阅读说明：本技术 包含表面活性剂体系和低聚胺的处理组合物 (Treatment compositions comprising a surfactant system and an oligoamine ) 是由 S·L·兰德尔 法布里奇奥·梅利 G·S·米瑞科 P·C·斯腾格 G·O·比安切蒂 于 2019-08-14 设计创作，主要内容包括：本发明公开了包含表面活性剂体系和低聚胺(优选二亚乙基三胺(DETA)、4-甲基二亚乙基三胺(4-MeDETA)、N,N’-双(3-氨基丙基)乙二胺)的处理组合物,该表面活性剂体系包含直链烷基苯磺酸盐。此类组合物的相关使用和制备方法。表面活性剂体系用于改善低聚胺涉及目标织物的恶臭控制有益效果的用途。(Treatment compositions comprising a surfactant system comprising linear alkylbenzene sulfonate and an oligoamine, preferably Diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), N' -bis (3-aminopropyl) ethylenediamine, are disclosed. Related methods of use and preparation of such compositions. Use of a surfactant system to improve the malodour control benefit of an oligomeric amine directed to a target fabric.)

1. A treatment composition comprising an oligoamine and/or a salt thereof and a surfactant system,

wherein the oligoamine is present at a level of from 0.01% to 3.0% by weight of the treatment composition,

wherein the oligoamine has a structure according to formula I:

wherein

Each L is independently- (C)_mH_2m) -, where for each L, subscript m is independently an integer of 2 to 6,

n is an integer of 1 to 10, and

R¹-R⁵each of which is uniqueIs selected from H and C₁-C₄An alkyl group; and is

Wherein the surfactant system comprises a Linear Alkylbenzene Sulphonate (LAS) surfactant.

2. The treatment composition of claim 1, wherein the oligoamine is present at a level of from 0.01% to 2%, or from 0.02% to 1%, or from 0.03% to 0.5%, or from 0.05% to 0.2%, by weight of the treatment composition.

3. The treatment composition of any one of claims 1 or 2 wherein the subscript m is 2 or 3, preferably m is 2.

4. The treatment composition of any preceding claim, wherein n is an integer from 1 to 5, preferably from 1 to 3, more preferably 1 or 2, even more preferably 1.

5. The treatment composition of any preceding claim, wherein R is¹-R⁵Each of which is independently selected from H and C₁Alkyl, preferably wherein R¹-R⁵Is H, more preferably wherein R¹-R⁴Is H, even more preferably wherein all are H.

6. The treatment composition of any preceding claim, wherein the oligomeric amine is characterized by a molecular weight of from 100Da to 1200Da, or from 100Da to 900Da, or from 100Da to 600Da, or from 100Da to 400Da, or preferably between 100Da to 250Da, more preferably between 100Da to 200Da, even more preferably between 100Da to 150 Da.

7. The treatment composition of any preceding claim, wherein the oligomeric amine is selected from the group consisting of: diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), Dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetramine (TETA),4-methyltriethylenetetramine (4-MeTETA), 4, 7-dimethyltriethylenetetramine (4, 7-Me)₂TETA), 1,4,7, 7-pentamethyldiethylenetriamine (M5-DETA), tripropylenetetramine (TPTA), Tetraethylenepentamine (TEPA), Tetrapropylenepentamine (TPPA), Pentaethylenehexamine (PEHA), pentapropylenehexamine (PPHA), hexaethyleneheptamine (HEHA), hexapropyleneptamin (HPHA), N' -bis (3-aminopropyl) ethylenediamine and mixtures thereof, preferably wherein the oligoamine is selected from the group consisting of: diethylene triamine (DETA), 4-methyl diethylene triamine (4-MeDETA), 1,4,7, 7-pentamethyl diethylene triamine (M5-DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), N '-bis (3-aminopropyl) ethylene diamine and mixtures thereof, even more preferably diethylene triamine (DETA), 4-methyl diethylene triamine (4-MeDETA), N' -bis (3-aminopropyl) ethylene diamine and mixtures thereof, more preferably wherein the oligoamine is diethylene triamine (DETA).

8. The treatment composition of any preceding claim, wherein the surfactant system comprises from 5%, or 10%, or 20%, or 40%, or 50%, or 60%, or 70%, or 80%, or 90% to 100%, by weight of the surfactant system, of LAS surfactant.

9. The treatment composition of any preceding claim, wherein the surfactant system further comprises a second surfactant comprising an Alkyl Ethoxylated Sulfate (AES), a nonionic ethoxylated alcohol, an Alkyl Ethoxylated Carboxylate (AEC), or mixtures thereof,

wherein if the second surfactant comprises AES, preferably the weight ratio of LAS to AES is from 10:90 to 99:1, or from 50:50 to 90:10, or from 80:20 to 90: 10;

wherein if the second surfactant comprises a nonionic ethoxylated alcohol surfactant, preferably the weight ratio of LAS to nonionic ethoxylated alcohol surfactant is from 10:90 to 99:1, or from 50:50 to 90:10, or from 80:20 to 90: 10; and/or

Wherein if the second surfactant comprises an Alkyl Ethoxylated Carboxylate (AEC), preferably the weight ratio of LAS to AEC is from greater than 50:50 to 99:1, or from 60:40 to 95:5, or from 75:25 to 90: 10.

10. The treatment composition of any preceding claim, wherein the surfactant system is present at a level of from 1% to 90%, or from 1% to 80%, or from 1% to 70%, or from 2% to 60%, or from 5% to 50%, by weight of the treatment composition.

11. The treatment composition of any preceding claim, wherein the surfactant system further comprises a zwitterionic surfactant, preferably wherein the zwitterionic surfactant comprises an amine oxide.

12. The treatment composition of any preceding claim, wherein the treatment composition comprises an additional treatment aid, preferably selected from: antioxidants, hueing agents, optical brighteners, additional chelants, enzymes, fatty acids and/or salts thereof, encapsulated benefit agents, soil release polymers, builders, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleaches, bleach catalysts, bleach activators, polymeric dispersants, soil removal/anti-redeposition agents, polymeric grease cleaners, amphipathic copolymers, suds suppressors, cosmetic dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, fillers, hydrotropes, solvents, biocides and/or preservatives, pH adjusters, processing aids, fillers, rheology modifiers, structurants, opacifiers, pearlescers, pigments, anticorrosion agents, rust inhibitors, antifoam agents, chlorine scavengers, and mixtures thereof.

13. A treatment composition according to any preceding claim, wherein the additional treatment adjunct comprises an antioxidant, preferably an antioxidant comprising a hindered phenol.

14. The treatment composition according to any preceding claim, wherein the additional treatment adjunct comprises an additional chelating agent, preferably an additional chelating agent selected from phosphonates, amino carboxylates, amino phosphonates, polyfunctional substituted aromatic chelating agents or mixtures thereof, more preferably selected from DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethane diphosphonic acid), EDDS (ethylenediamine disuccinate (EDDS)), DTPMP (diethylenetriaminepenta (methylenephosphonic acid)), EDTMP (ethylenediaminetetra (methylenephosphonic acid)), (ethylene diamine tetra (methylenephosphonic acid)), (ii) and (iii) mixtures thereof,(1, 2-dihydroxybenzene-3, 5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycinediacetic acid), GLDA (glutamic-N, N-diacetic acid), any suitable derivative thereof, a salt thereof, and mixtures thereof.

15. The treatment composition according to any preceding claim, wherein the treatment composition is a fabric care composition, preferably a fabric care composition selected from the group consisting of: light-duty liquid detergent compositions, heavy-duty liquid detergent compositions, laundry detergent gels, bleaching compositions, laundry additives, fabric enhancer compositions, and mixtures thereof, more preferably selected from heavy-duty liquid detergent compositions, fabric enhancer compositions, and mixtures thereof, even more preferably heavy-duty liquid detergent compositions.

16. The treatment composition according to claim 1, 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 lozenge or bead, a fibrous article, a tablet, a strip, a sheet, a dried sheet or a mixture thereof, preferably in the form of a liquid composition.

17. A method of treating a surface, the method comprising the steps of:

a. providing a surface, preferably a fabric, more preferably a fabric contaminated with sebum, and

b. contacting the surface with a composition according to any preceding claim, optionally in the presence of water.

18. Use of a surfactant system in a fabric care composition to ameliorate the malodour control benefit of oligoamines and/or salts thereof relating to target fabrics,

the surfactant system comprises a linear alkylbenzene sulfonate surfactant, and

wherein the oligoamine has a structure according to formula I:

wherein

Each L is independently- (C)_mH_2m) -, where for each L, subscript m is independently an integer of 2 to 6,

n is an integer of 1 to 10, and

R¹-R⁵each of which is independently selected from H and C₁-C₄An alkyl group;

preferably wherein the surfactant system further comprises AES, a non-ionic ethoxylated alcohol surfactant, AEC or a mixture thereof.

Technical Field

The present disclosure relates to treatment compositions comprising a surfactant system and an oligoamine. The disclosure also relates to related methods of using and making such compositions.

Background

Many treatment processes, such as laundry washing processes, are designed to remove soil from surfaces, such as fabrics. Some soils can cause malodor on fabrics, which can persist or even form after the treatment process is complete. Accordingly, manufacturers of consumer and industrial cleaning products are continually seeking to provide compositions and methods that provide improved malodor control.

Certain polyamines or oligoamines are known to be useful alone in detergent compositions. Such polyamines or oligoamines may be beneficial for certain cleaning benefits, such as grease removal. However, such compounds can cause discoloration, such as yellowing on fabrics.

There is a need to provide compositions that provide improved malodor control, especially if such compositions can more effectively utilize oligoamines.

Disclosure of Invention

The present disclosure relates to treatment compositions having certain oligoamines and/or salts thereof and specific surfactant systems.

For example, the present disclosure relates to treatment compositions comprising an oligomeric amine and/or salt thereof, wherein the oligomeric amine is present at a level of about 0.01% to 3.0% by weight of the treatment composition, and a surfactant system, wherein the oligomeric amine has a structure according to formula I:

wherein each L is independently- (C)_mH_2m) -, where for each L, subscript m is independently an integer of 2 to 6, n is an integer of 1 to 10, and R¹-R⁵Each of which is independently selected from H and C₁-C₄Alkyl, typically wherein R¹-R⁵At least one of which is H; and wherein the surfactant system comprises a Linear Alkylbenzene Sulphonate (LAS) surfactant.

