Leuco compounds and compositions comprising the same

Abstract

A leuco compound comprises an antioxidant moiety covalently bonded to a leuco moiety. A laundry care composition comprises (a) at least one laundry care ingredient and (b) a leuco compound as described above. A method of treating a textile comprises the steps of (a) providing such a laundry care composition; (b) adding the laundry care composition to a liquid medium; (c) placing textile articles in the liquid medium; (d) optionally, rinsing the textile; and (e) drying the textile articles.

Claims

1. A leuco compound comprising at least one antioxidant moiety covalently bound to at least one leuco moiety, wherein the leuco moiety is a triphenylmethane leuco moiety of Formula (I) ##STR00010## wherein G is hydrogen; each R.sub.o and R.sub.m is hydrogen; each R.sub.p is independently selected from hydrogen and —NR.sup.1R.sup.2, provided at least one R.sub.p is —NR.sup.1R.sup.2; each R.sup.1 and R.sup.2 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R.sup.4, provided at least one R.sup.1 is R.sup.4; R.sup.4 is selected from the group consisting of oxyalkylene and polyoxyalkylene; each antioxidant moiety is independently selected from the group consisting of aromatic alcohol moieties, benzofuranone moieties, benzopyran moieties, oxindole moieties, 1,2-dihydroquinoline moieties, 1,2-benzisothiazoline-3-one moieties, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid moieties, uric acid moieties, dihydroxy fumaric acid moieties, sorbic acid moieties, and phosphite moieties; and each antioxidant moiety is covalently bound to an R.sub.4.

2. The leuco compound of claim 1, wherein each R.sub.p is an independently selected —NR.sup.1R.sup.2.

3. The leuco compound of claim 1, wherein at least one of the antioxidant moieties of the leuco compound is an aromatic alcohol moiety.

4. The leuco compound of claim 3, wherein the aromatic alcohol moiety is an ortho-alkylated phenol moiety.

5. The leuco compound of claim 4, wherein the antioxidant moiety is a moiety of Formula (L) or Formula (LI) ##STR00011## wherein R.sup.51 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, and substituted alkaryl.

Description

SYNTHETIC EXAMPLES

(1) The following examples demonstrate the synthesis of precursor compounds and leuco compounds according to the invention, each of which comprises an antioxidant moiety covalently bound to a leuco moiety.

Synthetic Example I

(2) ##STR00003##

(3) The compound of Example I (EX I) was prepared according to the following procedure. In a 1 liter pressure reactor, 250 gram of 2-(n-ethylanilino)ethanol and 0.16 gram of potassium hydroxide were added. The reactor was purged with nitrogen at 60 psi three times before adding 166 grams of ethylene oxide. The reaction mixture was stirred at about 100° C. until the pressure stabilized. After stripping off any residual ethylene oxide, the product was collected as a light yellow liquid.

Synthetic Example II

(4) ##STR00004##

(5) The compound of Example II (EX II) was prepared according to the following procedure. In a three neck flask equipped with a stirrer, heating mantle, nitrogen inlet, and a Dean Stark trap, 60 grams of EX I and 30 grams of acetic acid were added. The reaction mixture was heated to 100-110° C. for 5 hours and the distillate was collected by the Dean-Stark trap. The reaction mixture was dried using a roto-vap, and then 100 mL of methanol was added to eliminate the residual anhydride. The mixture was again dried using a roto-vap followed by additional drying in a vacuum oven. The product (EX II) was collected as a viscous liquid.

Synthetic Example III

(6) ##STR00005##

(7) The compound of Example III (EX III) having the foregoing structure was prepared according to the following procedure. In a three-neck round bottom flask equipped with a temperature probe, nitrogen inlet, stirrer, and condenser, 48 grams of EX II and 1.91 grams of acetic anhydride were added. The reaction mixture was cooled to 7-12° C. with an ice batch while stirring.

