Stable compositions comprising leuco compounds

文档序号：863017 发布日期：2021-03-16 浏览：8次中文

阅读说明：本技术 包含隐色化合物的稳定的组合物 (Stable compositions comprising leuco compounds ) 是由 H·秦 W·A·弗罗因德 S·K·戴伊 G·S·米拉克莱于 2019-07-26 设计创作，主要内容包括：一种组合物,其包含：(a)隐色组合物；和(b)稳定量的抗氧化剂组合物。该抗氧化剂组合物包含至少一种空间受阻酚和至少一种取代的二芳基胺,其中受阻酚与取代的二芳基胺的摩尔比为大于1:1。在另一个实施方案中,组合物包含(a)隐色组合物和(b)抗氧化剂组合物；和任选存在的(c)溶剂组合物。所述组合物中存在的隐色化合物和抗氧化剂的组合质量是所述组合物总质量的10％或更多,和(b)所述组合物中存在的抗氧化剂与所述组合物中存在的隐色化合物的摩尔比为大于1:1。(A composition, comprising: (a) a leuco composition; and (b) a stabilizing amount of an antioxidant composition. The antioxidant composition comprises at least one sterically hindered phenol and at least one substituted diarylamine, wherein the molar ratio of hindered phenol to substituted diarylamine is greater than 1: 1. In another embodiment, the composition comprises (a) a leuco composition and (b) an antioxidant composition; and optionally (c) a solvent composition. The combined mass of the leuco compound and the antioxidant present in the composition is 10% or more of the total mass of the composition, and (b) the molar ratio of antioxidant present in the composition to leuco compound present in the composition is greater than 1: 1.)

1. A composition, comprising: (a) a leuco composition; and (b) a stabilizing amount of an antioxidant composition comprising at least one sterically hindered phenol and at least one substituted diarylamine, wherein the molar ratio of the hindered phenol to the substituted diarylamine is greater than 1: 1.

2. The composition of claim 1, wherein the composition comprises about 1 wt.% or more of the sterically hindered phenol compound.

3. The composition of claim 2, wherein the molar ratio of the hindered phenol to the substituted diarylamine is greater than 5.0:1.0, preferably greater than 10.0:1.0, more preferably greater than 20.0:1.0, and most preferably greater than 30.0: 1.0.

4. A composition, comprising: (a) a leuco composition; and (b) an antioxidant composition, wherein (i) the combined mass of the leuco compound and the antioxidant present in the composition is 10% or more of the total mass of the composition, and (b) the molar ratio of the antioxidant present in the composition to the leuco compound present in the composition is greater than 1: 1.

5. The composition of claim 4, wherein the antioxidant composition comprises at least one sterically hindered phenol and at least one substituted diarylamine.

6. The composition of any of the preceding claims, wherein the hindered phenol is selected from the group consisting of 2, 6-bis (1-methylpropyl) phenol; 2, 6-bis (1, 1-dimethylethyl) -4-methyl-phenol; 2- (1, 1-dimethylethyl) -1, 4-benzenediol; 2, 4-bis (1, 1-dimethylethyl) -phenol; 2, 6-bis (1, 1-dimethylethyl) -phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, methyl ester; 2- (1, 1-dimethylethyl) -4-methylphenol; 2- (1, 1-dimethylethyl) -4, 6-dimethyl-phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropanoic acid, 1,1' - [2, 2-bis [ [3- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] methyl ] -1, 3-propanediyl ] ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, octadecyl ester; 2,2' -methylenebis [6- (1, 1-dimethylethyl) -4-methylphenol; 2- (1, 1-dimethylethyl) -phenol; 2,4, 6-tris (1, 1-dimethylethyl) phenol; 4,4' -methylenebis [2, 6-bis (1, 1-dimethylethyl) -phenol; 4,4', 4"- [ (2,4, 6-trimethyl-1, 3, 5-benzenetriyl) tris (methylene) ] tris [2, 6-bis (1, 1-dimethylethyl) -phenol ]; n, N' -1, 6-hexanediylbis [3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylacrylamide; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxybenzoic acid, hexadecyl ester; p- [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methylphosphonic acid, diethyl ester; 1,3, 5-tris [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, 2- [3- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropyl ] hydrazide; 3- (1, 1-dimethylethyl) -4-hydroxy-5-methylpropanoic acid, 1,1' - [1, 2-ethanediylbis (oxy-2, 1-ethanediyl) ] ester; 4- [ (dimethylamino) methyl ] -2, 6-bis (1, 1-dimethylethyl) phenol; 4- [ [4, 6-bis (octylthio) -1,3, 5-triazin-2-yl ] amino ] -2, 6-bis (1, 1-dimethylethyl) phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropionic acid, 1,1' - (thiodi-2, 1-ethanediyl) ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxybenzoic acid, 2, 4-bis (1, 1-dimethylethyl) phenyl ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropionic acid, 1,1' - (1, 6-hexanediyl) ester; 3- (1, 1-dimethylethyl) -4-hydroxy-5-methylpropanoic acid, 1,1' - [2,4,8, 10-tetraoxaspiro [5.5] undecane-3, 9-diylbis (2, 2-dimethyl-2, 1-ethanediyl) ] ester; 3- (1, 1-dimethylethyl) - β - [3- (1, 1-dimethylethyl) -4-hydroxyphenyl ] -4-hydroxy- β -methylpropanoic acid, 1,1' - (1, 2-ethanediyl) ester; 2- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] -2-butylmalonic acid, 1, 3-bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, 1- [2- [3- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] ethyl ] -2,2,6, 6-tetramethyl-4-piperidyl ester; 3, 4-dihydro-2, 5,7, 8-tetramethyl-2- [ (4R,8R) -4,8, 12-trimethyltridecyl ] - (2R) -2H-1-benzopyran-6-ol; and mixtures thereof.

7. The composition of any of the preceding claims, wherein the substituted diarylamine is selected from one or more compounds selected from the group consisting of:

(j) mixtures thereof;

wherein X is N and Y is C-H, or X is C-H and Y is N; wherein G, when present, is selected from O, S, Se, -CH ═ CH-and- (CH)₂)_n-, where n is 0,1 or 2; and wherein at least one aryl ring is substituted with a group other than H;

wherein in the structure of formula (XI), R¹、R⁴、R⁵、R⁶、R⁹And R¹⁰Independently selected from H and C₁-C₁₂An alkyl group; more preferably R⁴And R⁹Is H, and R¹、R⁵、R⁶And R¹⁰Independently selected from H and C₁-C₄An alkyl group; r²And R⁷Independently of one another are H or may each be independently of R³Or R⁸Linked together to form a fused aromatic ring; when each is different from R²Or R⁷When connecting, R³And R⁸Independently selected from H, C₁-C₁₂Alkyl, -CF₃、-NO₂、-CN、-Cl、-Br、-F、C₆-C₁₂Aryl (preferably phenyl), C₇-C₁₂Alkylaryl, -OR, -SO₂N(R)₂and-N (R)₂Wherein each R is independently selected from H, C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl radical, C₆-C₁₀Aryl, substitutedC of (A)₆-C₁₀Aryl radical, C₇-C₁₂Alkylaryl, substituted C₇-C₁₂Alkylaryl, alkyleneoxy, and polyalkyleneoxy groups;

wherein in the structures of formulae (XII) to (XIX), R¹¹、R¹²、R¹⁴、R¹⁵、R¹⁷And R¹⁸Independently selected from H and C₁-C₁₂Alkyl, more preferably H and C₁-C₄An alkyl group; r¹³And R¹⁶Independently selected from H, C₁-C₁₂Alkyl, -CF₃、-NO₂、-CN、-Cl、-Br、-F、C₆-C₁₂Aryl (preferably phenyl), C₇-C₁₂Alkylaryl, -OR, -SO₂N(R)₂and-N (R)₂Wherein each R is independently selected from H, C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl radical, C₆-C₁₀Aryl, substituted C₆-C₁₀Aryl radical, C₇-C₁₂Alkylaryl, substituted C₇-C₁₂Alkaryl, alkyleneoxy and polyalkyleneoxy groups.

8. The composition of claim 7, wherein the substituted diaryl amine is a compound selected from the group consisting of formula (XI), formula (XII), and mixtures thereof.

9. The composition of claim 6, wherein the substituted diarylamine is selected from the group consisting of 4-butyl-N- (4-methylphenyl) aniline; 2,4, 6-trimethyl-N- (2,4, 6-trimethylphenyl) aniline; 4- (trifluoromethyl) -N- [4- (trifluoromethyl) phenyl]-aniline; 4- (1, 1-Dimethylethyl) -N- [4- (1, 1-Dimethylethyl) phenyl]Aniline; n is a radical of¹,N¹-dimethyl-N⁴-phenyl-1, 4-phenylenediamine; n is a radical of⁴- [4- (dimethylamino) phenyl group]-N¹,N¹-dimethyl-1, 4-phenylenediamine; 4-nitro-N- (4-nitrophenyl) aniline; 4-methoxy-N-phenylaniline; 4-methyl-N- (4-methylphenyl) aniline; n-phenyl-2-naphthylamine; 4-methoxy-N- (4-methoxyphenyl) aniline; 4-octyl-N- (4-octylphenyl) aniline; n- [1,1' -Biphenyl]-4-Radical- [1,1' -biphenyl]-4-amine; 4-heptyl-N- (4-heptylphenyl) -aniline; 4- (1-phenylethyl) -N- [4- (1-phenylethyl) phenyl]-aniline; 4,4' -iminodibenzonitrile; 4-nonyl-N- (4-nonylphenyl) -aniline; 2, 4-dimethylaniline, N- (2, 4-dimethylphenyl); 4- (1,1,3, 3-tetramethylbutyl) -N- [4- (1,1,3, 3-tetramethylbutyl) phenyl]-aniline; 4- (1-methyl-1-phenylethyl) -N- [4- (1-methyl-1-phenylethyl) phenyl]-aniline; 1, 9-bis (1, 1-dimethylethyl) -10H-phenothiazine; 1, 9-dimethyl-10H-phenothiazine; 3, 7-dichloro-10H-phenothiazine; 3, 7-dimethoxy-10H-phenothiazine; 10, 11-dihydro-5H-dibenzo [ b, f ]]Aza derivatives10H-phenoselenazine; 5H-dibenzo [ b, f ]]Aza derivatives10H-phenoxazine; 10H-phenothiazine; 9, 10-dihydroacridine; 9H-carbazole; 2- (trifluoromethyl) -10H-phenoxazine; 2- (1, 1-dimethylethyl) -10H-phenoxazine; 3- (trifluoromethyl) -10H-phenoxazine; 3, 7-bis (trifluoromethyl) -10H-phenoxazine; 3- (1, 1-dimethylethyl) -10H-phenoxazine; 3- (N, N-diethylsulfonyl) -10H-phenoxazine; 10H-phenoxazine-3-carbonitrile; 3-nitro-10H-phenoxazine; 3-methoxy-10H-phenoxazine; 2,4,6, 8-tetrakis (1, 1-dimethylethyl) -10H-phenoxazine; 2, 8-bis (1, 1-dimethylethyl) -10H-phenoxazine; 3-methoxy-7-nitro-10H-phenoxazine; 7-nitro-10H-phenoxazine-3-carbonitrile; 3, 7-dimethoxy-10H-phenoxazine; 3, 7-bis (1, 1-dimethylethyl) -10H-phenoxazine; 7-fluoro-10H-phenoxazine-3-carbonitrile; 7- (diethylamino) -10H-phenoxazine-3-carbonitrile; 10H-phenoxazine-2, 3-dicarbonitrile; 3, 7-dinitro-10H-phenoxazine; 2-methyl-3-nitro-10H-phenoxazine; 2-ethyl-3-nitro-10H-phenoxazine; n, N-diethyl-7-nitro-10H-phenoxazin-3-amine; 2, 3-dinitro-10H-phenoxazine; 7-chloro-2-ethyl-3-nitro-10H-phenoxazine; n, N-diethyl-7-methoxy-10H-phenoxazin-3-amine; and mixtures thereof.

10. The composition of claim 7, wherein R is selected from EO, PO, BO and mixtures thereof, more preferably from an alkyleneoxy or polyalkyleneoxy group selected from EO/PO mixtures alone or EO/PO mixtures.

11. The composition of any one of the preceding claims, wherein the leuco composition comprises a compound selected from the group consisting of diarylmethane leuco, triarylmethane leuco, oxazine leuco, thiazine leuco, hydroquinone leuco, arylamino phenol leuco, and mixtures thereof.

12. The composition of claim 11, wherein the leuco compound is selected from one or more compounds selected from the group consisting of:

(f) mixtures thereof;

wherein the ratio of formula I-V to its oxidized form is at least 1: 3; wherein A, B and each individual R on each of the C rings_o、R_mAnd R_pThe radicals are independently selected from hydrogen, deuterium and R⁵(ii) a Wherein each R⁵Independently selected from the group consisting of halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — (CH)₂)_n─O─R¹、─C(O)R¹、─C(O)OR¹、─C(O)O^-、─C(O)NR¹R²、─OC(O)R¹、─OC(O)OR¹、─OC(O)NR¹R²、─S(O)₂R¹、─S(O)₂OR¹、─S(O)₂O^-、─S(O)₂NR¹R²、─NR¹C(O)R²、─NR¹C(O)OR²、─NR¹C(O)SR²、─NR¹C(O)NR²R³、─NR¹R²、─P(O)₂R¹、─P(O)(OR¹)₂、─P(O)(OR¹)O^-and-P (O)^-)₂(ii) a Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; wherein R is in at least one of the three rings A, B or C_oAnd R_mAt least one of the radicals is hydrogen; each R_pIndependently selected from hydrogen, — OR¹and-NR¹R²；

Wherein G is independently selected from hydrogen, deuterium, C₁-C₁₆Alkoxides, phenoxides, biphenoxides, nitrites, nitriles, alkylamines, imidazoles, arylamines, polyalkylene oxides, halides, alkyl sulfides, aryl sulfides and phosphine oxides;

wherein R is¹、R²And R³Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R⁴；R⁴Is an organic group consisting of one or more organic monomers having a molecular weight of 28 to 500;

wherein e and f are independently integers from 0 to 4;

wherein each R²⁰And R²¹Independently selected from halogen, nitro, alkyl, substituted alkyl, — nc (o) OR¹、─NC(O)SR¹、─OR¹and-NR¹R²；

Wherein each R²⁵Independently selected from the group consisting of monosaccharide radicals, disaccharide radicals, oligosaccharide radicals, polysaccharide radicals, — C (O) R¹、─C(O)OR¹、─C(O)NR¹R²；

Wherein each R²²And R²³Independently selected from hydrogen, alkyl and substituted alkyl;

wherein R is³⁰Is located ortho OR para to the bridging amine group and is selected from-OR³⁸and-NR³⁶R³⁷Wherein each R is³⁶And R³⁷Independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, acyl, R⁴、─C(O)OR¹、─C(O)R¹And C (O) NR¹R²；

Wherein R is³⁸Selected from hydrogen, acyl, — C (O) OR¹、─C(O)R¹And C (O) NR¹R²；

Wherein g and h are independently integers from 0 to 4;

wherein each R³¹And R³²Independently selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — C (O) R¹、─C(O)OR¹、─C(O)O^-、─C(O)NR¹R²、─OC(O)R¹、─OC(O)OR¹、─OC(O)NR¹R²、─S(O)₂R¹、─S(O)₂OR¹、─S(O)₂O^-、─S(O)₂NR¹R²、─NR¹C(O)R²、─NR¹C(O)OR²、─NR¹C(O)SR²、─NR¹C(O)NR²R³、─OR¹、─NR¹R²、─P(O)₂R¹、─P(O)(OR¹)₂、─P(O)(OR¹)O^-and-P (O)^-)₂；

wherein-NR³⁴R³⁵In ortho or para position to the bridging amine group, and R³⁴And R³⁵Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R⁴；

Wherein R is³³Independently selected from hydrogen, — S (O)₂R¹、─C(O)N(H)R¹；─C(O)OR¹(ii) a and-C (O) R¹(ii) a Wherein when g is 2 to 4, any two adjacent R³¹The groups may be joined to form five or more fused rings, wherein no more than two atoms in the fused rings may be nitrogen atoms;

wherein X⁴⁰Selected from oxygen atom, sulfur atom and NR⁴⁵(ii) a Wherein R is⁴⁵Independently selected from hydrogen, deuterium, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — s (o)₂OH、─S(O)₂O^-、─C(O)OR¹、─C(O)R¹And C (O) NR¹R²；

Wherein R is⁴⁰And R⁴¹Independently selected from-CH₂)_n─O─R¹、─(CH₂)_n─NR¹R²Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0;

wherein j and k are independently integers from 0 to 3;

wherein R is⁴²And R⁴³Independently selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — s (o)₂R¹、─C(O)NR¹R²、─NC(O)OR¹、─NC(O)SR¹、─C(O)OR¹、─C(O)R¹、─OR¹、─NR¹R²；

Wherein R is⁴⁴is-C (O) R¹、─C(O)NR¹R²and-C (O) OR¹；

Wherein any charge present in any of the compounds is balanced by a suitable independently selected internal or external counterion.

13. The composition of claim 12, wherein the leuco compound is a compound of formula (I).

14. The composition of claim 13, wherein the different A, B s and the two Rs on the C ring_oThe groups combine to form a five or more membered fused ring.

15. The composition of claim 14 wherein the fused ring is six or more membered and the two R's on different A, B and C rings_oThe groups combine to form an organic linking group containing one or more heteroatoms.

16. The composition of claim 15, wherein two R on different A, B and C rings_oThe groups combine to form a heteroatom bridge selected from-O-and-S-)Giving rise to six-membered fused rings.

17. The composition of claim 13, wherein all four R's in at least one of the three rings of A, B or C_oAnd R_mThe radical is hydrogen.

18. The composition of claim 17 wherein all R on all A, B or C three rings_oAnd R_mThe radicals are all hydrogen.

19. The composition of claim 18, wherein each R is_pIs independently selected from-NR¹R²A group.

20. The composition of claim 12, wherein the organic group can be substituted with one or more additional leuco colorant groups conforming to the structure of formula I.

21. The composition of claim 12, wherein R⁴Selected from the group consisting of alkyleneoxy, oxoalkyleneoxy, oxoalkyleneamine, epichlorohydrin, quaternized epichlorohydrin, alkyleneamine, hydroxyalkylene, acyloxyalkylene, carboxyalkylene, carboalkoxyalkylene, and sugars.

22. The composition of claim 1, wherein the composition comprises at least one solvent selected from the group consisting of: water, ethanol, ethylene glycol, propylene carbonate, ethylene carbonate, polyalkylene oxide, polyester, polycarbonate, polyethylenimine, polyethylene glycol, polypropylene glycol, nonionic surfactant, and mixtures thereof.

23. The composition of claim 19, wherein the composition contains at least one solvent selected from the group consisting of: water, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, nonionic surfactants, and mixtures thereof.

24. The composition of claim 1, wherein the composition comprises at least one nonionic surfactant.

Technical Field

The present application describes stable compositions containing leuco compounds having reduced conversion upon storage and their use in the laundering of textile articles. By co-formulating a mixture of antioxidant and leuco compound, the composition containing the leuco compound is less converted upon storage. Furthermore, when such stable compositions are formulated in laundry care compositions, they retain the following ability: enhancing the apparent or visually perceived whiteness, or imparting a desired hue to a textile article washed or otherwise treated with the laundry care composition.