The present disclosure also relates to a method of treating a surface, the method comprising the steps of: (a) providing a surface, preferably a fabric, more preferably a fabric contaminated with sebum, and (b) contacting the surface with a composition described in the present disclosure, optionally in the presence of water.

The present disclosure also relates to the use of a surfactant system comprising a linear alkylbenzene sulfonate surfactant, and wherein the oligomeric amine has a structure according to formula I as described herein, in a fabric care composition to ameliorate the malodour control benefit of the oligomeric amine and/or salt thereof related to a target fabric.

Detailed Description

The present disclosure relates to treatment compositions comprising oligoamines and Linear Alkylbenzene Sulfonate (LAS) surfactants. It has been found that such oligoamines can provide surprising malodour benefits, for example in terms of laundering fabrics, and that the benefits can be improved in compositions comprising LAS.

Without being bound by theory, it is believed that metal ions in the treatment fluid, such as copper ions (e.g., Cu)²⁺) May facilitate the breakdown of certain soils, such as sebum, on the target surface. Such decomposition may release volatile malodorous compounds into the air. It is believed that the oligoamines of the present disclosure can chelate and sequester copper ions in treatment solutions, thereby inhibiting the release of such malodorous compounds.

Furthermore, it has been found that the combination of the oligoamines of the present invention and LAS surfactants can provide surprisingly good malodor control benefits. Without being bound by theory, it is believed that deposition of oligoamines on the target surface may be aided by LAS surfactants, for example, by hydrophobic interactions. The more effective the oligomeric amine deposition, the more it can inhibit the decomposition of foul odor causing soils. Such benefit generation mechanisms are not intuitive, as oligoamines and anionic surfactants such as LAS typically provide benefits by removing soil from a surface. The LAS may be part of a surfactant system which may comprise one or more additional surfactants.

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

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 "comprising," "including," and "containing" are intended to be non-limiting. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

The term "substantially free" may be used herein. This means that the referenced material is very small, is not intentionally added to the composition to form part of the composition, or preferably the referenced material is not present at analytically detected levels. This is meant to include compositions in which the material referred to is present only as an impurity in one of the other materials intentionally added. The referenced materials, if any, may be present at a level of less than 1%, or less than 0.1%, or less than 0.01%, or even 0%, by weight of the composition.

As used herein, the term "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 freshening compositions, laundry pre-washes, laundry pre-treatments, laundry additives, spray-on products, dry washes or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, drying 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 pre-treatment agents, laundry post-treatment agents, or may be added during the rinse cycle or wash cycle of a laundry washing operation.

As used herein, "liquid" includes free-flowing liquids as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light and heavy duty liquid detergent compositions, fabric enhancers, detergent gels commonly used in laundry, bleaching agents, and laundry additives. Gases (e.g., suspended bubbles) or solids (e.g., particles) may be contained in the liquid. The liquid composition may have from about 0% to about 90%, or from about 30% to about 90%, or from about 50% to about 80%, by weight of the composition, of water, and may include a non-aqueous liquid detergent.

As used herein, "solid" includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include: granules, microcapsules, beads, flakes, noodles, and pearlized beads.

Unless otherwise specified, all components or compositions are on average with respect to the active portion of that component or composition, and do not include impurities, such as residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

All temperatures herein are in degrees Celsius (. degree. C.) unless otherwise indicated. All measurements herein are made at 20 ℃ and atmospheric pressure unless otherwise indicated.

In all embodiments of the present disclosure, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios unless otherwise specifically noted.

It should 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 will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

Treatment composition

The present disclosure relates to treatment compositions suitable for treating surfaces. The treatment composition may comprise an oligoamine and a surfactant system comprising a linear alkylbenzene sulfonate surfactant. The composition may also comprise additional processing aids.

The treatment composition of the present disclosure may be a fabric care composition. Such compositions may be used as laundry pre-treatment agents, laundry post-treatment agents, or may be added during the rinse cycle or wash cycle of a laundry washing operation. It can also be used in a dry cleaning environment.

The composition may be selected from the group consisting of: light duty liquid detergent compositions, heavy duty liquid detergent compositions, detergent gels commonly used for laundry, bleaching compositions, laundry additives, fabric enhancer compositions, and mixtures thereof. The composition may be a heavy duty liquid detergent composition or a fabric enhancer composition. The composition may be intended for use during the wash cycle and/or during the rinse cycle of an automatic washing machine.

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 dissolvable sheet, a lozenge or bead, a fibrous product, a tablet, a strip, a sheet, a dry sheet, or a mixture thereof. The composition may be selected from a liquid, a solid, or a combination thereof.

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

The oligoamine and surfactant systems of the present disclosure are described in more detail below.

Oligoamines

The treatment compositions of the present disclosure comprise an oligomeric amine or salt thereof. Oligomeric amines according to the present disclosure contain amine functionality, which can be primary, secondary, or tertiary amines linked by specific alkylene groups. Without being bound by theory, it is believed that the oligoamines of the present disclosure are well suited for chelating certain metals, such as copper (Cu)²⁺) And such chelation may provide malodor control benefits.

The treatment compositions of the present disclosure comprise from about 0.01%, or from about 0.05% to about 3.0%, or to about 2.0%, or to about 1.0%, or 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%, or to about 0.1%, by weight of the treatment composition, of the oligoamine. For the purposes of this disclosure, the weight percent of linear oligoamines is calculated using the weight of the free base form. Depending on the intended use and/or formulation, relatively low levels (e.g., less than about 1%, or less than about 0.5%, or less than about 0.2%, or less than about 0.1%) of oligoamines may be preferred, as amines may cause some surface discoloration/yellowing.

The oligomeric amines of the present disclosure can be considered to be linear oligomeric amines. By "linear," it is meant that there are no additional amine-containing side chains grafted onto the oligomeric amine backbone represented by formula I. It is to be understood, however, that the linear oligomeric amines can have, at least in some cases, alkyl groups attached to the oligomeric amine backbone, such as methyl or ethyl groups.

The oligoamines of the present disclosure may have a structure according to formula I:

wherein

Each L is independently- (C)_mH_2m) -, where for each L, subscript m is independently an integer of 2 to 6, preferably m is 2 or 3, more preferably m is 2 (e.g., an ethylene group);

n is an integer from 1 to 10 (i.e., triamine, tetraamine, pentaamine, hexaamine, heptaamine, etc.), preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1 to 2, most preferably 1; and is

Wherein R is¹-R⁵Each of which is independently selected from H and C₁-C₄Alkyl, preferably H and methyl (i.e., C)₁Alkyl groups). It is understood that when n is greater than 1, each R is⁵Independently selected from the groups provided, although each R is⁵May be identical.

For each L, subscript m may independently be an integer of from 2 to 6, wherein for each of the two L groups directly connected to a common N atom, subscript m is 2 or 3, preferably 2. It is believed that having two such L groups adjacent to a common N atom will facilitate improved metal chelation even if the other L groups are relatively large (e.g., m is greater than 2).

R¹-R⁵Each of which isThis may be H. R⁵May be a methyl group. R⁵May be H. R¹And R³One or both of which may be methyl. R¹And R³Can be methyl, and R²And R⁴May be hydrogen. R¹-R⁵Each of which may be methyl. It is preferable that R is¹-R⁵Is H, and even more preferably, R¹-R⁴At least one of which is H. R¹-R⁴Can be H, and R⁵Can be independently selected from H and C₁An alkyl group.

The compositions of the present invention may comprise oligoamines having a structure according to formula I above, wherein L, m, n and R¹-R⁵As defined above, with the proviso that if n is equal to 1, then R5 is selected from H and moieties having 1 to 10 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

Depending on the type of product desired and/or the overall benefit space, the formulator may select oligoamines having primary, secondary and/or tertiary nitrogens, particularly at the terminal positions. Without being bound by theory, it is believed that the presence of primary nitrogen in the oligomeric amines of the present invention may provide improved malodor control benefits, which are believed to be due to improved chelation efficiency and/or coordination with a target surface such as a fabric. Without also being bound by theory, it is believed that the tertiary nitrogen in the oligoamines of the present invention may result in less interaction with other materials in the treatment composition, for example with certain perfume materials, which may otherwise result in a reaction (e.g. schiff base reaction) and subsequent color change of the liquid product.

Treatment compositions comprising mixtures of various oligomeric amines according to formula I are also part of the scope of the present disclosure.

Suitable oligoamines according to the present disclosure may include Diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), Dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetramine (TETA), 4-methyltriethylenetetramine (4-MeTETA), 4, 7-dimethyltriethylenetetramine (4, 7-Me)₂TETA), 1,4,7, 7-pentamethyldiethylenetriamine (M5-DETA), tripropylenetetramine (TPTA), tetraethylenepentamine(TEPA), Tetrapropylenepentamine (TPPA), Pentaethylenehexamine (PEHA), pentapropylenehexamine (PPHA), hexaethyleneheptamine (HEHA), hexapropyleneoheptamine (HPHA), N' -bis (3-aminopropyl) ethylenediamine or mixtures thereof.

The oligoamines may preferably be selected from Diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,4,7, 7-pentamethyldiethylenetriamine (M5-DETA), Dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetramine (TETA), tripropylenetetramine (TPTA), Tetraethylenepentamine (TEPA), tetrapropylenepentamine (TPTA), N '-bis (3-aminopropyl) ethylenediamine and mixtures thereof, more preferably Diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,4,7, 7-pentamethyldiethylenetriamine (M5-DETA), triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), N' -bis (3-aminopropyl) ethylenediamine and mixtures thereof, even more preferably Diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), N' -bis (3-aminopropyl) ethylenediamine and mixtures thereof, most preferably Diethylenetriamine (DETA). DETA can be preferred because of its low molecular weight and/or relatively low cost of production.

The oligoamines can include diethylenetriamine ("DETA", where m equals 2, n equals 1, and R¹-R⁵Each of which is H) or derivatives thereof, including alkylated forms (e.g., wherein R is¹-R⁵One or more of which is an alkyl group, such as methyl). The oligoamines 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), even more preferably the oligoamine consists of the form Diethylenetriamine (DETA). The oligoamines may be selected from: DETA; 4-methyl DETA; and mixtures thereof; preferably DETA (non-alkylated diethylenetriamine).