(8) In another three-neck round bottom flask equipped with a temperature probe, nitrogen inlet, stirrer, and condenser, 34.89 grams of dimethylformamide were added. The contents of the flask were cooled down to 4-10° C. with an ice bath, and then 30.39 grams of phosphorus oxychloride were slowly added while keeping the temperature at 4-10° C. After this addition, the reaction mixture was stirred for another 15 minutes at 4-10° C. The contents of this flask were slowly added to the first flask while stirring. The temperature was kept between 5-15° C. After this addition, the reaction mixture was stirred for another 15 minutes and then heated to 87-93° C. for 2 hours. The reaction mixture was then cooled down to 25-35° C., and the mixture was slowly added to a sodium hydroxide solution (70.2 grams of 50 wt. % sodium hydroxide solution diluted in 160 grams of water) to keep the temperature between 10 and 25° C. The product was extracted with ethyl acetate and washed with DI water. The product was a viscous liquid.

Synthetic Example IV

(9) ##STR00006##

(10) The leuco compound of Example IV (EX IV) was prepared according to the following procedure. In a 100 mL round bottom flask equipped with a mechanical stirrer, condenser, heating mantle, temperature probe, and a nitrogen inlet, 21 grams of EX III, 12.49 grams of N,N-dimethylaniline, and a urea solution (3.65 g urea dissolved in 6 grams water) were added. While stirring, 15.66 grams of concentrated hydrochloride acid (˜37 wt %) was slowly added to keep the exotherm below 50° C. After the addition, the reaction mixture was heated to 95° C. and stirred for 8 hours under nitrogen. Then, the reaction mixture was poured into 500 mL of 5 wt. % sodium bicarbonate solution. The product was extracted with ethyl acetate and washed with deionized water. The ethyl acetate was removed by roto-vap and vacuum oven to obtain the product (EX IV).

Synthetic Example V

(11) ##STR00007##

(12) The compound of Example V (EX V) was prepared according to the following procedure. In a 250 mL 3-neck flask equipped with an overhead stirrer and nitrogen cap, 11 grams of EX IV, 4.2 grams of N,N′-dicyclohexylcarbodiimide (DCC), 0.6 gram of 4-dimethylamino pyridine (DMAP), 5.57 grams of 3,5-Di-tert-butyl-4-hydroxybenzenepropanoic acid and 100 mL of methylene chloride were mixed. The reaction mixture was stirred at room temperature for 48 hours until TLC showed complete conversion. Then, about 1 mL of water was added to the reaction mixture to quench the excess DCC. The reaction mixture was filtered to remove any solid formed (dicyclohexylurea). The filtrate was dried with a roto-vap and then in a vacuum oven to remove solvent. The product (EX V) was a viscous liquid.

Synthetic Example VI

(13) ##STR00008##

(14) The compound of Example VI (EX VI) was prepared according to a method similar to that used to make EX IV by the reaction between an alkoxylated aniline (averaging five ethylene oxide repeat units per aniline) and p-dimethylaminobenzaldehyde. After the reaction, the sample was worked up by the following method. First, NaOH (50% solution) was carefully added to the reaction mixture to neutralize the acid catalyst. The sample was then dried with a roto-vap to remove water. Isopropanol was added to dissolve the product. After filtering to remove any undissolved salt, the product was dried again by roto-vap. The product (EX VI) was a viscous liquid.

Synthetic Examples VII, VIII, and IX

(15) The compounds EX VII, EX VIII, and EX IX having the respective structures set forth below were synthesized in accordance with a method similar to that used to make EX V. One, two, and four moles of 3,5-di-tert-butyl-4-hydroxybenzenepropanoic acid were used to obtain leuco molecules containing different numbers of antioxidant moieties.

(16) ##STR00009##

LAUNDRY CARE EXAMPLES

(17) Four heavy duty laundry detergent (HDL) samples (Samples A, B, C, and D) were prepared using AATCC HDL that contains no colorants or optical brightener (1993, distributed by Procter & Gamble, Cincinnati, Ohio). Sample A was the AATCC detergent (no leuco compounds or antioxidants added). Sample B was the AATCC detergent with 500 ppm of EX IV added. Sample C was the AATCC detergent with 737 ppm of EX V added. Sample D was the AATCC detergent with 500 ppm of EX IV and 253 ppm of an additional antioxidant (namely, 3,5-di-tert-butyl-4-hydroxybenzenepropanoic acid) added. The samples were formulated so that Samples B, C, and D contained the same molar amount of the leuco compound, and Samples C and D were formulated to contain the same molar amount of antioxidant.