Background

As textile substrates age, their color tends to fade or yellow due to exposure to light, air, soil, and the natural degradation of the fibers that make up the substrate. Thus, to visually enhance these textile substrates and counteract fading and yellowing, the use of polymeric colorants to color consumer products is well known in the art. For example, the use of brighteners, or optical brighteners or bluing agents, in textile applications is well known. However, while optical brighteners, which are colorless in the final product, have no effect in a room with no or little uv light, and conventional brighteners tend to undesirably darken liquid products if enough dye is used to deposit onto the textile substrate to obtain the whitening benefit.

Leuco dyes are also known in the art which exhibit a change from a colorless or slightly colored state to a colored state upon exposure to a particular chemical or physical trigger. The resulting coloration change is generally visually perceptible to the human eye. Many of these compounds have a certain absorbance in the visible region (400-750nm) and thus have more or less some color. In the present invention, a dye is considered to be a "leuco dye" if it has no significant color at its applied concentration and conditions, but exhibits significant color in its triggered form. The color change upon triggering results from a change in the molar attenuation coefficient (also referred to in some literature as molar extinction coefficient, molar absorption coefficient and/or molar absorbance) of the leuco dye molecule in the range 400-750nm, preferably in the range 500-650nm, most preferably in the range 530-620 nm. The increase in the molar decay coefficient of the leuco dye before and after triggering should be greater than 50%, more preferably greater than 200%, most preferably greater than 500%.

Thus, it is contemplated that the leuco colorants described herein are ideally suited for use as whitening agents within the scope of the present invention. However, while conventional leuco colorants may be effective to the extent that they remain in a colorless form during storage and undergo a triggering change to a colored or more highly colored state during or after consumer use, it is difficult to control the reaction. In particular, the difficulty is balancing the need to suppress the reaction leading to the coloured form prior to use with the need to allow the same reaction once the product is used.

Antioxidants can be used in the compositions to help retard the conversion of the leuco compound to its colored or more highly colored state during storage. Conventional antioxidants, such as hindered phenols, have some efficacy in this regard. At typical usage levels (less than or about 1 wt.%), conventional antioxidants are ineffective in stabilizing compositions containing greater than 2 wt.% leuco compounds. Thus, there remains a need for an ability to effectively slow the conversion of leuco compounds during storage of the formulation and to retain the converted molecules once used.

It has now been surprisingly found that a much higher antioxidant loading can minimize the reaction leading to the colored form prior to use, yet still provide the desired consumer whiteness effect on the textile article.

Disclosure of Invention

In one aspect, the present invention provides a composition comprising: (a) a leuco composition; and (b) a stabilizing amount of an antioxidant composition comprising at least one sterically hindered phenol and at least one substituted diarylamine, wherein the molar ratio of hindered phenol to substituted diarylamine is greater than 1: 1.

In another aspect, the present invention provides a composition comprising: (a) a leuco composition; and (b) an antioxidant composition, wherein (i) the combined mass of the leuco compound and the antioxidant present in the composition is 10% or more of the total mass of the composition, and (b) the molar ratio of the antioxidant present in the composition to the leuco compound present in the composition is greater than 1: 1.

In another aspect, the present invention provides a laundry care composition comprising: (a) at least one laundry care ingredient and (b) a composition of the present invention. The invention also includes a method of treating a textile article with such a laundry care composition.

Detailed Description

Definition of

As used herein, the term "alkoxy" is intended to include C₁-C₈Alkoxy groups and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidyl oxide, ethylene oxide or propylene oxide.

As used herein, the interchangeable terms "alkyleneoxy" and "oxyalkylene," and the interchangeable terms "polyalkyleneoxy" and "polyoxyalkylene," generally refer to molecular structures containing one or more than one of the following repeating units, respectively: -C₂H₄O-、-C₃H₆O-、-C₄H₈O-and their derivativesIn any combination. Non-limiting structures corresponding to these groups include, for example, -CH₂CH₂O-、-CH₂CH₂CH₂O-、-CH₂CH₂CH₂CH₂O-、-CH₂CH(CH₃) O-and-CH₂CH(CH₂CH₃) O-is formed. Further, the polyoxyalkylene constituent may be selected from the group consisting of one or more monomers selected from C_2-20An alkyleneoxy group, a glycidyl group, or mixtures thereof.

The terms "ethylene oxide", "propylene oxide" and "butylene oxide" may be illustrated herein by their typical names "EO", "PO" and "BO", respectively.

As used herein, the terms "alkyl" and "alkyl-capped" mean any monovalent group formed by removing a hydrogen atom from a substituted or unsubstituted hydrocarbon. Non-limiting examples include branched or unbranched, substituted or unsubstituted hydrocarbyl moieties including C₁-C₁₈An alkyl group, and in one aspect, C₁-C₆An alkyl group.

As used herein, unless otherwise specified, the term "aryl" is intended to include C₃-C₁₂An aryl group. The term "aryl" refers to both carbocyclic and heterocyclic aryl groups.

As used herein, the term "alkaryl" refers to any alkyl-substituted aryl substituent and aryl-substituted alkyl substituent. More specifically, the term is intended to mean C_7-16Alkyl-substituted aryl substituents and C_7-16Aryl-substituted alkyl substituents, which may or may not contain additional substituents.

As used herein, the term "detergent composition" is a subset of laundry care compositions and includes laundry care compositions, including but not limited to products for washing fabrics. Such compositions may be pre-treatment compositions used prior to the washing step, or may be rinse-added compositions, as well as cleaning aids, such as bleach additives and "stain-stick" or pre-treatment types.

As used herein, unless otherwise specified, the term "laundry care composition" includes granular, powder, liquid, gel, paste, unit dose, bar and/or flake type detergent and/or fabric treatment compositions, including but not limited to products for laundering fabrics, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, and other products for fabric care and care, and combinations thereof. Such compositions may be pre-treatment compositions used prior to the washing step, or may be rinse-added compositions, as well as cleaning aids such as bleach additives and/or "stain-stick" or pre-treatment compositions or substrate-borne products such as dryer add-on sheets.

As used herein, the term "leuco" (as used in connection with, for example, a compound, moiety, group, dye, monomer, fragment, or polymer) refers to an entity (e.g., an organic compound or portion thereof) that undergoes one or more chemical and/or physical changes upon exposure to a particular chemical or physical trigger, which results in a transition from a first color state (e.g., uncolored or substantially colorless) to a second, higher colored state. Suitable chemical or physical triggers include, but are not limited to, oxidation, pH change, temperature change, and change in electromagnetic radiation (e.g., light) exposure. Suitable chemical or physical changes that occur in the leuco entity include, but are not limited to, oxidative and non-oxidative changes, such as intramolecular cyclization. Thus, in one aspect, a suitable leuco entity may be a reversibly reduced form of a chromophore. In one aspect, the leuco moiety preferably comprises at least first and second pi-systems that are capable of converting to a third combined conjugated pi-system that binds the first and second pi-systems upon exposure to one or more of the above-described chemical and/or physical triggers.

As used herein, the term "leuco composition" or "leuco colorant composition" refers to a composition comprising at least one leuco compound having an independently selected structure as described in further detail herein.

As used herein, the "average molecular weight" of a leuco colorant is reported as the weight average molecular weight as determined by its molecular weight distribution: because of its manufacturing process, the leuco colorants disclosed herein may contain a distribution of repeating units in their polymer portion.

As used herein, the terms "maximum extinction coefficient" and "maximum molar extinction coefficient" are intended to describe the molar extinction coefficient at the wavelength of maximum absorption (also referred to herein as the maximum wavelength) in the range of 400 nanometers to 750 nanometers.

As used herein, the term "first color" is used to refer to the color of the laundry care composition prior to activation, and is intended to include any color, including colorless and substantially colorless.

As used herein, the term "second color" is used to refer to the color of the laundry care composition after triggering, and is intended to include any color that is distinguishable from the first color of the laundry care composition by visual inspection or using analytical techniques (such as spectrophotometric analysis).

As used herein, the term "converting agent" refers to any oxidizing agent known in the art, except for any known form of molecular oxygen (singlet and triplet).

As used herein, the term "trigger" refers to a reactant suitable for converting a leuco composition from a colorless or substantially colorless state to a colored state.

As used herein, the term "brightener" refers to a dye or leuco colorant that upon triggering can form a dye that provides a shade to a cloth having a relative hue angle of 210 to 345, or even 240 to 320, or even 250 to 300 (e.g., 250 to 290) when on white cotton.

As used herein, "cellulosic substrate" is intended to include any substrate comprising at least a majority of cellulose by weight. Cellulose is found in wood, cotton, flax, jute and hemp. Cellulosic substrates can be in the form of powders, fibers, pulps, and articles formed from powders, fibers, and pulps. Cellulosic fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetates (cellulose acetate), triacetates (cellulose triacetate), and mixtures thereof. Articles formed from cellulosic fibers include textile articles, such as fabrics. Articles formed from pulp include paper.

As used herein, articles such as "a" and "an" when used in a claim are understood to mean one or more of what is claimed or described.

As used herein, the terms "include", "including", "includes" and "including" mean non-limiting.

As used herein, the term "solid" includes granular, powder, stick, and tablet product forms.

As used herein, the term "fluid" includes liquid, gel, paste, and gaseous product forms.

The test methods disclosed in the test methods section of the present application should be used to determine the corresponding values of the parameters of applicants' invention.

Unless otherwise specified, all component or composition levels are in reference to the active portion of the component or composition and are exclusive of impurities, e.g., residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

All percentages and ratios are by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition, unless otherwise indicated.

In one aspect, the molar extinction coefficient of the second colored state at the maximum absorbance at a wavelength in the range of 200-1,000nm (more preferably 400-750nm) is preferably at least five times, more preferably 10 times, even more preferably 25 times, most preferably at least 50 times the molar extinction coefficient of the first colored state at the wavelength of the maximum absorbance of the second colored state. Preferably, the molar extinction coefficient at maximum absorbance in the wavelength range of 200-1,000nm (more preferably 400-750nm) of the second colored state is at least five times, preferably 10 times, even more preferably 25 times, most preferably at least 50 times, the molar extinction coefficient at maximum absorbance in the corresponding wavelength range of the first colored state. One of ordinary skill will recognize thatThe ratio can be much higher. For example, the first color state may have a wavelength range as small as 10M in the 400-750nm wavelength range^-1cm^-1And the second colored state may have a maximum molar extinction coefficient of up to 80,000M in the wavelength range of 400-750nm^-1cm^-1Or higher, in which case the ratio of the extinction coefficients will be 8000:1 or higher.

In one aspect, the maximum molar extinction coefficient of the first color state at a wavelength in the range of 400-750nm is less than 1000M^-1cm^-1And the maximum molar extinction coefficient of the second colored state at a wavelength in the range of 400-750nm is greater than 5,000M^-1cm^-1Preferably greater than 10,000, 25,000, 50,000 or even 100,000M^-1cm^-1. One skilled in the art will recognize and appreciate that a polymer comprising more than one leuco moiety can have a significantly higher maximum molar extinction coefficient in a first color state (e.g., due to the additive effect or presence of multiple leuco moieties or leuco moieties that convert to a second color state).

In one aspect, the composition comprises from about 0.001 wt.% to about 2 wt.% of the hindered phenol antioxidant. Preferably, the hindered phenol antioxidant is present at a concentration of 0.01 to 0.50 wt.%.

Antioxidants are the substances described in Kirk-Othmer (vol.3, p.424) and Ullmann's Encyclopedia (vol.3, p.91).

One class of antioxidants useful in the present invention are alkylated phenols having the general formula:

wherein R is C₁-C₂₂Straight chain alkyl or C₃-C₂₂Branched alkyl groups, each (1) optionally having one or more esters (-CO) therein₂-) or an ether (-O-), and (2) optionally substituted with a group comprising an alkyleneoxy or polyalkyleneoxy group (selected from EO, PO, BO and mixtures thereof, more preferably selected from the group consisting ofEO or an organic group selected from EO/PO mixtures); in one aspect, R is preferably methyl or branched C₃-C₆Alkyl radical, C₁-C₆Alkoxy, preferably methoxy; r¹Is C₃-C₆Branched alkyl, preferably tert-butyl; x is 1 or 2. Some hindered phenol compounds are the preferred type of alkylated phenols having this general formula. A preferred hindered phenol compound of this type is 3, 5-di-tert-butyl-4-hydroxytoluene (BHT). When any R group in the above structure comprises three or more contiguous monomers, the antioxidant is defined herein as a "polymeric hindered phenol antioxidant".

The term "hindered phenol" as used herein refers to a compound comprising a phenolic group having (a) at least one C attached in the ortho position to at least one phenol-OH group₃Or higher branched alkyl, preferably C₃-C₆A branched alkyl group, preferably a tert-butyl group, or (b) a substituent at each ortho position of at least one phenol-OH group, said substituents being independently selected from C₁-C₆Alkoxy, preferably methoxy, C₁-C₂₂Straight chain alkyl or C₃-C₂₂Branched alkyl, preferably methyl or branched C₃-C₆Alkyl groups, or mixtures thereof. If the phenyl ring contains more than one-OH group, the compound is a hindered phenol, provided that at least one such-OH group is substituted as described above.

Another class of hindered phenolic antioxidants suitable for use in the composition are benzofuran or benzopyran derivatives having the formula:

wherein R is₁And R₂Each independently is alkyl, or R₁And R₂May together form C₅-C₆A cyclic hydrocarbyl moiety; b is absent or CH₂；R₄Is C₁-C₆An alkyl group; r₅Is hydrogen or-C (O) R₃Wherein R is₃Is hydrogen or C₁-C₁₉Alkyl radical；R₆Is C₁-C₆An alkyl group; r₇Is hydrogen or C₁-C₆An alkyl group; x is-CH₂OH or-CH₂A, wherein A is a nitrogen-containing unit, a phenyl group or a substituted phenyl group. Preferred nitrogen-containing a units include amino, pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl, and mixtures thereof.

Hindered phenols suitable for use in the present invention include, but are not limited to, 3 '-bis (1, 1-dimethylethyl)) -5,5' -dimethoxy- [1,1 '-biphenyl ] -2,2' -diol; 3- (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid; 3- (1, 1-dimethylethyl) -1, 2-benzenediol; 2- (1, 1-dimethylethyl) -4, 6-dinitrophenol; 2,2' -butylidenebis [6- (1, 1-dimethylethyl) -4-methylphenol; 4,4' - [ thiobis (methylene) ] bis [2, 6-bis (1, 1-dimethylethyl) phenol; 3- (1, 1-dimethylethyl) -4-hydroxy-5-methylpropanoic acid, methyl ester; 2- (1, 1-dimethylethyl) -4- (1-methylethyl) phenol; 4,4' -dithiobis [2, 6-bis (1, 1-dimethylethyl) ] phenol; dimethyldithiocarbamate, [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ester; 2, 6-bis (1, 1-dimethylethyl) -4- (2-propen-1-yl) phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, nitrilotris-2, 1-ethanediyl ester; 4,4' -thiobis [2, 6-bis (1, 1-dimethylethyl) phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid; 3, 5-bis (1, 1-dimethylethyl) -1, 2-benzenediol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid hydrazide; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, ethyl ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxybenzoic acid, ethyl ester; 4,4' - [ oxybis (methylene) ] bis [2, 6-bis (1, 1-dimethylethyl) phenol; 2- [2- (4-chloro-2-nitrophenyl) diazenyl ] -6- (1, 1-dimethylethyl) -4-methylphenol; -3- [3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropyl ] - -hydroxy-poly (oxy-1, 2-ethanediyl); 2,2' -methylenebis [4, 6-bis (1, 1-dimethylethyl) ] phenol; 2, 6-bis [ [3- (1, 1-dimethylethyl) -2-hydroxy-5-methylphenyl ] methyl ] -4-methylphenol; 2, 6-bis (1, 1-dimethylethyl) -4-nonylphenol; 3,3 '-thiodipropionic acid, 1,1' -bis [2- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] ethyl ] ester; 2- (1, 1-dimethylethyl) -6-methyl-4- [3- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxol-6-yl ] oxy ] propyl ] phenol; 2- (1, 1-dimethylethyl) -1, 4-benzenediol, 4-acetate; 2, 4-bis (1, 1-dimethylethyl) -6- (1-phenylethyl) phenol; 3,4', 5-tris (1, 1-dimethylethyl) - [1,1' -biphenyl ] -4-ol; 3,3',5,5' -tetrakis (1, 1-dimethylethyl) - [1,1 '-biphenyl ] -2,2' -diol; 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, methyl ester; 4-hydroxy-3, 5-dimethylbenzonitrile; 2- [ (2-hydroxy-3, 5-dimethylphenyl) methyl ] -4, 6-dimethylphenol; 2-ethyl-6-methylphenol; 3, 4-dihydro-2, 2,5,7, 8-pentamethyl-2H-1-benzopyran-6-ol; 4-hydroxy-3, 5-dimethylbenzaldehyde; 3, 4-dihydro-6-hydroxy-2, 5,7, 8-tetramethyl-2H-1-benzopyran-2-carboxylic acid; 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenol; 2,2' -methylenebis [ 6-cyclohexyl-4-methylphenol ]; 2,3,5, 6-tetramethylphenol; 2,3,4,5, 6-pentamethylphenol; and mixtures thereof.

In one aspect, preferred hindered phenols for use in the present invention include, but are not limited to, 2, 6-dimethylphenol; 2, 6-diethylphenol; 2, 6-bis (1-methylethyl) phenol; 2,4, 6-trimethylphenol; 2- (1, 1-dimethylethyl) -4-methoxyphenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-benzoic acid; 3, 5-bis (1, 1-dimethylethyl) -2-hydroxy-benzoic acid; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-benzyl alcohol; 2- (2H-benzotriazol-2-yl) -4, 6-bis (1, 1-dimethylethyl) -phenol; 2- (1, 1-dimethylethyl) -4-ethyl-phenol; 2- (1, 1-dimethylethyl) -6-methyl-phenol; 2,2' -methylenebis [6- (1, 1-dimethylethyl) -4-ethylphenol; 2, 6-bis (1, 1-dimethylethyl) -4-ethylphenol; 4,4' -thiobis [2- (1, 1-dimethylethyl) -6-methylphenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, 1,1' - [ (1, 2-dioxo-1, 2-ethanediyl) bis (imino-2, 1-ethanediyl) ] ester; 2, 6-bis (1, 1-dimethylethyl) -4-nitrosophenol; 2,2' -thiobis [6- (1, 1-dimethylethyl) -4-methylphenol; 2, 6-bis (1, 1-dimethylethyl) -4- (1-methylpropyl) phenol; 2, 4-bis (1, 1-dimethylethyl) -6-methylphenol; 2,2' -ethylidenebis [4, 6-bis (1, 1-dimethylethyl) ] phenol; n, N' -1, 3-propanediylbis [3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylacrylamide; 2, 6-bis (1, 1-dimethylethyl) -1, 4-benzenediol; 4,4' - (1-methylethylidene) bis [2- (1, 1-dimethylethyl) phenol; 2- [ [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] thio ] acetic acid, 2-ethylhexyl ester; 4-butyl-2, 6-bis (1, 1-dimethylethyl) phenol; phosphorous acid, 2- (1, 1-dimethylethyl) -4- [1- [3- (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-methylethyl ] phenylbis (4-nonylphenyl) ester; 4,4' - (2,4,8, 10-tetraoxaspiro [5.5] undecane-3, 9-diyl) bis [2, 6-bis (1, 1-dimethylethyl) phenol ]; 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, octyl ester; 4,4' - (1-methylethylidene) bis [2, 6-bis (1, 1-dimethylethyl) phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropanoic acid, 1,1',1 "- [ (2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -triyl) tris-2, 1-ethanediyl ] ester; 2, 6-bis (1-methylethyl) phenol; 2, 6-diethylphenol; 2, 6-dimethyl-1, 4-benzenediol; 3,3',5,5' -tetramethyl- [1,1 '-biphenyl ] -4,4' -diol; 2, 6-bis (1, 1-dimethylethyl) -4- (1-methylpropyl) phenol; 2,2' -methylenebis [ 4-methyl-6- (1-methylcyclohexyl) phenol; 3, 5-bis (1, 1-dimethylethyl) - [1,1' -biphenyl ] -4-ol; 4- (1, 1-dimethylethyl) -2, 6-dimethylphenol; 2,3,4, 6-tetramethylphenol; 2,4, 6-tris (1-methylethyl) phenol; 2,2' - (2-methylpropylidene) bis [4, 6-dimethylphenol ]; and mixtures thereof.

