CN111479878A - Leuco colorants and compositions - Google Patents

Abstract

The present invention relates to a leuco composition comprising at least one leuco compound comprising a leuco moiety and a polyalkylene oxide moiety covalently bonded to the leuco moiety. The polyalkylene oxide moiety comprises at least one ethylene oxide group and at least one propylene oxide group. The present invention also relates to a laundry care composition comprising (a) at least one laundry care ingredient and (b) a leuco composition as described above. The invention further relates to a method of treating a textile, the method comprising the steps of: (a) providing the laundry care composition; (b) adding the laundry care composition to a liquid medium; (c) placing the textile into the liquid medium; (d) optionally, rinsing the textile; and (e) drying the textile.

Description

Leuco colorants and compositions

Technical Field

The present application describes leuco compositions, laundry care compositions (laundrycare compositions) containing the leuco compositions, and the use of these compositions in the laundering of textiles. These types of compositions are provided in a stable, substantially colorless state, which can then be converted to an intensely colored (intense colored) state after exposure to certain physical or chemical changes, such as exposure to oxygen, ion addition (ion addition), exposure to light, and the like. Laundry care compositions comprising leuco compounds are designed to enhance the apparent or visually perceptible whiteness of, or to impart a desired hue to, textiles washed or otherwise treated with the laundry care compositions.

Background

As textile substrates age, their color tends to fade or yellow due to exposure to light, air, dirt, and the natural degradation of the fibers comprising the substrate. Thus, to visually enhance these textile substrates and counteract fading and yellowing, it has become well known in the art to use polymeric colorants to color consumer products. For example, the use of brighteners (or optical brighteners or bluing agents) in textile applications is well known. However, conventional brighteners tend to lose efficacy on storage due to deleterious interactions with other formulation components (e.g., perfumes). In addition, such brighteners can deposit poorly on textile substrates. Thus, formulators tend to increase the level of whitening agent content to offset any loss of efficacy upon storage and/or increase the amount of whitening agent available to deposit on the textile substrate.

It is also known in the art that leuco dyes exhibit a change from a colorless or slightly colored (dark colored) state to a colored state upon exposure to a specific chemical or physical trigger condition (trigger). The resulting change in coloration is typically visually perceptible to the human eye. Many of these compounds have a certain absorbance in the visible region (400-750nm) and thus have a more or less certain color. In the present invention, a dye is considered to be a "leuco dye" if it does not exhibit a significant color at its applied concentration and conditions, but does exhibit a 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 absorption) of the leuco dye molecule in the range 400-750nm, preferably 500-650nm, and most preferably 530-620 nm. The leuco dye should have a molar decay coefficient increase of greater than 50%, more preferably greater than 200%, and most preferably greater than 500% before and after triggering.

The leuco compounds may be used as brighteners in laundry care compositions, such as laundry detergents. In such applications, the addition of a leuco compound in the uncolored or only slightly colored state does not significantly affect the aesthetics of the laundry care composition. The leuco compound can then be converted to a colored state in which it imparts the desired whitening benefit to the textile substrate.

One of the challenges in achieving whiteness benefits through the use of adjusted hue (hue) techniques is: consumers often have garments that are expected to be lightly colored (e.g., pink yellow), and the application of hue modifiers (hueing agents), shade modifiers (shading agents), or bluing agents can impair the expected color of such garments, resulting in consumer dissatisfaction. There remains a need to develop methods of adjusting hue that selectively deposit on aged consumer cotton garments (those garments most likely to yellow over time, where the yellowing requires color correction) and less well on new clean cotton garments that do not require color correction.

Although many leuco colorants show a greater preference for deposition on aged cotton garments obtained from consumers than the new clean cotton (cotton), we have found that substitution of certain ethoxylated derivatives of TAM dyes with propoxylated groups (propoxylatetegroup) leads to improved preference. These leuco colorants having both EO oxyalkylene groups and PO oxyalkylene groups show a greater bias than those having only EO oxyalkylene units. Thus, the leuco colorants of the present invention are better able to provide whitening benefits where needed and avoid adjusting the hue of new, clean cotton garments where it is likely to be considered undesirable.