(18) After preparation, the color of the examples was read with a color spectrophotometer (X-rite Color i7). Transmission mode was used with 10 mm light path. The sample was then aged in a 40° C. oven for 4 days and the color of the samples were read again under the same conditions. The change of the b* value (delta b*) were recorded in the following table to show the blue color development in the detergent, which blue color is the result of the oxidation of the leuco triarylmethane moiety present in the compounds EX IV and EX V.

(19) TABLE-US-00001 TABLE Formulation data, Delta b*, and Delta WI CIE results for Samples A, B, C, and D. Amount of Amount of Amount of Additional Sample EX IV (ppm) EX V (ppm) Antioxidant (ppm) Delta b* A 0 0 0 0.09 B 500 0 0 −40.11 C 0 737 0 −5.27 D 500 0 253 −36.76

(20) As can be seen from the data in the foregoing table, the detergent containing a leuco compound of the invention (i.e., a leuco compound comprising an antioxidant moiety covalently bonded to a leuco moiety (EX V)) showed much less color development upon aging as compared to the other samples. The stark difference between these samples is surprising given the fact that Sample D contained a separate antioxidant (the 3,5-di-tert-butyl-4-hydroxybenzenepropanoic acid) and was formulated so that this antioxidant was present in the same molar amount as the antioxidant moieties of EX V. The results are believed to show the synergy obtained by tethering the leuco moiety and the antioxidant moiety in the sample compound. Further, washing of bleached cotton fabric samples with the detergent samples showed that Sample C (the detergent containing a leuco compound of the invention) resulted in a measurable increase in the WI CIE of the fabric samples that was comparable with the WI CIE increases observed in fabrics laundered with Samples B and D.

FORMULATION EXAMPLES

(21) The following are illustrative examples of cleaning compositions according to the present disclosure and are not intended to be limiting.

Examples 1-7: Heavy Duty Liquid Laundry Detergent Compositions

(22) TABLE-US-00002 1 2 3 4 5 6 7 Ingredients % weight AE.sub.1.8S 6.77 5.16 1.36 1.30 — — — AE.sub.3S — — — — 0.45 — — LAS 0.86 2.06 2.72 0.68 0.95 1.56 3.55 HSAS 1.85 2.63 1.02 — — — — AE9 6.32 9.85 10.20  7.92 AE8 35.45  AE7 8.40 12.44  C.sub.12-14 0.30 0.73 0.23 0.37 — — — dimethyl Amine Oxide C.sub.12-18 Fatty Acid 0.80 1.90 0.60 0.99 1.20 — 15.00  Citric Acid 2.50 3.96 1.88 1.98 0.90 2.50 0.60 Optical Brightener 1 1.00 0.80 0.10 0.30 0.05 0.50  0.001 Optical Brightener 3  0.001 0.05 0.01 0.20 0.50 — 1.00 Sodium formate 1.60 0.09 1.20 0.04 1.60 1.20 0.20 DTI 0.32 0.05 — 0.60 — 0.60 0.01 Sodium hydroxide 2.30 3.80 1.70 1.90 1.70 2.50 2.30 Monoethanolamine 1.40 1.49 1.00 0.70 — — — Diethylene glycol 5.50 — 4.10 — — — — Chelant 1 0.15 0.15 0.11 0.07 0.50 0.11 0.80 4-formyl-phenylboronic — — — — 0.05 0.02 0.01 acid Sodium tetraborate 1.43 1.50 1.10 0.75 — 1.07 — Ethanol 1.54 1.77 1.15 0.89 — 3.00 7.00 Polymer 1 0.10 — — — — — 2.00 Polymer 2 0.30 0.33 0.23 0.17 — — — Polymer 3 — — — — — — 0.80 Polymer 4 0.80 0.81 0.60 0.40 1.00 1.00 — 1,2-Propanediol — 6.60 — 3.30 0.50 2.00 8.00 Structurant 0.10 — — — — — 0.10 Perfume 1.60 1.10 1.00 0.80 0.90 1.50 1.60 Perfume encapsulate 0.10 0.05 0.01 0.02 0.10 0.05 0.10 Protease 0.80 0.60 0.70 0.90 0.70 0.60 1.50 Mannanase 0.07 0.05  0.045 0.06 0.04  0.045 0.10 Amylase 1 0.30 — 0.30 0.10 — 0.40 0.10 Amylase 2 — 0.20 0.10 0.15 0.07 — 0.10 Xyloglucanase 0.20 0.10 — — 0.05 0.05 0.20 Lipase 0.40 0.20 0.30 0.10 0.20 — — Polishing enzyme — 0.04 — — —  0.004 — Nuclease 0.05 — — — — —  0.003 Dispersin B — — — 0.05 0.03  0.001  0.001 Liquitint ® V200 0.01 — — — — —  0.005 Leuco compound 0.5  0.35 0.1  0.2  0.04 0.02 0.04 Dye control agent — 0.3  — 0.03 — 0.3  0.3  Water, dyes & Balance minors pH 8.2