In another aspect, highly preferred hindered phenols for use in the present invention include, but are not limited to, 2, 6-bis (1-methylpropyl) phenol; 2, 6-bis (1, 1-dimethylethyl) -4-methyl-phenol; 2- (1, 1-dimethylethyl) -1, 4-benzenediol; 2, 4-bis (1, 1-dimethylethyl) -phenol; 2, 6-bis (1, 1-dimethylethyl) -phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-benzenepropanoic acid, methyl ester; 2- (1, 1-dimethylethyl) -4-methylphenol; 2- (1, 1-dimethylethyl) -4, 6-dimethyl-phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropanoic acid, 1,1' - [2, 2-bis [ [3- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] methyl ] -1, 3-propanediyl ] ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, octadecyl ester; 2,2' -methylenebis [6- (1, 1-dimethylethyl) -4-methylphenol; 2- (1, 1-dimethylethyl) -phenol; 2,4, 6-tris (1, 1-dimethylethyl) phenol; 4,4' -methylenebis [2, 6-bis (1, 1-dimethylethyl) -phenol; 4,4', 4"- [ (2,4, 6-trimethyl-1, 3, 5-benzenetriyl) tris (methylene) ] tris [2, 6-bis (1, 1-dimethylethyl) -phenol ]; n, N' -1, 6-hexanediylbis [3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylacrylamide; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxybenzoic acid, hexadecyl ester; p- [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methylphosphonic acid, diethyl ester; 1,3, 5-tris [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, 2- [3- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropyl ] hydrazide; 3- (1, 1-dimethylethyl) -4-hydroxy-5-methylpropanoic acid, 1,1' - [1, 2-ethanediylbis (oxy-2, 1-ethanediyl) ] ester; 4- [ (dimethylamino) methyl ] -2, 6-bis (1, 1-dimethylethyl) phenol; 4- [ [4, 6-bis (octylthio) -1,3, 5-triazin-2-yl ] amino ] -2, 6-bis (1, 1-dimethylethyl) phenol; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropionic acid, 1,1' - (thiodi-2, 1-ethanediyl) ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxybenzoic acid, 2, 4-bis (1, 1-dimethylethyl) phenyl ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropionic acid, 1,1' - (1, 6-hexanediyl) ester; 3- (1, 1-dimethylethyl) -4-hydroxy-5-methylpropanoic acid, 1,1' - [2,4,8, 10-tetraoxaspiro [5.5] undecane-3, 9-diylbis (2, 2-dimethyl-2, 1-ethanediyl) ] ester; 3- (1, 1-dimethylethyl) - [3- (1, 1-dimethylethyl) -4-hydroxyphenyl ] -4-hydroxy-methamphetamine, 1,1' - (1, 2-ethanediyl) ester; 2- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] -2-butylmalonic acid, 1, 3-bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) ester; 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid, 1- [2- [3- [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] ethyl ] -2,2,6, 6-tetramethyl-4-piperidyl ester; 3, 4-dihydro-2, 5,7, 8-tetramethyl-2- [ (4R,8R) -4,8, 12-trimethyltridecyl ] - (2R) -2H-1-benzopyran-6-ol; 2, 6-dimethylphenol; 2,3, 5-trimethyl-1, 4-benzenediol; 2,4, 6-trimethylphenol; 2,3, 6-trimethylphenol; 4,4' - (1-methylethylidene) -bis [2, 6-dimethylphenol ]; 1,3, 5-tris [ [4- (1, 1-dimethylethyl) -3-hydroxy-2, 6-dimethylphenyl ] methyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione; 4,4' -methylenebis [2, 6-dimethylphenol ]; 2, 6-bis (1-methylpropyl) phenol; and mixtures thereof.

It will be appreciated by those skilled in the art that hindered phenols may be used as the sole antioxidant to limit the conversion of the leuco colorant upon storage. For example, sufficient color stability can be achieved by using only 2, 6-bis (1, 1-dimethylethyl) -4-methyl-phenol or any of the other phenols listed above, such as 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-benzenepropanoic acid, methyl ester. However, as noted above, applicants have found that the incorporation of small amounts of diarylamines provides better overall color stability.

In one aspect, hindered phenol antioxidants that do not yellow are preferably used. On the other hand, the use of hindered phenolic antioxidants known to form yellow by-products can be beneficial, for example, to help counteract the blue color formed by the conversion of leuco colorants in laundry care formulations. Antioxidants that form yellow byproducts can be avoided if they result in a perceived negative attribute in the consumer experience (e.g., deposition of such yellow byproducts on fabrics). The person skilled in the art is able to make an informed decision as to the choice of antioxidant to be used.

Additional antioxidants may be used. Examples of suitable antioxidants for use in the compositions include, but are not limited to, the group consisting of alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, ethoxyquin, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 6-di-tert-butylhydroquinone, tert-butyl hydroxyanisole, lignosulfonic acid and its salts, and mixtures thereof. It is noted that ethoxyquin (1, 2-dihydro-6-ethoxy-2, 2, 4-trimethylquinoline) is prepared by Raschig^TMUnder the trade name Raluquin^TMAnd (4) selling.

Another type of antioxidant that can be used in the composition is 6-hydroxy-2, 5,7, 8-tetramethyl chroman-2-carboxylic acid (Trolox)^TM) And 1, 2-benzisothiazolin-3-one (Proxel GXL)^TM)。

Antioxidants such as tocopherol sorbate, butylated hydroxybenzoic acid and salts thereof, gallic acid and alkyl esters thereof, uric acid and salts thereof, sorbic acid and salts thereof, dihydroxy fumaric acid and salts thereof may also be used.

In one aspect, the molar ratio of hindered phenol antioxidant to substituted diarylamine antioxidant is greater than 1.0:1.0, preferably greater than 2.0:1.0, more preferably greater than 5.0:1.0, and most preferably greater than 10.0, 20.0, or even 30.0: 1.0. The molar ratio of hindered phenol antioxidant to substituted diarylamine antioxidant in the laundry care composition will vary with the rate of consumption of each antioxidant over storage time. One skilled in the art will recognize that in laundry care formulations where the hindered phenolic antioxidant is consumed more rapidly than the substituted diarylamine, the formulation may ultimately have a molar ratio of hindered phenolic antioxidant to substituted diarylamine antioxidant of less than 1.0: 1.0.

Without wishing to be bound by theory, it is believed that the benefits of this combination may be attributed to the combination of a stoichiometric hindered phenol antioxidant that forms thermodynamically more stable groups and a catalytically substituted diarylamine antioxidant that reacts kinetically faster than the hindered phenol but forms somewhat less stable groups. Surprisingly, little substituted diarylamine co-antioxidant is required to inhibit conversion during storage as compared to the use of hindered phenols alone. It has been found that the above combination of one or more hindered phenols and substituted diarylamine derivatives imparts a significantly higher degree of protection against oxidative degradation to leuco colorants than either of these materials used alone.

Substituted diarylamines useful in the practice of the invention can be represented by the general formula

Wherein Ar and Ar' are each independently selected from aryl groups, wherein at least one aryl group is substituted.

In one aspect, the present invention relates to a composition comprising one or more substituted diarylamine antioxidants corresponding to a group selected from:

(j) mixtures thereof;

In the structure of formula (XI), R¹、R⁴、R⁵、R⁶、R⁹And R¹⁰Independently selected from H and C₁-C₁₂An alkyl group; more preferably R⁴And R⁹Is H, and R¹、R⁵、R⁶And R¹⁰Independently selected from H and C₁-C₄An alkyl group; r²And R⁷Independently of one another are H or may each be independently of R³Or R⁸Linked together to form a fused aromatic ring; when each is different from R²Or R⁷When connecting, R³And R⁸Independently selected from H, C₁-C₁₂Alkyl, -CF₃、-NO₂、-CN、-Cl、-Br、-F、C₆-C₁₂Aryl (preferably phenyl), C₇-C₁₂Alkylaryl, -OR, -SO₂N(R)₂and-N (R)₂Wherein each R is independently selected from H, C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl radical, C₆-C₁₀Aryl, substituted C₆-C₁₀Aryl radical, C₇-C₁₂Alkylaryl, substituted C₇-C₁₂Alkaryl, alkyleneoxy and polyalkyleneoxy groups.

In the structures of formulae (XII) to (XIX), R¹¹、R¹²、R¹⁴、R¹⁵、R¹⁷And R¹⁸Independently selected from H and C₁-C₁₂Alkyl, more preferably H and C₁-C₄An alkyl group; r¹³And R¹⁶Independently selected from H, C₁-C₁₂Alkyl, -CF₃、-NO₂、-CN、-Cl、-Br、-F、C₆-C₁₂Aryl (preferably phenyl), C₇-C₁₂Alkylaryl, -OR, -SO₂N(R)₂and-N (R)₂Wherein each R is independently selected from H, C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl radical, C₆-C₁₀Aryl, substituted C₆-C₁₀Aryl radical, C₇-C₁₂Alkylaryl, substituted C₇-C₁₂Alkaryl, alkyleneoxy and polyalkyleneoxy groups.

In one aspect, R in the above structures (XI) - (XIX) is selected from EO, PO, BO and mixtures thereof, more preferably selected from EO alone or an alkyleneoxy or polyalkyleneoxy selected from EO/PO mixtures. When any substituted diarylamine contains R groups with three or more contiguous monomers, the antioxidant is defined herein as a "polymeric diarylamine antioxidant.

As noted above, in some cases, the hindered phenol antioxidant or diarylamine antioxidant comprises an alkyleneoxy or polyalkyleneoxy moiety. In one aspect, the alkyleneoxy or polyalkyleneoxy moiety comprises at least one ethylene oxide group and optionally at least one propylene oxide group. In another aspect, the alkyleneoxy or polyalkyleneoxy moiety comprises from 1 to about 50 ethylene oxide groups and optionally from 1 to about 20 propylene oxide groups. In such a polyalkyleneoxy moiety, different alkyleneoxy groups may be arranged in a block structure or a random structure. In one aspect, the alkyleneoxy groups of the polyalkyleneoxy moiety are arranged in a block structure.

The alkyleneoxy or polyalkyleneoxy moiety can be covalently bonded to the hindered phenol or diarylamine antioxidant by any suitable linking group. In one aspect, the alkyleneoxy or polyalkyleneoxy moiety is covalently bonded to the diarylamine antioxidant via a linking group selected from the group consisting of an oxygen atom and a nitrogen atom. When the linking group is an oxygen atom, one of the valencies of the oxygen atom is occupied by an alkyleneoxy or polyalkyleneoxy moiety, and an oxy atomThe second valence of the seed is occupied by the remainder of the hindered phenolic or diarylamine antioxidant. When the linking group is a nitrogen atom, one of the valencies of the nitrogen atom is occupied by the remainder of the hindered phenolic or diarylamine antioxidant and one of the valencies of the nitrogen atom is occupied by an alkyleneoxy or polyalkyleneoxy moiety. The remaining valencies of the nitrogen atom may be occupied by any suitable group, such as a second alkyleneoxy or polyalkyleneoxy moiety. In one aspect, the alkyleneoxy or polyalkyleneoxy moiety is covalently bonded to the hindered phenolic or diarylamine antioxidant, preferably through a nitrogen atom. In this embodiment, the nitrogen atom and the alkyleneoxy or polyalkyleneoxy moiety together have-NR (C)₂H₄O)_n(C₃H₆O)_qH, wherein n is independently selected from an integer from 1 to 50, q is independently selected from 0 to 20, and R is selected from H, C₁To C₁₂Alkyl, substituted C₁To C₁₂Alkyl radical, C₆To C₁₀Aryl, substituted C₆To C₁₀Aryl radical, C₇To C₁₂Alkylaryl, substituted C₇To C₁₂Alkaryl, alkyleneoxy, and polyalkyleneoxy moieties. In another aspect, the antioxidant compound comprises two independently selected alkyleneoxy or polyalkyleneoxy moieties, each moiety covalently bonded to the antioxidant moiety through a nitrogen atom, the nitrogen atom and the moieties together having the structure

Wherein subscripts n 'and r are independently selected from integers of 1 to 50, the sum of n' and r is 2 to 50, subscripts q 'and s are independently selected from integers of 0 to 20, and the sum of q' and s is 0 to 20.

In one aspect, the substituted diarylamine antioxidant is selected from the group consisting of N, N-dihexyl-5H-pyrimido [4,5-b][1,4]Benzoxazine-2-amine, N, N-diethyl-5H-pyrimido [4,5-b ]][1,4]Benzothiazin-2-amines, N⁵- [4- (1, 1-Dimethylethyl) phenyl group]-N²,N²Di-hexyl-2, 5-pyridinediamine,N⁵- [4- (1, 1-Dimethylethyl) phenyl group]-N²,N²Di-hexyl-2, 5-pyrimidinediamine, N, N-di-hexyl-5H-pyrimido [4,5-b][1,4]Benzothiazin-2-amine, N, N-diethyl-5H-pyrimido [4,5-b][1,4]Benzoxazine-2-amine, 2- (1-pyrrolidinyl) -5H-pyrimido [4,5-b][1,4]Benzothiazine, 8- (1, 1-dimethylethyl) -2-heptyl-4-methyl-5H-pyrimido [4,5-b][1,4]Benzoxazines, N⁵- [4- (1, 1-Dimethylethyl) phenyl group]-N²,N²Dioctyl-2, 5-pyrimidinediamine, N⁵- [4- (1, 1-Dimethylethyl) phenyl group]-N²,N²-dimethyl-2, 5-pyridinediamine, N⁵- [4- (1, 1-Dimethylethyl) phenyl group]-N²,N²-dimethyl-2, 5-pyrimidinediamine, N²,N²-dibutyl-N⁵- (2-hexyl-5-pyrimidinyl) -2, 5-pyrimidinediamine, N²,N²-dihexyl-N⁵-phenyl-2, 5-pyrimidinediamine, N²,N²-dihexyl-N⁵-phenyl-2, 5-pyridinediamine, N²,N²-dibutyl-N⁵- [2- (dibutylamino) -5-pyrimidinyl]2, 5-pyrimidinediamine, N²,N²-dibutyl-N⁵- [6- (dihexylamino) -3-pyridyl group]2, 5-pyrimidinediamine, N⁵- [2- (dimethylamino) -5-pyrimidinyl]-N²,N²-dimethyl-2, 5-pyrimidinediamine, N⁵- [6- (dimethylamino) -3-pyridinyl group]-N²,N²-dimethyl-2, 5-pyrimidinediamine, N²,N²-dimethyl-N⁵-5-pyrimidinyl-2, 5-pyrimidinediamine, N²,N²-dimethyl-N⁵-3-pyridyl-2, 5-pyrimidinediamine, N²,N²-dimethyl-N⁵-5-pyrimidinyl-2, 5-pyridinediamine, N²,N²-dimethyl-N⁵-3-pyridyl-2, 5-pyridinediamine, 6-octyl-N- (6-octyl-3-pyridyl) -3-pyridineamine, 6- (1-methyl-1-phenylethyl) -N- [6- (1-methyl-1-phenylethyl) -3-pyridinylethyl]-3-pyridylamine, 6-butoxy-N- [6- (2-phenylethoxy) -3-pyridinyl]-3-pyridylamine, N- (6-heptyl-3-pyridinyl) -2-hexyl-5-pyrimidinamine, N⁵- [4- (dipropylamino) phenyl group]-N²,N²Di-propyl-2, 5-pyrimidinediamine, N⁵- [6- (dipentylamino)) -3-pyridyl]-N²,N²2, 5-pyridinediamine, N, diamyl-diamyl¹,N¹-dimethyl-N⁴-5-pyrimidinyl-1, 4-phenylenediamine, 2-methoxy-N- (4-methoxyphenyl) -5-pyrimidinamine, 6- (1-hexyn-1-yl) -N- [6- (1-hexyn-1-yl) -3-pyridinyl]-3-pyridylamine, 2- (2-phenylethoxy) -N- [4- (2-phenylethoxy) phenyl]-5-pyrimidinamine, 2- (cyclohexyloxy) -N-phenyl-5-pyrimidinamine, N- (4-butylphenyl) -3-pyridinamine, 2-heptyl-N-phenyl-5-pyrimidinamine, 6-hexyl-N-phenyl-3-pyridinamine, 1, 9-bis (1, 1-dimethylethyl) -10H-phenothiazine, N¹,N¹-dimethyl-N⁴-2-pyridyl-1, 4-phenylenediamine, 6-methyl-N- (6-methyl-3-pyridyl) -3-pyridylamine, N- [4- (dodecyloxy) phenyl]-5-pyrimidinamine, N- (4-butoxyphenyl) -3-pyridinamine, 2- (heptyloxy) -N-phenyl-5-pyrimidinamine, 6-methoxy-N-phenyl-3-pyridinamine, N¹,N¹-dibutyl-N⁴-5-pyrimidinyl-1, 4-benzenediamine, N²,N²-dimethyl-N⁵-phenyl-2, 5-pyrimidinediamine, N²,N²-dimethyl-N⁵-phenyl-2, 5-pyridinediamine, N- (6-butoxy-3-pyridyl) -2- (2-phenylethoxy) -5-pyrimidinamine, 6-methoxy-N- (6-methoxy-3-pyridyl) -3-pyridinamine, N- (4-butoxyphenyl) -2- (2-phenylethoxy) -5-pyrimidinamine, 6-methoxy-N- (4-methoxyphenyl) -3-pyridinamine, N⁵- [6- (diethylamino) -3-pyridinyl]-N²,N²-dimethyl-2, 5-pyrimidinediamine, 2-heptyl-N- (6-heptyl-3-pyridinyl) -5-pyrimidineamine, N- (4-butylphenyl) -2-heptyl-5-pyrimidineamine, N- (4-methoxyphenyl) -5-pyrimidineamine, N-3-pyridinyl-5-pyrimidineamine, N¹,N¹-dipropyl-N⁴-5-pyrimidinyl-1, 4-benzenediamine, N⁵- [2- (diethylamino) -5-pyrimidinyl]-N²,N²Diethyl-2, 5-pyrimidinediamine, N⁵- [6- (dimethylamino) -3-pyridinyl group]-N²,N²Diethyl-2, 5-pyrimidinediamine, N⁵- [6- (dimethylamino) -3-pyridinyl group]-N²,N²-dimethyl-2, 5-pyridinediamine, N⁵- [4- (dimethylamino) phenyl group]-N²,N²-dimethyl-2, 5-pyrimidinediamine, N⁵- [4- (dimethylamino) phenyl group]-N²,N²-dimethyl-2, 5-pyridinediamine, 2-heptyl-N- (2-heptyl-5-pyrimidinyl) -5-pyrimidinamine, 2-heptyl-N- (6-hexyl-3-pyridinyl) -5-pyrimidinamine, 6-hexyl-N- (6-hexyl-3-pyridinyl) -3-pyridinamine, N- (4-butylphenyl) -2-hexyl-5-pyrimidinamine, N- (4-butylphenyl) -6-hexyl-3-pyridinamine, N-5-pyrimidinyl-5-pyrimidinamine, 4-butyl-N- (4-methylphenyl) -aniline, n is a radical of¹,N¹-dimethyl-N⁴-3-pyridyl-1, 4-phenylenediamine, N- (4-methoxyphenyl) -3-pyridylamine, 1, 9-dimethyl-10H-phenothiazine, N-phenyl-5-pyrimidinamine, 4- (trifluoromethyl) -N- [4- (trifluoromethyl) phenyl]-aniline, N-phenyl-2-pyridylamine, 2,4, 6-trimethyl-N- (2,4, 6-trimethylphenyl) aniline, N-phenyl-3-pyridylamine, 4- (1, 1-dimethylethyl) -N- [4- (1, 1-dimethylethyl) phenyl]Aniline, N¹,N¹-dimethyl-N⁴-phenyl-1, 4-phenylenediamine, N-3-pyridyl-3-pyridylamine, 4-nitro-N- (4-nitrophenyl) aniline, N- [1,1' -biphenylyl]-4-yl- [1,1' -biphenyl]-4-amine, 4-heptyl-N- (4-heptylphenyl) -aniline, 4- (1-phenylethyl) -N- [4- (1-phenylethyl) phenyl]-aniline, 4,4' -iminodibenzonitrile, 4-nonyl-N- (4-nonylphenyl) -aniline, N- (2, 4-dimethylphenyl) -2, 4-dimethyl-aniline, 4- (1,1,3, 3-tetramethylbutyl) -N- [4- (1,1,3, 3-tetramethylbutyl) phenyl-aniline]-aniline, 4- (1-methyl-1-phenylethyl) -N- [4- (1-methyl-1-phenylethyl) phenyl]-aniline, 4-octyl-N- (4-octylphenyl) -aniline, 3, 7-dichloro-10H-phenothiazine, 3, 7-dimethoxy-10H-phenothiazine, 4-methoxy-N-phenyl-aniline, N⁴- [4- (dimethylamino) phenyl group]-N¹,N¹-dimethyl-1, 4-phenylenediamine, 4-methyl-N- (4-methylphenyl) aniline, 1, 9-bis (1, 1-dimethylethyl) -10H-phenothiazine, 1, 9-dimethyl-10H-phenothiazine, 3, 7-dichloro-10H-phenothiazine, 3, 7-dimethoxy-10H-phenothiazine, 10, 11-dihydro-5H-dibenzo [ b, f ] phenothiazine, and pharmaceutically acceptable salts thereof]Aza derivatives10H-Phenylselenazine, 5H-Dibenzo [ b, f ]]Aza derivatives10H-phenoxazine, 10H-phenothiazine, 9, 10-dihydroacridine, 9H-carbazole, 2- (trifluoromethyl) -10H-phenoxazine, 2- (1, 1-dimethylethyl) -10H-phenoxazine, 3- (trifluoromethyl) -10H-phenoxazine, 3, 7-bis (trifluoromethyl) -10H-phenoxazine, 3- (1, 1-dimethylethyl) -10H-phenoxazine, 3- (N, N-diethylsulfonyl) -10H-phenoxazine, 10H-phenoxazine-3-carbonitrile, 3-nitro-10H-phenoxazine, 3-methoxy-10H-phenoxazine, 2,4,6, 8-tetrakis (1, 1-dimethylethyl) -10H-phenoxazine, 2, 8-bis (1, 1-dimethylethyl) -10H-phenoxazine, 3-methoxy-7-nitro-10H-phenoxazine, 7-nitro-10H-phenoxazine-3-carbonitrile, 3, 7-dimethoxy-10H-phenoxazine, 3, 7-bis (1, 1-dimethylethyl) -10H-phenoxazine, 7-fluoro-10H-phenoxazine-3-carbonitrile, 7- (diethylamino) -10H-phenoxazine-3-carbonitrile, 10H-phenoxazine-2, 3-dimethacryl, 3, 7-dinitro-10H-phenoxazine, 2-methyl-3-nitro-10H-phenoxazine, 2-ethyl-3-nitro-10H-phenoxazine, N, N-diethyl-7-nitro-10H-phenoxazine-3-amine, 2, 3-dinitro-10H-phenoxazine, 7-chloro-2-ethyl-3-nitro-10H-phenoxazine, N, N-diethyl-7-methoxy-10H-phenoxazine-3-amine and mixtures thereof.