Disclosure of Invention

In a first embodiment, the present invention provides a leuco composition comprising at least one leuco compound comprising a leuco portion and an alkylene oxide portion covalently bonded to the leuco portion, wherein the alkylene oxide portion comprises at least one ethylene oxide group and at least one propylene oxide group.

In a second embodiment, the present invention provides a laundry care composition comprising (a) at least one laundry care ingredient and (b) a leuco composition as described above.

In a third embodiment, the present invention provides a method of treating a textile, the method comprising the steps of: (a) providing a laundry care composition as described herein; (b) adding the laundry care composition to a liquid medium; (c) placing the textile into the liquid medium; (d) optionally, rinsing the textile; and (e) drying the textile.

In a fourth embodiment, the present invention provides a laundry care composition comprising a laundry care ingredient and a leuco composition as described herein. In one aspect, the present invention provides a laundry care composition comprising: (i)2 to 70 wt% of a surfactant; and (ii) from 0.0001% to 20.0% by weight of a leuco composition as described herein.

In a fifth embodiment, the present invention provides a method of treating a textile, the method comprising the steps of: (a) providing a laundry care composition comprising a leuco composition described herein, (b) adding the laundry care composition to a liquid medium; (c) placing the textile into the liquid medium; (d) optionally, rinsing the textile; and (e) drying the textile.

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 "alkylene oxide" and "alkylene oxide", and the interchangeable terms "polyalkylene oxide" and "polyoxyalkylene", respectively, generally refer to molecular structures comprising one or more than one of the following repeat units: -C₂H₄O-、-C₃H₆O-、-C₄H₈O-and any combination thereof. Non-limiting structures corresponding to these groups include, for example, -CH₂CH₂O-、-CH₂CH₂CH₂O-、-CH₂CH₂CH₂CH₂O-、-CH₂CH(CH₃) O-and-CH₂CH(CH₂CH₃) O-is formed. Furthermore, the polyoxyalkylene constituent may be selected from one or more selected from C_2-20Alkylene oxide, glycidyl, or mixtures thereof.

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

As used herein, the terms "alkyl" and "alkyl-terminated" are intended to mean prepared by extractingAny 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-C₁₈Alkyl and in one aspect C₁-C₆An alkyl group.

As used herein, unless otherwise specified, the term "aryl" is intended to include C₃-C₁₂And (4) an 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 means C_7-16Alkyl-substituted aryl substituents and C_7-16An aryl-substituted alkyl substituent which may or may not contain additional substituents.

As used herein, the term "detergent composition" is a subset of laundry care compositions and includes cleaning compositions, including but not limited to products for laundering fabrics. Such compositions may be pre-treatment compositions used prior to the washing step, or may be rinse-added compositions, as well as cleaning adjuncts, 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 tablet 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 for use prior to the washing step, or may be rinse-added compositions, as well as cleaning adjuncts, such as bleach additives and/or "stain-release bars" or pre-treatment compositions or substrate-borne products such as dryer-added sheets.

As used herein, the term "leuco" (as used in reference to, for example, a compound, moiety, group, dye, monomer, fragment, or polymer) refers to an entity (e.g., an organic compound or a portion thereof) that undergoes one or more chemical and/or physical changes upon exposure to a particular chemical or physical trigger condition (trigger), thereby resulting in a conversion from a first color state (e.g., uncolored or substantially colorless) to a second, more highly colored (more highly colored) state. Suitable chemical or physical trigger conditions include, but are not limited to, oxidation, pH change, temperature change, and change in exposure to electromagnetic radiation (e.g., light). 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 being converted to a third bound conjugated pi-system that binds said first and second pi-systems upon exposure to one or more of the above-described chemical and/or physical triggering conditions.