Depending on the finished product or wash solution pH, the nitrogen atom may be partially or fully protonated, resulting in the salt form of the oligoamine according to formula I. These (partially) protonated oligoamines are also considered to be 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.

The oligomeric amines of the present disclosure may have a molecular weight of between about 100Da to about 1200Da, or about 100Da to about 900Da, or about 100Da to about 600Da, or about 100Da to about 400Da, preferably between about 100Da and about 250Da, most preferably between about 100Da and about 175Da, or even between about 100Da and about 150 Da. For the purposes of this disclosure, the molecular weight is determined using the oligomeric amine in free base form.

One skilled in the art will know how to obtain oligoamines according to the present disclosure. For example, oligoamines according to formula I (wherein L has an m equal to 2) can be obtained by a reaction involving ammonia and ethylene dichloride, followed by fractional distillation. Common oligoamines obtained are Diethylenetriamine (DETA), triethylenetetramine (TETA) and Tetraethylenepentamine (TEPA). Other oligoamines according to formula I, wherein m is equal to 2 to 6, can be formed by using suitable halogen disubstituted alkylene groups.

Above the pentamines, i.e. hexamine, heptamine, octamine and possibly nonamine, the generic derived mixture does not appear to be separated by distillation and may contain other substances such as cyclic amines and especially piperazine.

Suitable ethylene-based oligoamines according to the present disclosure are commercially available from a variety of chemical suppliers including Dow, BASF, Huntsman, and Akzo Nobel Corporation.

Surfactant system

The treatment compositions of the present disclosure comprise a surfactant system. The surfactant system comprises Linear Alkylbenzene Sulphonate (LAS). The surfactant of the surfactant system may be of synthetic origin, of natural origin or mixtures thereof. The surfactant of the surfactant system may be derived from petroleum, waste (such as plastic waste), or renewable resources.

The surfactant system may consist of one type of surfactant (e.g., LAS). The surfactant system may comprise more than one surfactant. In particular, a laundry detergent (such as a heavy duty liquid laundry detergent) may comprise a surfactant system comprising LAS and at least one secondary surfactant. The surfactant system may comprise a second surfactant which may be selected from Alkyl Ethoxylated Sulfates (AES), nonionic ethoxylated alcohols, Alkyl Ethoxylated Carboxylates (AEC) or mixtures thereof.

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

1. Linear Alkylbenzene Sulfonate (LAS) surfactants

The treatment compositions and surfactant systems of the present disclosure may comprise linear alkylbenzene sulfonate surfactants, otherwise known as "LAS". LAS are common anionic surfactants used in various cleaning applications and products such as laundry detergents.

LAS surfactants comprise an alkyl group in a linear or linear configuration. For environmental reasons, straight chain alkyl groups are generally preferred over branched groups.

The alkyl group may contain an average of about 9 to about 15 carbon atoms, or about 11 to about 14, or about 11 to about 13, or about 11 to about 12, or about 11.8 carbon atoms by weight. In the latter case, the material may be abbreviated as C11.8 LAS.

The LAS may comprise 2-phenyl alkylbenzene sulphonate wherein the benzene ring is attached to the alkyl group at a carbon atom adjacent to the terminal substantially linear carbon. Thus, in a 2-phenylalkylbenzene, the carbon atom attached to the benzene ring has a methyl group and another alkyl group attached thereto. Most often and preferably, the sulfonate group is attached to the benzene ring at the para position relative to the alkyl group. The LAS may comprise at least 15% of the 2-phenyl LAS isomer, or at least 20% of the 2-phenyl isomer.

LAS may be in the acid form (known as HLAS) and/or in the salt form. Suitable salts may be formed from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, alkylammonium hydroxides, alkanolamines such as monoethanolamine, or any other chemical agent known to those skilled in the art to react with linear alkylbenzene sulfonic acid to form a water soluble linear alkylbenzene sulfonate. Alkali metal salts, typically sodium salts, and/or alkanolamine salts, typically monoethanolamine, of LAS may be preferred.

It may be desirable for LAS to be pre-neutralized, for example, prior to combination with the oligomeric amines of the present disclosure. This may be preferred for improving the pH control of the oligoamines and/or for improving the malodor control performance.

Linear alkylbenzenes are typically manufactured on an industrial scale using one of three commercial processes which differ from each other primarily by the catalyst system used. One method uses an aluminum trichloride catalyst, another uses a hydrogen fluoride catalyst, and a third uses what is known as DETAL^TMThe solid alkylation catalyst of (1). Suitable alkyl benzene sulfonates (LAS) may be obtained by sulfonating commercially available Linear Alkyl Benzenes (LAB). Suitable LAB include lower 2-phenyl LAB, such as under the trade name LABThose supplied by Sasol, or under the trade nameThose supplied by petresca. Other suitable LABs include higher 2-phenyl LABs, such as those under the trade name LABThose supplied by Sasol.

The surfactant system may comprise at least about 5%, or at least about 10%, or at least about 20%, or at least about 25%, 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 75%, or at least about 80%, or at least about 90%, or even about 100%, by weight of the surfactant system, of LAS. The surfactant system may comprise no greater than about 95%, or no greater than about 90%, or no greater than about 80%, or no greater than about 75%, or no greater than about 70%, or no greater than about 60%, or no greater than about 50%, or no greater than about 40%, or no greater than about 30%, no greater than about 25%, or no greater than about 20%, or no greater than about 15%, or no greater than about 10%, by weight of the surfactant system, of LAS.

The treatment composition comprises from about 1%, or about 2%, or about 3%, or about 5%, or about 8%, or about 10%, or about 15%, or about 20%, to about 60%, or to about 50%, or to about 40%, to about 30%, or to about 25%, or to about 20% LAS by weight of the treatment composition.

2. Alkyl ethoxylated sulfates

The treatment compositions and surfactant systems of the present disclosure may comprise an Alkyl Ethoxylated Sulfate (AES) surfactant. The second surfactant may comprise AES.

AES, also known as alkyl ether sulfate, alkyl polyethoxylated sulfate, or ethoxylated alkyl sulfate, may include water-soluble salts, particularly alkali metal, ammonium, and alkanolammonium salts, of organic sulfuric acid reaction products having in their molecular structure an alkyl group containing from about 8 to about 30 carbon atoms and sulfonic acids and salts thereof. Included in the term "alkyl" are the alkyl portions of acyl groups.

The alkyl group of AES may contain from about 8 to about 30, or from about 10 to about 18, or from about 12 to about 16 carbon atoms. The AES surfactant may be a mixture of alkyl ether sulfates having an average (arithmetic average) carbon chain length (by weight) in the range of about 12 to 30 carbon atoms, and in some examples about 12 to 15 carbon atoms.

The AES may have an average (arithmetic mean) degree of ethoxylation of from about 1mol to about 8mol, or to about 6mol, or to about 5mol, or to about 4mol, or to about 3mol of ethylene oxide. The AES may have an average (arithmetic average) degree of ethoxylation of from about 1.8 moles to about 2.5 moles of ethylene oxide. The alkyl ether sulfate surfactant may contain a peak ethoxylate distribution.

The AES may have an average carbon chain length between about 10 carbon atoms to about 18 carbon atoms and an average degree of ethoxylation of about 1mol to about 6mol of ethylene oxide. Suitable AES surfactants may have an average carbon chain length of from about 12 to about 15 carbon atoms, preferably from about 13 to about 15 carbon atoms, and an average degree of ethoxylation of from about 1 to about 3 moles of ethylene oxide, preferably from about 1.5 to about 2.5 moles of ethylene oxide.

The LAS and AES may be present in a weight ratio. The weight ratio of LAS to AES may be from about 10:90 to about 99:1, or from about 50:50 to about 90:10, or from about 80:20 to about 90: 10.

The treatment composition may be substantially free of AES.

3. Nonionic ethoxylated alcohols

The treatment compositions and surfactant systems of the present disclosure may comprise a nonionic ethoxylated alcohol. The second surfactant may comprise a nonionic ethoxylated alcohol.

The nonionic ethoxylated alcohol can have the formula R (OC)₂H₄)_nOH, wherein R is selected from aliphatic hydrocarbon groups comprising an average of about 8 to about 18 or 10 to about 16 carbon atoms, and wherein n has an average value of about 5 to about 15, or about 6 to about 10, or about 7 to about 9. Suitable materials of this type may include: c₈-C₁₈Alkyl ethoxylates, such as those from ShellA nonionic surfactant.

The LAS and the nonionic ethoxylated alcohol may be present in a weight ratio. The weight ratio of LAS to nonionic ethoxylated alcohol surfactant may be from about 10:90 to about 99:1, or from about 50:50 to about 90:10, or from about 80:20 to about 90: 10.

The treatment composition may be substantially free of nonionic ethoxylated alcohol surfactant.

4. Alkyl ethoxylated carboxylates

The treatment compositions and surfactant systems of the present disclosure may comprise Alkyl Ethoxylated Carboxylate (AEC) surfactants, also known as alkyl ether carboxylates. The second surfactant may comprise AEC.

AEC surfactants can have the general formula R2- (OCH)₂CH₂)_n-OCH₂COOH wherein R2 is an alkyl chain, preferably having an average of about 10 to about 20 carbon atoms by weight, and wherein n is an average of about 1 to about 15, or about 3 to about 11 by weight. The alkyl chain may be linear or branched, preferably linear. The alkyl chain may be aliphatic or contain one cis or trans double bond. The alkyl chain (e.g., R2) may be selected from: CH (CH)₃(CH₂)₁₁、CH₃(CH₂)₁₃、CH₃(CH₂)₁₅、CH₃(CH₂)₁₇And CH₃(CH2)₇CH＝(CH₂)₈。

AEC surfactants can be present in the acid/protonated form, the salt form, or both. Suitable salts may be sodium and/or amine salts. The AEC may be at least partially pre-neutralized. The weight of AEC was calculated as the protonated form.