In one aspect, it is preferred to use a substituted diarylamine antioxidant that does not yellow. In another aspect, the use of substituted diarylamine antioxidants known to form yellow by-products can be beneficial, for example, to help counteract the blue color formed by the conversion of leuco colorants in laundry care formulations. Antioxidants that form yellow byproducts can be avoided if they result in a perceived negative attribute in the consumer experience (e.g., deposition of such yellow byproducts on fabrics). The person skilled in the art is able to make an informed decision as to the choice of antioxidant to be used.

In one aspect, more hydrophilic antioxidants may be preferred, which are more easily removed from the fabric during the rinse step of the wash cycle than less hydrophilic antioxidants. As known to those skilled in the art, water solubility can be improved by attaching one or more hydrophilic groups to the antioxidant. The hydrophilic groups may be ionic, such as sulfate, phosphate or carboxylate groups, quaternary ammonium or betaine. The hydrophilic group may also be non-ionic, such as a hydroxyl group, or a polymer (or copolymer) chain comprising one or more hydrophilic monomers. Suitable hydrophilic monomers include, but are not limited to, ethylene oxide, ethylene imine, 2-hydroxyethyl (meth) acrylate, 1-vinyl-2-pyrrolidone, and vinyl alcohol. In one aspect, the antioxidant preferably has a partition coefficient (n-octanol/water) of less than 500000, more preferably less than 10000, even more preferably less than 500, most preferably less than 10, according to the EPA test guidelines document OPPTS 830.7550.

In one aspect, preferred antioxidants having hydrophilic groups can be selected from the following structures;

and mixtures thereof, wherein R⁵¹Selected from hydrogen and C₁-C₄Alkyl, preferably CH₃And a tertiary butyl group; each R⁵²Independently selected from hydrogen, CH₃、SO₃Na, succinate groups and groups corresponding to the formula:

wherein denotes a connection point; each R⁵³Independently selected from hydrogen or CH₃；R⁵⁴Selected from H, C1 to C16 alkyl and C2 to C16 alkenyl; g is selected from oxygen, sulfur or substituted nitrogen; a is 0 or 1; b is 0 or 1; d is 0 to 2, preferably 2; c. n and (x + y) may be any integer from 1 to 100. More preferably, c, n and x or y are greater than 3.

The present invention relates to a class of leuco colorants useful in laundry care compositions, such as liquid laundry detergents, to provide a shade that whitens textile substrates. Leuco colorants are compounds that are substantially colorless or only light in color but are capable of producing an intense color when activated. One advantage of using leuco compounds in laundry care compositions is that these compounds are colorless prior to activation, such that the laundry care composition exhibits its own color. Leuco colorants do not generally alter the primary color of the laundry care composition. Thus, manufacturers of these compositions can formulate colors that are most attractive to consumers without fear that added ingredients, such as bluing agents, affect the final color values of the compositions.

The amount of leuco compound used in the compositions of the present invention may be at any level suitable to achieve the purposes of the present invention. In one aspect, the composition comprises the leuco compound in an amount from about 1% to about 99% by weight, preferably from 2% to about 50% by weight, even more preferably from about 5% to about 20% by weight.

In another aspect, the composition comprises a leuco colorant in an amount of from 5.0 to 3000 meq/kg, preferably from 10 to 1500 meq/kg, even more preferably from 25 to 600 meq/kg, where the unit meq/kg refers to the number of milliequivalents of leuco groups per kg of composition. For leuco colorants comprising more than one leuco group, the number of milliequivalents is related to the number of millimoles of the leuco colorant by the formula: (mmoles of leuco colorant) × (mmoles of leuco groups/mmoles of leuco colorant) ═ number of milliequivalents of leuco groups. In the case where only one leuco group is present per leuco colorant, the number of milliequivalents/kg will be equal to the number of millimoles of leuco colorant per kg of composition.

In one aspect, the present invention relates to a leuco composition selected from the group consisting of diarylmethane leuco bodies, triarylmethane leuco bodies, oxazine leuco bodies, thiazine leuco bodies, hydroquinone leuco bodies, arylamino phenol leuco bodies, and mixtures thereof.

Diarylmethane leuco compounds suitable for use in the present invention include, but are not limited to, diarylmethylene derivatives capable of forming a second colored state as described herein. Suitable examples include, but are not limited to, Michler methane, diarylmethylene substituted with-OH groups (e.g., Michler alcohols) and ethers and esters thereof, diarylmethylene substituted with photocleavable groups such as-CN groups (bis (p-N, N-dimethyl) phenyl) acetonitrile), and similar such compounds.

In one aspect, the present invention relates to a composition comprising one or more leuco compounds conforming to a group selected from:

(f) and mixtures thereof;

wherein the ratio of formula I-V to its oxidized form is at least 1:19, 1:9 or 1:3, preferably at least 1:1, more preferably at least 3:1, most preferably at least 9:1 or even 19: 1.

In the structure of formula (I), each A, B and each individual R on the C ring_o、R_mAnd R_pThe radicals are independently selected from hydrogen, deuterium and R⁵(ii) a Each R⁵Independently selected from the group consisting of halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — (CH)₂)_n─O─R¹、─(CH₂)_n─NR¹R²、─C(O)R¹、─C(O)OR¹、─C(O)O^-、─C(O)NR¹R²、─OC(O)R¹、─OC(O)OR¹、─OC(O)NR¹R²、─S(O)₂R¹、─S(O)₂OR¹、─S(O)₂O^-、─S(O)₂NR¹R²、─NR¹C(O)R²、─NR¹C(O)OR²、─NR¹C(O)SR²、─NR¹C(O)NR²R³、─P(O)₂R¹、─P(O)(OR¹)₂、─P(O)(OR¹)O^-and-P (O)^-)₂Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; wherein A, B and two R on the C ring are different_oMay be combined to form five or more membered condensed rings; when the condensed ring is six-membered or more, different A,Two R on the B and C rings_oMay combine to form an organic linking group optionally containing one or more heteroatoms; in one embodiment, two R on different A, B and C rings_oCombine to form a heteroatom bridge selected from-O-and-S-, resulting in a six-membered fused ring; r on the same ring_oAnd R_mOr R on the same ring_mAnd R_pMay be combined to form a fused aliphatic ring or a fused aromatic ring, any of which may contain heteroatoms; at least one of the three rings A, B or C, R_oAnd R_mPreferably at least two, more preferably at least three, most preferably all four of the groups are hydrogen, preferably all four R's on at least two of the A, B and C rings_oAnd R_mThe radicals are hydrogen; in some embodiments, A, B and all R on the C ring_oAnd R_mThe radicals are all hydrogen; preferably, each R_pIndependently selected from hydrogen, -OR¹and-NR¹R²(ii) a Not more than 2R_pPreferably not more than one R_pIs hydrogen, preferably none is hydrogen; more preferably at least one R_pPreferably two R_pMost preferably all three R_pis-NR¹R²(ii) a In some embodiments, A, B and C wherein one or even both of the C rings can be independently selected₃-C₉A heteroaryl ring comprising one or two heteroatoms independently selected from O, S and N, optionally substituted with one or more independently selected R⁵Substituted by groups; g is independently selected from hydrogen, deuterium, C₁-C₁₆Alkoxides, phenoxides, biphenoxides, nitrites, nitriles, alkylamines, imidazoles, arylamines, polyalkylene oxides, halides, alkyl sulfides, aryl sulfides or phosphine oxides; in one aspect, the fraction of G [ (deuterium)/(deuterium + hydrogen)]Is at least 0.20, preferably at least 0.40, even more preferably at least 0.50, most preferably at least 0.60 or even at least 0.80; in which R is bound to the same heteroatom¹、R²And R³Any two of which may be combined to form a five or more membered ring, optionally containing one or more groups selected from-O-, -NR¹⁵-and-S-are further heteroatoms.

In the structures of formulae (II) - (III), e and f are independently integers from 0 to 4; each R²⁰And R²¹Independently selected from halogen, nitro, alkyl, substituted alkyl, — nc (o) OR¹、─NC(O)SR¹、─OR¹and-NR¹R²(ii) a Each R²⁵Independently selected from the group consisting of monosaccharide, disaccharide, oligosaccharide and polysaccharide groups, — C (O) R¹、─C(O)OR¹、─C(O)NR¹R²(ii) a Each R²²And R²³Independently selected from hydrogen, alkyl and substituted alkyl.

In the structure of formula (IV), wherein R³⁰Is located ortho OR para to the bridging amine group and is selected from-OR³⁸and-NR³⁶R³⁷Each R³⁶And R³⁷Independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, acyl, R⁴、─C(O)OR¹、─C(O)R¹And C (O) NR¹R²；R³⁸Selected from hydrogen, acyl, — C (O) OR¹、─C(O)R¹And C (O) NR¹R²(ii) a g and h are independently integers from 0 to 4; each R³¹And R³²Independently selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — (CH)₂)_n─O─R¹、─(CH₂)_n─NR¹R²、─C(O)R¹、─C(O)OR¹、─C(O)O^-、─C(O)NR¹R²、─OC(O)R¹、─OC(O)OR¹、─OC(O)NR¹R²、─S(O)₂R¹、─S(O)₂OR¹、─S(O)₂O^-、─S(O)₂NR¹R²、─NR¹C(O)R²、─NR¹C(O)OR²、─NR¹C(O)SR²、─NR¹C(O)NR²R³、─OR¹、─NR¹R²、─P(O)₂R¹、─P(O)(OR¹)₂、─P(O)(OR¹)O^-and-P (O)^-)₂Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; -NR³⁴R³⁵In ortho or para position to the bridging amine group, and R³⁴And R³⁵Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R⁴；R³³Independently selected from hydrogen, — S (O)₂R¹、─C(O)N(H)R¹；─C(O)OR¹(ii) a and-C (O) R¹(ii) a When g is 2 to 4, any two adjacent R³¹The groups may be joined to form five or more fused rings, wherein no more than two atoms in the fused rings may be nitrogen atoms.

In the structure of formula (V), wherein X⁴⁰Selected from oxygen atom, sulfur atom and NR⁴⁵；R⁴⁵Independently selected from hydrogen, deuterium, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — s (o)₂OH、─S(O)₂O^-、─C(O)OR¹、─C(O)R¹And C (O) NR¹R²；R⁴⁰And R⁴¹Independently selected from-CH₂)_n─O─R¹、─(CH₂)_n─NR¹R²Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; j and k are independently integers from 0 to 3; r⁴²And R⁴³Independently selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, — s (o)₂R¹、─C(O)NR¹R²、─NC(O)OR¹、─NC(O)SR¹、─C(O)OR¹、─C(O)R¹、─(CH₂)_n─O─R¹、─(CH₂)_n─NR¹R²Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; r⁴⁴is-C (O) R¹、─C(O)NR¹R²and-C (O) OR¹。

In the structures of formulae (I) - (V), any charge present in any of the foregoing groups therein is balanced by a suitable independently selected internal or external counterion. Suitable independently selected external counterions can be cationic or anionic. Examples of suitable cations include, but are not limited to, one or more metals, preferably selected from group I and group II metals, most preferably Na, K, Mg and Ca, or organic cations such as iminium, ammonium and phosphonium. Examples of suitable anions include, but are not limited to: fluoride, chloride, bromide, iodide, perchlorate, hydrogensulfate, sulfate, aminosulfate, nitrate, dihydrogenphosphate, hydrogenphosphate, phosphate, hydrogencarbonate, carbonate, methylsulfate, ethylsulfate, cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluoroborate, acetate, chloroacetate, cyanoacetate, hydroxyacetate, aminoacetate, methylamoacetate, dichloroacetate, trichloroacetate, 2-chloropropionate, 2-hydroxypropionate, glycolate, mercaptoglycolate, thioacetate, phenoxyacetate, pivalate, valerate, palmitate, acrylate, oxalate, malonate, crotonate, succinate, citrate, methylene-bis-thioglycolate, ethylene-bis-iminoacetate, Nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate, chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate, indoleacetate, chlorobenzenesulfonate, benzenesulfonate, toluenesulfonate, biphenyl sulfonate and chlorotoluenesulfonate. It will be clear to one of ordinary skill in the art that different counterions can be used in place of those listed above.

In the structures of formulae (I) to (V), R¹、R²、R³And R¹⁵Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R⁴(ii) a Wherein R is⁴Is an organic group consisting of one or more organic monomers having a molecular weight in the range of from 28 to 500, preferably from 43 to 350, even more preferably from 43 to 250, wherein said organic group may be substituted by one or more additional leuco colorant groups corresponding to the structure of formula I-V. In one aspect, R⁴Selected from alkyleneoxy radicals(polyethers), oxoalkyleneoxy (polyesters), oxoalkyleneamines (polyamides), epichlorohydrin, quaternized epichlorohydrin, alkyleneamines, hydroxyalkylene, acyloxyalkylene, carboxyalkylene, carbonylalkoxyalkylene and sugars. In one aspect, R⁴Selected from EO, PO, BO and mixtures thereof, more preferably from EO alone or from EO/PO mixtures. When any leuco colorant includes R having three or more contiguous monomers⁴When a group, the leuco colorant is defined herein as a "polymeric leuco colorant". Those skilled in the art know that the nature of a compound, which relates to any of a number of characteristic attributes, such as solubility, partitioning, deposition, removal, staining, etc., is related to the location, identity and amount of these adjacent monomers incorporated therein. Thus, the person skilled in the art can adjust the position, the nature and the number of these adjacent monomers, changing any particular property in a more or less predictable manner.

Preferred leuco colorants include those conforming to the structure of formula VI,

wherein each R⁴Independently selected from H, methyl, ethyl, ((CH)₂CH₂O)_a(C₃H₆O)_b) H and mixtures thereof; preferably at least one R⁴The radical being ((CH)₂CH₂O)_a(C₃H₆O)_b) H; wherein each index a is independently an integer from 1 to 100, each index b is independently an integer from 0 to 50, and wherein all R's are⁴The sum of all independently selected a integers in the group does not exceed 200, preferably 100, and all R⁴The sum of all independently selected b integers in the group is not more than 100, preferably not more than 50. Preferably at least two R⁴The groups are selected from methyl and ethyl, most preferably at least one N in structure VI is replaced by two R selected from methyl and ethyl, preferably methyl⁴And (4) substituting the group. When a non-depositing leuco colorant is desired, all R' s⁴The sum of all independently selected a integers in the group is not less than 20, preferably not less than 30, 40 or even not less than 50, and all R⁴The sum of all independently selected b integers in the group is no more than 20 or even no more than 10. In one aspect, the non-depositing leuco colorant may have a color distribution in all R' s⁴The sum of all independently selected b integers in the group is 0.

