. Examples 2C, 2D, and 2E also show improved malodor control compared to Example 2B, indicating that the oligoamines perform better than a different amine-containing chelating agent, EDDS.

[0128] Example 3. Comparison of linear oligoamines with other amines (1) for odor control To demonstrate the malodor control effectiveness of the oligoamines of the present disclosure compared to other amines, various additional amines are formulated into Liquid Detergent Composition A (see Example 1, Table 1 above) as shown in Table 3. Fabrics are treated with the compositions on a North American style vertical machine. The compositions are tested for percent reduction in oxidation products according to the test method provided above. The results are shown in Table 3.

[0129] [Table 6] 1 DETA is diethylenetriamine commercially available from Aldrich.

[0130] [ka] 2 Methylated DETA is N1-(2-aminoethyl)-N1-methylethane-1,2-diamine.

[0131] [ka] 3 Dytec DHC 99 is a 1,2-diaminocyclohexane marketed by Aldrich.

[0132] [ka] 4Jeffamine ERD 148 is 2,2'-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine) marketed by Huntsman.

[0133] [ka] 5 Dytec EP is a 1,3-pentanediamine marketed by Aldrich.

[0134] [ka]

[0135] As shown in Table 3, Examples 3B and 3C, which contain linear oligoamines of the present disclosure, show improved malodor control efficacy compared to the control composition (Example 3A), whereas Comparative Examples 3D, 3E, and 3F do not show comparable malodor control efficacy according to the data in Table 3.

[0136] Example 4. Comparison of Oligoamines with Other Amines (2) for Malodor Control To demonstrate the malodor control effectiveness of the oligoamines of the present disclosure compared to other amines, various additional amines are formulated into Liquid Detergent Composition A (see Example 1, Table 1 above) as shown in Table 4. Fabrics are treated with the compositions on a North American style vertical machine. The compositions are tested for percent reduction in oxidation products according to the test method provided above. The results are shown in Table 4.

[0137] [Table 7] 1 N1-(3-aminopropyl)-N1-methylpropane-1,3-diamine has the following structure:

[0138] [ka]

[0139] As shown in Table 4, Examples 4B and 4C, which contain oligoamines of the present disclosure, show improved malodor control efficacy compared to the control composition (Example 4A), whereas Comparative Examples 4D, 4E, and 4F do not show comparable malodor control efficacy according to the data in Table 4.

[0140] Example 5. Control of the odor of DETA To demonstrate the malodor control effect of diethylenetriamine (DETA), various amounts of DETA are incorporated into liquid detergent composition 1A (see Table 1 above) according to the amounts shown in Table 5 (shown as weight % of the composition). Test fabrics were treated in a drum machine. The amount of DETA present in the treatment solution is shown in parts per million (ppm). Table 5 also shows the molar ratio of anionic surfactant to protonatable amine present in the oligoamine. The composition is tested for percent reduction in oxidation products according to the test method provided above.

[0141] [Table 8]

[0142] The results shown in Table 5 show the malodor prevention on fabrics washed with a liquid composition containing the linear oligoamine of the present disclosure in the composition of Example 1A compared to an otherwise similar detergent without the linear oligoamine, where the amine, if present, is present at a concentration of 0.1 wt% or less in the composition and / or less than 4 ppm, or even less than 3 ppm in the treatment liquor.

[0143] Example 6. Oligoamines and Antioxidants To demonstrate the malodor control effect of the oligoamines of the present disclosure, including in combination with an antioxidant, the liquid detergent compositions of Example 1A, Table 1 above are provided. Various combinations of linear oligoamines and antioxidants are added to the liquid detergent compositions at the concentrations set forth in Table 6. The antioxidant added in Examples 6D and 6E is a hindered phenol antioxidant (specifically, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, commercially available as Tinogard TS (e.g., BASF)).

[0144] The compositions are tested for percent reduction in oxidation products according to the test methods provided above, and the results are shown in Table 6.

[0145] [Table 9]

[0146] The presence of DETA amine provides improved malodor control, as shown in Table 6. The data in Table 6 further demonstrates that the tested combinations of oligoamines and antioxidants of the present disclosure provide improved malodor control.

[0147] Notably, although the concentration of DETA is the same in Liquid Compositions 6B and 6E, Liquid Composition 6E (which also contains an antioxidant) provides nearly twice the percentage (%) of removal of oxidation products, and the performance of Liquid Composition 6E is equal to that of Liquid Composition 6C, which contains twice the DETA amine.

[0148] Example 7. Effect of alkylation To demonstrate the effectiveness that the oligoamines described herein with various degrees of alkylation may have in reducing malodor, the following molecules are tested at the concentrations provided according to the test method described above. The tests are performed on North American manufactured drum-type automatic washing machines.

