Phenolic compositions for reducing malodor

Abstract

Disclosed herein are phenolic compositions and laundry care compositions comprising such phenolic compositions that can reduce malodor in fabrics or articles laundered therewith.

Description

FIELD OF THE INVENTION

[0001] The present disclosure relates to phenolic compositions for use as antioxidants to reduce malodor in fabric treatment compositions.

[0002] Malodor is a persistent problem in laundry. There are several sources of malodor-causing materials in textiles. One source of malodor comes from the fact that as consumers move to using less water, shorter wash cycles, and lower wash water temperatures, soils are less efficiently removed from clothing during the wash cycle and remain on the surface of the fabric. These soils that remain on the fabric surface (service) may consist of human sebum and other oils that are prone to autoxidation and decomposition into volatile malodorous compounds.

[0003] Manufacturers are continually searching for ways to reduce this malodor. One approach involves the use of antioxidants in laundry that deposit on the clothing during washing. These antioxidants reduce the rate of autoxidation of oils, which in turn prevents the development of malodorous compounds.

[0004] There remains a need for improved antioxidant compositions for reducing malodors in fabrics and textiles. There remains a need for improved methods of preventing oxidation of sebum and other oils in fabrics and textiles. There remains a need for improved antioxidant compositions that effectively reduce and block malodors for an increased period of time. There remains a need for improved antioxidant compositions that effectively reduce and block malodors when applied at lower concentrations. There remains a need for improved antioxidant compositions that are more easily formulated into detergent compositions. There remains a need for improved antioxidant compositions that are more easily transferred to fabrics and textiles when laundered. Overview

[0005] In accordance with the objectives of the disclosed materials and methods, as embodied and broadly described herein, the disclosed subject matter relates in one aspect to compounds, compositions, and methods of making and using the compounds and compositions.

[0006] Additional advantages will be set forth in part in the description that follows, and in part will be obvious from the description, or may be learned by practice of the aspects that are described below. The advantages will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.

[0007] The details of one or more embodiments are set forth in the description below. Other features, objects, and advantages will be apparent from the description, and from the claims.

[0008] Before the present methods and systems are disclosed and described, it is to be understood that the methods and systems are not limited to specific synthetic methods, specific components, or particular compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0009] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to, and independent of, the other endpoint.

[0010] "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which said event or circumstance occurs and instances in which it does not occur.

[0011] Throughout the description and claims of this specification, the word "comprise" and variations of that word, such as "comprising" and "comprises," mean "including, but not limited to," and are not intended to exclude, for example, other additives, components, integers, or steps. "Exemplary" means "an example of" and is not intended to convey an indication of a preferred or ideal embodiment. "For example," is not used in a limiting sense, but rather for illustrative purposes.

[0012] Disclosed are components that can be used to practice the disclosed methods and systems. Where these and other components are disclosed herein, and where combinations, subsets, interactions, groups, etc. of these components are disclosed, it is understood that specific reference to each of these various individual and collective combinations and permutations may not be explicitly disclosed, but that each is specifically contemplated and described herein for all methods and systems. This applies to all aspects of this application, including, but not limited to, steps in the disclosed methods. Thus, where there are various additional steps that may be performed, it is understood that each of these additional steps may be performed with any specific aspect or combination of aspects of the disclosed methods.

[0013] As used herein, the phrase "fabric treatment composition" includes compositions and formulations designed to treat fabrics or other textiles, including clothing. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric refreshing compositions, laundry prewashes, laundry pretreatments, laundry additives, spray products, dry cleaning agents or compositions, laundry wash additives, pre-rinse fabric treatments, ironing aids, single-dose package formulations, delayed-release formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that will become apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as pre-laundry treatments, post-laundry treatments, or added during the wash cycle of a laundry operation.

[0014] As used herein, "liquid" includes free-flowing liquids, as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light-duty and heavy-duty liquid detergent compositions, fabric strengtheners, detergent gels, commonly used in laundry, bleaching, and laundry additives. Gases, e.g., suspended bubbles, or solids, e.g., particles, may be contained within the liquid.

[0015] As used herein, "granules" and "particles" refer to a volume of solid or sufficiently solid material having a finite mass. Granules and particles may be free-flowing or may be suspended within a secondary composition. The free-flowing particles may be similar to those commercially available under the trademark UNSTOPABLES® from The Procter & Gamble Company, Cincinnati, Ohio, United States.

[0016] The terms "substantially free of" or "substantially free of" may be used herein. This means that the indicated material is minimally present, not intentionally added to and forming part of the composition, or preferably is not present at analytically detectable levels. This is intended to include compositions in which the indicated material is present only as an impurity in one of the other materials intentionally included therewith. The indicated material may be present, if at all, at a level of less than 10% by weight of the composition, or less than 1% by weight, or less than 0.1% by weight, or less than 0.01% by weight, or even 0% by weight.

[0017] As used herein, the phrases "sufficiently solid" and "solid" mean that the material is capable of maintaining its shape without significant deformation when free-standing at room temperature. "Solid," as used herein, may include, but is not limited to, granules, particles, powders, agglomerates, microcapsules, flakes, noodles, pearlescent balls, and mixtures thereof.

[0018] As used herein, the terms "water-soluble," "water-soluble material," and "water-soluble carrier material" mean that the material or carrier material is soluble or dispersible in water, preferably having a water solubility of at least 50%, preferably at least 75%, or even at least 95%, as measured using a glass filter with a maximum pore size of 20 microns by the method specified below: 50 grams ± 0.1 grams of material and / or carrier material are added to a pre-weighed 400 mL beaker, and 245 mL ± 1 mL of distilled water is added. This is vigorously stirred for 30 minutes with a magnetic stirrer set at 600 rpm. The mixture is then filtered through a sintered glass filter with a pore size as defined above (maximum 20 microns). The process is carried out at ambient conditions. "Ambient conditions," as used herein, means 23°C ± 1.0°C and 50% ± 2% relative humidity. The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material (this is the dissolved or dispersed fraction) is determined. The percentage of solubility or dispersibility can then be calculated.

[0019] Unless otherwise noted, all ingredient / material or composition levels refer to the active portion of that ingredient / material or composition and exclude impurities, such as residual solvents or by-products, that may be present in commercial sources of such ingredient / material or composition.

[0020] Disclosed herein are phenolic compositions for use as antioxidants in fabric treatment compositions. The phenolic compositions comprise a compound of formula (I) and a compound of formula (II):

[0021] [ka]

[0022] [In the formula, L 1 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 1is an integer between 2 and 50; R a1 is C 1~8 is an alkyl group; R a2 is C 1~8 is an alkyl group; Each R a3 are independently selected from the group consisting of H, CH3 and CH2CH3;

[0023] [ka]

[0024] [In the formula, L 2 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 2 is an integer between 2 and 50; 1 and x 2 is not the same; R b1 is C 1~8 is an alkyl group; R b2 is C 1~8 is an alkyl group; Each R b3 are independently selected from the group consisting of H, CH3, and CH2CH3. At least includes.

[0025] In the context of Formula (I) and Formula (II) and subsequent formulas for other phenolic compounds, the term "null" is intended to convey that the phenolic moiety is directly bonded to the carbonyl carbon atom through a carbon atom of the phenolic moiety that is positioned para to the hydroxy group of the phenolic moiety. -[CH-CHR 3 The use of square brackets around the -O]- group indicates that each R 3 Unless specified to the contrary, a given compound may contain the same or different R groups in each repeat unit of the chain. 3For example, in some embodiments of compounds of Formula (I), x=4. In some such embodiments, R a3 can be hydrogen in each case, while in other cases, two R a3 The group can be hydrogen, and the other two R a3 The group can be methyl.

[0026] Without wishing to be bound by theory, it is believed that the use of multiple phenolic antioxidants provides advantageous antioxidant strength and stability compared to the use of a single phenolic compound as an antioxidant.

[0027] In some embodiments, the phenolic composition has formula (III):

[0028] [ka]

[0029] [In the formula, L 3 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 3 is an integer between 2 and 50; 1 , x 2 and x 3 None of these are the same; R c1 is C 1~8 is an alkyl group; R c2 is C 1~8 is an alkyl group; Each R c3 are independently selected from the group consisting of H, CH3, and CH2CH3. The compound may further comprise:

[0030] In some embodiments, the phenolic composition has formula (IV):

[0031] [ka]

[0032] [In the formula, L 4 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 4 is an integer between 2 and 50; 1 , x 2 , x 3 and x 4 None of these are the same; R d1 is C 1~8 is an alkyl group; R d2 is C 1~8 is an alkyl group; Each R d3 are independently selected from the group consisting of H, CH3, and CH2CH3. The compound may further comprise:

[0033] In some embodiments, the phenolic composition has Formula (V):

[0034] [ka]

[0035] [In the formula, L 5 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 5 is an integer between 2 and 50; 1 , x 2 , x 3 , x 4 and x 5 None of these are the same; R e1 is C 1~8 is an alkyl group; R e2 is C 1~8 is an alkyl group; Each R e3are independently selected from the group consisting of H, CH3, and CH2CH3. The compound may further comprise:

[0036] In some embodiments, the phenolic composition has formula (VI):

[0037] [ka]

[0038] [In the formula, L 6 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 6 is an integer between 2 and 50; 1 , x 2 , x 3 , x 4 , x 5 and x 6 None of these are the same; R f1 is C 1~8 is an alkyl group; R f2 is C 1~8 is an alkyl group; Each R f3 are independently selected from the group consisting of H, CH3, and CH2CH3. The compound may further comprise:

[0039] In some embodiments, the phenolic composition has formula (VII):

[0040] [ka]

[0041] [In the formula, L 7 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 7 is an integer between 2 and 50; 1 , x2 , x 3 , x 4 , x 5 , x 6 and x 7 None of these are the same; R g1 is C 1~8 is an alkyl group; R g2 is C 1~8 is an alkyl group; Each R g3 are independently selected from the group consisting of H, CH3, and CH2CH3. The compound may further comprise:

[0042] In some embodiments, the phenolic composition has formula (VIII):

[0043] [ka]

[0044] [In the formula, L 8 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 8 is an integer between 2 and 50; 1 , x 2 , x 3 , x 4 , x 5 , x 6 , x 7 and x 8 None of these are the same; R h1 is C 1~8 is an alkyl group; R h2 is C 1~8 is an alkyl group; Each R h3 are independently selected from the group consisting of H, CH3, and CH2CH3. The compound may further comprise:

[0045] In some embodiments, each of the L substituents (i.e., L1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 and L 8 ) are preferably the same. For example, each L substituent can be null, or each L substituent can be -CH-, or each L substituent can be -CHCH-, or each L substituent can be -CHCHCH-. In a preferred embodiment, each L substituent is -CHCH-.