Highly preferred leuco colorants include those conforming to the structure of formula VII,

wherein each index c is independently 0,1 or 2, preferably each c is 1; each R⁴Independently selected from H, methyl, ethyl, ((CH)₂CH₂O)_a(C₃H₆O)_b) H and mixtures thereof; preferably each R⁴Is ((CH)₂CH₂O)_a(C₃H₆O)_b) H, wherein each index a is independently an integer from 1 to 50, more preferably from 1 to 25, even more preferably from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 5 or even from 1 to 2; each index b is independently an integer from 0 to 25, more preferably from 0 to 15, even more preferably from 1 to 5 or even from 1 to 3, and wherein the sum of all independently selected a integers in the leuco colorant does not exceed 100, more preferably does not exceed 80, most preferably does not exceed 60, 40, 20, 10 or even does not exceed 5, and the sum of all independently selected b integers in the leuco colorant does not exceed 50, more preferably does not exceed 40, most preferably does not exceed 30, 20 or even 10.

In one aspect, the leuco colorants and/or substituted diarylamines of the present invention have surface tension values greater than 45mN/m, more preferably greater than 47.5mN/m, and most preferably greater than 50 mN/m. In another aspect, the second color state of the leuco colorant has a surface tension value of greater than 45mN/m, more preferably greater than 47.5mN/m, and most preferably greater than 50 mN/m. In yet another aspect of the invention, the leuco colorants and their corresponding second color states each have a surface tension value of greater than 45mN/m, more preferably greater than 47.5mN/m, and most preferably greater than 50 mN/m.

The above leuco compounds are believed to be suitable for use in treating textile materials, for example, in a home laundering process. In particular, it is believed that the leuco compound may deposit on the fibers of the textile material due to the nature of the leuco compound. Furthermore, once deposited on the textile material, the leuco compound may be converted into a colored compound by application of a suitable chemical or physical trigger that converts the leuco compound into its colored form. For example, the leuco compound may be converted into its colored form by oxidizing the leuco compound to an oxidized compound. By selecting the appropriate leuco group, the leuco compound can be designed to impart a desired hue to the textile material when the leuco compound is converted into its colored form. For example, leuco compounds that exhibit a blue hue when converted to their colored form can be used to counteract the yellowing of textile materials that typically occurs as a result of the passage of time and/or repeated laundering. Accordingly, in other embodiments, the present invention provides laundry care compositions comprising the above-described leuco compounds, and domestic methods for treating textile materials (e.g., methods of washing laundry or articles of clothing).

Preferably, the leuco compound provides the cloth with a hue having a relative hue angle of 210 to 345, or even 240 to 320, or even 250 to 300 (e.g. 250 to 290). The relative hue angle may be determined by any suitable method known in the art. Preferably, however, it can be determined as described in further detail herein with respect to depositing the leuco entity on cotton relative to cotton without any leuco entity.

In a preferred embodiment, the hue angle of the laundry care composition and the relative hue angle provided by the leuco colorant are different. Preferably, the laundry care composition has a hue angle and a relative hue angle provided by the leuco colorant (both described in further detail herein) of at least 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 105, 120, 140 and 160 from each other.

In one embodiment, the present invention provides a laundry care composition comprising at least one laundry care ingredient, a leuco composition and a stabilizing amount of an antioxidant composition comprising at least one sterically hindered phenol and at least one substituted diarylamine, the antioxidant composition having a Color Formation Index (Color Formation Index) of less than or equal to 75, preferably less than or equal to 50, more preferably less than or equal to 40, even more preferably less than or equal to 30, most preferably less than or equal to 20 or even 10, as determined according to the methods disclosed herein.

The compositions of the present invention may optionally comprise a solvent system. The solvent system can utilize any material that facilitates formation of a stable mixture of the leuco composition and the antioxidant. Preferably, the solvent system comprises harmless components. In a preferred embodiment, the solvent system comprises at least one component selected from the group consisting of: water, ethanol, ethylene glycol, propylene carbonate, ethylene carbonate, polyalkylene oxide, polyester, polycarbonate, polyaziridine, nonionic surfactant, and mixtures thereof. More preferably, the solvent system comprises a component selected from the group consisting of water, propylene glycol, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, nonionic surfactants, and mixtures thereof. In such embodiments, the polyethylene glycol, polypropylene glycol, and copolymers of ethylene glycol and propylene glycol used in the solvent system may contain polymer chains that are capped with end groups selected from alkoxy groups, alkylcarbonyloxy groups, aryloxy groups, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium groups, and sugar groups. In a particularly preferred embodiment, the solvent system comprises a nonionic surfactant, such as the nonionic surfactants disclosed later in this application as laundry care ingredients.

Laundry care compositions

Surfactant system

The products of the present invention may include about 0.00 wt%, more typically about 0.10 to 80 wt% of a surfactant. In one aspect, these compositions can include about 5% to 50% by weight of a surfactant. The surfactant used may be anionic, nonionic, amphoteric, zwitterionic or cationic, or may comprise compatible mixtures of these types. If the fabric care product is a laundry detergent, anionic and nonionic surfactants are typically used. On the other hand, if the fabric care product is a fabric softener, cationic surfactants are typically used.

Anionic surfactants

Useful anionic surfactants can themselves be of several different types. For example, water soluble salts of higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions of the present invention. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, or even from about 12 to about 18 carbon atoms. Soaps can be prepared by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, i.e., tallow and sodium or potassium coconut soaps.

Preferred alkyl sulfates are C8-18 alkyl alkoxylated sulfates, preferably C12-15 alkyl or hydroxyalkyl alkoxylated sulfates. Preferably, the alkoxylated group is an ethoxylated group. Typically, the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 30 or 20, or from 0.5 to 10. The alkyl group may be branched or straight-chain. The alkoxylated alkyl sulfate surfactant may be a mixture of alkoxylated alkyl sulfates having an average (arithmetic mean) carbon chain length of from about 12 to about 30 carbon atoms, or an average carbon chain length of from about 12 to about 15 carbon atoms, an average (arithmetic mean) degree of alkoxylation of from about 1 mole to about 4 moles of ethylene oxide, propylene oxide, or mixtures thereof, or an average (arithmetic mean) degree of alkoxylation of about 1.8 moles of ethylene oxide, propylene oxide, or mixtures thereof. The alkoxylated alkyl sulfate surfactant may have a carbon chain length of from about 10 carbon atoms to about 18 carbon atoms and a degree of alkoxylation of from about 0.1 to about 6 moles of ethylene oxide, propylene oxide, or mixtures thereof. The alkoxylated alkyl sulfates may be alkoxylated with ethylene oxide, propylene oxide or mixtures thereof. The alkyl ether sulfate surfactant may contain a peaked ethoxylate distribution. Specific examples include derivativesFrom ShellC12-C15 EO 2.5 sulfates, C14-C15 EO 2.5 sulfates and C12-C15 EO 1.5 sulfates of alcohols, and C12-C14 EO3 sulfates, C12-C16 EO3 sulfates, C12-C14 EO2 sulfates and C12-C14 EO1 sulfates derived from natural alcohols from Huntsman. AES may be linear, branched, or a combination thereof. The alkyl group may be derived from synthetic or natural alcohols, such as that sold under the trade name ShellProvided of SasolAndor midcut alcohols from vegetable oils such as coconut and palm kernel. Another suitable anionic detersive surfactant is an alkyl ether carboxylate comprising C10-C26 linear or branched, preferably C10-C20 linear, most preferably C16-C18 linear alkyl alcohols and from 2 to 20, preferably from 7 to 13, more preferably from 8 to 12, most preferably from 9.5 to 10.5 ethoxylates. Acid or salt forms, such as sodium or ammonium salts, may be used and the alkyl chain may contain one cis or trans double bond. The alkyl ether carboxylic acid can be obtained from KaoHuntsmanAnd ClariantAnd (4) obtaining.

Other useful anionic surfactants may include alkali metal salts of alkylbenzene sulfonic acids wherein the alkyl group contains from about 9 to about 15 carbon atoms in a linear or branched configuration. In some embodiments, the alkyl group is linear. These linear alkylbenzene sulfonates are known as "LAS". In other embodiments, the linear alkylbenzene sulfonate may have an average number of carbon atoms in the alkyl group of from about 11 to 14. In one particular embodiment, the linear alkylbenzene sulfonate may have an average number of carbon atoms in the alkyl group of about 11.8 carbon atoms, which may be abbreviated as C11.8 LAS. A preferred sulfonate is C10-13 alkylbenzene sulfonate. Suitable alkyl benzene sulfonates (LAS) may be obtained by sulfonating commercially available Linear Alkyl Benzenes (LAB); suitable LAB include low 2-phenyl LAB, such as that sold under the trade name SasolThose provided or under the trade name PetresaOther suitable LABs include high 2-phenyl LABs such as those provided by Sasol under the trade name SasolThose provided. Suitable anionic detersive surfactants are alkyl benzene sulphonates obtained by DETAL catalyzed processes, although other synthetic routes such as HF may also be suitable. In one aspect, a magnesium salt of LAS is used. Anionic sulfonate surfactants suitable for use in the present invention include water soluble salts of C8-C18 alkyl or hydroxyalkyl sulfonic acids; C11-C18 alkyl benzene sulphonate (LAS), modified alkyl benzene sulphonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549 and WO 00/23548; methyl Ester Sulfonate (MES); and alpha-olefin sulfonates (AOS). Those also include paraffin sulfonates, which may be mono-and/or di-sulfonates, obtained by sulfonating paraffins of 10 to 20 carbon atoms. The sulfonate surfactant may also include an alkyl glyceryl sulfonate surfactant.

The anionic surfactants of the present invention may be present in the acid form, and the acid form may be neutralized to form the surfactant salts desired for use in the detergent compositions of the present invention. Typical reagents for neutralization include metal counter-ion bases such as hydroxides, e.g., NaOH or KOH. Other preferred agents for neutralizing the anionic surfactants and co-anionic surfactants or co-surfactants in acid form of the present invention include ammonia, amines or alkanolamines. Alkanolamines are preferred. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; for example, highly preferred alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine or 1-amino-3-propanol.

Nonionic surfactant

Preferably, the composition comprises a nonionic detersive surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols. The nonionic surfactant can be selected from those having the formula R (OC)₂H₄)_nOH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals having from about 8 to about 15 carbon atoms, and alkylphenyl radicals having from about 8 to about 12 carbon atoms in the alkyl radical, and n has an average value of from about 5 to about 15. Other non-limiting examples of nonionic surfactants useful in the present invention include: C8-C18 alkyl ethoxylates, e.g. from ShellA nonionic surfactant; C6-C12 alkylphenol alkoxylates wherein the alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof; condensates of C12-C18 alcohols and C6-C12 alkylphenols with ethylene oxide/propylene oxide block polymers, e.g. of BASFC14-C22 medium chain branched alcohol, BA; C14-C22 mid-chain branched alkyl alkoxylates, BAE_XWherein x is 1 to 30; an alkyl polysaccharide; in particular alkyl polyglycosides; polyhydroxy fatty acid amides; and ether-terminated poly (oxyalkylated) alcohol surfactants. Specific examples include C12-C15 EO7 and C14-C15 EO7 from ShellNonionic surfactantC12-C14 EO7 and C12-C14 EO9 from HuntsmanA nonionic surfactant.

Highly preferred nonionic surfactants are the condensation products of Guerbet alcohols (Guerbet alcohols) with from 2 to 18 moles, preferably from 2 to 15, more preferably from 5 to 9, of ethylene oxide per mole of alcohol. Suitable nonionic surfactants include those available from BASF under the trade name BASFThose of (a). Lutensol XP-50 is a Guerbet ethoxylate containing an average of about 5 ethoxy groups. The Lutensol XP-80 contains an average of about 8 ethoxy groups. Other suitable nonionic surfactants for use herein include fatty alcohol polyglycol ethers, alkyl polyglucosides and fatty acid glucamides, alkyl polyglucosides based on Guerbet alcohols.

Amphoteric surfactant (Amphoteric surfactant)

The surfactant system may include an amphoteric surfactant, such as an amine oxide. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amidopropyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides, especially coco dimethyl amine oxide. The amine oxide may have a linear or intermediately branched alkyl portion.

Amphoteric surfactant (Ampholytic surfactant)

The surfactant system may include an amphoteric surfactant. Specific non-limiting examples of amphoteric surfactants include: aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight-chain or branched. One of the aliphatic substituents can contain at least about 8 carbon atoms, for example from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. For suitable examples of amphoteric surfactants, see U.S. Pat. No.3,929,678 at column 19, lines 18-35.

Zwitterionic surfactants (zwitterionics surfactants)

Zwitterionic surfactants are known in the art and generally include surfactants that are generally electrically neutral but carry at least one positively charged atom/group and at least one negatively charged atom/group. Examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. For examples of zwitterionic surfactants, see U.S. Pat. No.3,929,678 at column 19, line 38 to column 22, line 48; betaines, including alkyldimethyl betaine and coco dimethyl amidopropyl betaine, C₈To C₁₈(e.g. C)₁₂To C₁₈) Amine oxides and sulpho and hydroxy betaines, e.g. N-alkyl-N, N-dimethylamino-1-propanesulphonates, where the alkyl radical may be C₈To C₁₈And in certain embodiments may be C₁₀To C₁₄. A preferred zwitterionic surfactant for use in the present invention is cocamidopropyl betaine.

Cationic surfactants (Cationic surfactants)

Examples of cationic surfactants include quaternary ammonium surfactants, which specifically may have up to 26 carbon atoms. Additional examples include a) Alkoxylated Quaternary Ammonium (AQA) surfactants, as described in U.S. patent No. 6,136,769; b) dimethyl hydroxyethyl quaternary ammonium, as described in U.S. Pat. No. 6,004,922; c) polyamine cationic surfactants, such as described in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006, which are incorporated herein by reference; d) cationic ester surfactants, as described in U.S. patent nos. 4,228,042, 4,239,660, 4,260,529 and U.S. patent No. 6,022,844, which are incorporated herein by reference; and e) an amino surfactant, as described in U.S. Pat. No. 6,221,825 and WO 00/47708, which are incorporated herein by reference, particularly amidopropyldimethylamine (APA). Useful cationic surfactants also include U.S. Pat. No. 4,222 issued to Cockrell at 16.9.1980905, and Murphy, in U.S. patent No. 4,239,659 issued at 16.12.1980, both of which are also incorporated herein by reference. The quaternary ammonium compound may be present in a fabric enhancer composition, such as a fabric softener, and comprises a quaternary ammonium cation which is NR₄ ⁺A positively charged polyatomic ion of structure wherein R is an alkyl or aryl group.

The fabric care compositions of the present invention may comprise up to about 30%, alternatively from about 0.01% to about 20%, more alternatively from about 0.1% to about 20%, by weight of the composition, of a cationic surfactant. For purposes of the present invention, cationic surfactants include those surfactants which provide fabric care benefits. Non-limiting examples of useful cationic surfactants include: fatty amines, imidazoline quaternary ammonium materials and quaternary ammonium surfactants, preferably N, N-bis (stearoyl-oxy-ethyl) N, N-dimethylammonium chloride, N-bis (tallowoyloxy-ethyl) N, N-dimethylammonium chloride, N-bis (stearoyl-oxy-ethyl) N- (2-hydroxyethyl) N-methylammonium methylsulfate; 1,2 bis (stearoyloxy) 3 trimethylammonium propane chloride; dialkylene dimethyl ammonium salts such as ditallocaine dimethyl ammonium chloride, di (hard) tallow dimethyl ammonium chloride, ditallocaine dimethyl ammonium methyl sulfate; 1-methyl-1-stearoylaminoethyl-2-stearoylimidazolium methyl sulfate; 1-tallowamidoethyl-2-tallowimidazoline; n, N "-dialkyldiethylenetriamine; esterification of the reaction product of N- (2-hydroxyethyl) -1, 2-ethylenediamine or N- (2-hydroxyisopropyl) -1, 2-ethylenediamine with glycolic acid with fatty acids, wherein the fatty acids are (hydrogenated) tallow fatty acid, palm fatty acid, hydrogenated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid; polyglycerol esters (PGEs), oily sugar derivatives and wax emulsions and mixtures thereof.

It is to be understood that combinations of the above disclosed softener actives are suitable for use in the present invention.

Additive for assisting cleaning

The laundry care compositions of the present invention may also contain adjunct cleaning additives. The precise nature of the cleaning adjunct additive and its level of incorporation will depend on the physical form of the laundry care composition, as well as the exact nature of the cleaning operation in which it is used.

The secondary cleaning additives may be selected from self-cleaning agents (building ders), structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, polymeric dispersing agents, polymeric grease cleaners, enzymes, enzyme stabilizing systems, bleaching compounds, bleaches, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibitors, chelants, suds suppressors (suds supressors), softeners and perfumes. The list of supplemental detergent additives herein is merely exemplary and is not intended to limit the types of supplemental detergent additives that may be used. In principle, any supplemental cleaning additive known in the art can be used in the present invention.

Polymer and method of making same

The composition may include one or more polymers. Non-limiting examples include polyethyleneimine, carboxymethylcellulose, poly (vinylpyrrolidone), poly (ethylene glycol), poly (vinyl alcohol), poly (vinylpyridine-N-oxide), poly (vinylimidazole), polycarboxylate or Alkoxylated Substituted Phenol (ASP), all of which may be optionally modified, as described in WO 2016/041676. Examples of ASP dispersants include, but are not limited to, hospal BV CONC S1000 available from Clariant.

Polyamines can be used for grease removal, particle removal, or soil removal. Various amines and polyalkyleneimines can be alkoxylated to varying degrees to achieve hydrophobic or hydrophilic cleaning. These compounds may include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylene diamine, and sulfated versions thereof. Useful examples of these polymers are HP20 available from BASF or a polymer having the following general structure or sulfated or sulfonated variants thereof:

bis ((C)₂H₅O)(C₂H₄O)_n)(CH₃)-N+-C_xH_2x-N+-(CH₃) -bis ((C)₂H₅O)(C₂H₄O)_n) Wherein n is 20 to 30 and x is 3 to 8. Can also be usedPolypropoxylated-polyethoxylated amphiphilic polyethyleneimine derivatives are included to achieve better grease removal and emulsification. These may include alkoxylated polyalkyleneimines, preferably having an internal polyethylene oxide block and an external polypropylene oxide block. The detergent composition may also contain unmodified polyethyleneimine, which may be used to enhance beverage stain removal. PEI's having various molecular weights are available under the trade name BASF CorporationCommercially available, examples of suitable PEI include, but are not limited to, LupasolLupasol

The composition may include one or more carboxylate polymers, such as a maleate/acrylate random copolymer or a polyacrylate homopolymer, which may be used as a polymeric dispersant. Alkoxylated polycarboxylates such as those prepared from polyacrylates may also be used to provide clay dispersibility. These materials are described in WO 91/08281. Chemically, these materials include polyacrylates having one ethoxy side chain per 7-8 acrylate units. The side chain has the formula- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2 to 3 and n is 6 to 12. The side chains are esters or ethers linked to the polyacrylate "backbone" to provide a "comb" polymeric structure.