Alkyl ether Carboxylic acids from Kao、HuntsmanAnd ClariantAnd Sasol. An example of a C12-C14 alcohol polyglycol ether carboxylic acid is Marlowet 4541, which is commercially available from Sasol. The sodium salt of an alkyl ether carboxylate may be used.

The LAS and AEC may be present in a weight ratio. The weight ratio of LAS to AEC may be greater than about 50:50 to 99:1, or about 60:40 to about 95:5, or about 75:25 to about 90: 10.

The treatment composition may be substantially free of AEC surfactant.

5. Other surfactants

The treatment composition and surfactant system may comprise any other suitable surfactant. The second surfactant may comprise any other suitable surfactant.

Other suitable surfactants may include zwitterionic surfactants. The zwitterionic surfactant may comprise any conventional zwitterionic surfactant, such as betaines, including alkyl dimethyl betaine and coco dimethyl amidopropyl betaine, C₈To C₁₈(e.g., C)₁₂To C₁₈) Amine oxides (e.g. C)_12-14Dimethyl amine oxide), and/or sulphobetaines and hydroxybetaines, such as N-alkyl-N, N-dimethylamino-1-propanesulfonate, where the alkyl group may be C₈To C₁₈Or C₁₀To C₁₄. The zwitterionic surfactant can include an amine oxide.

Other suitable surfactants may include other anionic surfactants, which may be linear or branched. Other anionic surfactants may include non-alkoxylated alkyl sulfates such as by C₈-C₂₀Those produced by sulfation of higher aliphatic alcohols. Other suitable anionic surfactants may include methyl ester sulfonates, alkane sulfonates, alpha-olefin sulfonates, internal olefin sulfonates, and mixtures thereof. Other anionic surfactants may include mid-chain branched anionic surfactants, for example mid-chain branched anionic detersive surfactants such as mid-chain branched alkyl sulphates and/or mid-chain branched alkyl benzene sulphonates. Other anionic surfactants may include 2-alkyl branched primary alkyl sulfates, such as those derived from oxo synthesis; such materials may be, for example, under the trade nameAnd(which is produced by a fractional distillation processAlcohol made) is commercially available from Sasol. C14/C15 branched primary alkyl sulfates are also commercially available, e.g., i.e.145 sulfate salt. The mole ratio of total anionic surfactant to protonatable amine in the oligoamine can be less than about 15: 1. In such cases, the oligoamines can have a structure according to formula I, wherein subscript n is an integer from 2 to 5.

Other suitable surfactants may include other nonionic surfactants such as C₆-C₁₂An alkylphenol alkoxylate, wherein the alkoxylate unit may be an ethyleneoxy unit, a propyleneoxy unit, or mixtures thereof; c₁₂-C₁₈Alcohol and C₆-C₁₂Condensates of alkylphenols with ethylene oxide/propylene oxide block polymers, such as from BASF；C₁₄-C₂₂Mid-chain branched alcohols, BA; c₁₄-C₂₂Mid-chain branched alkyl alkoxylates, BAE_xWherein x is 1 to 30; an alkyl polysaccharide; in particular alkyl polyglycosides; polyhydroxy fatty acid amides; and ether-terminated poly (alkoxylated) alcohol surfactants.

Other suitable surfactants may include cationic surfactants, such as quaternary ammonium surfactants, which may have up to 26 carbon atoms and may include Alkoxylated Quaternary Ammonium (AQA) surfactants, dimethyl hydroxyethyl quaternary ammonium and/or dimethyl hydroxyethyl lauryl ammonium chloride; a polyamine cationic surfactant; an ester cationic surfactant; amino surfactants such as amidopropyl dimethylamine (APA); and mixtures thereof.

Other suitable surfactants can include amphoteric surfactants such as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains at least about 8 carbon atoms, alternatively from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains a water-solubilizing anionic group, e.g., carboxy, sulfonate, sulfate. Suitable amphoteric surfactants may also include sarcosinates, glycinates, taurates and mixtures thereof.

Additional processing aids

The treatment compositions of the present disclosure may comprise one or more additional treatment aids. Additional treatment aids may be suitable for delivering treatment benefits to a target surface such as a fabric or other textile. As used herein, a treatment aid may also include agents that facilitate chemical or physical stability in the treatment composition, such as buffers, structurants/thickeners, and/or carriers.

The processing aid may be present in the composition at a level suitable for the intended use of the composition. Typical use levels range from as low as 0.001% by weight of the composition for adjuncts such as optical brighteners to 50% by weight of the composition for builders/chelating agents.

Processing aids may include antioxidants, hueing agents, optical brighteners, additional chelants, enzymes, fatty acids and/or salts thereof, encapsulated benefit agents, soil release polymers, builders, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersing agents, soil removal/anti-redeposition agents, polymeric grease cleaners, amphipathic copolymers, suds suppressors, cosmetic dyes, perfumes (including encapsulated perfumes), perfumes, structure elasticizing agents, fabric softeners, carriers, fillers, hydrotropes, solvents, antimicrobial agents and/or preservatives, neutralizing agents and/or pH adjusting agents, processing aids, fillers, rheology modifiers or structurants, opacifiers, pearlescers, pigments, anticorrosion and/or rust inhibitors, antifoam agents, chlorine scavengers, and mixtures thereof.

The processing aids may include antioxidants, whitening or brightening agents (such as tints or optical brighteners), additional chelating agents, enzymes, or mixtures thereof. The additional adjunct may comprise an encapsulated benefit agent, which may be an encapsulated perfume, preferably wherein the encapsulated perfume comprises a shell surrounding a core, preferably wherein the shell comprises an amine compound and/or an acrylate polymer.

Several processing aids are discussed in more detail below.

Fabric conditioning actives

The treatment compositions of the present disclosure may comprise a Fabric Conditioning Active (FCA). Compositions comprising such actives, such as liquid fabric enhancing compositions, can be used to provide a variety of benefits to target fabrics, including softness, wrinkle resistance, antistatic properties, conditioning, stretch resistance, color and/or appearance benefits. Fabric Conditioning Actives (FCAs) suitable for use in the compositions of the present disclosure may include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof.

Antioxidant agent

The compositions of the present disclosure may comprise an antioxidant. Without being bound by theory, it is believed that antioxidants can help improve malodor control and/or cleaning performance of the compositions, particularly in combination with the oligomeric amines of the present disclosure. Antioxidants can also help reduce yellowing that can be associated with amines, allowing amines to be formulated at relatively high levels. Antioxidants are substances as described in Kirk-Othmer (vol.3, p.424) and Ullmann's Encyclopedia (vol.3, p.91).

The compositions of the present disclosure may comprise an antioxidant, preferably a hindered phenolic antioxidant, in an amount from about 0.001% to about 2%, preferably from about 0.01% to about 0.5%, by weight of the composition.

Suitable antioxidants may include alkylated phenols having the general formula:

wherein R is C₁-C₂₂Straight chain alkyl or C₃-C₂₂Branched alkyl groups, each (1) optionally having one or more esters (-CO) therein₂-) or an ether (-O-) linkage, and (2) is optionally substituted with an organic group comprising an alkyleneoxy or polyalkyleneoxy group selected from EO (ethoxy), PO (propoxy), BO (butoxy), and mixtures thereof, more preferably EO alone or a mixture of EO/PO; r may preferably be methyl, branched C₃-C₆Alkyl or C₁-C₆Alkoxy, preferably methoxy; r¹Is C₃-C₆A branched alkyl group, preferably a tert-butyl group; x is 1 or 2.

Preferred types of alkylated phenols having this general formula may include hindered phenol compounds. As used herein, the term "hindered phenol" is used to refer to a compound comprising a phenolic group having (a) at least one C attached at an ortho position to at least one phenol-OH group₃Or higher branched alkyl, preferably C₃-C₆A branched alkyl group, preferably a tertiary butyl group, or (b) a substituent independently selected from the group consisting of: c₁-C₆Alkoxy, preferably methoxy; c₁-C₂₂Straight chain alkyl or C₃-C₂₂Branched alkyl, preferably methyl or branched C₃-C₆An alkyl group; or mixtures thereof. If the phenyl ring contains more than one-OH group, the compound is a hindered phenol, provided that at least one such-OH group is substituted as described immediately above. When any R group in the above structure comprises three or more contiguous monomers, the antioxidant is defined herein as a "polymeric hindered phenol antioxidant. Compositions according to the present disclosure may comprise a hindered phenol antioxidant. Preferred hindered phenol antioxidants include 3, 5-di-tert-butyl-4-hydroxytoluene (BHT).

Another class of hindered phenolic antioxidants that may be useful in the composition are benzofuran or benzopyran derivatives having the formula:

wherein R is₁And R₂Each independently is alkyl, or R₁And R₂Can be taken together to form C₅-C₆A cyclic hydrocarbyl moiety; b is absent or CH₂；R₄Is C₁-C₆An alkyl group; r₅Is hydrogen or-C (O) R₃Wherein R is₃Is hydrogen or C₁-C₁₉An alkyl group; r₆Is C₁-C₆An alkyl group; r₇Is hydrogen or C₁-C₆An alkyl group; x is-CH₂OH or-CH₂A, wherein A is a nitrogen-containing unit, a phenyl group or a substituted phenyl group. Preferred nitrogen-containing a units include amino, pyrrole, piperidine, morpholine, piperazine and mixtures thereof.

Suitable hindered phenol antioxidants may include: 2, 6-bis (1, 1-dimethylethyl) -4-methyl-phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylpropionic acid methyl ester; octadecyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate; or mixtures thereof.

Commercially available antioxidants that may be suitable include BHT, RALOX 35^TMAnd/or TINOGARD TS^TM。

Additional antioxidants may be employed. Examples of suitable antioxidants for use in the compositions include, but are not limited to, alpha-, beta-, gamma-, delta-tocopherol, ethoxyquin, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and salts thereof, and mixtures thereof. Notably, ethoxyquinoline (1, 2-dihydro-6-ethoxy-2, 2, 4-trimethylquinoline)^TMUnder the trade name Raschig^TMCommercially available from the company Raschig. Another type of antioxidant that may be used in the composition is 6-hydroxy-2, 5,7, 8-tetramethylchroman-2-carboxylic acid (Trolox)^TM) And 1, 2-benzisothiazolin-3-one (Proxel GXL)^TM). Antioxidants such as tocopherol sorbate, butylated hydroxybenzoic acid and salts thereof, gallic acid and alkyl esters thereof, uric acid and salts thereof, sorbic acid and salts thereof, and dihydroxy fumaric acid and salts thereof may also be useful. Other useful antioxidants may be includedIncluding tannins, such as tannins selected from the group consisting of: gallotannins, ellagitannins, complex tannins, condensed tannins and combinations thereof.