As used herein, the term "leuco composition" or "leuco colorant composition" refers to a composition comprising at least two leuco compounds having independently selected structures, 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 from its molecular weight distribution: the leuco colorants disclosed herein may comprise a distribution of repeating units in their polymer portion as a result of their manufacturing process.

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 (e.g., spectrophotometric analysis).

As used herein, the term "converting agent" refers to any oxidizing agent known in the art other than molecular oxygen in any of its known forms (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 can form a dye upon activation that, when on white cotton (white cotton), provides a shade to a fabric at a relative hue angle of 210 to 345, or even 240 to 320, or even 250 to 300 (e.g., 250 to 290).

As used herein, "cellulosic substrate" is intended to include any substrate comprising at least a majority by weight of cellulose. Cellulose may be present in wood, cotton, flax, jute, and hemp. The cellulosic substrate may be in the form of powder, fiber, pulp, and articles formed from powder, fiber, and pulp. Cellulosic fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (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 should be understood to mean one or more or one or more of what is claimed or described.

As used herein, the terms "include" and "comprise" are non-limiting.

As used herein, the term "solid" includes granular, powder, bar, 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 components or compositions contain water in the average of the active portion of the component or composition and are exclusive of impurities, such as residual solvents or by-products, that may be present in commercially available sources of such 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 in the wavelength range of 200nm to 1,000nm (more preferably, 400nm to 750nm) is preferably at least 5 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 of the second colored state at maximum absorbance in the wavelength range of 200nm to 1,000nm (more preferably, 400nm to 750nm) is at least 5 times, preferably 10 times, even more preferably 25 times, most preferably at least 50 times, the maximum molar extinction coefficient of the first colored state in the corresponding wavelength range. The skilled person will appreciate that these ratios may be much higher. For example, the first color state may have as little as 10M in the wavelength range of 400nm to 750nm^-1cm^-1And the second tinting state may have up to 80,000M in the wavelength range of 400nm to 750nm^-1cm^-1Or higher, in which case the ratio of extinction coefficients is 8000:1 or higher.

In one aspect, the maximum molar extinction coefficient of the first color state at a wavelength in the range of 400nm to 750nm is less than 1000M^-1cm^-1And the maximum molar extinction coefficient of the second colored state at a wavelength in the range of 400nm to 750nm is greater than 5000M^-1cm^-1Preferably greater than 10000M^-1cm^-1、25000M^-1cm^-1、50000M^-1cm^-1Or even 100000M^-1cm^-1. Those skilled in the art will recognize and appreciate that polymers comprising more than one leuco moiety may have significantly higher maximum molar extinction coefficients in a first color state (e.g., due to additive effects of multiple leuco moieties or the presence of one or more leuco moieties that convert to a second color state).

The present invention relates to a class of leuco colorants which are useful in laundry care compositions, such as liquid laundry detergents, to provide a blue shade to whiten textile substrates. Leuco colorants are compounds that are substantially colorless or only slightly colored but are capable of exhibiting a strong color upon activation. One advantage of using leuco compounds in laundry care compositions is that such compounds, which are colorless before being activated, are able to cause the laundry care composition to assume its own color. Leuco colorants do not generally alter the primary color of the laundry care composition. Thus, manufacturers of such compositions can formulate colors that are most attractive to consumers without fear that added ingredients (e.g., bluing agents) will affect the final color values of the compositions.

The range of textiles found in consumer homes is very large and often includes garments constructed from: various natural and synthetic fibers, and mixtures of these fibers in the same wash load (wash load) or even in the same garment. These textiles may be constructed in a variety of ways and may include any of a number of finishes (finish) that may be applied by the manufacturer. The amount of any such finish that remains on the consumer's textiles depends on a number of factors including the durability of the finish under the particular wash conditions employed by the consumer, the particular detergents and additives that the consumer may have used, and the number of cycles the textiles have been washed. Depending on the history of each textile, the finish may be present to varying degrees or substantially absent, while other materials present in the wash or rinse cycle, as well as contaminants encountered during wear, may begin to accumulate on the textile.