Preferred amphiphilic graft copolymers include (i) a polyethylene glycol backbone; and (ii) at least one side chain moiety selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, and mixtures thereof. An example of an amphiphilic graft copolymer is Sokalan HP22 supplied by BASF.

Alkoxylated substituted phenols as described in WO 2016/041676 are also suitable examples of polymers to provide clay dispersibility. Hostapal BV Conc S1000, available from Clariant, is one non-limiting example of an ASP dispersant.

Preferably, the composition comprises one or more soil release polymers. Suitable soil release polymers are polyester soil release polymers such as Rebel-o-tex polymers, including Rebel-o-tex SF, SF-2 and SRP6 supplied by Rhodia. Other suitable soil release polymers include Texcare polymers including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN260, SRN300, and SRN325, available from Clariant. Other suitable soil release polymers are Marloquest polymers such as Marloquest SL supplied by Sasol, HSCB, L235M, B, G82. Other suitable soil release polymers include methyl terminated ethoxylated propoxylated soil release polymers as described in US9,365,806.

Preferably, the composition comprises one or more polysaccharides, which may be chosen in particular from carboxymethyl cellulose, methylcarboxymethyl cellulose, sulfoethyl cellulose, methylhydroxyethyl cellulose, carboxymethyl xyloglucan, carboxymethyl xylan, sulfoethyl galactomannan, carboxymethyl galactomannan, hydroxyethyl galactomannan, sulfoethyl starch, carboxymethyl starch and mixtures thereof. Other polysaccharides suitable for use in the present invention are dextrans. The preferred dextran is poly alpha-1, 3-dextran, which is a polymer comprising glucose monomer units linked together by glycosidic bonds (i.e., glucosidic bonds), wherein at least about 50% of the glycosidic bonds are alpha-1, 3-glycosidic bonds. Poly alpha-1, 3-glucan is a polysaccharide. Poly alpha-1, 3-glucan can be enzymatically produced from sucrose using one or more glucosyltransferases, for example, as described in U.S. patent No. 7,000,000 and U.S. patent application publication nos. 2013/0244288 and 2013/0244287 (all of which are incorporated herein by reference).

Other suitable polysaccharides for use in the composition are cationic polysaccharides. Examples of cationic polysaccharides include cationic guar derivatives, quaternary nitrogen-containing cellulose ethers, and synthetic polymers that are copolymers of etherified cellulose, guar and starch. When used, the cationic polymers of the present invention are soluble in the composition or in the complex coacervate phase in the composition formed by the cationic polymer and the anionic, amphoteric and/or zwitterionic surfactant component described above. Suitable cationic polymers are described in U.S. Pat. nos. 3,962,418; 3,958,581; and U.S. patent application publication No. 2007/0207109a 1.

The polymers may also be used as deposition aids for other detergent materials. Preferred deposition aids are selected from cationic and nonionic polymers. Suitable polymers include cationic starch, cationic hydroxyethyl cellulose, polyvinyl formaldehyde, locust bean gum, mannan, xyloglucan, tamarind gum, polyethylene terephthalate and polymers containing dimethylaminoethyl methacrylate and optionally one or more monomers selected from acrylic acid and acrylamide.

Other amines

Polyamines are known to improve grease removal. The preferred cyclic and linear amines for performance are 1, 3-bis (methylamine) -cyclohexane, 4-methylcyclohexane-1, 3-diamine (Baxxodur ECX 210 from BASF), 1, 3-propanediamine, 1, 6-hexanediamine, 1, 3-pentanediamine (dyek EP from Invista), 2-methyl 1, 5-pentanediamine (dyek a from Invista). US6710023 discloses hand dishwashing compositions containing said diamines and polyamines containing at least 3 protonatable amines. The polyamines according to the present invention have at least one pka above the wash pH and at least two pka above about 6 and below the wash pH. Preferred polyamines are selected from tetraethylenepentamine, hexaethylhexamine, heptaethylheptamine, octaethyloctamine, nonaethylnonanamine, and mixtures thereof, commercially available from Dow, BASF, and Huntman. Particularly preferred polyetheramines are lipophilically modified, as described in US9752101, US9487739, US 9631163.

Dye Transfer Inhibitors (DTI)

The composition may include one or more dye transfer inhibiting agents. In one embodiment of the present invention, the inventors have surprisingly found that compositions comprising polymeric dye transfer inhibiting agents in addition to the specified dyes have improved performance. This is surprising because these polymers prevent dye deposition. Suitable dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylsOxazolidinones and polyvinylimidazoles or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, Chromabond S-400, Chromabond S-403E and Chromabond S-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59, from BASF,HP 56K、HP 66. Other suitable DTIs are described in WO 2012/004134. When present in the subject compositions, the dye transfer inhibiting agents may be present at a level of from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from about 0.1% to about 3% by weight of the composition.

Enzyme

Enzymes may be included in laundry care compositions for a variety of purposes, including the removal of protein-based, carbohydrate-based or triglyceride-based stains from substrates, for the prevention of shed dye transfer in fabric washing, and for fabric repair. Suitable enzymes include proteases, amylases, lipases, carbohydrases, cellulases, oxidases, peroxidases, mannanases and mixtures thereof of any suitable origin, e.g., of plant, animal, bacterial, fungal and yeast origin. Other enzymes useful in the laundry care compositions described herein include hemicellulases, peroxidases, proteases, cellulases, endoglucanases, xylanases, lipases, phospholipases, amylases, glucoamylases, xylanases, esterases, cutinases, pectinases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof, esterases, mannanases, pectate lyases, and/or mixtures thereof. Other suitable enzymes include nucleases. The composition can include a nuclease. Nucleases are enzymes that are capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids. The nuclease herein is preferably a deoxyribonuclease or ribonuclease or a functional fragment thereof. Enzyme selection is influenced by factors such as pH activity and/or optimum stability, thermostability, and stability to active detergents, builders, etc.

The enzyme may be added to the laundry care composition at a level of from 0.0001 wt% to 5 wt% active enzyme of the laundry care composition. The enzymes may be added as a single component alone or as a mixture of two or more enzymes.

In some embodiments, a lipase may be used. Lipases are commercially available from novozymes (denmark) under the trade name Lipex. Amylase (A)Stainzyme) Available from Novozymes, Bagsvaerd, Denmark. The protease may be produced by Genencor International, Palo Alto, Calif., USA (e.g., Purafect)) Or Novozymes, Bagsvaerd, Denmark (e.g. ) Provided is a method. Other preferred enzymes include pectate lyases, preferably under the trade name pectate lyase Those sold under the trade nameMannanases sold (all from Novozymes A/S, Bagsvaerd, Denmark)) And(Genencor International Inc., Palo Alto, California). WO 9307263A; WO 9307260A; WO 8908694A; U.S. patent nos. 3,553,139; 4,101,457, respectively; and a series of enzyme materials and methods for their incorporation into synthetic laundry care compositions are disclosed in U.S. patent No. 4,507,219. Enzymatic materials useful in liquid laundry care compositions and methods of incorporating such compositions are disclosed in U.S. patent No. 4,261,868.

Enzyme stabilizing system

The enzyme-containing compositions described herein may optionally include an enzyme stabilizing system in an amount from about 0.001% to about 10%, in some embodiments from about 0.005% to about 8%, and in other embodiments, from about 0.01% to about 6% by weight of the composition. The enzyme stabilizing system may be any stabilizing system compatible with detersive enzymes. Such systems may be provided internally by other formulation actives or added separately, for example by the formulator or the manufacturer of the detergent enzyme. Such stabilizing systems may, for example, include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, chlorine bleach scavengers, and mixtures thereof, and are designed to address different stabilization issues depending on the type and physical form of the laundry care composition. For a review of borate stabilizers see U.S. Pat. No. 4,537,706.

Chelating agents

Preferably, the composition comprises a chelating agent and/or a crystal growth inhibitor. Suitable molecules include copper, iron and/or manganese chelating agents and mixtures thereof. Suitable molecules include aminocarboxylates, aminophosphonates, succinates, salts thereof, and mixtures thereof. Non-limiting examples of suitable chelating agents for use in the present invention include ethylene diamine tetra acetate, N- (hydroxyethyl) -ethylene-diamine-triacetate, nitrilotriacetate, ethylene diamine tetra propionate, triethylene tetramine hexanoate, diethylene triamine pentaacetate, ethanol diglycine, ethylene diamine tetra (methylene phosphonate), diethylene triamine penta (methylene phosphonic acid) (DTPMP), Ethylene Diamine Disuccinate (EDDS), hydroxy ethane dimethylene phosphonic acid (HEDP), Methyl Glycine Diacetic Acid (MGDA), Diethylene Triamine Pentaacetic Acid (DTPA) and 1, 2-dihydroxybenzene-3, 5-disulfonic acid (Tiron), salts thereof and mixtures thereof. Tiron and other sulfonated catechols may also be used as effective heavy metal chelators. Other non-limiting examples of chelating agents useful in the present invention are found in U.S. patent nos. 7445644, 7585376, and 2009/0176684a 1. Other suitable chelating agents for use in the present invention are the commercial DEQUEST series, as well as chelating agents from Monsanto, DuPont and Nalco Inc.

Brightening agent

Optical brighteners or other brightening or whitening agents may be incorporated into the laundry care compositions described herein at levels from about 0.01% to about 1.2% by weight of the composition. Commercial optical brighteners which may be used herein may be classified into subgroups including, but not necessarily limited to, derivatives of: stilbene (stilbene), pyrazoline, coumarin, carboxylic acids, methine cyanine, dibenzothiophene-5, 5-dioxide, azoles, 5-and 6-membered ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents," M.Zahradnik, John Wiley & Sons, New York (1982). Specific non-limiting examples of optical brighteners that can be used in the compositions of the present invention are those described in U.S. Pat. No. 4,790,856 and U.S. Pat. No.3,646,015. Very preferred brighteners include disodium 4,4 '-bis { [ 4-anilino-6- [ bis (2-hydroxyethyl) amino-s-triazin-2-yl ] -amino } -2,2' -stilbene disulfonate, disodium 4,4 '-bis { [ 4-anilino-6-morpholino-s-triazin-2-yl ] -amino } -2,2' -stilbene disulfonate, 4,4 "-bis [ (4, 6-di-anilino-s-triazin-2-yl) -amino ] -2,2 '-stilbene disulfonic acid disodium and 4,4' -bis- (2-sulfostyryl) biphenyl disodium.

Bleaching agent

The composition preferably comprises one or more bleaching agents. Suitable bleaching agents include photobleaches, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, and mixtures thereof.

(1) Photobleaches such as sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanine, xanthene dyes, and mixtures thereof;

(2) preformed peracid: suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of: preformed peroxyacids or salts thereof, usually percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, e.g.And mixtures thereof. Suitable examples include peroxycarboxylic acids or salts thereof, or peroxysulfonic acids or salts thereof. A particularly preferred peroxy acid is phthalimido-peroxy-alkanoic acid, particularly epsilon-phthalimido peroxy caproic acid (PAP). Preferably, the melting point of the peroxyacid or salt thereof ranges from 30 ℃ to 60 ℃.

(3) Sources of hydrogen peroxide, such as inorganic perhydrate salts, include alkali metal salts such as sodium salts as follows: perborate (usually as a monohydrate or tetrahydrate), percarbonate, persulfate, perphosphate, persilicate and mixtures thereof.

Fabric shading dye (shading dyes)

Fabric shading dyes (sometimes referred to as hueing agents, bluing agents, or brighteners) typically provide a blue or violet shade to the fabric. Such dyes are well known in the art and may be used alone or in combination to produce a particular shade of hueing and/or to tint different fabric types. The fabric shading dye may be selected from any chemical class of dyes known in the art including, but not limited to, acridines, anthraquinones (including polycyclic quinones), azines, azos (e.g., monoazo, disazo, trisazo, tetrazo, polyazo), benzodifurans, benzodifuranones, carotenoids, coumarins, cyanines, diaza hemicyanines, diphenylmethanes, formazans, hemicyanines, indigoids, methanes, naphthalimides, naphthoquinones, nitro groups, nitroso groups, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof. The amount of adjunct fabric shading dye present in the laundry care compositions of the present invention is generally from 0.0001 to 0.05 wt%, preferably from 0.0001 to 0.005 wt%, based on the total laundry care composition. The concentration of the fabric shading dye is generally from 1ppb to 5ppm, preferably from 10ppb to 500ppb, based on the washing liquor.

Suitable fabric shading dyes include small molecule dyes, polymeric dyes, and dye-clay conjugates. Preferred fabric shading dyes are selected from small molecule dyes and polymeric dyes. Suitable small molecule dyes may be selected from dyes falling into the color index (c.i., Society of Dyers and Colourists, Bradford, UK) classification of acid dyes, direct dyes, basic dyes, reactive dyes, solvent dyes or disperse dyes.

Suitable polymeric dyes include dyes selected from polymers containing covalently bonded (sometimes referred to as conjugated) chromogens (also referred to as dye-polymer conjugates), such as polymers having chromogen monomers copolymerized into the polymer backbone and mixtures thereof. Preferred polymeric dyes include optionally substituted alkoxylated dyes, such as alkoxylated triphenylmethane polymer colorants, alkoxylated carbocyclic and alkoxylated heterocyclic azo colorants, including alkoxylated thiophene polymer colorants, and mixtures thereof, for example, toFabric substantive colorants sold under the name (Milliken, Spartanburg, South Carolina, USA).

Suitable dye clay conjugates include dye clay conjugates selected from at least one cationic/basic dye and montmorillonite clay; preferred clays can be selected from montmorillonite clays, hectorite clays, saponite clays, and mixtures thereof.

Pigments are well known in the art and may also be used in the laundry care compositions herein. Suitable pigments include c.i. pigment Blue 15 to 20, in particular 15 and/or 16, c.i. pigment Blue 29, c.i. pigment violet 15, Monastral Blue and mixtures thereof.

Builder

The laundry care compositions of the present invention may optionally include a builder.

Builders selected from the group consisting of aluminosilicates and silicates can help control mineral hardness in wash water or can help remove particulate soils from surfaces. Suitable builders may be selected from phosphates, polyphosphates, especially their sodium salts; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sodium sesquicarbonate; organic monocarboxylates, dicarboxylates, tricarboxylates and tetracarboxylic acids, especially water-soluble non-surfactant carboxylates in the form of the acid, sodium salt, potassium salt or alkanolammonium salt, and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types; and phytic acid. These may be supplemented with borates, for example for pH buffering purposes, or sulfates (especially sodium sulfate) and any other fillers or carriers that may be important for the design of stable surfactant and/or builder containing laundry care compositions.

pH buffer system

The composition may also include a pH buffering system. The laundry care compositions of the present invention may be formulated such that the pH of the wash water, when used in an aqueous cleaning operation, is between about 6.0 and about 12, and in some examples between about 7.0 and 11. Techniques for controlling pH at the recommended usage levels include the use of buffers, bases, or acids, and are well known to those skilled in the art. These include, but are not limited to, the use of sodium carbonate, citric acid or sodium citrate, monoethanolamine or other amines, boric acid or borates, and other pH adjusting compounds well known in the art. The laundry care compositions herein may include a dynamic in-wash pH profile by delaying the release of citric acid.

Structurants/thickeners

The structured liquid may be internally structured, such that the structure is formed from a major component (e.g., a surfactant material), and/or externally structured by providing a three-dimensional matrix structure using a minor component (e.g., a polymer, clay, and/or silicate material). The composition may include from about 0.01% to about 5%, in some embodiments from about 0.1% to about 2.0% by weight of the composition of the structuring agent. The structuring agent may be selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulose-based materials, microfibrillar cellulose, biopolymers, xanthan gum, gellan gum, and mixtures thereof. In some examples, suitable structurants include hydrogenated castor oil and non-ethoxylated derivatives thereof. Other suitable structurants are disclosed in U.S. patent No. 6,855,680. Such structurants have a linear structuring system with a range of aspect ratios. Other suitable structurants and methods for their preparation are described in WO 2010/034736.

Suds suppressor

Compounds for reducing or inhibiting foam formation may be incorporated into the laundry care compositions described herein. Suppression of foam is particularly important in the so-called "high consistency cleaning process" described in us patent nos. 4,489,455, 4,489,574, as well as in drum washing machines.

A variety of materials can be used as suds suppressors, which are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3 rd edition, volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples of suds suppressors include monocarboxylic fatty acids and soluble salts thereof, high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C18-C40 ketones (e.g., stearyl ketone), N-alkylated aminotriazines, waxy hydrocarbons having a melting point preferably below about 100 ℃, silicone suds suppressors, and secondary alcohols. Suds suppressors are described in U.S. Pat. nos. 2,954,347; 4,075,118, respectively; 4,265,779, respectively; 4,265,779, respectively; 3,455,839; 3,933,672; 4,652,392; 4,978,471, respectively; 4,983,316, respectively; 5,288,431, respectively; 4,639,489, respectively; 4,749,740, respectively; and 4,798,679.

The laundry care compositions of the present invention may comprise from 0% to about 10% by weight of the composition of suds suppressors. When used as suds suppressors, the monocarboxylic fatty acids and salts thereof may be present in amounts up to about 5% by weight of the laundry care composition, and in some examples, from about 0.5% to about 3% by weight of the laundry care composition. The silicone suds suppressors can be used in amounts up to about 2.0 wt.% of the laundry care composition, and higher amounts can also be used. Monostearyl phosphate suds suppressors can be used in amounts of from about 0.1% to about 2% by weight of the laundry composition. The hydrocarbon suds suppressors can be used in amounts of from about 0.01% to about 5.0% by weight of the laundry care composition, although higher levels can also be used. Alcohol suds suppressors can be used at from about 0.2% to about 3% by weight of the laundry care composition.

Foam accelerator

If high sudsing is desired, suds boosters such as C10-C16 alkanolamides may be incorporated into laundry care compositions at from about 1% to about 10% by weight of the laundry care composition. Some examples include C10-C14 monoethanol and diethanolamide. If desired, water soluble magnesium and/or calcium salts such as MgCl may be added at levels of from about 0.1% to about 2% by weight of the laundry care composition₂、MgSO₄、CaCl₂、CaSO₄Etc. to provide additional foam and improve grease removal performance.

Fillers and carriers

Fillers and carriers are useful in the laundry care compositions described herein. As used herein, the terms "filler" and "carrier" have the same meaning and are used interchangeably. Liquid laundry care compositions and other forms of laundry care compositions that include a liquid component (e.g., liquid unit dose laundry care compositions) can contain water and other solvents as fillers or carriers. Low molecular weight primary or secondary alcohols, such as methanol, ethanol, propanol, isopropanol, and phenoxyethanol are suitable. Monohydric alcohols may be used in some embodiments to solubilize the surfactant, and polyhydric alcohols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., 1, 2-propanediol, 1, 3-propanediol, 2, 3-butanediol, ethylene glycol, and glycerol) may be used. Amine-containing solvents may also be used.