(23) Based on total cleaning and/or treatment composition weight. Enzyme levels are reported as raw material.

Examples 8 to 18: Unit Dose Compositions

(24) These examples provide various formulations for unit dose laundry detergents. Compositions 8 to 12 comprise a single unit dose compartment. The film used to encapsulate the compositions is polyvinyl-alcohol-based film.

(25) TABLE-US-00003 8 9 10 11 12 Ingredients % weight LAS 19.09 16.76 8.59 6.56 3.44 AE3S 1.91 0.74 0.18 0.46 0.07 AE7 14.00 17.50 26.33 28.08 31.59 Citric Acid 0.6 0.6 0.6 0.6 0.6 C12-15 Fatty Acid 14.8 14.8 14.8 14.8 14.8 Polymer 3 4.0 4.0 4.0 4.0 4.0 Chelant 2 1.2 1.2 1.2 1.2 1.2 Optical Brightener 1 0.20 0.25 0.01 0.01 0.50 Optical Brightener 2 0.20 — 0.25 0.03 0.01 Optical Brightener 3 0.18 0.09 0.30 0.01 — DTI 0.10 — 0.20 — — Glycerol 6.1 6.1 6.1 6.1 6.1 Monoethanol amine 8.0 8.0 8.0 8.0 8.0 Tri-isopropanol amine — — 2.0 — — Tri-ethanol amine — 2.0 — — — Cumene sulfonate — — — — 2.0 Protease 0.80 0.60 0.07 1.00 1.50 Mannanase 0.07 0.05 0.05 0.10 0.01 Amylase 1 0.20 0.11 0.30 0.50 0.05 Amylase 2 0.11 0.20 0.10 — 0.50 Polishing enzyme 0.005 0.05 — — — Nuclease 0.- 0.05 — — 0.005 Dispersin B 0.010 0.05 0.005 0.005 — Cyclohexyl dimethanol — — — 2.0 — Leuco compound 0.6 0.3 1.0 0.1 0.4 Liquitint ® V200 — — 0.01 0.05 — Structurant 0.14 0.14 0.14 0.14 0.14 Perfume 1.9 1.9 1.9 1.9 1.9 Dye control agent 0.1 0.3 0.2 0.5 0.3 Water and miscellaneous To 100% pH 7.5-8.2

(26) Based on total cleaning and/or treatment composition weight. Enzyme levels are reported as raw material.

(27) In the following examples the unit dose has three compartments, but similar compositions can be made with two, four or five compartments. The film used to encapsulate the compartments is polyvinyl alcohol.