It is keenly known to those skilled in the art that any detergent formulation used by the consumer will encounter a spectrum of potential textiles and it is expected that the mode of action of the formulation on certain textiles will not only be possible but will actually be significantly different compared to other textiles. These differences can be found by routine experimentation. For example, the leuco colorants of the present invention have been found to increase the whiteness of consumers' aged garments, as well as garments to which a fabric enhancer has been applied, to a greater extent than the leuco colorants increase the whiteness of new garments from which the finish has been removed by successive washes. Thus, formulations containing such leuco colorants may be preferred over traditional formulations, even formulations containing conventional color shade modulators, because newer garments are generally less prone to yellowing problems, while older consumer aged garments are more prone to yellowing problems. The leuco colorants of the present invention have a bias to increase the whiteness of aged garments relative to clean new garments, which is greater than the bias exhibited by many conventional tone modulators.

As noted above, in a first embodiment, the present invention provides a leuco composition comprising at least one leuco compound comprising a leuco portion and an alkylene oxide portion covalently bonded to the leuco portion, wherein the alkylene oxide portion comprises at least one ethylene oxide group and at least one propylene oxide group.

The leuco compound may comprise any suitable leuco moiety as defined above. In one aspect, the leuco moiety is preferably selected from the group consisting of diarylmethane leuco moieties, triarylmethane leuco moieties, oxazine moieties, thiazine moieties, hydroquinone moieties, and arylaminophen moieties.

Suitable diarylmethane leuco moieties for use herein include, but are not limited to, monovalent or polyvalent diarylmethylene moieties capable of forming the second colored state described herein. Suitable examples include, but are not limited to, moieties derived from Michler's methane, diarylmethylenes substituted with-OH groups (e.g., Michler's alcohol) and ethers and esters thereof, diarylmethylenes substituted with photocleavable groups such as-CN groups (bis (p-N, N-dimethyl) phenyl) acetonitrile), and similar such moieties.

In a more particularly preferred aspect, the leuco moiety is a monovalent or multivalent moiety derived by removing one or more hydrogen atoms from the structure of formula (I), (II), (III), (IV) or (V) below

Wherein the ratio of formulae I to V to their oxidized forms 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), wherein each individual R on each of rings A, B and C_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)^-)₂(ii) a Wherein subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0; wherein at different A, B andtwo R on the C ring_oMay combine to form five or more membered fused rings; when the fused ring is a six-or more-membered ring, the two Rs on different A, B and C rings_oCan combine to form an organic linker optionally comprising one or more heteroatoms; in one embodiment, the two R's on the different A, B and C rings_oCombine to form a heteroatom bridge selected from-O-and-S-, thereby forming a six-membered fused ring; r on the same ring_oAnd R_mOr R on the same ring_mAnd R_pMay combine to form aliphatic fused rings or aromatic fused rings, any of which may contain heteroatoms; on 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 on at least two of rings A, B and C_oAnd R_mThe radicals are hydrogen; in some embodiments, all R on rings A, B and C_oAnd R_mThe radicals are hydrogen; preferably each R_pIndependently selected from hydrogen, — OR¹and-NR¹R²(ii) a Not more than two, preferably not more than one R_pIs hydrogen, preferably all R_pAre not hydrogen; more preferably at least one, preferably two, most preferably all three R_pis-NR¹R²(ii) a In some embodiments, one or even two of rings A, B and C may be independently selected C comprising one or two heteroatoms independently selected from O, S and N₃–C₉Heteroaryl ring substitution, said C₃–C₉Heteroaryl rings are 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, and 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 ring members selected from-O-NR¹⁵and-S-additional 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 moieties, — c (o) R¹、─C(O)OR¹、─C(O)NR¹R²(ii) a And each R²²And R²³Independently selected from hydrogen, alkyl and substituted alkyl.