[0046] In certain embodiments, R 1 Substituents (i.e., R a1 , R b1 , R c1 , R d1 , R e1 , R f1 , R g1 and R h1 ) but R 2 Substituents (i.e., R a2 , R b2 , R c2 , R d2 , R e2 , R f2 , R g2 and R h2 ) is preferably not the same as R 1 Each of the substituents can be a tert-butyl group, while R 2 Each of the substituents is a linear C 1~8 It can be an alkyl group (i.e., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl). 1 each of the substituents is a tert-butyl group, and R 2 each of the substituents is a methyl group, or R 2 Preferably, each of the substituents is an ethyl group.

[0047] In some embodiments, R 3 Each of the substituents (i.e., R a3 , Rb3 , R c3 , R d3 , R e3 , R f3 , R g3 and R h3 ) are preferably the same. For example, R 3 Each of the substituents can be H or R 3 Each of the substituents can be CH. In other embodiments, R 3 At least one of the substituents is H, and R 3 At least one of the substituents is CH3.

[0048] R 1 Each of the substituents is the same, and R 2 Each of the substituents is the same, and R 3 In embodiments where each of the substituents is the same and each of the L substituents is the same, the phenolic composition has the general formula:

[0049] [ka]

[0050] [In the formula, L is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; R 1 is C 1~8 is an alkyl group; R 2 is C 1~8 is an alkyl group; R 3 is H, CH3 or CH2CH3; n is greater than 2 and less than 50, preferably greater than 3 and less than 50, greater than 4 and less than 25, greater than 4 and less than 10, greater than 5 and less than 15, greater than 8 and less than 20, or greater than 12 and less than 25. The compounds may be described as compounds having the formula:

[0051] The "n" value for a given phenolic composition may be determined by HPLC analysis using a UV / Vis detector. This type of analysis is the preferred method for quantifying the levels of each component of a polymer distribution, as it will likely provide the most accurate and reproducible results with this type of phenolic composition. In other embodiments, mass spectrometry data may also be used.

[0052] In some embodiments, the compound of formula I is x 1 = 4, and the compound of formula II is 2 = 3. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0053] In certain embodiments, the compound of formula I is x 1 = 4, and the compound of formula II is 2 = 3, and the compound of formula III is 3 = 5. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0054] In some embodiments, the compound of formula I is x 1 = 5, and the compound of formula II is 2 = 4. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0055] In certain embodiments, the compound of formula I is x 1 = 5, and the compound of formula II is 2= 4, and the compound of formula III is 3 = 6. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0056] In some embodiments, the compound of formula I is x 1 = 6, and the compound of formula II is 2 = 5. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0057] In certain embodiments, the compound of formula I is x 1 = 6, and the compound of formula II is 2 = 5, and the compound of formula III is 3 = 7. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75%, based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75%, based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75%, based on the total weight of the phenolic composition.

[0058] In some embodiments, the compound of formula I is x 1 = 7, and the compound of formula II is 2 = 6. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0059] In certain embodiments, the compound of formula I is x 1= 7, and the compound of formula II is 2 = 6, and the compound of formula III is 3 = 8. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75%, based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75%, based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75%, based on the total weight of the phenolic composition.

[0060] In some embodiments, the compound of formula I is x 1 = 8, and the compound of formula II is 2 = 7. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0061] In certain embodiments, the compound of formula I is x 1 = 8, and the compound of formula II is 2 = 7, and the compound of formula III is 3 = 9. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0062] In some embodiments, the compound of formula I is x 1 = 9, and the compound of formula II is 2 = 7. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0063] In certain embodiments, the compound of formula I is x 1 = 9, and the compound of formula II is 2 = 7, and the compound of formula III is 3 = 10. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0064] In some embodiments, the compound of formula I is x 1 = 10, and the compound of formula II is 2 = 9. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0065] In certain embodiments, the compound of formula I is x 1 = 10, and the compound of formula II is 2 = 9, and the compound of formula III is 3 = 11. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0066] In some embodiments, the compound of formula I is x 1 = 11, and the compound of formula II is 2 = 10. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0067] In certain embodiments, the compound of formula I is x 1 = 11, and the compound of formula II is 2 = 10, and the compound of formula III is 3 = 12. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0068] In some embodiments, the compound of formula I is x 1 = 12, and the compound of formula II is 2 = 11. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0069] In certain embodiments, the compound of formula I is x 1 = 12, and the compound of formula II is 2 = 11, and the compound of formula III is 3 = 13. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0070] In some embodiments, the compound of formula I is x 1 = 13, and the compound of formula II is 2= 12. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0071] In certain embodiments, the compound of formula I is x 1 = 13, and the compound of formula II is 2 = 12, and the compound of formula III is 3 = 14. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0072] In some embodiments, the compound of formula I is x 1 = 14, and the compound of formula II is 2 = 13. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0073] In certain embodiments, the compound of formula I is x 1 = 14, and the compound of formula II is 2 = 13, and the compound of formula III is 3 = 15. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0074] In some embodiments, the compound of formula I is x 1= 15, and the compound of formula II is 2 = 14. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0075] In certain embodiments, the compound of formula I is x 1 = 15, and the compound of formula II is 2 = 14, and the compound of formula III is 3 = 16. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0076] In some embodiments, the compound of formula I is x 1 = 16, and the compound of formula II is 2 = 15. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0077] In certain embodiments, the compound of formula I is x 1 = 16, and the compound of formula II is 2 = 15, and the compound of formula III is 3 = 17. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0078] In some embodiments, the compound of formula I is x 1 = 17, and the compound of formula II is 2 = 16. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0079] In certain embodiments, the compound of formula I is x 1 = 17, and the compound of formula II is 2 = 16, and the compound of formula III is 3 = 18. The compound of formula I may be present in the phenolic composition in an amount of 15 to 75% based on the total weight of the phenolic composition, the compound of formula II may be present in an amount of 15 to 75% based on the total weight of the phenolic composition, and the compound of formula III may be present in an amount of 15 to 75% based on the total weight of the phenolic composition.

[0080] In certain embodiments, the compound of formula I is x 1 = 3, and the compound of formula II is 2 = 4, and the compound of formula III is 3 = 5, and the compound of formula IV is 4 = 6, and the compound of formula V is 5 = 7, and the compound of formula VI is 6 = 8, and the compound of formula VII is 7 = 9, and the compound of formula VIII is 8 = 10. These compounds may be present in the phenolic composition as shown in the table below (expressed as weight percent relative to the total mass of the phenolic composition):

[0081] [Table 1-1]

[0082] [Table 1-2]

[0083] In certain embodiments, the compound of formula I is x 1 = 6, and the compound of formula II is 2 = 7, and the compound of formula III is 3 = 8, and the compound of formula IV is 4 = 9, and the compound of formula V is 5 =10, and the compound of formula VI is 6 =11, and the compound of formula VII is 7 = 12, and the compound of formula VIII is 8 = 13. These compounds may be present in the phenolic composition as shown in the following table (expressed as weight percent relative to the total mass of the phenolic composition):

[0084] [Table 2-1]

[0085] [Table 2-2]

[0086] In certain embodiments, the compound of formula I is x 1 = 10, and the compound of formula II is 2 = 11, and the compound of formula III is 3 = 12, and the compound of formula IV is 4 = 13, and the compound of formula V is 5 = 14, and the compound of formula VI is 6 =15, and the compound of formula VII is 7= 16, and the compound of formula VIII is 8 = 17. These compounds may be present in the phenolic composition as shown in the following table (expressed as weight percent relative to the total mass of the phenolic composition):

[0087] [Table 3]

[0088] Exemplary phenolic compounds that may be used in the phenolic composition include:

[0089] [Table 4-1]

[0090] [Table 4-2]

[0091] The manufacture, processing, transportation, storage and use of inventive materials may result in impurities.

[0092] Such impurities may be present in the reaction process for making the inventive material, e.g., R 1 or R 2 These may be present from by-products of loss of a group, hydrolysis of the ester bond with the carboxylic acid, and a single transesterification with the PEG chain, resulting in a PEGylated ester in which the PEG terminates with an -OH group. Additional impurities of monoesters of PEG impurities may result in autoxidation products, where the -OH may form a -CHO or -COH group. These molecules may be considered impurities, and their presence does not negate the invention, so long as the majority (and preferably a substantial majority) of the molecules of the composition are as described. In any event, compositions exhibiting this type of variability should be construed as encompassed by the invention and the statement that the material is "represented by" the indicated formula.

[0093] Impurities in phenolic compositions may also result from autoxidation of the product or from radical scavenging. These impurities are expected to be part of the product, especially during use in detergents or applications. Examples of impurities expected from oxidation can be found in Zhang et al., J Material Sci Eng. 6:393.