Application method

The present invention includes a method of whitening a fabric. Compact fluid detergent compositions suitable for sale to consumers are suitable for use in laundry pretreatment applications, laundry cleaning applications, and home care applications. These methods include, but are not limited to, the steps of contacting the detergent composition in undiluted form or diluted in a wash liquor with at least a portion of the fabric that may or may not be soiled, and then optionally rinsing the fabric. The fabric material may be subjected to a washing step prior to the optional rinsing step. The machine washing method may comprise treating soiled laundry in a washing machine with an aqueous wash solution in which an effective amount of a machine wash detergent composition according to the invention is dissolved or dispensed. An "effective amount" of a detergent composition refers to about 20g to about 300g of the product dissolved or dispersed in a volume of wash solution of about 5L to about 65L. The water temperature may range from about 5 ℃ to about 100 ℃. The ratio of water to dirt (e.g., fabric) can be from about 1:1 to about 30: 1. The composition may be used in a concentration of about 500ppm to about 15,000ppm in solution. In the case of fabric laundry compositions, the level of use may also vary not only according to the type and severity of the soils and stains, but also according to the wash water temperature, the volume of wash water and the type of washing machine (e.g. pulsator, tumble, vertical axis japanese-type automatic washing machines).

The detergent compositions of the present invention are useful for laundering fabrics at reduced wash temperatures. These methods of laundering fabrics comprise the steps of delivering a laundry detergent composition to water to form a wash liquor, wherein the temperature of the wash liquor is from about 0 ℃ to about 20 ℃, or from about 0 ℃ to about 15 ℃, or from about 0 ℃ to about 9 ℃, and adding the laundered fabrics to the wash liquor. The fabric may be contacted with water before, after or simultaneously with contacting the laundry detergent composition with water.

Another method involves contacting the nonwoven substrate impregnated with the detergent composition with soil. As used herein, "nonwoven substrate" may include any conventionally formed nonwoven sheet or web having suitable basis weight, caliper, absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those sold under the trade name DuPontThose sold and sold by James River Corp. as POLYThose that are sold.

Also included are hand wash/soak methods, and combinations of hand wash and semi-automatic washing machines.

In one aspect, a method is disclosed that includes the steps of: optionally washing and/or rinsing the surface or fabric, contacting the surface or fabric with any of the compositions disclosed in the specification, and then optionally washing and/or rinsing the surface or fabric, with an optional drying step.

Drying of these surfaces or fabrics may be accomplished by any of the usual methods used in the domestic or industrial environment. The fabric may comprise any fabric capable of being laundered under normal consumer or institutional use conditions and the present invention is applicable to cellulosic substrates and in some aspects also to synthetic textiles such as polyester and nylon and to the treatment of mixed fabrics and/or fibers including synthetic and cellulosic fabrics and/or fibers. Examples of synthetic fabrics are polyester, nylon, which may be present in a mixture with cellulose fibres, for example polyester cotton fabric. The pH of the solution is typically from 7 to 11, more typically from 8 to 10.5. The composition is typically used in a concentration of 500ppm to 5,000ppm in solution. The water temperature is typically from about 5 ℃ to about 90 ℃. The ratio of water to fabric is typically from about 1:1 to about 30: 1.

Packaging for a composition

The container may consist of bulk cargo in any suitably sized tank truck, tote, tank, carafe, or drum. Most preferably the container is made of stainless steel or HDPE. The container may be an open or closed container. The stainless steel vessel may be unlined or optionally lined with any suitable coating, such as an epoxy or epoxy phenolic coating. Some containers may contain at least one discharge valve, and the containers are preferably ruggedized, stackable, and DOT/UN approved. Suitable Packaging is available from a variety of suppliers, such as General Steel, Mauser, Schutz, Cardinal Packaging, or others. As non-limiting examples, suitable onesThe instruments may be Ecobulk MX, Ecobulk MX-EX, Ecobulk MX-EV, Ecobulk MX, Cleancert, Ecobulk MX-EX-EV Cleancert, Ecobulk SX-EX and Ecobulk MX impelleter supplied by Schuetz, Ecobulk MX impelleter supplied by MauserSM 6、SM 13、SM 15、SM EX、SM LP. Optionally, the HDPE container may contain additives to protect the contents from UV and visible light, for exampleSM LP totes, etc. In addition, HDPE containers may contain additional protection provided by an EVOH permeation barrier or Dualprotect system available frompackaging systems。

As explained, the compositions of the present invention are relatively stable and do not require specific shipping or packaging requirements. For example, the material need not be packaged under an inert atmosphere or shipped equipped with a climate control system to remain stable. However, the storage stability of the leuco compositions can be improved by implementing certain measures. For example, it may be preferable to transport and store the material or other less stable materials in an oxygen deficient environment, at low temperatures, or both. One way to create an oxygen deficient environment is to use an inert gas such as nitrogen, argon or carbon dioxide. The vessel may be purged with an inert gas for a period of time or by evacuating and refilling the vessel with an inert gas. When purging, the purge time should be at least three times longer, more preferably five times longer, than the time required to fill the headspace of the vessel. During purging or recharging, the internal pressure should be close to atmospheric pressure, or slightly above atmospheric pressure. A preferred internal pressure range is from 0.5 to 2atm, more preferably from 0.8 to 1.5atm, and most preferably from 0.95 to 1.2 atm. Those skilled in the art will recognize that the ideal pressure is the value under the conditions encountered during purging or recharging, and that as the temperature changes, the pressure of the gas will generally change following the ideal gas law. Alternatively, the material itself may be purged with an inert gas by bubbling the inert gas through the product for a period of time, either before or after packaging.

For any container in which the composition of the invention or an even less stable material is present, the percentage of the container volume occupied by the material should be at least 50%, more preferably 80%, even more preferably 90% or even 95%, thereby limiting the volume constituting the headspace occupied by ambient air, inert gas or mixtures thereof. For oxygen sensitive materials, limiting the amount of oxygen present in the container will slow the conversion of the leuco compound to the second color state. Furthermore, a container design that minimizes the surface area of the interface between the material and the headspace is generally preferred. Thus, transporting the material by limiting the movement of the material within the container reduces the time-averaged surface area and may help increase the stability of the material, particularly materials containing less stable leuco compounds.

The compositions of the present invention are sufficiently stable to be stored and transported without climate control, wherein the temperature may range from-40 ℃ to 60 ℃, depending on the climate and location. However, lower temperatures are preferred. Suitable temperature ranges for storing and transporting chemicals are-30 ℃ to 60 ℃, more preferably-10 ℃ to 50 ℃, most preferably 0 ℃ to 35 ℃.

Additional protection of the product may be used, for example, oxygen scavengers in films, pouches or by direct incorporation into the packaging material to maintain an oxygen deficient environment within the container.

Any precautions used to reduce the conversion of the leuco composition prior to incorporation into the laundry care composition as described above may similarly be applied to the storage and transport of the laundry care composition comprising the composition.

The laundry care compositions described herein may be packaged in any suitable container, including containers constructed of paper, paperboard, plastic materials, and any suitable laminate materials. An alternative type of packaging is described in european application No. 94921505.7.

Multi-compartment bag

The laundry care compositions described herein may also be packaged as multi-compartment laundry care compositions.

Other auxiliary ingredients

A variety of other ingredients may be used in the laundry care compositions herein, including, for example, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid or other liquid fillers, erythrosine, colloidal silica, waxes, probiotics, surfactants, amino cellulose polymers, zinc ricinoleate, perfume microcapsules, rhamnolipids, sophorolipids, glycopeptides, methyl ester ethoxylates, sulfonated estolides (estolides), cleavable surfactants, biopolymers, silicones, modified silicones, aminosilicones, deposition aids, hydrotropes (especially cumene sulfonate, toluene sulfonate, xylene sulfonate, and naphthalene salts), PVA particle encapsulating dyes or perfumes, pearlescers, effervescent agents, color change systems, silicone polyurethanes, opacifiers, tablet disintegrants, biomass filler materials, processing aids, dyes or pigments, solvents for liquid formulations, solid or other liquid fillers, erythrosine, colloidal silica, waxes, probiotics, surfactants, amino cellulose polymers, zinc ricinoleate, perfume microcapsules, rhamnolipids, rhamno, Quick-drying silicones, ethylene glycol distearate, starch perfume encapsulates, emulsified oils including hydrocarbon oils, polyolefins and fatty esters, bisphenol antioxidants, microfibrous cellulose structurants, properfume, styrene/acrylate polymers, triazines, soaps, superoxide dismutase, benzophenone protease inhibitors, functionalized titanium dioxide, dibutyl phosphate, silica perfume capsules and other adjunct ingredients, choline oxidase, triarylmethane blue and violet basic dyes, methine blue and violet basic dyes, anthraquinone blue and violet basic dyes, azo dyes basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, basic blue 19, basic violet 35, basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, basic, Nile blue a (nile blue a) and xanthene dye basic violet 10, alkoxylated triphenylmethane polymer colorants; an alkoxylated thiophene polymer colorant; thiazolium dyes, mica, titanium dioxide coated mica, bismuth oxychloride, and other actives.

Antioxidant: the composition may optionally contain an antioxidant present in the composition in an amount of about 0.001 to about 2% by weight. Preferably, the antioxidant is present at a concentration of 0.01-0.08 wt.%. Mixtures of antioxidants may be used.

One class of antioxidants useful in the present invention are alkylated phenols. Hindered phenol compounds are a preferred type of alkylated phenols having this general formula. A preferred hindered phenol compound of this type is 3, 5-di-tert-butyl-4-hydroxytoluene (BHT).

Further, the antioxidant used in the composition may be selected from the group consisting of alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, ethoxyquin, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and its salts, and mixtures thereof.

The laundry care compositions described herein may also contain vitamins and amino acids, such as: water-soluble vitamins and derivatives thereof, water-soluble amino acids and salts and/or derivatives thereof, water-insoluble amino acid viscosity modifiers, dyes, non-volatile solvents or diluents (both water-soluble and insoluble), pearlescent aids, insecticides (pidiculocide), pH modifiers, preservatives, skin active agents, sunscreens, uv light absorbers, niacinamide, caffeine and minoxidil.

The laundry care compositions of the present invention may also contain pigment materials such as nitroso, monoazo, disazo, carotenoids, triphenylmethane, triarylmethane, xanthene, quinoline, oxazine, azine, anthraquinone, indigo, thioindigo (thioindigo), quinacridone, phthalocyanine, vegetable and natural colors, including water soluble components such as those having the name CI.

The laundry care compositions of the present invention may also contain an antimicrobial agent. The cationic active ingredients may include, but are not limited to, N-alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, dialkyl dimethyl quaternary ammonium compounds such as didecyl dimethyl ammonium chloride, N-didecyl-N-methyl-poly (oxyethyl) ammonium propionate, dioctyl didecyl ammonium chloride, and quaternary amines such as benzethonium chloride and quaternary ammonium compounds having inorganic or organic counterions such as bromine, carbonate or other moieties, including dialkyl dimethyl ammonium carbonate, and antibacterial amines such as chlorhexidine gluconate, PHMB (polyhexamethylene biguanide), biguanide salts, substituted biguanide derivatives, organic salts containing quaternary ammonium compounds or inorganic salts containing quaternary ammonium compounds or mixtures thereof.

Liquid compositions, preferably laundry care compositions herein, may be prepared by combining the components thereof in any convenient order and by mixing, e.g. stirring, the resulting components combine to form a phase stable liquid laundry care composition. In a process for making such compositions, a liquid matrix is formed containing at least a majority, or even substantially all, of the liquid components, e.g., nonionic surfactant, non-surface active liquid carrier, and other optional liquid components, which are thoroughly mixed by applying shear agitation to the liquid composition. For example, rapid stirring with a mechanical stirrer may be usefully employed. Substantially all of any anionic surfactant and ingredients in solid form may be added while maintaining shear agitation. Agitation of the mixture is continued and, if desired, can be increased at this point to form a solution or homogeneous dispersion of the insoluble solid phase particles within the liquid phase. After some or all of the material in solid form has been added to the stirred mixture, any particles of enzyme material to be included, such as enzyme pellets, are added. As a variation of the above-described method of preparation of the composition, one or more solid components may be added to the agitated mixture in the form of a solution or slurry of particles premixed with a minor portion of one or more liquid components. After all composition components are added, the mixture is continued to be stirred for a period of time sufficient to form a composition having the desired viscosity and phase stability characteristics. Typically this will require stirring for a period of about 30-60 minutes.

Of course, it will be appreciated by those skilled in the art that care must be taken in preparing the laundry care compositions of the present invention to avoid undesirable conversion of the leuco colorant to the second color state, or even to avoid undesirable fading of the second color state in any proportion that may be initially present. Such an event may occur if the oxidizing agent is introduced into the laundry care composition without proper control. For example, it is known that oxidants are often used to inhibit microbial growth within many materials, including many materials that are raw materials for detergent manufacturing processes. Typical oxidizing agents for this purpose include, but are not limited to, certain oxygen allotropes (e.g., ozone), peroxides (e.g., hydrogen peroxide, benzoyl peroxide, persulfates, perborates, percarbonates), and halogen oxides (e.g., hypochlorites, chlorites, iodates). In addition, many raw materials may contain levels of transition metals, such as iron, which may be incorporated into laundry care compositions. The skilled artisan is aware of methods to overcome potential problems that may exist due to the presence of these oxidizing agents, introduced from controlled or uncontrolled sources, including, but not limited to, conventional detergent materials feedstocks. Typical methods that may be utilized by one skilled in the art include, but are not limited to, chemical treatment (including, but not limited to, reduction by a common reducing agent, dechlorination by a common amine, catalytic hydrogen peroxide degradation by catalase, chelation of transition metals), adsorption systems (such as, but not limited to, activated carbon adsorption), ultraviolet energy treatment, and/or thermal treatment. Those skilled in the art are aware of methods that incorporate these methods as separate steps of a manufacturing system or as a single overall operation that utilizes techniques that may include, but are not limited to, additive sequence optimization, system residence time distribution optimization and/or spatial separation to overcome potential problems that may arise in formulating and preparing laundry care formulations of the present invention. These are not specific to this particular invention, but are relevant to any laundry care formulation incorporating a leuco colorant.

The leuco colorants of the present invention have been found to be suitable for use in liquid laundry care compositions having a wide range of pH values. For example, the leuco colorants of the present invention have been found to be suitable for use in liquid laundry care compositions having a pH greater than or equal to 10. The leuco colorants of the present invention have also been found to be suitable for use in liquid laundry care compositions having a pH of less than 10. Thus, the leuco colorants are stable in laundry care compositions having a pH greater than or equal to 10 and less than or equal to 10. In some embodiments, a preferred pH range may be between about 7 to about 10. It is known that the conversion of a leuco colorant to a second color state can proceed more rapidly in an acidic environment than in a neutral or basic environment.

Test method

The fabric samples used in the test methods herein were obtained from Testfabrics, inc. west Pittston, PA and were 100% cotton, type 403 (cut at 2 "x 2") and/or type 464 (cut at 4 "x 6"), and unbleached multi-fiber fabrics, specifically type 41(5cm x 10 cm).

Measurements of all reflectance spectra and colors, including L, a, b, K/S and whiteness index (WI CIE) values, on dry fabric samples were performed using one of four spectrophotometers: (1) Konica-Minolta 3610D reflectance spectrophotometer (Konica Minolta Sensing America, Inc., Ramsey, NJ, USA; D65 Lighting, 10 ℃ Observation, excluding ultraviolet light), (2) LabScan XE reflectance spectrophotometer (HunterLabs, Reston, VA; D65 Lighting, 10 ℃ Observation, excluding ultraviolet light), (3)7000A (GretagMacbeth, New Windsor, NY, USA; D65 light, excluding UV light), or (4) Color i7 spectrophotometer (X-rite, Inc., Grand Rapids, MI, USA; D65 light, excluding UV light).

When irradiating the fabric, unless otherwise stated, the designated fabric after drying was exposed to an irradiance of 0.77W/m²@420nm simulated sunlight using an Atlas Xenon Fade-Ometer Ci3000+ (Atlas Material Testing Technology, Mount project, Illinois, USA) equipped with an S-type borosilicate inner (part number 20277300) and outer (part number 20279600) filter, set upMaximum cabinet temperature at 37 ℃, maximum black panel temperature (BPT black panel geometry) at 57 ℃, and 35% RH (relative humidity). Unless otherwise specified, the irradiation is continuous over the period.

I. Method for determining the efficiency of leuco compounds from washing solutions

The cotton sample (model 464) was cleaned prior to use by washing twice with a heavy duty liquid laundry detergent without brightener (1.55g/L aqueous solution) at 49 ℃. Concentrated stock solutions of each leuco conjugate to be tested were prepared in a solvent selected from ethanol or 50:50 ethanol to water, preferably ethanol.

All L, a, b and whiteness index (WI CIE) values of the cotton fabric were measured on the dried samples using a Konica-Minolta 3610d reflectance spectrophotometer.

An alkaline wash solution was prepared by dissolving AATCC heavy duty liquid laundry detergent no brightener (5.23g/1.0L) in deionized water. Four stripped cotton samples were weighed together and placed into a 250mL Erlenmeyer flask with two 10mm glass marbles. A total of three such flasks were prepared for each wash solution to be tested. Adding a leuco conjugate stock solution to an alkaline wash solution to obtain the desired 2.00X 10 with leuco conjugate^-6equivalent/L washing concentration of the washing solution.

Aliquots of this wash solution sufficient to provide a liquid to fabric (w/w) ratio of 10.0:1.0 were placed into three 250mL erlenmeyer flasks, respectively. 1000gpg of stock hardness solution was added to each flask to achieve a final wash hardness of 6gpg (3:1Ca: Mg).

The flask was placed on a Model 75 wrist shaker (Burrell Scientific, inc., Pittsburg, PA) and stirred at maximum setting for 12 minutes, after which the wash solution was removed by aspiration and a volume of rinse water (0gpg) corresponding to the amount of wash solution used was added. 1000gpg of stock hardness solution was added to each flask to achieve a final rinse hardness of 6gpg (3:1Ca: Mg) before additional 4 minutes of stirring. The rinse solution was removed by suction and The fabric samples were Spin dried (Mini counter Spin Dryer, The Laundry Alternative inc., Nashua, NH) for 1 minute and then placed in a food dehydrator set at 135 ° F and dried for 2 hours in The dark. After this drying procedure, the samples can be stored in the dark or exposed to light for various times before measuring the properties of the fabric.

Since consumer habits vary widely around the world, the method used must allow the benefits of leuco compounds to be measured under a variety of conditions. One such condition is exposure to light after drying. Some leuco compounds do not show as great a benefit under dark storage as under light storage, so each leuco compound must be tested under both sets of conditions to determine the best benefit. Thus, method I included exposing the dried fabric to simulated sunlight at different time duration increments prior to making the measurements, and setting the LCE value to the maximum value obtained from the set of exposure times described below.

A. Dark conditions after drying

After drying, the fabrics were stored at room temperature in the dark between the measurement time points. L, a, b and whiteness index (WI CIE) values of the cotton fabric were measured at times t 0, 6, 24 and 48 hours after the end of the two-hour drying period. The values for the 12 samples generated for each leuco colorant (three flasks with four samples each) were averaged to give sample values for L, a, b, and WI CIE at each time point t.