Non-yellowing antioxidants, such as non-yellowing hindered phenolic antioxidants, may preferably be used. The use of antioxidants that form such yellow byproducts can be avoided if they result in a negative attribute in the consumer experience that is perceptible (such as, for example, the deposition of the yellow byproduct on the fabric). The skilled person is able to make informed decisions about the choice of antioxidant to be employed.

Whitening agent/whitening agent

Additional treatment aids of the present disclosure may include whitening agents or brighteners. Such agents may be selected from colorants, optical brighteners or mixtures thereof. The use of such agents can further reduce the effects of discoloration or yellowing and can enable oligoamines to be formulated at higher levels.

The compositions of the present disclosure may comprise a hueing agent. It has been surprisingly found that graft polymers according to the present disclosure can inhibit the transfer of fugitive dyes with little effect on the deposition and/or performance of the toner on the target fabric.

Hueing agents (sometimes referred to as shading dyes, fabric shading dyes or bluing or whitening agents) typically provide a blue or violet shade to fabrics. Such agents are well known in the art and may be used alone or in combination to produce a particular shade of hueing and/or to tint different fabric types. The toner 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., monoazo, disazo, trisazo, tetraazo, polyazo), benzodifurans, benzodifuranones, carotenoids, coumarins, cyanines, diaza-hemicyanines, diphenylmethane, formazan, hemicyanines, indigoids, methane, naphthalimides, naphthoquinones, nitro, nitroso, oxazines, phthalocyanines, pyrazoles, stilbene, styryl, triarylmethanes, triphenylmethane, xanthenes, and mixtures thereof. The hueing agent may be selected from azo agents, triarylmethane agents, triphenylmethane agents, or mixtures thereof.

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 may be selected from dyes from the group consisting of: dyes falling into the color index (c.i., Society of Dyers and Colourists, Bradford, UK) classification of acid dyes, direct dyes, basic dyes, reactive dyes, solvent-type dyes or disperse dyes.

Suitable polymeric dyes include dyes selected from the group consisting of: polymers (also known as dye-polymer conjugates) containing covalently bonded (sometimes referred to as conjugated) chromogens (e.g., polymers having chromogen monomers copolymerized into the polymer backbone), and mixtures thereof. Preferred polymeric dyes include optionally substituted alkoxylated dyes such as alkoxylated triphenyl-methane polymeric colorants, alkoxylated carbocyclic and alkoxylated heterocyclic azo colorants (including alkoxylated thiophene polymeric colorants), and mixtures thereof, such as under the trade name(Milliken, Spartanburg, South Carolina, USA).

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

Pigments are well known in the art and may also be used as hueing agents in the fabric care compositions disclosed herein. Suitable pigments may include c.i. pigment blue 15 to 20 (especially 15 and/or 16), c.i. pigment blue 29, c.i. pigment violet 15, monastral blue and mixtures thereof.

The amount of adjunct hueing agent present in the laundry care compositions of the present invention may be from 0.0001 wt% to 0.05 wt%, preferably from 0.0001 wt% to 0.005 wt%, based on the total cleaning composition. The concentration of the toner may be 1ppb to 5ppm, preferably 10ppb to 500ppb, based on the washing liquid.

The compositions of the present disclosure may comprise an optical brightener. Brighteners, sometimes also referred to as optical brighteners, emit at least some visible light.

Commercial optical brighteners useful herein can be classified into subclasses, which include, but are not necessarily limited to, stilbenes, pyrazolines, coumarins, carboxylic acids, methionins, 5-dibenzothiophenes dioxide, oxazoles, derivatives of 5-and 6-membered ring heterocycles, and other miscellaneous agents. The whitening agent may be added in particulate form or as a pre-mixture with a suitable solvent (e.g., nonionic surfactant, monoethanolamine and/or propylene glycol).

Suitable optical brighteners may include: 4,4 '-bis { [ 4-anilino-6-morpholino-s-triazin-2-yl ] -amino } -2,2' -stilbene disulfonic acid disodium salt (brightener 15, commercially available under the trade name Tinopal AMS-GX by BASF); 4,4 '-bis { [ 4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl ] -amino } -2,2' -stilbene disulfonic acid disodium salt (commercially available under the trade name Tinopal UNPA-GX by BASF); 4,4 '-bis { [ 4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl ] -amino } -2,2' -stilbene disulfonic acid disodium salt (commercially available under the trade name Tinopal 5BM-GX by BASF); and/or 4,4 '-bis ((4-amino-6-anilino-1, 3, 5-triazin-2-yl) amino) stilbene-2, 2' -disulfonic acid disodium salt (brightener 49). The whitening agent can be whitening agent 49, whitening agent 15, whitening agent 3, or a mixture thereof.

Additional chelating agent

Additional processing aids of the present disclosure can include additional chelating agents (also known as chelates or chelating agents). The additional chelating agent may be selected so as to have an affinity for a metal ion different from the metal ion having an affinity for the oligoamine. For example, the oligomeric amine DETA according to the present disclosure has a specific affinity for copper ions, while a different chelator, DTPA, has a specific affinity for calcium ions. Thus, compositions with a combination of chelating agents can provide broad spectrum chelation, thereby providing improved performance. To optimize cleaning performance, for example by improving/maximizing chelant loading in the composition formulation while maintaining enzyme stability, it may be preferred to couple a copper chelant such as the oligoamines of the present disclosure with a calcium chelant such as DTPA and/or HEDP.

The additional chelating agent may be present at a level of from about 0.1% to about 10%, or to about 5%, or to about 2%, by weight of the composition. The oligoamine and the additional chelant may be present in the treatment composition at a combined level of from about 0.1% to about 10%, preferably to about 5%, by weight of the treatment composition. The weight ratio of oligoamines to additional chelating agents can be from about 10:1 to about 1:50, or from about 2:1 to about 1:25, or from about 1:2 to about 1: 20. The oligoamine may be present in an amount by weight that is less than the amount by weight of the additional chelating agent.

Suitable additional chelating agents may include phosphonates, aminocarboxylates, organic phosphonates, polyfunctional substituted aromatic chelating agents or mixtures thereof, preferably aminocarboxylates.

Aminocarboxylates useful as chelating agents include, but are not limited to, ethylenediaminetetraacetate, N- (hydroxyethyl) ethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine hexaacetate, diethylenetriaminepentaacetate, and ethanoldiaminediacetic acid, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof. Organic phosphonates are also suitable as chelating agents in the compositions of the present invention when low levels of total phosphorus are permitted and include ethylenediamine tetra (methylene phosphonate), diethylenetriamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), 1, 6-hexamethylenediamine tetra (methylene phosphonate), alpha-hydroxy-2-phenylethyl bisphosphonate, methylene bisphosphonate, hydroxy 1, 1-hexylene, vinylidene 1, 1-bisphosphonate, 1, 2-dihydroxyethane-1, 1-bisphosphonate and hydroxyethylene-1, 1-bisphosphonate, available under the trade mark DEQUEST; the phosphonate may not contain alkyl or alkenyl groups having more than 6 carbon atoms. The multifunctional substituted aromatic chelating agent may include a catechol, such as a sulfonated catechol.

Additional chelating agents may include: DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethanediol)Phosphonic acid), EDDS (ethylenediamine disuccinate (EDDS)), DTPMP (diethylenetriamine penta (methylene phosphonic acid)), EDTMP (ethylenediamine tetra (methylene phosphonic acid)), (ethylene diamine tetra (methylene phosphonic acid)), (ii) and (iii) a salt thereof,(1, 2-dihydroxybenzene-3, 5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycinediacetic acid), GLDA (glutamic acid-N, N-diacetic acid), any suitable derivative thereof, a salt thereof, and a mixture thereof.

As used herein, traditional builders such as citric acid and carbonates are not considered chelating agents and are not included when determining percent levels or weight ratios.

Enzyme

The treatment compositions 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: hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, mailanases, β -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, amylases, nucleases (such as deoxyribonuclease and/or ribonuclease), phosphodiesterases or mixtures thereof. Particularly preferred may be a mixture of proteases, amylases, lipases, cellulases, phosphodiesterases and/or pectate lyases. The compositions of the present disclosure may comprise an oligoamine of the present disclosure, a calcium binding chelator (such as DTPA), and an amylase.

Other agents

The treatment compositions of the present disclosure may comprise a solvent, preferably an organic solvent, such as an organic solvent free of amino functional groups. Suitable organic solvents may include glycerol, ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, 2, 3-butylene glycol, 1,3 butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol formal dipropylene glycol, polypropylene glycol, dipropylene glycol n-butyl ether, and mixtures thereof.

The treatment compositions of the present disclosure may include a chlorine scavenger. It is believed that chloride ions in the treatment fluid, such as from hypochlorite bleach or naturally occurring in the water source, may cause discoloration or other discoloration. The chlorine scavenger may be incorporated at a level sufficient to neutralize at least about 1ppm, or at least about 2ppm, or at least about 5ppm, or at least about 10ppm of chlorine in the treatment fluid. The chlorine scavenger may include an amine (other than the oligoamines described above) and/or an ammonium salt. Preferred amines may include those comprising primary and/or secondary amines, and may include alkanolamines such as Monoethanolamine (MEA), Diethanolamine (DEA), and/or Triethanolamine (TEA).

The treatment compositions of the present disclosure may comprise a cleaning and/or dispersing polymer, which may provide cleaning and/or whiteness benefits. Suitable cleaning and/or dispersing polymers may include: a polymeric detergent, which may be anionic or nonionic and/or may include terephthalate moieties; alkoxylated polyamines such as ethoxylated and/or propoxylated polyethyleneimines (such as PEI600 EO20 and/or PEI EO24PO16), ethoxylated hexamethylenediamine and their sulfated forms; alkoxylated polycarboxylates, including those derived from polyacrylates; amphiphilic graft copolymers, such as those derived from a polyethylene glycol backbone and having at least one side chain moiety selected from polyvinyl acetate, polyvinyl alcohol, or mixtures thereof (such as Sokalan HP 22); cellulosic polymers such as carboxymethyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof; carboxylate polymers such as maleate/acrylate random copolymers or polyacrylate homopolymers; or mixtures thereof. Cellulosic polymers and/or carboxylate polymers may be particularly useful in dry or powder treatment compositions because they may be more difficult to formulate in liquid and gel forms.