[0094] The phenolic compositions disclosed herein may be formulated into a wide variety of laundry care compositions. Suitable laundry care compositions include powder laundry detergents, detergent tablets and bars, cleaning additives, laundry detergent liquids, including light-duty liquids, heavy-duty liquids, concentrated liquid detergents, non-aqueous or low-aqueous laundry liquids, single-serving sachets, soap bars, laundry beads, dryer sheets, dissolvable sheets, and combinations thereof. The phenolic compositions may be present in an amount of 0.0001% to 1.0% by weight, 0.0001% to 0.5% by weight, 0.0001% to 0.1% by weight, 0.0001% to 0.01% by weight, 0.0001% to 0.001% by weight, 0.001% to 1.0% by weight, 0.001% to 1.0% by weight, 0.001% to 1.0% by weight, 0.01% to 1.0% by weight, 0.1% to 1.0% by weight, or 0.5% to 1.0% by weight, based on the total weight of the laundry care composition.

[0095] The laundry care composition may be in the form of a liquid composition. The liquid composition may comprise from about 0% to about 99%, or from about 30% to about 90%, or from about 50% to about 80% water by weight of the composition. The liquid composition may also comprise a non-aqueous liquid detergent.

[0096] The laundry care composition may be in the form of a solid composition. The solid composition may comprise from about 20% to about 98% by weight of the composition of a water-soluble carrier for forming the solid composition. In a non-limiting, but preferred, example, the water-soluble carrier for forming the solid composition may be polyethylene glycol. The polyethylene glycol carrier may have a weight average molecular weight of from about 2000 to about 20,000 daltons, preferably from about 5000 to about 15,000 daltons, and more preferably from about 6000 to about 12,000 daltons. The solid composition may comprise less than about 20% by weight of the composition of water, preferably less than about 15% by weight, more preferably less than about 5% by weight, and even more preferably less than about 1% by weight. In a preferred example, the laundry care composition is in the form of granules or particles. The granules and particles may have a shape selected from the group consisting of spherical, hemispherical, compressed hemispherical, lentil-shaped, ellipsoidal, and mixtures thereof. Those skilled in the art will recognize that these shapes are non-limiting and that the granules and particles may have any other shape known in the art for such granules and particles. The granules may have maximum dimensions (i.e., length, width, height, diameter) of about 0.1 mm to about 2 mm and minimum dimensions (i.e., length, width, height, diameter) of about 0.05 mm to about 1.5 mm. The particles may have maximum dimensions (i.e., length, width, height, diameter) of about 2 mm to about 10 mm and minimum dimensions (i.e., length, width, height, diameter) of about 1.5 mm to about 4 mm.

[0097] The laundry care composition may be free-flowing. Such free-flowing laundry care composition may be packaged in a container so that a consumer can easily open the container and dispense the desired amount of laundry care composition. The container may be any container known in the art that is suitable for containing laundry care compositions. For example, the container may be about 50 cm 3 ~Approx. 1500cm 3 The container may be of any suitable size and shape for placement on a grocery store shelf, for placement in a consumer's home, or for use in a commercial setting, such as a laundromat.

[0098] It is also contemplated that the laundry care composition may be incorporated into a single-dose packaged article, such as, for example, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, a fibrous article, a tablet, a bar, or a mixture thereof. Such pouches typically include a water-soluble film, such as a polyvinyl alcohol water-soluble film, that at least partially encapsulates the laundry care composition. Suitable films include those commercially available from MonoSol, LLC, Indiana, United States. The multi-compartment pouch may include at least two, at least three, or at least four compartments. The multi-compartment pouch may include adjacent and / or overlapping compartments. The laundry care composition contained in the pouch or its compartments may be in liquid form, solid form, or a combination thereof.

[0099] The laundry care composition encapsulated within the pouch may 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% by weight of the laundry care composition.

[0100] The laundry care composition may further comprise one or more surfactants, for example, in an amount of about 0.1% to about 80% by weight of the laundry care composition. The surfactant may be selected from the group consisting of nonionic surfactants, anionic surfactants, amphoteric surfactants, zwitterionic surfactants, cationic surfactants, and mixtures thereof. Anionic and nonionic surfactants are typically used when the laundry care composition is a laundry cleaning composition or detergent. Cationic surfactants are typically used when the laundry care composition is a fabric softening composition. The surfactant may provide stain removal and aid in dispersing the antioxidant while not adversely affecting the deposition of the antioxidant on the fabric.

[0101] Suitable nonionic surfactants may include, but are not limited to, alkoxylated fatty alcohols (e.g., ethoxylated fatty alcohols); alkoxylated alkylphenols; alkylphenol condensates; mid-chain branched alcohols; mid-chain branched alkyl alkoxylates; alkyl polysaccharides; polyhydroxy fatty acid amides; ether-capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof. The alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof. The nonionic surfactants may be linear, branched (e.g., mid-chain branched), or a combination thereof. Examples of suitable nonionic surfactants may include those commercially available under the trade name PLURONIC® from BASF, Ludwigshafen, Germany, those commercially available under the trade name NEODOL® nonionics from Shell, The Hague, The Netherlands, and those commercially available under the trade name SURFONIC® from Huntsman Corporation, The Woodlands, Texas, United States.

[0102] Suitable anionic surfactants may include, but are not limited to, sulfate detersive surfactants (e.g., alkoxylated and / or non-alkoxylated alkyl sulfate materials); and / or sulfonic acid detersive surfactants (e.g., alkyl benzene sulfonates). The anionic surfactants may be linear, branched, or a combination thereof. Preferred anionic surfactants may include, but are not limited to, linear alkyl benzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), and mixtures thereof. Other suitable anionic surfactants may include branched-modified alkyl benzene sulfonates (MLAS), methyl ester sulfonates (MES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactants may be present in acid form, salt form, or a mixture thereof. The anionic surfactants may be partially or totally neutralized, for example, with an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine). The anionic surfactant may be pre-neutralized, preferably with an alkali metal, alkaline earth metal, an amine, such as ethanolamine, or mixtures thereof.

[0103] Suitable amphoteric surfactants may include any conventional amphoteric surfactant known to those skilled in the art, such as amine oxides. Preferred amine oxides may include alkyl dimethyl amine oxides or alkylamidopropyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides, and even more preferably coco dimethyl amine oxides. Amine oxides may have linear or mid-branched alkyl moieties. Typical linear amine oxides include one C 8~18 The alkyl portion and C 1~3 Alkyl group, C 1~3 and two moieties selected from the group consisting of hydroxyalkyl groups and mixtures thereof. Preferably, the amine oxide is of the formula R 4 -N(R 5 )(R6 )O[wherein, R 4 is a C8-18 alkyl, and R 5 and R 6 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. The amine oxide surfactant is characterized by a linear C 10~ C 18 Alkyl dimethyl amine oxides and linear C8-C 12 Alkoxyethyl dihydroxyethylamine oxide may also be included.

[0104] Suitable zwitterionic surfactants may include any conventional zwitterionic surfactant known to those skilled in the art, such as betaines, particularly alkyl betaines, alkylamido betaines, amidazolinium betaines, sulfobetaines, hydroxybetaines, and phosphobetaines. Examples of suitable betaines may include alkyl dimethyl betaines and cocodimethylamidopropyl betaines, N-alkyl-N,N-dimethylamino-1-propanesulfonates, where the alkyl group is C8 to C6. 18 , or C8~C 14 Suitable cationic surfactants may include, but are not limited to, alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulfonium compounds, and mixtures thereof. Preferred cationic surfactants have the general formula: (R 7 )(R 8 )(R 9 )(R 10 -)N + X - [In the formula, R 7 is a linear or branched, substituted or unsubstituted C 6~18 is an alkyl or alkenyl moiety, R 8 and R 9 is independently selected from a methyl or ethyl moiety, and R 10is a hydroxyl, hydroxymethyl, or hydroxyethyl moiety, and X is an anion that provides charge neutrality, with preferred anions including halides, preferably chloride; sulfate; and sulfonate. For purposes of the present invention, cationic surfactants include those that can create fabric care benefits. Non-limiting examples of useful cationic surfactants include fatty amines, imidazoline quat materials, and quaternary ammonium surfactants, preferably N,N-bis(stearoyl-oxy-ethyl)N,N-dimethylammonium chloride, N,N-bis(tallow oil-oxy-ethyl)N,N-dimethylammonium chloride, N,N-bis(stearoyl-oxy-ethyl)N-(2hydroxyethyl)N-methylammonium methyl sulfate; 1,2-di(stearoyl-oxy)3-trimethylammonium propane chloride; dialkylene dimethyl ammonium salts, such as dicanola dimethyl ammonium chloride, di(hydrogenated) tallow dimethyl ammonium chloride, and the like. ammonium chloride dicanoladimethylammonium methyl sulfate; 1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium methyl sulfate; 1-tallowylamidoethyl-2-tallowylimidazoline; N,N″-dialkyldiethylenetriamine; reaction products of N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropyl)-1,2-ethylenediamine with glycolic acid esterified with a fatty acid, wherein the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydrogenated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid, and mixtures of the above.

[0105] The detergent compositions of the present invention may also contain a number of additional optional ingredients. These include conventional laundry detergent composition components, such as non-colored dyes, detergency builders, enzymes, enzyme stabilizers (e.g., propylene glycol, boric acid, and / or borax), suds suppressors, soil suspending agents, hue imparting agents, soil release agents, other fabric care benefit agents, pH adjusters, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structurants, dye transfer inhibitors, opacifiers, optical brighteners, fragrances, and colorants. The various optional detergent composition ingredients, when present in the compositions herein, should be utilized at concentrations customarily used to provide their desired contribution to the composition or laundry operation. Frequently, the total amount of such optional detergent composition ingredients can range from about 0.01% to about 50% by weight of the composition, more preferably from about 0.1% to about 30% by weight.

[0106] Builders—The compositions of the present invention can include one or more detergent builders or builder systems. When present, the compositions typically contain at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight of said builder. Builders include, but are not limited to, alkali metal, ammonium, and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builder polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, various alkali metal, ammonium, and substituted ammonium salts of polyacetic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.