(28) TABLE-US-00004 Base compositions 13 14 15 16 Ingredients % weight HLAS 26.82 16.35 7.50 3.34 AE7 17.88 16.35 22.50 30.06 Citric Acid 0.5 0.7 0.6 0.5 C12-15 Fatty acid 16.4 6.0 11.0 13.0 Polymer 1 2.9 0.1 — — Polymer 3 1.1 5.1 2.5 4.2 Cationic cellulose polymer — — 0.3 0.5 Polymer 6 — 1.5 0.3 0.2 Chelant 2 1.1 2.0 0.6 1.5 Optical Brightener 1 0.20 0.25 0.01 0.005 Optical Brightener 3 0.18 0.09 0.30 0.005 DTI 0.1 — 0.05 — Glycerol 5.3 5.0 5.0 4.2 Monoethanolamine 10.0 8.1 8.4 7.6 Polyethylene glycol — — 2.5 3.0 Potassium sulfite 0.2 0.3 0.5 0.7 Protease 0.80 0.60 0.40 0.80 Amylase 1 0.20 0.20 0.200 0.30 Polishing enzyme — — 0.005 0.005 Nuclease 0.05 — — — Dispersin B — 0.010 0.010 0.010 MgCl.sub.2 0.2 0.2 0.1 0.3 Structurant 0.2 0.1 0.2 0.2 Acid Violet 50 0.04 0.03 0.05 0.03 Perfume/encapsulates 0.10 0.30 0.01 0.05 Dye control agent 0.2 0.03 0.4 — Solvents and misc. To 100% pH 7.0-8.2 Finishing compositions 17 18 Compartment A B C A B C Volume of each compartment 40 ml 5 ml 5 ml 40 ml 5 ml 5 ml Ingredients Active material in Wt. % Perfume 1.6 1.6 1.6 1.6 1.6 1.6 Liquitint ® V200 0 0.006 0 0 0.004 — Leuco compound 0.2 0.4 — — TiO2 — — 0.1 — 0.1 Sodium Sulfite 0.4 0.4 0.4 0.1 0.3 0.3 Polymer 5 — 2 — — Hydrogenated castor oil 0.14 0.14 0.14 0.14 0.14 0.14 Base Composition 13, 14, 15 Add to 100% or 16

(29) Based on total cleaning and/or treatment composition weight, enzyme levels are reported as raw material.

(30) TABLE-US-00005 AE1.8S is C.sub.12-15 alkyl ethoxy (1.8) sulfate AE3S is C.sub.12-15 alkyl ethoxy (3) sulfate AE7 is C.sub.12-13 alcohol ethoxylate, with an average degree of ethoxylation of 7 AE8 is C.sub.12-13 alcohol ethoxylate, with an average degree of ethoxylation of 8 AE9 is C.sub.12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9 Amylase 1 is Stainzyme ®, 15 mg active/g, supplied by Novozymes Amylase 2 is Natalase ®, 29 mg active/g, supplied by Novozymes Xyloglucanase is Whitezyme ®, 20 mg active/g, supplied by Novozymes Chelant 1 is diethylene triamine pentaacetic acid Chelant 2 is 1-hydroxyethane 1,1-diphosphonic acid Dispersin B is a glycoside hydrolase, reported as 1000 mg active/g DTI is either poly(4-vinylpyridine-1-oxide) (such as Chromabond S- 403E ®), or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as Sokalan HP56 ®). Dye control agent Dye control agent in accordance with the invention, for example Suparex ® O.IN (M1), Nylofixan ® P (M2), Nylofixan ® PM (M3), or Nylofixan ® HF (M4) HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443 LAS is linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.9-C.sub.15 (HLAS is acid form). Leuco colorant Any suitable leuco colorant or mixtures thereof according to the instant invention. Lipase is Lipex ®, 18 mg active/g, supplied by Novozymes Liquitint ® V200 is a thiophene azo dye provided by Milliken Mannanase is Mannaway ®, 25 mg active/g, supplied by Novozymes Nuclease is a Phosphodiesterase SEQ ID NO 1, reported as 1000 mg active/g Optical Brightener 1 is disodium 4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}- 2,2′-stilbenedisulfonate Optical Brightener 2 is disodium 4,4′-bis-(2-sulfostyryl)biphenyl (sodium salt) Optical Brightener 3 is Optiblanc SPL10 ® from 3V Sigma Perfume encapsulate is a core-shell melamine formaldehyde perfume microcapsules. Polishing enzyme is Para-nitrobenzyl esterase, reported as 1000 mg active/g Polymer 1 is bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)—N.sup.+—C.sub.xH.sub.2x—N.sup.+—(CH.sub.3)— bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n), wherein n = 20-30, x = 3 to 8 or sulphated or sulfonated variants thereof Polymer 2 is ethoxylated (EO.sub.15) tetraethylene pentamine Polymer 3 is ethoxylated polyethylenimine Polymer 4 is ethoxylated hexamethylene diamine Polymer 5 is Acusol 305, provided by Rohm&Haas Polymer 6 is a polyethylene glycol polymer grafted with vinyl acetate side chains, provided by BASF. Protease is Purafect Prime ®, 40.6 mg active/g, supplied by DuPont Structurant is Hydrogenated Castor Oil

(31) The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, 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.”

(32) Every 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 thereof, is hereby incorporated herein 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 alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

(33) 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.