[0149] Tables 7A and 7B below show a comparison of the percent reduction of each compound between the oxidation products and the reference composition.

[0150] [Table 10]

[0151] As shown by the structures above, Example 7B features a terminal primary amine, Example 7C features a terminal secondary amine, and Example 7D features a terminal tertiary amine. As shown in Table 7A, Examples 7B-7D each provide a malodor reduction effect, with Example 7B providing the greatest malodor reduction relative to the rest.

[0152] [Table 11]

[0153] As shown in Table 7B, Example 7F provides the greatest relative malodor reduction.

[0154] Example 8. Oligoamines and Whiteness To demonstrate that oligoamines (and their % concentration) can affect whiteness, certain amines are added to North American made liquid TIDE® (a commercial heavy duty liquid laundry detergent) as shown in Table 8. Various fabrics (cotton, polycotton, and polyester) are treated with the compositions for 10 wash cycles under North American conditions.

[0155] After 10 cycles, the brightness loss is measured according to the Brightness Loss Test Method described above in the Test Methods section. The results are shown in Table 8. A negative number indicates brightness loss, with higher degrees of number indicating greater brightness loss (e.g., -10 indicates greater brightness loss than -5). Preferably, the brightness loss is between 0 and -5, or between 0 and -4. A greater degree of brightness loss indicates that the product may be less suitable for consumer use.

[0156] [Table 12]

[0157] As shown in Table 8, the presence of amines can result in brightness loss over multiple treatments. However, the brightness loss provided at amine concentrations below 0.1 wt. % (see Tests 8B and 8C) is relatively acceptable to manufacturers. In comparison, Test 8D, which contains DETA at levels above 1%, exhibits brightness loss that is considered less favorable. It is believed that alkylated oligoamines may further improve brightness loss and / or allow for the incorporation of higher concentrations of oligoamines while maintaining brightness loss within acceptable limits.

[0158] The 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."

[0159] All documents cited in this application, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, 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.

[0160] 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: 0.01% to 0.2% by weight of the treatment composition of an oligoamine and / or salt thereof, and additional processing aids; The oligoamine has a structure according to formula I: 【Chemistry 1】 [In the formula, Each L is independently -(C ｍ H ２ｍ )-, the subscript m of each L is independently an integer from 2 to 6; n is an integer from 1 to 10, R １ ~R ５ are each independently H and C １ ~C ４ is selected from alkyl. The treatment composition is a laundry detergent composition; the oligoamine is diethylenetriamine (DETA), N1-(3-aminopropyl)-N1-methylpropane-1,3-diamine or N1-(2-aminoethyl)-N1-methylethane-1,2-diamine; A processing composition, wherein said additional processing aid does not include said oligoamine.

2. 10. The treatment composition of claim 1, wherein the treatment composition comprises from 0.01% to 0.15% by weight of the treatment composition of the oligoamine.

3. 2. The treatment composition of claim 1, wherein the treatment composition comprises 0.01% to 0.2% by weight of the treatment composition of the oligoamine, the oligoamine being diethylenetriamine (DETA).

4. 4. The treatment composition of any one of claims 1 to 3, wherein the additional processing aids are selected from surfactant systems, fabric conditioning actives (FCAs), antioxidants, hueing agents, optical brighteners, additional chelating agents, enzymes, fatty acids and / or salts thereof, encapsulated benefit agents, soil release polymers, builders, dye transfer inhibitors, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersants, soil removal / anti-redeposition agents, polymeric grease cleaners, amphiphilic copolymers, suds suppressors, aesthetic dyes, fragrances, structural elastifiers, fabric softeners, carriers, fillers, hydrotropes, solvents, antimicrobials and / or preservatives, pH adjusters, processing aids, fillers, rheology modifiers, structurants, opacifiers, pearlescent agents, pigments, corrosion inhibitors, discoloration inhibitors, defoamers, chlorine scavengers, and mixtures thereof.

5. The processing composition of any one of claims 1 to 4, wherein the additional processing aid comprises a surfactant system.

6. The processing composition of any one of claims 1 to 5, wherein the additional processing aid comprises an antioxidant comprising a hindered phenol.

7. The treatment composition of any one of claims 1 to 6, wherein the additional treatment aid comprises a whitening agent or a brightening agent.

8. The processing composition of any one of claims 1 to 7, wherein the additional processing aid comprises an additional chelating agent.

9. The treatment composition of any one of claims 1 to 8, wherein the additional treatment aid comprises an enzyme.

10. The treatment composition according to any one of claims 1 to 9, wherein the treatment composition is in the form of a liquid composition.

11. 1. A process for laundering a fabric surface, comprising: providing a fabric soiled with sebum; Contacting the surface with a composition according to any one of claims 1 to 10, optionally in the presence of water; The process includes:

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