[0107] Chelating Agents - The compositions herein may also optionally contain one or more copper, iron, and / or manganese chelating agents. If utilized, the chelating agents will generally comprise from about 0.1% to about 15% by weight of the compositions herein, or even from about 3.0% to about 15% by weight of the compositions herein.

[0108] Hueing Agents—The compositions of the present invention may also include one or more hueing agents. Suitable hueing agents include blue or purple azo colorants, triarylmethane dyes, or various leuco dyes. Non-limiting examples of hueing agents are disclosed in U.S. Pat. Nos. 10,731,112 and 10,876,079. When present in the compositions herein, the hueing dyes are present at levels of from about 0.0001% by weight of the cleaning composition, from about 0.01% by weight, from about 0.05% by weight to about 1% by weight of the cleaning composition, or even about 0.1% by weight.

[0109] Dye Transfer Inhibitors—The compositions of the present invention may also include one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone, and polyvinylimidazole, or mixtures thereof. When present in the composition, the dye transfer inhibitor is present at a level of from about 0.0001%, from about 0.01%, from about 0.05% to about 10%, about 2%, or even about 1% by weight of the cleaning composition.

[0110] Dispersant - The compositions of the present invention can also contain a dispersant. Suitable water-soluble organic materials are homo- or copolymeric acids or salts thereof, where the polycarboxylic acid may contain at least two carboxyl radicals separated from each other by no more than two carbon atoms.

[0111] Enzymes - The composition can contain one or more detergent enzymes that provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof. A typical combination is a cocktail of conventional applicable enzymes, such as protease, lipase, cutinase, and / or cellulase, in combination with amylase.

[0112] Enzyme Stabilizers - Enzymes for use in compositions, e.g., detergents, may be stabilized by a variety of techniques. The enzymes used herein may be stabilized by the presence of a water-soluble source of calcium and / or magnesium ions in the finished composition, which provides such ions to the enzyme.

[0113] The detergent composition may also contain a bleaching agent. Suitable bleaching agents include, for example, hydrogen peroxide sources, such as those described in detail in "Bleaching Agents (Survey)" by Kirk Othmer, Encyclopedia of Chemical Technology, 4th Edition (1992, John Wiley & Sons), Vol. 4, pp. 271-300, incorporated herein by reference. These hydrogen peroxide sources include various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.

[0114] The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborates, such as sodium perborate (any hydrate, but preferably the mono- or tetrahydrate), sodium carbonate perhydrogenate or equivalent percarbonate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Sources of available oxygen, such as persulfate bleach (e.g., Oxone, manufactured by DuPont), are also useful. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.

[0115] Bleach Activator—Preferably, the peroxygen bleaching component in the composition is formulated with an activator (peracid precursor). The activator is present at a level of from about 0.01% by weight of the composition, preferably from about 0.5% by weight, more preferably from about 1% to about 15% by weight, preferably up to about 10% by weight, and more preferably up to about 8% by weight. As used herein, a bleach activator is any compound that, when used in conjunction with hydrogen peroxide, leads to the in situ generation of a peracid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Pat. Nos. 5,576,282; 4,915,854; and 4,412,934. See also U.S. Pat. No. 4,634,551 for other exemplary bleaches and activators useful herein.

[0116] Preferred activators are tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulfonate (C 10The bleach activator is selected from the group consisting of benzoyl caprolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters, and mixtures thereof, most preferably benzoyl caprolactam and benzoyl valerolactam. Particularly preferred bleach activators within the pH range of about 8 to about 11 are selected with an OBS or VL leaving group.

[0117] Preferred hydrophobic bleach activators are nonanoyloxybenzenesulfonate (NOBS); 4-[N-(nonanoyl)aminohexanoyloxy]-benzenesulfonic acid sodium salt (NACA-OBS), an example of which is described in U.S. Pat. No. 5,523,434; dodecanoyloxybenzenesulfonate (LOBS or C 12 -OBS); 10-undecenoyloxybenzenesulfonate (UDOBS or C with unsaturation at the 10-position) 11 -OBS); and decanoyloxybenzoic acid (DOBA).

[0118] Preferred bleach activators are those described in U.S. Pat. No. 5,998,350 to Burns et al.; U.S. Pat. No. 5,698,504 to Christie et al.; U.S. Pat. No. 5,695,679 to Christie et al.; U.S. Pat. No. 5,686,401 to Willey et al., U.S. Pat. No. 5,686,014 to Hartshorn et al.; U.S. Pat. No. 5,405,412 to Willey et al.; U.S. Pat. No. 5,405,413 to Willey et al.; U.S. Pat. No. 5,130,045 to Mitchel et al.; and U.S. Pat. No. 4,412,934 to Chung et al., and co-pending patent application Ser. No. 08 / 064,564, all of which are incorporated herein by reference.

[0119] Metal-Containing Bleach Catalyst - The compositions and methods of the present invention may also optionally include a metal-containing bleach catalyst, preferably a manganese- and cobalt-containing bleach catalyst.

[0120] One type of metal-containing bleach catalyst is a catalyst system containing a transition metal cation of defined bleach catalytic activity (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation), an auxiliary metal cation having little or no bleach catalytic activity (e.g., zinc or aluminum cation), and a sequestrate, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and their water-soluble salts, with defined stability constants for the catalyst and auxiliary metal cation. Such catalysts are disclosed in U.S. Patent No. 4,430,243 to Bragg.

[0121] Bleach Boost Compound - Wherein the composition may comprise one or more bleach boost compounds. The bleach boost compounds provide increased bleaching effectiveness in low temperature applications. The bleach booster works in conjunction with a conventional peroxygen bleach source to provide increased bleaching effectiveness. This is typically accomplished through the in situ formation of an active oxygen transfer agent, such as a dioxirane, oxaziridine, or oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines, and oxaziridiniums may be used.

[0122] Among the preferred bleach boost compounds for use in accordance with the present invention are cationic imines, zwitterionic imines, anionic imines and / or polyionic imines, and mixtures thereof, having a net charge of from about +3 to about -3. These imine bleach boost compounds of the present invention have the general structure:

[0123] [ka]

[0124] [In the formula, R 11 , R 12 , R 13 and R 14 are each independently hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic, alkyl, and cycloalkyl radicals. Includes:

[0125] Among the preferred bleach boost compounds are the zwitterionic bleach boosters described in U.S. Patent Nos. 5,576,282 and 5,718,614.Other bleach boost compounds include the cationic bleach boosters described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO95 / 13351, WO95 / 13352 and WO95 / 13353.

[0126] Peroxygen sources are well known in the art, and the peroxygen source used in the present invention may include any of these well-known sources, including peroxygen compounds and compounds that provide an effective amount of peroxygen in situ under consumer use conditions. The peroxygen source may include a hydrogen peroxide source, in situ formation of peroxygen anions via reaction of a hydrogen peroxide source with a bleach activator, a preformed peroxygen compound, or a mixture of suitable peroxygen sources. Of course, those skilled in the art will recognize that other sources of peroxygen may be used without departing from the scope of the present invention. When present, a bleach boost compound is preferably used in conjunction with the peroxygen source in the bleaching system of the present invention.

[0127] Photobleaches - Suitable photobleaches for use in the treatment compositions of the present invention include, but are not limited to, the photobleaches described in US Pat. Nos. 4,217,105 and 5,916,481.

[0128] Enzyme bleaching - Enzyme systems may be used as bleaching agents. Hydrogen peroxide may be present by adding an enzyme system (i.e., an enzyme and a substrate therefor) capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing process. Such an enzyme system is disclosed in European Patent Application No. 91202655.6, filed October 9, 1991.

[0129] Liquid detergent compositions are in the form of aqueous solutions or homogeneous dispersions or suspensions of surfactants, phenolic compositions, and certain other optional ingredients, some of which may be in normally solid form, combined with the normally liquid components of the composition, such as liquid alcohol ethoxylate nonionics, aqueous liquid carriers, and any other normally liquid optional ingredients. Such solutions, dispersions, or suspensions will be acceptably phase stable and will typically have viscosities ranging from about 100 to 600 cps, more preferably from about 150 to 400 cps. For purposes of this invention, viscosity is measured using a Brookfield LVDV-II+ viscometer apparatus with a #21 spindle.

[0130] Liquid detergent compositions can be prepared by combining the components in any convenient order and mixing, e.g., by agitating, the resulting combination of components to form a phase-stable liquid detergent composition. In a preferred method for preparing such compositions, a liquid matrix is ​​formed containing at least a large proportion, preferably substantially all, of the liquid components, such as nonionic surfactants, non-surface-active liquid carriers, and any other optional liquid components, and the liquid components are thoroughly mixed by applying shear agitation to the liquid combination. For example, rapid agitation using a mechanical stirrer may be useful. While shear agitation is maintained, any anionic surfactant and substantially all of the solid form ingredients can be added. Agitation of the mixture can be continued, and if necessary, increased at this point, to form a solution or uniform dispersion of insoluble solid phase particles within the liquid phase. After some or all of the solid form materials have been added to the agitated mixture, any included enzyme material, e.g., enzyme prill particles, are incorporated. As a variation of the composition preparation procedure described above, one or more solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a small portion of one or more liquid components. After all of the composition components have been added, agitation of the mixture is continued for a time sufficient to form a composition having the requisite viscosity and phase stability characteristics. Frequently, this will involve agitation for about 30 to 60 minutes.

[0131] In an alternative embodiment for forming a liquid detergent composition, the phenolic composition is first combined with one or more liquid ingredients to form a phenolic composition premix, and this premix is ​​added to a composition formulation containing a substantial proportion, e.g., greater than 50%, more specifically greater than 70%, and even more specifically greater than 90% by weight, of the remaining ingredients of the laundry detergent composition. For example, in the methodology described above, both the phenolic composition premix and the enzyme component are added at the final stage of ingredient addition. In a further embodiment, the phenolic composition is encapsulated prior to addition to the detergent composition, the encapsulated phenolic composition is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial proportion of the remaining ingredients of the laundry detergent composition.