It is desirable to limit or even eliminate certain adjuncts, particularly where detergents primarily from natural or sustainable sources are desired. The detergent compositions of the present disclosure may be free of silicones, dyes, brighteners, or combinations thereof. The detergent compositions of the present disclosure may comprise less than 5%, or less than 3%, or less than 1%, by weight of the composition, of an amine-containing compound, provided that the amine oxide surfactant (if present) is not included in the total amount of amine-containing compound.

The compositions of the present disclosure may be substantially free of selenium compounds. The compositions of the present disclosure may be substantially free of halopropargyl (halopropagyl) compounds.

Method for preparing composition

The present disclosure relates to methods of making fabric care compositions comprising the oligomeric amines described herein. The method may comprise mixing the components of the composition described herein in the proportions described. For example, an oligoamine according to the present disclosure can be provided and combined with at least one additional processing aid to form a treatment composition.

The liquid compositions according to the present disclosure may be prepared according to conventional methods, for example in a batch process or a continuous cycle process.

The solid compositions according to the present disclosure may be prepared according to conventional methods, for example by a spray drying process or an agglomeration process.

The detergent compositions described herein can be enclosed in a pouch, preferably a pouch made from a water-soluble film, to form a unit dose article useful for treating fabrics. The pouch may comprise one compartment or may have a plurality of compartments, which may be side-by-side and/or overlapping. It may be preferred that such compositions have a relatively small amount of water, for example less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% water by weight of the detergent composition.

Methods of using the compositions

The present disclosure relates to methods of using the compositions described herein. The detergent composition may be a fabric care composition and may be used to treat a surface, such as a fabric or other textile.

The method of treating a surface may comprise the steps of: the provision of a surface is provided that,preferably a fabric, and contacting the surface with a composition according to the present disclosure as described above. The method may comprise agitating the fabric in the presence of water. The method may further comprise the step of performing a washing or cleaning operation. Water may be added before, during, or after the contacting step to form a treatment fluid. The water and/or treatment fluid may contain copper ions (Cu) at levels of, for example, about 0.1ppm to about 25ppm²⁺)。

The present disclosure also relates to a method of treating a fabric, preferably a stained fabric, for example by machine, using a composition according to the present disclosure, the method comprising the steps of: a composition according to the present disclosure is placed in contact with a fabric to be treated and a treatment operation, such as a laundering, cleaning, or fabric enhancement operation, is performed. The contacting step may occur during a wash cycle or during a rinse cycle of the automatic washing machine.

Any suitable washing machine may be used, for example, a top-loading or front-loading automatic washing machine. Those skilled in the art will recognize machines suitable for use in connection with processing operations. The articles of the present disclosure may be used in conjunction with other compositions such as fabric additives, fabric softeners, rinse aids, and the like. Additionally, the detergent compositions of the present disclosure can be used in known hand washing processes.

The invention may also relate to a method of treating a fabric, the method comprising the steps of: the fabric is contacted with the detergent composition described herein, a washing step is performed, and then the fabric is contacted with the fabric softening composition. The entire method or at least the washing step can be performed manually, machine-assisted or in an automatic washing machine. The step of contacting the fabric with the fabric softening composition may be carried out in the presence of water, for example during the rinse cycle of an automatic washing machine.

Use of a surfactant system

The present disclosure also relates to the use of a surfactant system, for example in a fabric care composition, to improve the deposition and/or malodor control properties of oligoamines with respect to a target surface, such as a target fabric. The surfactant system comprises a linear benzenesulfonate surfactant, as described in more detail above. Oligoamines are also described in more detail above. The surfactant system may further comprise AES, a non-ionic ethoxylated alcohol, AEC, or a mixture thereof, for example, in any weight ratio to LAS, as described in more detail above.

Combination of

Specifically contemplated combinations of the present disclosure are described herein in the following alphabetic paragraphs. These combinations are exemplary in nature and not limiting.

A. A treatment composition, comprising: an oligomeric amine and/or salt thereof, and a surfactant system, wherein the oligomeric amine is present at a level of about 0.01% to 3.0% by weight of the treatment composition, wherein the oligomeric amine has a structure according to formula I:

wherein each L is independently- (C)_mH_2m) -, where for each L, the subscript m is independently an integer of 2 to 6, n is an integer of 1 to 10, and R¹-R⁵Each of which is independently selected from H and C₁-C₄An alkyl group; and wherein the surfactant system comprises a Linear Alkylbenzene Sulphonate (LAS) surfactant.

B. The treatment composition of paragraph a, wherein the oligoamine is present at a level of from about 0.01% to about 2%, or from about 0.02% to about 1%, or from about 0.03% to about 0.5%, or from about 0.05% to about 0.2%, by weight of the treatment composition.

C. The treatment composition according to any of paragraphs a or B, wherein the subscript m is 2 or 3, preferably m is 2.

D. The treatment composition of any of paragraphs a-C, wherein n is an integer from 1 to 5, preferably from 1 to 3, more preferably 1 or 2, even more preferably 1.

E. The treatment composition of any of paragraphs a-D, wherein R¹-R⁵Each of which is independently selected from H and C₁Alkyl, preferablyWherein R is¹-R⁵Is H, more preferably wherein R¹-R⁴Is H, even more preferably wherein all are H.

F. The treatment composition of any of paragraphs a-E, wherein the oligomeric amine is characterized by a molecular weight of about 100Da to about 1200Da, or about 100Da to about 900Da, or about 100Da to about 600Da, or about 100Da to about 400Da, or preferably between 100Da to 250Da, more preferably between 100Da to 200Da, even more preferably between 100Da to 150 Da.

G. The treatment composition of any of paragraphs a-F, wherein the treatment composition comprises from about 0.01% to about 5%, or to about 3%, or to about 2%, or to about 1%, or 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 the oligoamine.

H. The treatment composition of any of paragraphs a-G, wherein the oligomeric amine is selected from the group consisting of: diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), Dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetramine (TETA), 4-methyltriethylenetetramine (4-MeTETA), 4, 7-dimethyltriethylenetetramine (4, 7-Me)₂TETA), 1,4,7, 7-pentamethyldiethylenetriamine (M5-DETA), tripropylenetetramine (TPTA), Tetraethylenepentamine (TEPA), Tetrapropylenepentamine (TPPA), Pentaethylenehexamine (PEHA), pentapropylenehexamine (PPHA), hexaethyleneheptamine (HEHA), hexapropylenheptamine (HPHA), N' -bis (3-aminopropyl) ethylenediamine, and mixtures thereof.

I. The treatment composition of any of paragraphs a-H, wherein the oligoamine is selected from the group consisting of: diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,4,7, 7-pentamethyldiethylenetriamine (M5-DETA), triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), N '-bis (3-aminopropyl) ethylenediamine and mixtures thereof, even more preferably Diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), N' -bis (3-aminopropyl) ethylenediamine and mixtures thereof.

J. The treatment composition of any of paragraphs a-I, wherein the oligoamine comprises Diethylenetriamine (DETA).

K. The treatment composition of any of paragraphs a-J, wherein the surfactant system comprises from about 5%, or about 10%, or about 20%, or about 40%, or about 50%, or about 60%, or about 70%, or about 80%, or about 90% to about 100%, by weight of the surfactant system, of LAS surfactant.

L. the treatment composition of any of paragraphs a-K, wherein the surfactant system further comprises a second surfactant comprising an Alkyl Ethoxylated Sulfate (AES), a nonionic ethoxylated alcohol, an Alkyl Ethoxylated Carboxylate (AEC), or a mixture thereof.

M. the treatment composition of any of paragraphs a-L, wherein the second surfactant comprises AES, preferably wherein the weight ratio of LAS to AES is from about 10:90 to about 99:1, or from about 50:50 to about 90:10, or from about 80:20 to about 90: 10.

N. the treatment composition of any of paragraphs a-M, wherein the second surfactant comprises a nonionic ethoxylated alcohol surfactant, preferably wherein the weight ratio of LAS to nonionic ethoxylated alcohol surfactant is from about 10:90 to about 99:1, or from about 50:50 to about 90:10, or from about 80:20 to about 90: 10.

O. the treatment composition of any of paragraphs a-N, wherein the second surfactant comprises an Alkyl Ethoxylated Carboxylate (AEC) surfactant, preferably wherein the weight ratio of LAS to AEC is greater than about 50:50 to 99:1, or about 60:40 to about 95:5, or about 75:25 to about 90: 10.

P. the treatment composition of any of paragraphs a-O, wherein the surfactant system is present at a level of from about 1% to about 90%, or from about 1% to about 80%, or from about 1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50%, by weight of the treatment composition.

Q. the treatment composition of any of paragraphs a-P, wherein the surfactant system further comprises a zwitterionic surfactant, preferably wherein the zwitterionic surfactant comprises an amine oxide.

R. the treatment composition according to any of paragraphs a-Q, wherein the treatment composition comprises an additional treatment aid, preferably selected from: antioxidants, hueing agents, optical brighteners, additional chelants, enzymes, fatty acids and/or salts thereof, encapsulated benefit agents, soil release polymers, builders, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleaches, bleach catalysts, bleach activators, polymeric dispersants, soil removal/anti-redeposition agents, polymeric grease cleaners, amphipathic copolymers, suds suppressors, cosmetic dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, fillers, hydrotropes, solvents, biocides and/or preservatives, pH adjusters, processing aids, fillers, rheology modifiers, structurants, opacifiers, pearlescers, pigments, anticorrosion agents, rust inhibitors, antifoam agents, chlorine scavengers, and mixtures thereof.

S. the treatment composition of any of paragraphs a-R, wherein the additional treatment adjunct comprises an antioxidant, preferably an antioxidant comprising a hindered phenol.