To obtain control treated L, a, b and whiteness index (WI CIE) values, the above process was repeated with the following exceptions: (1) control alkaline wash solutions were prepared in deionized water using AATCC heavy duty liquid laundry detergent no brightener (5.23g/1.0L), and (2) the values of the 12 samples from the control measured after the drying period were averaged to give sample values for L, a, b, and WI CIE, and the control value at t 0 was also used as the control value at t 6, 24, and 48 hours.

The Leuco Colorant Efficiency (LCE) of the leuco colorant in the laundry care formulation was calculated from the data collected at each time point t using the following equation:

LCE_t＝DE*＝((L*_c-L*_s)²+(a*_c–a*_s)²+(b*_c–b*_s)²)^1/2

wherein the subscripts c and s refer to the control, i.e., fabric washed in AATCC heavy duty liquid laundry detergent without brightener, and the sample, i.e., fabric washed in a laundry care formulation containing a leuco colorant, respectively, used to calculate LCE_tIs the value at the corresponding point in time t (0, 6, 24 or 48 hours).

The WI CIE values of the 12 samples produced for each wash solution (three flasks with four samples each) were averaged and the change in whiteness index at wash was calculated using the following equation:

WI-WI CIE (after wash) -WI CIE (before wash)

Laundry care formulations (WI)_{Sample (I)}) And AATCC HDL no brightener (WI)_Control) There will be a single value. The change in whiteness between the two formulations is given by the formula:

WI＝WI_{sample (I)}–WI_Control

B. Light conditions after drying

The designated cotton fabric after drying was exposed to simulated sunlight for 15 minutes, 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 120 minutes and 240 minutes. After each exposure period, L, a, b and whiteness index (WI CIE) values of the cotton fabric were measured on the samples. Calculation of LCE and Δ WI values for each exposure time point as described in method i.a. above, the LCE and Δ WI values for the sample and control laundry care formulations were set to the maximum values obtained from the set of exposure times listed.

Method of determining relative hue angle (compared to AATCC control)

The relative hue angle provided by the leuco colorant to cotton fabrics treated according to method I above was determined as follows.

a) The values of a and b were averaged for the 12 samples from each solution and Δ a and were determined using the following formula

Δb*：

Δa*＝a*_s-a*_cAnd Δ b ═ b-_s-b*_c

Where subscripts c and s refer to fabrics washed in AATCC heavy duty liquid detergent without brightener (control) and in a laundry care formulation containing a leuco colorant (sample), respectively.

b) If the absolute values of Δ a and Δ b are <0.25, no Relative Hue Angle (RHA) is calculated. If the absolute value of Δ a or Δ b is ≧ 0.25, then the RHA is determined using one of the following equations:

if Δ b >0, RHA ═ ATAN2(Δ a, Δ b ·)

If Δ b <0, then RHA 360+ ATAN2(Δ a, Δ b)

The relative hue angle may be calculated for each time point at which data is collected in a post-dry dark assessment or a post-dry light assessment. Any of these points may be used to satisfy the requirements of the claims.

Measuring surface tension values of the oxidized forms of substituted diarylamines, leuco colorants, and leuco colorants A method.

The material to be tested is a substituted diarylamine, a leuco colorant according to the present invention, or a dye representing a second color state of the leuco colorant (e.g., a triarylmethane dye). A total of 250-255mg of the material to be tested was weighed into a 4oz glass vial and 50.0mL of deionized water (Barnstead B-Pure System, about 17.27ohm) was added along with the magnetic stir bar. The vial was capped, placed on a magnetic stir plate, and the mixture was stirred at 22.0 ℃ for one hour. Stirring was then stopped and the mixture was allowed to stand for one hour. At the end of this time, 10.0mL of the solution was drawn into a syringe, which was then fitted with glass fibersFilter, and filter the sample into a 20mL scintillation vial. The 45.0 microliters of filtered solution was pipetted into each of the eight separate wells of the 96-well plate using a VWR LabMax pipette. The solution was assayed at about 22.0 ℃ with a Kibron Delta 8 tensiometer and the average of eight measurement replicates was recorded as the surface tension value in mN/m.

Method for determining lightness (L), Chroma (C) and Hue (Hue, H) of laundry care formulations

The aesthetic appearance of the laundry care formulation was determined on a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, VA; D65 illuminated, 10 ℃ View, excluding ultraviolet light) using a translucent sample set (part number LSXE-SC-ASSY) comprising a sample cup, ring and disk set, a sample cup port insert (1.75 ") and an opaque cover. For a detailed description see Hunter Labs Applications Note, Vol.11, No.3,2008. The final value for a given laundry care formulation is the average of three external replicate measurements.

The purpose of the ring and disk set is to control the liquid properties and the additional light interaction (diffusion and transmission) associated with translucent liquid samples, making these samples more like opaque samples that the sensor design measures.

When the ring and disk set are used for measuring liquids, a black plastic ring is first placed in the sample cup to fix the light to 10mm through the internal path length of the liquid sample while excluding external light that may cause measurement interference. The liquid was poured into the cup until the liquid level was above the top of the black ring.

The white ceramic disk was lowered into the liquid until it was on top of the ring. The disc provides a white background to direct light that has traveled through the liquid back to the detector. A black sample cup lid was then placed over the sample cup to prevent any ambient light from outside the instrument from leaking into the detector. The liquid sample is measured through the bottom of a good optical quality quartz sample cup as part of the ring and disk set and inserted using an attached port. A detailed description of the use of the ring and disk stack is provided below.

1. The instrument is oriented so that the sample port faces upward. The conventional port insert is replaced with the dedicated port insert of the sample cup.

2. Instruments with dedicated port inserts in situ are standardized.

3. A 10-mm black ring was inserted into the cup so that it lay flat on the bottom of the cup.

4. The cup is filled with the liquid sample until the liquid is above the level of the ring.

5. The white ceramic disk was floated down through the liquid sample until it rested firmly on top of the black floating ring. The goal is to make the sample appear smooth and opaque through the glass bottom of the sample cup.

V. a method for determining the Color Formation Index (CFI) of an antioxidant and/or an antioxidant composition.

The efficacy of an antioxidant and/or antioxidant composition to control the conversion of a leuco colorant during storage is related to the Color Formation Index (CFI) value of the antioxidant composition. To determine this value, liquid detergent samples were prepared, all using AATCC heavy duty liquid laundry detergent without brightener (hereinafter simply designated as AATCC HDL). A series of heavy duty liquid detergent formulations were prepared having the compositions set forth in table 1 below, some of which contained leuco colorant 1. Leuco colorant 1 can be as per U.S. patent application No. 2016/0326467A1 No. [0331 ]]-[0038]Prepared by the general synthetic methods described in the paragraph. AE7 is C_12-13Alcohol ethoxylate having an average degree of ethoxylation of 7.

Leuco colorant 1(a + b is 2.5, the sum of all a + b is 5.0)

Table 1: heavy duty liquid detergent formulations A-H.

When present, the concentration of each material is as follows:

leuco colorant 1: 0.020% by weight.

Hindered phenol: equimolar with 0.10 wt.% BHT.

Substituted diarylamines: equimolar with 0.01% by weight of 4- (1,1,3, 3-tetramethylbutyl) -N- [4- (1,1,3, 3-tetramethylbutyl) phenyl ] -aniline.

AE 7: 2.0 wt%; each antioxidant was dissolved into AE7 NI for incorporation into the formulation.

After preparation, the color of each detergent formulation was measured using method IV above, and each formulation was then stored in the dark at 40 ℃. 7. After 14 and 28 days, the color of the samples was re-measured using method IV. The absorbance of each formulation was measured on days 0, 7, 14 and 28 (597 nm; 1.0cm path length).

CFI was calculated from the following pair of formulations using absorbance values at 597 nm:

control	Sample (I)	Note
			A	E	Conversion without any antioxidant
B	F	CFI_{Hindered phenols}Conversion with hindered phenols only
			C	G	CFI_{Substituted diarylamines}Conversion with substituted diarylamines only
D	H	CFI_{Antioxidant composition}Conversion using an antioxidant composition

For any given formulation pair (A/E, B/F or C/G or D/H), the equation that yields the CFI value on day x (where x is 7, 14 and 28) is:

CFI_{day x}＝[(A_S(x-0)–A_C(x-0))/(A_E(x-0)–A_A(x-0))]x 100％

Where A refers to the change in absorbance at 597nm between day x and day 0 of the formulation, subscripts C and S refer to the control and sample formulations in formulation pairs A/E, B/F, C/G and D/H, respectively, and subscripts A and E refer to formulations A and E.

For example, at day 14, the CFI of hindered phenol alone (formulation pair B/F) can be calculated using the formula:

CFI_{day 14}＝[(A_F(14-0)–A_B(14-0))/(A_E(14-0)–A_A(14-0))]x 100％

CFI values were calculated for each time point (days 7, 14 and 28) at which data was collected. The CFI value at any of these points can be used to satisfy the requirements of the claims.

Example 1

The CFI values for the hindered phenol 2, 6-bis (1, 1-dimethylethyl) -4-methyl-phenol, the substituted diarylamine 4- (1,1,3, 3-tetramethylbutyl) -N- [4- (1,1,3, 3-tetramethylbutyl) phenyl ] -aniline, and the combination of these two antioxidants were determined according to method V. The absorbance data collected over time are as follows:

CFI values calculated from the above data are shown in the table below.

Day X	CFI_{Hindered phenols}	CFI_{Substituted diarylamines}	CFI_{Antioxidant composition}
				7	30.8	29.4	15.2
14	41.1	42.4	22.4
				28	39.3	36.1	18.2

The use of hindered phenols alone, or substituted diarylamines alone, provides a substantially similar amount of color control in storage at each time point. However, it is clear that when a combination of both a hindered phenol and a substituted diarylamine is used over either alone, the CFI value at each time point is significantly reduced.

Formulation examples

The following are illustrative examples of laundry care compositions according to the present invention, and are not limiting. The addition system in a commercial facility allows for the amount of additive to vary by as much as ± 20% of the target value, such that the specific levels disclosed in any formulation herein should be understood to include values encompassed by a ± 20% variance.

Examples 3 to9: heavy duty liquid laundry detergent compositions.

Based on total cleaning and/or treatment composition weight. Enzyme levels are raw material levels.

Examples 10 to 20: a unit dosage composition.

These examples provide various formulations for unit dose laundry detergents. The compositions 10 to 14 comprise a single unit dose compartment. The film used to enclose the compartment is a polyvinyl alcohol based film.

Based on total cleaning and/or treatment composition weight. Enzyme levels are raw material levels.

In the following examples, the unit dose has three compartments, but similar compositions may be made in two, four or five compartments. The film used to enclose the compartments is polyvinyl alcohol.

Enzyme levels are raw material levels based on total cleaning and/or treatment composition weight.

AE1.8S is C_12-15Alkyl ethoxy (1.8) sulfate

AE3S is C_12-15Alkyl ethoxy (3) sulfate

AE7 is C_12-13Alcohol ethoxylate having an average degree of ethoxylation of 7

AE8 is C_12-13Alcohol ethoxylates having an average degree of ethoxylation of 8

AE9 is C_12-13Alcohol ethoxylate having an average degree of ethoxylation of 9

The amylase 1 is15mg active substance/g, supplied by Novozymes

The amylase 2 is29mg active substance/g, supplied by Novozymes

The amylase 3 is a Stainzyme20mg active substance/g, supplied by Novozymes

AS is C_12-14Alkyl sulfates

The xyloglucanase is20mg active substance/g, supplied by Novozymes

Chelant 1 is diethylene triamine pentaacetic acid; can be combined with chelating agent 3

Chelating agent 2 is 1-hydroxyethane 1, 1-diphosphonic acid; can be combined with chelating agent 3

Chelant 3 is diethylenetriamine; can be combined with chelating agent 1 or 2

Dispersin B is a glycoside hydrolase with an active substance/g of 1000mg

DTI is poly (4-vinylpyridine-1-oxide) (e.g. Chromabond)) Or poly (1-vinylpyrrolidone-co-1-vinylimidazole) (e.g., Sokalan))。

Dye control agent: dye control agents according to the invention, e.g.O.IN(M1)、P(M2)、PM (M3) orHF(M4)

Hindered phenol: an antioxidant selected from the group consisting of 2, 6-bis (1, 1-dimethylethyl) -4-methyl-phenol, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylpropionic acid, methyl ester and (1, 1-dimethylethyl) -4-methoxyphenol.

HSAS is a mid-branched alkyl sulfate, as disclosed in US6,020,303 and US6,060,443.

LAS is a linear alkylbenzene sulphonate having C₉-C₁₅Average aliphatic carbon chain length (HLAS is acid form).

The leuco colorant is any suitable leuco colorant according to the present invention or a mixture thereof.

The lipase is18mg active substance/g, supplied by Novozymes

V200 is a thiophene azo dye supplied by Milliken

The mannanase is25mg active substance/g, supplied by Novozymes

The nuclease is phosphodiesterase SEQ ID NO 1, and is 1000mg active substance/g

Optical brightener 1 is disodium 4,4 '-bis { [ 4-anilino-6-morpholino-s-triazin-2-yl ] -amino } -2,2' -stilbene disulfonate

Optical brightener 2 is disodium 4,4' -bis- (2-sulfostyryl) biphenyl (sodium salt)

Optical brightener 3 is Optiblanc from 3V Sigma

The perfume packaging material is a core-shell melamine formaldehyde perfume microcapsule.

The polishing enzyme is p-nitrobenzyl esterase, and is 1000mg of active substance/g

Polymer 1 is bis ((C)₂H₅O)(C₂H₄O)n)(CH₃)-N⁺-C_xH_2x-N⁺-(CH₃) -bis ((C)₂H₅O)(C₂H₄O) n), where n ═ 20-30, x ═ 3 to 8, or sulfated or sulfonated variants thereof

Polymer 2 is Ethoxylated (EO)₁₅) Tetraethylenepentamine

Polymer 3 is an ethoxylated polyethyleneimine

Polymer 4 is ethoxylated hexamethylene diamine

Polymer 5 is Acusol 305 supplied by Rohm & Haas

Polymer 6 is a polyethylene glycol polymer grafted with vinyl acetate side chains, supplied by BASF.

The protease is Purafect40.6mg active substance/g, supplied by DuPont

Protease 2 is32.89mg active substance/g, supplied by Novozymes

Protease 3 is84mg active substance/g, supplied by DuPont

The structurant is hydrogenated castor oil

Substituted diarylamines: an antioxidant selected from the group consisting of 4- (1,1,3, 3-tetramethylbutyl) -N- [4- (1,1,3, 3-tetramethylbutyl) phenyl ] aniline and 4- (1-methyl-1-phenylethyl) -N- [4- (1-methyl-1-phenylethyl) phenyl ] aniline.

Example 21

A representative leuco composition (sample 21-1) was prepared by the following procedure. 1 mole of p-dimethylaminobenzaldehyde is combined with 2.1 moles of alkoxylated aniline, 3 moles of hydrochloric acid and a catalytic amount of urea. The reaction was stirred at 95 ℃ for 6 hours under nitrogen. The reaction was cooled to room temperature and then neutralized with sodium hydroxide to a pH of about 8. The aqueous phase was separated and the organic phase was further washed with sodium sulfate solution. The product was then diluted with polyethylene glycol to about 33% concentration. In addition to the leuco compound and polyethylene glycol, the leuco composition also contained about 5% water, excess alkoxylated aniline, trace amounts of sodium salt and urea.

To stabilize the leuco compositions, the following compositions were prepared by mixing the leuco compositions with various amounts of 3, 5-di-tert-butyl-4-hydroxytoluene (BHT). The percentages used in each composition are listed in the table below.

Sample (I)	BHT
		21-1
21-2	1％
		21-3	0.25％
21-4	0.05％

Samples (21-1 to 21-4) were aged at 40 ℃ for 12 weeks. Samples were taken after 4,8 and 12 weeks. The sample was dissolved in methanol at about 1 g/L. The methanol solution was read by UV-vis with a 1cm UV cell to obtain a maximum absorbance at about 597 nm. The Color Value (CV) was calculated using the following formula:

CV is absorbance/(sample concentration, unit g/L)

The resulting CV is directly related to the concentration of the oxidized leuco compound.

As can be seen from the above table, samples 21-2 through 21-4, which contained BHT, performed substantially the same as sample 21-1, which was a leuco composition without the addition of BHT. Thus, the addition of up to 1 wt.% BHT (molar ratio about 0.1) does not appear to show any benefit. The inventors then tried to determine if antioxidant levels much higher than those typically used (molar ratio of total antioxidant to leuco compound greater than 0.5:1, or 1:1, or even 2:1) would better stabilize the leuco compound.

Example 22

A composition (sample 22) was prepared using the components listed in the table below:

in sample 22, the molar ratio of AO (BHT) to leuco colorant was about 20: 1. Sample 22 was stored at 40 ℃ for 4 weeks and dissolved in methanol at 2 wt.% (corresponding to 1.4g/L of preparation example 1 in methanol). The CV of sample 22 after 4 weeks of storage was zero, as measured by the uv-vis method, compared to the CV of 0.008 obtained for sample 21-1.

After 4 weeks of storage, 4.28% of sample 22 was added to AATCC HDL. For control, 3000ppm of sample 21-1 was also added to AATCC detergent. These different amounts of the two samples were used to ensure that both detergents contained the same initial amount of the leuco compound.

AATCC detergent samples were measured in transmission mode with a 1cm cell using a Color i7 spectrophotometer (X-rite, Inc., Grand Rapids, MI, USA; D65 light, excluding ultraviolet light). The L, a and b values for the two AATCC detergent samples were as follows:

sample (I)	L*	a*	b*
				22	95.66	-1.52	5.11
21-1	93.14	-2.59	3.41

As can be seen from the table, the AATCC sample prepared with sample 22 had less blue color (higher b) than the AATCC sample prepared with sample 21-1 without antioxidant. More importantly, the AATCC sample prepared from sample 22 also had a higher L value, which indicates a lighter color.

Example 23

Two compositions (samples 23-1 and 23-2) were prepared with the components listed in the following table:

material	Sample 23-1	Sample 23-2
			AE7	61.3％	59.8％
BHT	5％	0
			Ralox 35	0	6.6％
MD 40	5％	5％
			P-diol (propylene glycol)	3.2％	3.1％
Leuco (33% active)	25.5％	25.5％

Ralox35 is methyl 4-hydroxy-3, 5-di-tert-butylphenyl propionate (CAS number 6386-38-5) and MD-40 is 4,4' -bis (phenylisopropyl) diphenylamine (CAS number 10081-67-1). The molar ratio of total antioxidant to leuco compound in each sample was about 3: 1.

The samples of the examples were stored at 40 ℃ and 60 ℃ for 4 weeks. After storage, CV were determined and listed in the table below. Higher concentrations were used when dissolved in methanol, since the CV value was very low. The sample concentration used for these measurements corresponded to 5.1g/L of sample 21-1.

	Sample 23-1	Sample 23-2	Sample 21-1
				Storage at 40 ℃	0	0.0012	0.008
Storage at 60 ℃	0	0.0008	--

It can be seen that samples 23-1 and 23-2, which contained higher levels of antioxidant, exhibited improved stability relative to sample 21-1, which did not contain antioxidant.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Each document cited herein, including any cross-referenced or related patent or application and any patent application or patent to which this application claims priority or benefit, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it teaches, suggests or discloses any such invention alone or in any combination with any other reference. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

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

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Stable compositions comprising leuco compounds

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