[0132] The compositions of the present invention prepared as described above can be used to form aqueous wash solutions for use in laundering textile substrates, such as fabrics. Generally, an effective amount of such a composition is added to water, preferably in a conventional automatic fabric laundering machine, to form such an aqueous wash solution. The aqueous wash solution thus formed is then contacted with the fabrics to be laundered, preferably with agitation. An effective amount of the liquid detergent composition described herein is added to water to form an aqueous wash solution containing about 500 to 7,000 ppm of the detergent composition in the aqueous wash solution. More preferably, about 1,000 to 3,000 ppm of the detergent composition described herein will be provided in the aqueous wash solution.

[0133] Fabric Treatment Compositions / Rinse Liquor Added Fabric Softening Compositions In another specific embodiment, the phenolic composition of the present invention may be included in a fabric treatment composition. The fabric treatment composition may be comprised of at least one phenolic composition and a rinse-added fabric softening composition ("RAFS"; also known as a rinse-added fabric conditioning composition). An example of a typical rinse-added fabric softening composition can be found in U.S. Provisional Patent Application No. 60 / 687,582, filed October 8, 2004. The rinse-added fabric softening composition of the present invention may comprise (a) a fabric softening active ("FSA") and (b) a phenolic composition. The rinse-added fabric softening composition may comprise from about 1% to about 90% by weight of the FSA, more preferably from about 5% to about 50% by weight of the FSA. The phenolic composition may be present in the rinse-added fabric softening composition in an amount of from about 0.5 ppb to about 10,000 ppm, more preferably from about 0.5 ppm to about 1,000 ppm.

[0134] In one embodiment of the present invention, the fabric softening active is a quaternary ammonium compound suitable for softening fabrics during the rinse step. In one embodiment, the FSA is formed from the reaction product of a fatty acid with an amino alcohol to obtain a mixture of mono-, di-, and in one embodiment, triester compounds. In another embodiment, the FSA comprises one or more softener quaternary ammonium compounds, such as, but not limited to, monoalkyl quaternary ammonium compounds, diamide quaternary compounds, and diester quaternary ammonium compounds, or combinations thereof.

[0135] In one aspect of the invention, the FSA comprises a diester quaternary ammonium (hereinafter "DQA") compound composition. In certain embodiments of the invention, the DQA compound composition also encompasses the description of diamide FSAs, as well as FSAs with mixed amide and ester linkages and the aforementioned diester linkages, all of which are referred to herein as DQAs.

[0136] A first type of DQA suitable as an FSA (“DQA(1)”) has the formula: {R 15 4~m -N + -[(CH2)n -YR 16 ] m}X - [In the formula, each R 15 The substituents may be hydrogen, short chain C1-C6, preferably C1-C3 alkyl or hydroxyalkyl groups such as methyl (most preferred), ethyl, propyl, hydroxyethyl, etc., poly(C 2~3 each m is 2 or 3; each n is 1 to about 4, preferably 2; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)-NR-, and each Y can be the same or different; when Y is -O-(O)C- or -NR-C(O)-, each R 1 The sum of the carbons in plus one is C 12 ~C 22 , preferably C 14 ~C 20 and each R 16 is a hydrocarbyl or substituted hydrocarbyl group; R 1 can be unsaturated or saturated and branched or linear, preferably it is linear; each R 1 are allowed to be the same or different, preferably they are the same; X - can be any softener compatible anion, preferably chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate and nitrate, more preferably chloride or methyl sulfate. Preferred DQA compounds are typically made by reacting alkanolamines, such as MDEA (methyldiethanolamine) and TEA (triethanolamine), with fatty acids. Some materials typically resulting from such reactions include N,N-di(acyloxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyloxyethyl)-N,N-methylhydroxyethylammonium methylsulfate, where the acyl groups are derived from animal fats, unsaturated and polyunsaturated fatty acids, such as tallow, hardened tallow, oleic acid, and / or partially hydrogenated fatty acids, and vegetable oils and / or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, and the like.

[0137] Non-limiting examples of suitable fatty acids are listed in U.S. Patent No. 5,759,990, column 4, lines 45-66. In one embodiment, the FSA contains DQA (1) or other actives in addition to DQA. In yet another embodiment, the FSA contains only DQA (1) or DQA, and is free or essentially free of any other quaternary ammonium compounds or other actives. In yet another embodiment, the FSA contains the precursor amine used to produce DQA.

[0138] In another aspect of the invention, the FSA has the formula: [R 17 4~m -N (+) -R 18 m ]A - wherein each m is 2 or 3, and each R 18 C6~C 22 , preferably C 14 ~C 20 However, one or less is approximately C 12 and if so, the other is at least about 16, hydrocarbyl or substituted hydrocarbyl substituents, preferably C 10 ~C 20Alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, sometimes also referred to as "alkylene"), most preferably C 12 ~C 18 alkyl or alkenyl, and branched or unbranched] In one embodiment, the FSA has an iodine value (IV) of about 1 to 70; 17 is H or a short chain C1-C6, preferably C1-C3 alkyl or hydroxyalkyl group, such as methyl (most preferred), ethyl, propyl, hydroxyethyl, etc., benzyl or (R 19 O) 2~4 H, where each R 19 is C 1~6 an alkylene group; A - is a softener compatible anion, preferably chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate or nitrate; more preferably chloride or methyl sulfate.

[0139] Examples of these FSAs include dialkyldimethylammonium salts and dialkylenedimethylammonium salts, such as ditallowdimethylammonium and ditallowdimethylammonium methyl sulfate. Examples of commercially available dialkylenedimethylammonium salts that can be used in the present invention are dihydrogenated tallowdimethylammonium chloride and ditallowdimethylammonium chloride, available from Degussa under the trade names Adogen® 442 and Adogen® 470, respectively. In one embodiment, the FSA contains other actives in addition to DTTMAC. In yet another embodiment, the FSA contains only the compound DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other actives.

[0140] In one embodiment, the FSA includes those described in U.S. Patent Publication No. 2004 / 0204337A1 to Corona et al., published October 14, 2004, paragraphs 30-79. In another embodiment, the FSA is one described in U.S. Patent Publication No. 2004 / 0229769A1 to Smith et al., published November 18, 2005, paragraphs 26-31; or U.S. Patent No. 6,494,920, column 1, lines 51 et seq., which details "ester quats" or quaternized fatty acid triethanolamine ester salts.

[0141] In one embodiment, the FSA is selected from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated tallowoyloxyethyl dimethyl ammonium chloride, ditallowoyl dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.

[0142] In one embodiment, the FSA may also include an amide-containing compound composition. An example of a diamide-containing compound may include, but is not limited to, methyl-bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from Degussa under the trade names Varisoft 110 and Varisoft 222). An example of an amide-ester-containing compound is N-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl]-N-methylamine.

[0143] Another specific embodiment of the present invention provides a rinse-added fabric softening composition further comprising a cationic starch. Cationic starches are disclosed in US 2004 / 0204337 A1. In one embodiment, the rinse-added fabric softening composition comprises from about 0.1% to about 7%, by weight of the fabric softening composition, of the cationic starch. In one embodiment, the cationic starch is HCP401 manufactured by National Starch.

[0144] Exemplary Laundry Care Composition Formulations: Liquid detergent formulations: Table A provides examples of liquid detergent formulations containing at least one phenolic composition of the present invention.

[0145] [Table 5-1]

[0146] [Table 5-2]

[0147] Granular detergent formulations: Table B provides examples of granular detergent formulations containing at least one phenolic composition of the present invention.

[0148] [Table 6-1]

[0149] [Table 6-2]

[0150] Fabric Treatment Composition: Table C provides examples of liquid fabric treatment compositions comprising at least one phenolic composition of the present invention.

[0151] [Table 7-1]

[0152] [Table 7-2]

[0153] The textile substrates treated with the laundry care compositions comprising the phenolic compositions of the present invention may be composed of synthetic fibers, natural fibers, or a combination of synthetic and natural fibers. Synthetic fibers include, for example, polyester, acrylic, polyamide, polyolefin, polyaramid, polyurethane, regenerated cellulose (i.e., rayon), and blends thereof. The term "polyamide" is intended to describe any long-chain polymer having repeating amide groups (--NH--CO--) as an integral part of the polymer chain. Examples of polyamides include nylon 6; nylon 6,6; nylon 1,1; and nylon 6,10. The term "polyester" is intended to describe any long-chain polymer having repeating ester groups (--C(O)--O--). Examples of polyesters include aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polytriphenylene terephthalate, as well as aliphatic polyesters such as polylactic acid (PLA). "Polyolefin" includes, for example, polypropylene, polyethylene, and combinations thereof. "Polyaramid" includes, for example, poly-p-phenylene teraphthalamide (i.e., Kevlar®), poly-m-phenylene teraphthalamide (i.e., Nomex®), and combinations thereof. Natural fibers include, for example, wool, cotton, flax, and blends thereof.

[0154] The textile substrate may be of any variety, including, but not limited to, woven, knitted, nonwoven, or combinations thereof. The textile substrate may optionally be colored by various dyeing techniques, such as high-temperature jet dyeing with disperse dyes, vat dyeing, thermosol dyeing, pad dyeing, transfer printing, screen printing, or any other technique common in the art for comparable textile products. The yarns or fibers comprising the textile substrate may optionally be dyed by a suitable method, such as, for example, package dyeing or solution dyeing, prior to fabric formation.