T. the treatment composition according to any of paragraphs a-S, wherein the additional treatment adjunct comprises an additional chelating agent, preferably an additional chelating agent selected from the group consisting of phosphonates, aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents or mixtures thereof, more preferably selected from DTPA (diethylenetriamine pentaacetic acid), HEDP (hydroxyethane diphosphonic acid), EDDS (ethylenediamine disuccinate (EDDS)), DTPMP (diethylenetriamine penta (methylenephosphonic acid)), EDTMP (ethylenediamine tetra (methylenephosphonic acid)), (ethylene diamine tetra (methylenephosphonic acid)), (di-methyl-phosphonic acid)), and (di-methyl-phosphonic acid (di-ethylenephosphonic acid)), a combination thereof,(1, 2-dihydroxybenzene-3, 5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycinediacetic acid), GLDA (glutamic acid-N, N-diacetic acid), any suitable derivative thereofAdditional chelating agents for their salts and mixtures thereof.

U. the treatment composition according to any of paragraphs a-T, wherein the treatment composition is a fabric care composition, preferably a fabric care composition selected from the group consisting of: light duty liquid detergent compositions, heavy duty liquid detergent compositions, laundry detergent gels, bleaching compositions, laundry additives, fabric enhancer compositions, and mixtures thereof, more preferably selected from the group consisting of heavy duty liquid detergent compositions, fabric enhancer compositions, and mixtures thereof.

V. the treatment composition of any of paragraphs a-U, 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 lozenge or bead, a fibrous product, a tablet, a strip, a sheet, a dried sheet, or a mixture thereof.

A method of treating a surface, preferably wherein the surface is a fabric, comprising the steps of: (a) providing a surface, preferably a fabric, more preferably a fabric soiled with sebum, and (b) contacting said surface with a composition according to any of paragraphs a-V, optionally in the presence of water.

Use of a surfactant system comprising a linear alkylbenzene sulfonate surfactant in a fabric care composition to ameliorate the malodour control benefit of an oligoamine and/or salt thereof relating to a target fabric, and wherein the oligoamine has a structure according to formula I:

wherein each L is independently- (C)_mH_2m) -, where for each L, subscript m is independently an integer of 2 to 6, n is an integer of 1 to 10, and R¹-R⁵Each of which is independently selected from H and C₁-C₄An alkyl group.

Y. the use according to paragraph X, wherein the surfactant system further comprises AES, a non-ionic ethoxylated alcohol surfactant, AEC, or a mixture thereof.

Test method

Malodor reduction test method

The following methods were used to test the malodor reduction benefits of the compositions.

A. Preparation of 75 g malodor marker

Fatty acids and malodor markers were added to a 100ml glass jar with a Teflon-lined lid according to table a and mixed thoroughly using a vortex.

Table a: malodor marker compositions

Material	CAS number	Composition%	Required weight (g)
				Isovaleric acid	503-74-2	12.00	9.0
Undecanal aldehyde	112-44-7	0.20	0.15
				Undecanoic acid	112-37-8	62.80	47.1
Stink-eliminating agent	83-34-1	1.00	0.75
				Capric acid	334-48-5	22.00	16.5
Undecanoic acid ethyl ester	627-90-7	2.00	1.5

B. Preparation of body-stain malodor compositions

Specific amounts of each material according to table 2 were provided into a 200mL glass jar with a Teflon-lined lid. Artificial body fouling (ABS) was obtained commercially by Accurate Product Development (2028Bohlke Blvd, Fairfield, OH 45014).

Table B: body scale malodor compositions

Material	Weight (g)
		Malodor markers (from Table A)	17.1
Artificial body dirt (ABS)	15.8
		Dipropylene glycol monomethyl ether (CAS: 34590-94-8)	105
Squalene (cas number 111-02-4)	15.8

C. Preparation of malodor test Fabric

Sixteen malodor test fabrics per wash load were prepared by applying 300 μ l of the body soil malodor composition described in table B to a degummed 2 x 5 inch white polyester cotton cloth 50/50(PCW50/50) sample. Adding 48 grams of the liquid detergent to be tested (see, e.g., table 1 in example 1 below) to a Duet 9200 washing appliance set to a normal cycle; a 77 ° f wash cycle followed by a 60 ° f rinse cycle. Tap water is used, which contains copper at ambient levels, for example, due to copper piping. The malodor test fabrics were washed in 7gpg wash water with 3.9kg, 50 x 50cm clean cotton and polyester cotton ballast and then dried in a Maytag double stack tumble dryer set low for 20 minutes. The dried fabric was placed in a polyester film bag and sealed for 24 hours.

D. Malodor detection on textiles

Malodor reduction using ABS/squalene malodor sensor was quantified by gas chromatography mass spectrometry using Agilent gas chromatograph 7890B equipped with mass selective detector (5977B), Chemstation quantification pack and Gerstel multi-purpose sampler equipped with Solid Phase Microextraction (SPME) probe. Calibration standards for 6-methyl-5-hepten-2-one (CAS 110-93-0), trans-2-heptenal (18829-55-5), and 3-methyl-2-butenal (107-86-8) were prepared by dissolving known weights of these materials in light mineral oil (CAS 8020-83-5), each purchased from Sigma Aldrich. The fabric was cut into uniform 2 inch by 2.5 inch pieces and placed in 10mL headspace jaw vials. Prior to analysis, vials were equilibrated for greater than 12 hours. The following settings were used in the autosampler: 80 ℃ incubation temperature, 90min incubation time, VT32-10 sample tray type, 22mm vial penetration, 20min extraction time, 54mm injection penetration and 300s desorption time. The following settings were used for the front split/no split inlet helium: split mode, 250 ℃ temperature, 12psi pressure, 79.5mL/min total flow, 3mL/min membrane purge flow, 50:1 split ratio, and 22.5min GC run time. The following settings were used in the oven: initial temperature of 40 ℃, heating program of 12 ℃/min, temperature of 250 ℃ and holding time of 5 min. The total nMol/L liter of 6-methyl-5-hepten-2-one (K ═ 3353), trans-2-heptenal (K ═ 3434), and 3-methyl-2-butenal (K ═ 1119) was calculated based on the partition coefficient (K at 80 ℃) of each component.

These values (in nmol/L) from these three measurements were added together to provide the total ABS/squalene marker (nmol/L) for the given test set.

E. Malodor reduction Oxidation products calculation

Malodor reduction% oxidation products are provided in percentages that compare the reduction in the amount of the selected malodor markers provided by the test composition compared to the (no-oligoamine) reference composition. The values were determined as follows:

percent reduction of oxidized product ═ marker_ref-a marker_test) X 100/marker_ref

Marker substance_refAnd markers_testThe values of (a) are defined as follows:

marker substance_refTotal ABS/squalene marker (nmol/L) for fabrics washed with formulations without oligoamines (e.g. reference or control formulations)

Marker substance_testTotal ABS/squalene marker (nmol/L) for fabrics washed with formulations containing the oligoamines tested

Since the measured oxidation products are generally considered malodorous, it is believed that the greater the% reduction in oxidation products provided by the composition, the less malodorous the treated fabric may have. Thus, a larger malodor reduction oxidation product% value is generally preferred. The compositions and methods of the present disclosure can provide a% malodor reduction oxidation product value 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%.

Malodor reduction may also be reported as Markers_refAnd Markers_testThe difference between, thus showing an absolute difference (e.g. Δ ABS/squalene oxidation).

Whiteness loss test method test

Whiteness loss (e.g., Δ WI) was tested according to the following procedure.

A. Preparation of whiteness test fabrics

Degummed cotton, polyester cotton and polyester whiteness test fabrics are available from WFK. (WFK Testgewell GmbH, Christenfeld 10, D-41379 Brufgen, Germany). Four of each fabric type (12 fabrics in total) were prepared for whiteness testing by washing four times in 48 grams (750ppm) Tide Free and clean and 25 grams (390ppm) Downy Free rinse in a Kenmore top-loading washing machine set to normal wash cycle, 77F wash, 60F rinse, 7 grain/gallon. Initial whiteness reference measurements were made using a Konica Minolta spectrophotometer and reported as the initial whiteness index CIE. Whiteness index CIE values are common whiteness indices and refer to measurements made under D65 illumination (standard representation of outdoor daylight). For a perfectly reflective non-fluorescent white material, the CIE whiteness would be 100. In technical terms, whiteness is a single numerical index that relates to the relative degree of whiteness of a near-white material under particular lighting conditions. The index is designed such that most people will agree that the higher the whiteness index, the whiter the material.

B. Whiteness measurement

The fabrics were placed in a 7.57 liter custom wash bucket under the conditions summarized in table 3 below. In the wash cycle, 5.65 grams (746ppm) of detergent (liquid) was used) Wash fabrics with background soil and then rinse cycle with 3 grams (396ppm) of liquid fabric softener: (B)Free) washing. Once the rinse cycle is complete, all fabrics are removed and placed in a tumble dryer. The washing, rinsing and drying cycles were repeated 10 times. After 10 cycles, the fabric was measured for loss of whiteness using a Konica Minolta spectrophotometer and the measurement was reported as the final whiteness index. The average Δ WI (i.e., Δ WI) for each test fabric (representing the difference between the initial and treated whiteness index measurements) was calculated and represented by the following calculation: Δ WI is the initial whiteness index after preparation-the treated whiteness index after 10 to 20 cycles. Generally, Δ WI is negative because whiteness tends to decrease after washing with background soils. The whiteness index is reported in the table as Δ Δ WI ═ Δ WI- Δ WI REF tested with oligoamines (no oligoamines). Δ aw is negative if the whiteness tends to decrease after washing with the test liquid detergent composition comprising the oligoamine, compared to a reference liquid detergent composition comprising no oligoamine. A number close to zero would represent a low polyamine with little effect on fabric yellowing.

Table C: washing, rinsing and drying conditions

Examples

The embodiments provided below are intended to be illustrative in nature and not limiting.

Example 1: exemplary formulations (heavy duty liquid laundry detergents)

The following heavy duty liquid laundry detergent compositions can be prepared by mixing the ingredients listed in table 1 in a conventional manner known to those of ordinary skill in the art. Composition 1A is a conventional premium laundry detergent that does not contain the linear oligomeric amines of the present disclosure. Composition 1B is a comparative example containing EDDS chelant. All provided compositions comprise linear alkylbenzene sulfonate surfactants.