[0155] Textile substrates include, for example, articles of clothing such as outerwear (e.g., rainwear), workwear (e.g., uniforms), fashion apparel (e.g., shirts, pants, and other garments); curtains; table linens (e.g., table linens and napkins); residential upholstery; commercial upholstery; automotive upholstery; wall coverings; floor covering articles (e.g., carpets, rugs, and mats); human bedding (e.g., mattresses, mattress covers, etc.); pet bedding; outdoor fabrics (e.g., outdoor furniture, awnings, boat covers, and grill covers); medical bandages (e.g., fabrics for use in wound care); and any other article that can retain discoloration and for which it is desirable to control (e.g., prevent, remove, and / or ameliorate) said discoloration.

[0156] Description of certain specific embodiments The following sections describe certain specific embodiments of the phenolic compositions and laundry care compositions described above.

[0157] 1. a) a surfactant; and b) i) Formula:

[0158] [ka]

[0159] [In the formula, L 1 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 1 is an integer between 2 and 50; R a1 is C 1~8 is an alkyl group; R a2 is C 1~8 is an alkyl group; R a3 is H, CH3 or CH2CH3] a first phenolic compound having ii) Formula:

[0160] [ka]

[0161] [In the formula, L 2 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 2 is an integer between 2 and 50; 1 and x 2 is not the same; R b1 is C 1~8 is an alkyl group; R b2 is C 1~8 is an alkyl group; R b3 is H, CH3 or CH2CH3] a second phenolic compound having a phenolic composition comprising 1. A laundry care composition comprising:

[0162] 2. The laundry care composition according to any preceding embodiment, wherein the phenolic composition is present in an amount of 0.0001 wt.% to 1.0 wt.%, 0.0001 wt.% to 0.5 wt.%, 0.0001 wt.% to 0.1 wt.%, 0.0001 wt.% to 0.01 wt.%, 0.0001 wt.% to 0.001 wt.%, 0.001 wt.% to 1.0 wt.%, 0.001 wt.% to 1.0 wt.%, 0.01 wt.% to 1.0 wt.%, 0.1 wt.% to 1.0 wt.%, or 0.5 wt.% to 1.0 wt.%, based on the total weight of the laundry care composition.

[0163] 3.R a1 and R a2 However, the laundry care composition according to any preceding embodiment is not the same.

[0164] 4.R b1 and R a2 However, the laundry care composition according to any preceding embodiment is not the same.

[0165] 5.R a2 and R b2 However, each 3~5 The laundry care composition according to any preceding embodiment, wherein

[0166] 6.R a2 and R b2 The laundry care composition according to any preceding embodiment, wherein is t-butyl.

[0167] 7.R a1 and R b1 are linear C 1~8 The laundry care composition according to any preceding embodiment, wherein R is an alkyl group.

[0168] 8.R a1 and R b1 are linear C 1~4 The laundry care composition according to any preceding embodiment, wherein R is an alkyl group.

[0169] 9.R a1 and R b1 are each methyl, or R a1 and R b1 The laundry care composition according to any preceding embodiment, wherein each is ethyl.

[0170] 10.L 1 The laundry care composition according to any preceding embodiment, wherein is —CH 2 CH 2 — or —CH 2 CH 2 CH 2 —.

[0171] 11.L 2 The laundry care composition according to any preceding embodiment, wherein is —CH 2 CH 2 — or —CH 2 CH 2 CH 2 —.

[0172] 12.x 1 is an integer from 4 to 25, from 4 to 20, from 4 to 15, from 4 to 10, from 4 to 8, or from 4 to 6.

[0173] 13.x 2is an integer from 2 to 25, from 2 to 20, from 2 to 15, from 2 to 10, from 2 to 8, from 2 to 6, or from 2 to 4.

[0174] 14.R a3 and R b3 5. The laundry care composition of any preceding claim, wherein each of

[0175] 15. The laundry care composition according to any preceding embodiment, wherein the molar ratio of the first phenolic compound to the second phenolic compound is from 50:1 to 1:50, from 25:1 to 1:25, from 20:1 to 1:20, from 10:1 to 1:10, from 5:1 to 1:5, or from 2:1 to 1:2.

[0176] 16.Formula:

[0177] [ka]

[0178] [In the formula, L 3 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 3 is an integer between 2 and 50; 1 , x 2 and x 3 None of these are the same; R c1 is C 1~8 is an alkyl group; R c2 is C 1~8 is an alkyl group; R c3 is H, CH3 or CH2CH3] The laundry care composition according to any preceding embodiment, further comprising a third phenolic compound having the formula:

[0179] 17.Formula:

[0180] [ka]

[0181] [In the formula, L 4 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 4 is an integer between 2 and 50, where x 1 , x 2 , x 3 and x 4 None of them are the same, R d1 is C 1~8 is an alkyl group, R d2 is C 1~8 is an alkyl group, R d3 is H, CH3 or CH2CH3] The laundry care composition according to any preceding embodiment, further comprising a fourth phenolic compound having the formula:

[0182] 18.Formula:

[0183] [ka]

[0184] [In the formula, L 5 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 5 is an integer between 2 and 50; 1 , x 2 , x 3 , x 4 and x 5 None of these are the same; R e1 is C 1~8 is an alkyl group; R e2 is C 1~8 is an alkyl group; R e3 is H, CH3 or CH2CH3] The laundry care composition according to any preceding embodiment, further comprising a fifth phenolic compound having the formula:

[0185] 19.Formula:

[0186] [ka]

[0187] [In the formula, L 6 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 6 is an integer between 2 and 50; 1 , x 2 , x 3 , x 4 , x 5 and x 6 None of these are the same; R f1 is C 1~8 is an alkyl group; R f2 is C 1~8 is an alkyl group; R f3 is H, CH3 or CH2CH3] The laundry care composition according to any preceding embodiment, further comprising a sixth phenolic compound having the formula:

[0188] 20.Formula:

[0189] [ka]

[0190] [In the formula, L 7 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 7 is an integer between 2 and 50; 1 , x 2 , x 3 , x 4 , x5 , x 6 and x 7 None of these are the same; R g1 is C 1~8 is an alkyl group; R g2 is C 1~8 is an alkyl group; R g3 is H, CH3 or CH2CH3] The laundry care composition according to any preceding embodiment, further comprising a seventh phenolic compound having the formula:

[0191] 21.Formula:

[0192] [ka]

[0193] [In the formula, L 8 is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x 8 is an integer between 2 and 50; 1 , x 2 , x 3 , x 4 , x 5 , x 6 , x 7 and x 8 None of these are the same; R h1 is C 1~8 is an alkyl group; R h2 is C 1~8 is an alkyl group; R h3 is H, CH3 or CH2CH3] The laundry care composition according to any preceding embodiment, further comprising an eighth phenolic compound having the formula:

[0194] 22. The laundry care composition according to any preceding embodiment, wherein the composition is selected from the group consisting of powder laundry detergents, detergent tablets and bars, cleaning additives, laundry detergent liquids including light duty liquids, heavy duty liquids, concentrated liquid detergents, non-aqueous or low-aqueous laundry liquids, single-serving sachets, soap bars, and the like.

[0195] 23. The composition is liquid and contains water, C 3~8 Monoalcohol, C 3~8 The laundry care composition according to any preceding embodiment, comprising one or more solvents selected from polyalcohols and the like.

[0196] 24. Alkali metal salts, alkaline earth metal salts or inorganic or C 1~6 The laundry care composition according to any preceding embodiment, comprising a salt of an alkyl organic acid, or a mixture thereof.

[0197] 25. The laundry care composition according to any preceding embodiment, wherein the laundry care composition does not comprise an oligoamine.

[0198] 26. A method of laundering an article, comprising contacting the article with a composition according to any preceding embodiment.

[0199] 27. The method according to any preceding embodiment, wherein the article is contacted with the composition in the presence of water.

[0200] 28. The method according to any preceding embodiment, wherein the article is contacted with the composition in the presence of water at a temperature of 40°C or less, 35°C or less, 30°C or less, 25°C or less, 20°C or less, 15°C or less, 10°C or less, or 5°C or less.

[0201] 29. The method according to any preceding embodiment, wherein the article is contacted with the composition in the presence of water at or below room temperature.

[0202] 30. A method of making a laundry care composition, comprising combining a water-soluble carrier, a surfactant, and a phenolic composition, wherein the phenolic composition comprises: formula:

[0203] [ka]

[0204] [In the formula, A is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; x is an integer from 2 to 50; R a1 is C 1~8 is an alkyl group; R a2 is C 1~8 is an alkyl group; R a3 is H, CH3 or CH2CH3] a first phenolic compound having the formula: formula:

[0205] [ka]

[0206] [In the formula, B is selected from null, -CH2-, -CH2CH2- and -CH2CH2CH2-; y is an integer from 2 to 50; provided that x and y are not the same; R b1 is C 1~8 is an alkyl group; R b2 is C 1~8 is an alkyl group; R b3 is H, CH3 or CH2CH3] a second phenolic compound having A method comprising:

[0207] 31. A laundry care composition obtained by the method of any preceding embodiment.

[0208] [example] The following examples are intended to be illustrative of the present invention only and are not intended to limit the scope of the present invention in any way.

[0209] Example 1 Synthesis of phenolic compositions Compound 1: Methyl 3-[3-(tert-butyl)-4-hydroxy-5-tolyl]propionate

[0210] [ka]

[0211] A 1000 mL four-neck round-bottom flask was equipped with a temperature probe, overhead stirring, and a reflux condenser under a nitrogen atmosphere. The reaction flask was charged with 100 g of 2-[2-(2-{3-[3-(tert-butyl)-4-hydroxy-5-tolyl]propionoxy}ethoxy)ethoxy]ethyl 3-[3-(tert-butyl)-4-hydroxy-5-tolyl]propionate (Irganox 245, available from BASF), 6 g of a 30% sodium methoxide solution in methanol, and 200 g of methanol. The reaction was stirred at 20-25 °C for 16 hours and then neutralized with 2 g of acetic acid. 100 mL of distilled water and 100 mL of hexane were added to the reaction flask, and the contents of the flask, followed by an additional 300 mL of distilled water, were then transferred to a separatory funnel. The phases were separated and the organic layer was collected and dried under reduced pressure to give methyl 3-[3-(tert-butyl)-4-hydroxy-5-tolyl]propionate as an oil that solidified on standing.

[0212] Composition 1

[0213] [ka]

[0214] [In the formula, average n≒4.1] A 100 mL three-neck round-bottom flask was equipped with a temperature probe, overhead stirring, and a Dean-Stark trap with condenser under a nitrogen atmosphere. 20 g of methyl 3-[3-(tert-butyl)-4-hydroxy-5-tolyl]propionate, 8 g of PEG 200, and 0.4 g of dibutyltin oxide were added to the reaction flask. The reaction was heated to 240 °C and stirred until complete (approximately 18-24 hours) as determined by TLC analysis. The product was obtained as a brown oil. The product is a composition containing a distribution of phenolic compounds encompassed by the formula above, where n is the average number of ethylene oxide repeat units of the phenolic compounds present in the composition.

[0215] Composition 2

[0216] [ka]

[0217] [In the formula, average n≒6.5] The same procedure as for Composition 1 was followed, except that 12 g of PEG 300 was used instead of PEG 200. The product was obtained as a dark yellow oil. The product was a composition containing a distribution of phenolic compounds encompassed by the formula above, where the value of n is equal to the average number of ethylene oxide repeat units of the phenolic compounds present in the composition.

[0218] Composition 3

[0219] [ka]

[0220] [In the formula, average n≒13.2] The same procedure as for Composition 1 was followed, except that 24 g of PEG 600 was used instead of PEG 200. The product was obtained as a dark yellow oil. The product was a composition containing a distribution of phenolic compounds encompassed by the formula above, where the value of n is equal to the average number of ethylene oxide repeat units of the phenolic compounds present in the composition.

[0221] Composition 4

[0222] [ka]

[0223] [In the formula, average n≒4.1] A three-necked, 100 mL round-bottom flask was equipped with a temperature probe, overhead stirring, and a Dean-Stark trap with condenser under a nitrogen atmosphere. 23.4 g of methyl 3-[3,5-bis(tert-butyl)-4-hydroxyphenyl]propionate, 8 g of PEG 200, and 0.4 g of dibutyltin oxide were added to the reaction flask. The reaction was heated to 140 °C until completion, as monitored by TLC. The product was a composition containing a distribution of phenolic compounds encompassed by the formula above, where the value of n is equal to the average number of ethylene oxide repeat units of the phenolic compounds present in the composition.

[0224] Composition 5

[0225] [ka]

[0226] [In the formula, average n≒9] A 100 mL three-neck round-bottom flask was equipped with a temperature probe, overhead stirring, and a Dean-Stark trap with condenser under a nitrogen atmosphere. The reaction flask was charged with 20 g of methyl 3-[3-(tert-butyl)-4-hydroxy-5-tolyl]propionate, 16 g of PEG 400, and 0.4 g of sodium acetate. The reaction was heated to 100 °C and vacuum was applied for 1 hour to remove residual water. The reaction mixture was then heated to 160 °C and stirred until complete as determined by TLC analysis. The product was cooled and transferred to a jar. The product was a composition containing a distribution of phenolic compounds encompassed by the formula above, where the value of n is equal to the average number of ethylene oxide repeat units of the phenolic compounds present in the composition.

[0227] compound 2

[0228] [ka]

[0229] [In the formula, n=4] A 100 mL three-neck round-bottom flask was equipped with a temperature probe, overhead stirring, and a Dean-Stark trap with condenser under a nitrogen atmosphere. The reaction flask was charged with 20 g of methyl 3-[3-(tert-butyl)-4-hydroxy-5-tolyl]propionate, 7.2 g of tetraethylene glycol (available from Sigma-Aldrich), and 0.4 g of sodium acetate. The reaction was heated to 100 °C and vacuum was applied for 1 hour to remove residual water. The reaction mixture was then heated to 160 °C and stirred until complete by TLC analysis. The product was cooled and transferred to a jar.

[0230] Example 2 Odor reduction evaluation To test the efficiency of antioxidants for malodor reduction, artificial body soil (ABS) was prepared. The artificial body soil is a modified version of the soil from ASTM D4265-21. To prepare the ABS, the ingredients in Table 1 were combined in an 8-ounce jar and heated to 70°C until completely solubilized.

[0231] [Table 8]

[0232] Fabric Preparation: 50 / 50 cotton / poly interlock fabric (Model 7439OB, Testfabrics, Inc.) was cut into 2" x 5" swatches. Three 0.36 mL portions of the artificial body soil composition were administered to the cut swatches at equal intervals. The fabrics were then sealed together in a Mylar bag and incubated at 37°C for 4-7 days before being washed.

[0233] Washing water: Wash water was used at 7 gpg hardness and 800 ng / mL copper by dissolving the ingredients listed in Table 2 in DI water.

[0234] [Table 9]

[0235] Antioxidant solution preparation: Antioxidant solutions were prepared by dissolving the antioxidant compounds to be tested in methanol at 0.5% w / w. The antioxidant solutions were dispensed into the wash water (500 mL) using a micropipettor according to Table 3 to obtain the desired concentration of antioxidant in the wash water required for testing.

[0236] [Table 10]

[0237] Cleaning and rinsing instructions: To a 1 L wash beaker was added 0.4 g of Tide Free and Gentle detergent, 500 mL of wash water (as prepared in Table 2), and the antioxidant solution as described in Table 3. The wash beaker was placed in a Tergotometer. Two incubated fabric swatches (4 g) were added to the wash beaker, followed by one 11-inch by 11-inch clean 50 / 50 cotton / poly interlock knit fabric swatch (16 g, Model 7439OB, Testfabrics, Inc.) to achieve a total liquor-to-fabric ratio of 25:1. The fabric was then washed in the Tergotometer for 15 minutes and spin-dried in a spin-drier (Mini Spin Dryer Model LASD-1, available from The Laundry Alternative, Inc.) for 1 minute. The fabrics were then transferred from the spin dryer to 500 mL of fresh wash water (as prepared above) and rinsed in a targetometer for 15 minutes. The fabrics were then spun in the spin dryer for 1 minute and transferred to a dryer where they were dried over medium heat for 1 hour. Once dry, the artificial body soil treated and washed fabrics were cut in half (1 inch x 5 inch swatches), rolled, and placed in gas chromatography vials for headspace analysis. The test was performed three times, and the average malodor reduction percentage was calculated.

[0238] Malodor analysis in fabrics using GCMS analysis The GC data tracks the concentration of malodor markers in the headspace that occur due to the oxidative degradation of ABS. The marker tracked for this degradation of ABS is 3-methyl-2-butenal.

[0239] Percent malodor reduction is determined by GCMS using an Agilent Intuvo 9000GC equipped with an Agilent 7000D GC / TQ mass spectrometer and a Trajan PAL3 RTC sampler equipped with a solid-phase microextraction (SPME) probe. The calibration standard for the tracer malodor marker, 3-methyl-2-butenal (107-86-8), is prepared by dissolving a known weight of mineral oil (CAS 8020-83-5). The fabric is cut into uniform 1-inch x 5-inch pieces and placed in 10 mL headspace crimp vials. The vials are allowed to equilibrate for >12 hours before analysis. The following settings are used on the autosampler: 90°C incubation temperature, 90 minutes incubation time, VT25 sample tray type, 22 mm vial penetration, 10 minutes extraction time, 50 mm injection penetration, and 3 minutes desorption time. The column was an Agilent DB-624 Ultra Inert, 60 m x 250 μm x 1.4 μm (part number 122-1364UI-INT). The following settings were used for the front split / splitless inlet helium: split mode, temperature 250 °C, pressure 39.3 psi, total flow rate 30.5 mL / min, septum purge flow rate 3 mL / min, split ratio 10:1, and GC run time 18.5 min. The following settings were used for the oven: initial temperature 35 °C, hold at 35 °C for 1 min, then heating program 30 °C / min, final temperature 260 °C, and hold time 10 min at 260 °C. The extracted ion chromatogram for 3-methyl-2-butenal included 84 quantitation, 55 confirmation, and ratio 35.7.

[0240] result: Antioxidants were tested for the reduction of malodor markers according to the test method as listed above. All tests were performed three times and the average of the three swatches was taken. The difference in counts between the control and the antioxidant-containing composition was used to calculate the percentage reduction of malodor markers. The percentage reduction of malodor markers was calculated by the following equation: Odor Marker Reduction % = 100 - (Amount of Marker Test / marker amount Control ×100) Comparing substitution patterns: Comparisons were made between the invention compounds and antioxidants using di-tert-butyl substitution on the phenolic ring of the antioxidant. Each antioxidant was subjected to cleaning tests at various concentrations (2, 4, and 8 ppm AO in the wash water) throughout the wash, and the results are listed in Table 4. The preferred phenolic compositions of the invention (Compositions 1-3) are compared to a control (a detergent without antioxidant) and a comparative example (Composition 4) that does not contain the preferred substitution pattern on the hindered phenolic moiety.

[0241] [Table 11]

[0242] As can be seen from the table above, all of the inventive phenolic compositions perform better than the control in reducing malodor, with the preferred compositions, especially the most preferred composition, Composition 1, performing as well as or better than Comparative Composition 4 in reducing the levels of malodor markers.

[0243] Multiple molecules vs. single compound comparison: A comparison of the malodor reduction of the inventive composition was made with Irganox 245, a commercially available antioxidant from BASF that contains a 3EO chain linker as a single molecule. Each antioxidant was subjected to wash tests at various concentrations (2, 4, and 8 ppm AO in the wash water) throughout the wash, and the results are listed in Table 5. The preferred phenolic composition of the present invention was compared to a control (a detergent without antioxidant), and a comparative example (Irganox 245) that did not contain multiple molecules was also created.