TABLE 1：

1. Linear alkylbenzene sulfonates having average aliphatic carbon chain lengths of C11-C12, supplied by Stepan (Northfield, Illinois, USA)

AE9 is a C12-14 alcohol ethoxylate having an average degree of ethoxylation of 9 supplied by Huntsman (Salt Lake City, Utah, USA)

3. Diethylene Tetramine Pentaacetic 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. Polyethyleneimine (MW 600) with 20 ethoxylated groups per NH.

5. The amphiphilic alkoxylated grease cleaning polymer was a polyethyleneimine (MW 600) with 24 ethoxylated groups per-NH and 16 propoxylated groups per-NH.

6. Proteases may be supplied by Genencor International (Palo Alto, California, USA) (e.g., Purafect) Or supplied by Novozymes (Bagsvaerd, Denmark) (e.g., )。

7.are all products of Novozymes (Bagsvaerd, Denmark).

8. Suitable fluorescent whitening agents are, for exampleAMS、CBS-X

9. Diethylenetriamine (DETA)

N, N' -bis (3-aminopropyl) ethylenediamine

11. Tetraethylenepentamine (TEPA)

Example 2: malodor control of linear oligoamines over known chelants

To demonstrate the malodor control effect of the linear oligomeric amines of the present disclosure, various liquid detergent compositions according to example 1 in table 1 above were prepared. Each composition comprises Linear Alkylbenzene Sulphonate (LAS). Some have one or more conventional chelating agents; some comprise linear oligomeric amines according to the present disclosure.

Example 2A is a premium type laundry detergent containing a conventional chelant (diethylenetetramine pentaacetic acid (DTPA)). For examples 2B, 2C, 2D and 2E, additional amine was added. Example 2B contained an additional amino chelator, ethylenediamine disuccinic acid (EDDS). Examples 2C, 2D, and 2E comprise linear oligomeric amines of the present disclosure, as detailed in table 2 below. The compositions were tested for% reduction in oxidation products according to the test methods provided above. The results are shown in Table 2.

TABLE 2：

N, N' -bis (3-aminopropyl) ethylenediamine having the structure:

the results in table 2 show the malodor control benefit of the linear oligoamines of examples 2C, 2D, and 2E compared to the no added amine composition of 2A. Examples 2C, 2D, and 2E also showed improved malodor control compared to example 2B, indicating that oligoamines perform better than EDDS, a different amine-containing chelating agent.

Example 3: malodor control of linear oligoamines in combination with LAS and optionally AES

To illustrate the benefits of the linear oligomeric amines of the present disclosure in combination with LAS and optionally with AES, liquid detergent compositions having the ingredients shown in table 3A below were prepared. Group a does not contain linear oligoamines according to the present disclosure; group B contains diethylene triamine (DETA), a representative linear oligoamine, in an amount of 0.2 wt%. In addition, the compositions of each group contained a surfactant system at a level of 18.1%. However, the surfactant system contained LAS and AES in various ratios as shown in table 3B.

To test the malodor control benefits of DETA in various surfactant systems, fabrics were treated as described above (north american top loading washing machine, water: 87 ° f/7 gpg) and tested for malodor removal. The results of the malodor removal test are shown in table 3B.

TABLE 3A：

3. Diethylene Tetramine Pentaacetic 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. Polyethyleneimine (MW 600) with 20 ethoxylated groups per NH.

5. The amphiphilic alkoxylated grease cleaning polymer was a polyethyleneimine (MW 600) with 24 ethoxylated groups per-NH and 16 propoxylated groups per-NH.

6. Proteases may be supplied by Genencor International (Palo Alto, California, USA) (e.g., Purafect) Or supplied by Novozymes (Bagsvaerd, Denmark) (e.g., )。

7.are all products of Novozymes (Bagsvaerd, Denmark).

8. Suitable fluorescent whitening agents are, for exampleAMS、CBS-X

Octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, commercially available as Tinogard TS (BASF).

10. The oligoamines of the present disclosure are Diethylenetriamine (DETA).

TABLE 3B：

1. Linear alkylbenzene sulfonates having average aliphatic carbon chain lengths of C11-C12, supplied by Stepan (Northfield, Illinois, USA)

C12-15 Alkylethoxy (1.8) sulfate

As shown in table 3B, the compositions comprising a combination of LAS and DETA provided improved malodor reduction benefits compared to DETA in a no LAS surfactant system (e.g., example 3G). Furthermore, as the relative amount of LAS in the surfactant system increases (e.g., a weight ratio of LAS: AES of greater than 40: 60), the beneficial effects become more pronounced. This is particularly surprising considering that the amount of malodorous oxidation products generally increases with the relative amount of LAS in the DETA-free group (group a).

Example 4: combination of linear oligoamines with LAS and optionally with nonionic ethoxylated alcohol surfactants Combined malodor control

To illustrate the benefits of the linear oligoamines of the present disclosure in combination with LAS, and optionally in combination with a nonionic ethoxylated alcohol surfactant, a liquid detergent composition having the general ingredients as shown in table 3A of example 3 above was prepared. Group a does not contain linear oligoamines according to the present disclosure; group B contains diethylene triamine (DETA), a representative linear oligoamine, in an amount of 0.2 wt%. In addition, the compositions of each group contained a surfactant system at a level of 18.1%. However, for the purpose of example 4, the surfactant system comprised LAS and nonionic ethoxylated alcohol surfactant in various ratios, as shown in table 4.

To test the malodor control benefits of DETA in various surfactant systems, fabrics were treated as described above (north american top load, water: 87 ° f/7 gpg) and tested for malodor reduction. The results of the malodor reduction test are shown in table 4.

TABLE 4：

1. Linear alkylbenzene sulfonates having average aliphatic carbon chain lengths of C11-C12, supplied by Stepan (Northfield, Illinois, USA)

2. Nonionic ethoxylated alcohol surfactants, specifically C12-14 alcohol ethoxylates having an average degree of ethoxylation of 9, supplied by Huntsman (Salt Lake City, Utah, USA)

As shown in table 4, the compositions comprising a combination of LAS and DETA provide improved malodor reduction benefits compared to DETA in a no LAS surfactant system (e.g., example 4G). In addition, the malodor reduction benefit becomes more pronounced as the relative amount of LAS in the surfactant system is increased (e.g., a LAS: NI weight ratio of 40:60 or greater).

Example 5: oxiranes of linear oligoamines in combination with LAS and Alkyl Ethoxylated Carboxylate (AEC) surfactants Odor control

To illustrate the benefits of the linear oligoamines of the present disclosure in combination with LAS and AEC surfactants, liquid detergent compositions having the general ingredients as shown in table 3A of example 3 above were prepared. Group a does not contain linear oligoamines according to the present disclosure; group B contains diethylene triamine (DETA), a representative linear oligoamine, in an amount of 0.2 wt%. In addition, the compositions of each group contained a surfactant system at a level of 18.1%. However, for the purposes of example 5, the surfactant system comprised LAS and Alkyl Ethoxylated Carboxylate (AEC) surfactants in various ratios, as shown in table 5.

The fabrics were treated in a north american top loading automatic washing machine (water: 30.6 ℃,7 gpg). The malodor reduction benefit is provided in table 5 as a percentage reduction of oxidation products on the textiles treated in the second group (group B, with DETA) relative to the first group (group a, without DETA).

TABLE 5：

1. Linear alkylbenzene sulfonates having average aliphatic carbon chain lengths of C11-C12, supplied by Stepan (Northfield, Illinois, USA)

C12-C14 Alcoholic polyglycol ether carboxylic acids (Marlowet 4541, supplied by Sasol)

As shown in table 5, example 5D, which included the greatest relative amount of LAS, provided the greatest malodor reduction benefit.

Example 6: effect of alkylation

To show the effect that various degrees of alkylation of the oligoamines of the present invention can have on the malodor reduction benefit, the following molecules were tested at the levels provided according to the test methods provided above. The oligoamine is added to a liquid detergent comprising LAS, AES and a nonionic surfactant. The tests were performed in a north american front loading automatic washing machine.

The percent reduction in oxidation products for each compound relative to the reference composition is provided in tables 6A and 6B below.

TABLE 6A：

As shown in the above structure, example 6B is characterized by a terminal primary amine, example 6C is characterized by a terminal secondary amine, and example 6D is characterized by a terminal tertiary amine. As shown in table 6A, examples 6B-6D each provided a malodor reduction benefit, with example 6B providing the relatively greatest malodor reduction.

TABLE 6B：

As shown in table 6B, example 6F provided the relatively largest malodor reduction.

Example 7: para-whiteness of oligoamines

To show that low polyamines (and% thereof) can have an effect on whiteness, certain amines were added to north american liquids as provided in table 7(commercially available heavy duty liquid laundry detergents). The detergent composition comprises LAS, AES and a nonionic surfactant. Various fabrics (cotton, polyester cotton and polyester) were treated with these compositions under north american conditions for ten wash cycles.

After ten cycles, the loss of whiteness was determined according to the Δ WI test provided in the test methods section above. The results are provided in table 7. Negative numbers indicate loss of whiteness, and larger numbers indicate greater loss of whiteness (e.g., -10 indicates greater loss of whiteness than-5). The loss of whiteness is preferably between 0 and-5, or between 0 and-4. A higher amount of whiteness loss indicates that the product may be less preferred for consumer use.

TABLE 7：

As shown in table 7, the presence of the amine may result in loss of whiteness over multiple treatments. However, the loss of whiteness provided by, for example, an amine content of less than 0.1 wt.% (see runs 7B and 7C) is relatively acceptable to the manufacturer. By comparison, run 7D (which contains DETA content above 1%) shows a loss of whiteness that is believed to be less preferred. It is believed that alkylating the oligoamines can further improve whiteness loss and/or allow the oligoamines to be formulated at relatively high levels while keeping whiteness loss within acceptable ranges.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, 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".

Each document cited herein, including any cross referenced or related patent or patent application and any patent application or patent to which this application claims priority or its benefits, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with any disclosure of the invention or the claims herein or that it alone, or in combination with any one or more of the references, teaches, suggests or discloses any such invention. Further, 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.

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.