[0244] [Table 12]

[0245] As can be seen from the table above, inventive phenolic composition 1 performs better than the control in reducing malodor, and preferred composition 1 performs better than the single molecule Irganox 245, especially at lower concentrations in the wash water.

[0246] Stability evaluation A comparison of antioxidant stability in standard AATCC detergents was performed to highlight the benefits of having multiple molecules. Due to the highly crystalline nature of many commercially available antioxidants, they tend to be incompatible in detergents and will crystallize out of the detergent over time. The inventive compounds of the present invention show improvements in remaining stable in liquid detergents.

[0247] The antioxidants in Table 6 were combined with AATCC HE liquid detergent without added optical brighteners (available from Test Fabrics, Inc., product number 0501001) in 20 mL glass scintillation vials. The vials were placed in an ultrasonicator for 1 hour and then heated at 80°C for 30 minutes, which allowed all samples to completely dissolve. The samples were removed from the oven, swirled briefly, and then allowed to cool to room temperature. Once the vials had cooled to room temperature, the bottom of the vials was scraped several times with a metal spatula to aid in the crystallization process, which can take a long time if left unattended. After an additional 3 days, observations were recorded in Table 6 as crystallization present or absent.

[0248] [Table 13-1]

[0249] [Table 13-2]

[0250] As can be seen from the results in Table 6, several molecules are beneficial for preventing the precipitation of antioxidants from detergent formulations over time. This allows formulators to incorporate higher levels of antioxidants into detergents, if desired, without concerns about incompatibility.

[0251] Lower concentrations of antioxidants in detergent tests: To demonstrate the malodor-reducing efficacy of the inventive composition at lower concentrations of phenolic antioxidant, slight modifications to the procedure were made. The wash method was the same, except adjustments were made to the copper loading in the wash water and the antioxidant use level. For the experiment, the antioxidant level was reduced to 700 ppm in Tide Free and Gentle detergent (which equates to an antioxidant concentration of 0.56 ppm in the wash water), and copper in the wash water was used at a level of 100 ng Cu per gram of wash water. Table 7 shows the results of the test.

[0252] [Table 14]

[0253] As can be seen from Table 7, all of the inventive compositions perform well in reducing malodor markers on fabrics that have had their loading levels reduced throughout the wash.

[0254] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described therein, but are intended as illustrations of certain aspects of the claims, with all compositions and methods that are functionally equivalent being intended to be within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to be within the scope of the appended claims. Furthermore, while only certain representative compositions and method steps disclosed herein have been specifically described, other combinations of compositions and method steps, even if not specifically recited, are intended to be within the scope of the appended claims. Thus, although a combination of steps, elements, components, or ingredients may be explicitly recited herein or less, other combinations of steps, elements, components, and ingredients are included even though not explicitly recited. The term "comprising" and variations thereof, when used herein, is used synonymously with the term "including" and variations thereof, and is an open, non-limiting term. Although the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, which are also disclosed. Other than in the examples, or unless otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims should, at the very least, be construed in light of the number of significant digits and ordinary rounding approaches, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims. The following additionally describes embodiments of the present invention. [1] a) a surfactant; b) iii) Formula: [ka] [In the formula, L1 is null, -CH 2 -, -CH 2 CH 2 - and -CH 2 CH 2 CH 2 - selected from x 1 is an integer between 2 and 50; R a1 is C 1~8 is an alkyl group; R a2 is C 1~8 is an alkyl group; R a3 H, CH 3 or CH 2 CH 3 is] a first phenolic compound having iv) Formula:

change

[0023] The laundry care composition according to any one of [1] and [2], wherein the two are not the same. [4] R b1 and R a2 However, the laundry care composition according to any one of [1] to [3] is not the same. [5] R a2 and R b2 However, each 3~5 The laundry care composition according to any one of [1] to [4], wherein the alkyl is alkyl. [6] R a2 and R b2 [5] The laundry care composition according to [5], wherein is t-butyl. [7] R a1 and R b1 are linear C 1~8 The laundry care composition according to any one of [1] to [6], wherein the alkyl group is an alkyl group. [8] R a1 and R b1 are linear C 1~4 [7] The laundry care composition according to [7], wherein the alkyl group is an alkyl group. [9] R a1 and R b1 are each methyl, or R a1 and R b1 [8] The laundry care composition according to [8], wherein each of

[10] L 1 But -CH 2 CH 2 -or-CH 2 CH 2 CH 2 The laundry care composition according to any one of [1] to [9], wherein

[11] L 2 But -CH 2 CH 2 -or-CH 2 CH 2 CH 2 The laundry care composition according to any one of [1] to

[10] , wherein

[12] x 1 The laundry care composition according to any one of [1] to

[11] , wherein is an integer of 4 to 25.

[13] x 2 The laundry care composition according to any one of [1] to

[12] , wherein is an integer of 2 to 25.

[14] R a3 and R b3 and each represent H.

[0023] The laundry care composition according to any one of [1] to

[13] .

[15] The laundry care composition according to any one of [1] to

[14] , wherein the molar ratio of the first phenolic compound to the second phenolic compound is 50:1 to 1:50.

[16] Formula:

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[15] , further comprising a third phenolic compound having the formula:

[17] Formula:

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[16] The laundry care composition according to

[16] , further comprising a fourth phenolic compound having the formula:

[18] A method for washing an article, comprising contacting the article with the composition according to any one of [1] to

[17] .

[19] The method of

[18] , wherein the article is contacted with the composition in the presence of water.

[20] A method of making a laundry care composition, comprising combining a water-soluble carrier, a surfactant, and a phenolic composition, wherein the phenolic composition comprises: formula:

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Claims

1. a) a surfactant; b) i) Formula: 【Chemistry 1】 [In the formula, L １ is -CH ２ -, -CH ２ CH ２ - and -CH ２ CH ２ CH ２ - is selected from, x １ is an integer from 2 to 50; R ａ１ is a linear C １～８ is an alkyl group; R ａ２ is t-butyl; R ａ３ is H, CH ３ or CH ２ CH ３ is] a first phenolic compound having the formula: ii) Formula: 【Chemistry 2】 [In the formula, L ２ is -CH ２ -, -CH ２ CH ２ - and -CH ２ CH ２ CH ２ - is selected from, x ２ is an integer from 2 to 50; １ and x ２ is not the same; R ｂ１ is a linear C １～８ is an alkyl group; R ｂ２ is t-butyl; R ｂ３ is H, CH ３ or CH ２ CH ３ is] a second phenolic compound having a phenolic composition comprising 1. A laundry care composition comprising:

2. 10. The laundry care composition of claim 1, wherein the phenolic composition is present in an amount of from 0.0001% to 1.0% by weight, based on the total weight of the laundry care composition.

3. R ａ１ and R ｂ１ are linear C １～４ 10. The laundry care composition of claim 1, wherein the alkyl group is an alkyl group.

4. R ａ１ and R ｂ１ are each methyl, or R ａ１ and R ｂ１ 4. The laundry care composition of claim 3, wherein each is ethyl.

5. L １ But -CH ２ CH ２ - or -CH ２ CH ２ CH ２ 2. The laundry care composition of claim 1, wherein

6. L ２ But -CH ２ CH ２ - or -CH ２ CH ２ CH ２ 6. The laundry care composition of claim 5, wherein

7. x １ 10. The laundry care composition of claim 1, wherein is an integer from 4 to 25.

8. x ２ 10. The laundry care composition of claim 1, wherein is an integer from 2 to 25.

9. R ａ３ and R ｂ３ 10. The laundry care composition of claim 1, wherein each of

10. 10. The laundry care composition of claim 1, wherein the molar ratio of the first phenolic compound to the second phenolic compound is from 50:1 to 1:

50.

11. formula: 【Transformation 3】 [In the formula, L ３ is -CH ２ -, -CH ２ CH ２ - and -CH ２ CH ２ CH ２ - is selected from, x ３ is an integer from 2 to 50; １ , x ２ and x ３ None of these are the same; R ｃ１ is a linear C １～８ is an alkyl group; R ｃ２ is t-butyl; R ｃ３ is H, CH ３ or CH ２ CH ３ is] 10. The laundry care composition of claim 1, further comprising a third phenolic compound having the formula:

12. formula: 【Chemistry 4】 [In the formula, L ４ is -CH ２ -, -CH ２ CH ２ - and -CH ２ CH ２ CH ２ - is selected from, x ４ is an integer from 2 to 50; １ , x ２ , x ３ and x ４ None of these are the same; R ｄ１ is a linear C １～８ is an alkyl group; R ｄ２ is t-butyl; R ｄ３ is H, CH ３ or CH ２ CH ３ is] 12. The laundry care composition of claim 11, further comprising a fourth phenolic compound having the formula:

13. A method of laundering an article, comprising contacting said article with a composition according to any one of claims 1 to 12.

14. The method of claim 13, wherein the article is contacted with the composition in the presence of water.

15. 1. A method of making a laundry care composition, comprising combining a water-soluble carrier, a surfactant, and a phenolic composition, wherein the phenolic composition comprises: formula: 【Transformation 5】 [In the formula, A is -CH ２ -, -CH ２ CH ２ - and -CH ２ CH ２ CH ２ - is selected from, x is an integer from 2 to 50; R ａ１ is a linear C １～８ is an alkyl group; R ａ２ is t-butyl; R ａ３ is H, CH ３ or CH ２ CH ３ is] a first phenolic compound having the formula: formula: 【Transformation 6】 [In the formula, B is -CH ２ -, -CH ２ CH ２ - and -CH ２ CH ２ CH ２ - is selected from, y is an integer from 2 to 50; provided that x and y are not the same; R ｂ１ is a linear C １～８ is an alkyl group; R ｂ２ is t-butyl; R ｂ３ is H, CH ３ or CH ２ CH ３ is] a second phenolic compound having A method comprising:

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