In the structure of formula (IV), R³⁰Ortho OR para to the bridging amine moiety 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、─P(O)₂R¹、─P(O)(OR¹)₂、─P(O)(OR¹)O^-and-P (O)^-)₂(ii) a Wherein subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0; -NR³⁴R³⁵In ortho or para position to the bridging amine moiety, 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)OR¹and-C (O) R¹(ii) a When g is 2 to 4, any two adjacent R³¹The groups may combine to form five or more membered fused rings, wherein no more than two atoms in the fused ring may be nitrogen atoms.

In the structure of formula (V), 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 subscript n is an integer of 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 subscript n is an integer of 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 is balanced with an appropriately independently selected internal or external counterion. Suitably independently selected external counterions can be cationic or anionic. Examples of suitable cations include, but are not limited to: one or more metals, preferably one or more metals selected from groups I and II, of which the most preferred are 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, methosulfate, ethylsulfate, cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluoroborate, acetate, chloroacetate, cyanoacetate, hydroxyacetate, aminoacetate, methylamoacetate, dichloroand trichloroacetate, 2-chloropropionate, 2-hydroxypropionate, glycolate, thioglycollate, thioacetate, phenoxyacetate, pivalate, valerate, palmitate, acrylate, oxalate, malonate, crotonate, succinate, citrate, methylene-bis-thioglycolate, Ethylene-bis-imino acetate, nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate, chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate, indolyl acetate, chlorobenzenesulfonate, benzenesulfonate, toluenesulfonate, biphenylsulfonate and chlorotoluenesulfonate. It is clear to one of ordinary skill in the art that different counterions can be used in place of those listed above.

As described above, the leuco compound includes an alkylene oxide moiety in addition to a leuco moiety. In one aspect, the alkylene oxide moiety comprises at least one ethylene oxide group and at least one propylene oxide group. In another aspect, the alkylene oxide moiety comprises from 1 to about 20 ethylene oxide groups and from 1 to about 20 propylene oxide groups. In the alkylene oxide moiety, the different alkylene oxide groups may be arranged in a block configuration or a random configuration. In one aspect, the alkylene oxide groups of the alkylene oxide moieties are arranged in a block configuration.

The alkylene oxide moiety can be covalently bonded to the leuco moiety by any suitable linking group. In one aspect, the alkylene oxide moiety is covalently bonded to the leuco moiety through 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 valence of the oxygen atom is occupied by an alkylene oxide moiety and a second valence of the oxygen atom is occupied by the remainder of the leuco moiety. When the linking group is a nitrogen atom, one valence of the nitrogen atom is occupied by the remainder of the leuco moiety and one valence of the nitrogen atom is occupied by the alkylene oxide moiety. The remaining valencies of the nitrogen atom may be occupied by any suitable group, such as a second alkylene oxide moiety. In one aspect, the alkylene oxide moiety is covalently bonded to the leuco moiety, preferably through a nitrogen atom. In this embodiment, the nitrogen atom and alkylene oxide moiety together have the structure-NR¹(C₂H₄O)_n(C₃H₆O)_qH, wherein n and q are independently selected from integers of 1 to 5, and R¹Selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and alkylene oxide moieties. In another aspect, the leuco compound comprises two alkylene oxide moieties, each alkylene oxide moiety being covalently bonded to the leuco moiety through a nitrogen atom, wherein the nitrogen atom and the alkylene oxide moieties together have the structure

Wherein n, q, r and s are independently selected from integers of 0 to 5, the sum of n and r is 2 to 10, and the sum of q and s is 2 to 10. In a more particular aspect, the sum of n and r is 2 to 5 and the sum of q and s is 2 to 5.

The leuco compounds included in the compositions can comprise any suitable structure having the characteristics described above. In one aspect, the leuco compound conforms to the structure of formula (CI), (CII), (CIII), (CIV), or (CV) below

Wherein the ratio of formulae CI to CV to their oxidized forms 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 (CI), each individual R on each of rings A, B and C_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)^-)₂(ii) a Wherein subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0; wherein the two R's on different A, B and C rings_oCan combine to form five or more membersA condensed ring; when the fused ring is a six-or more-membered ring, the two Rs on different A, B and C rings_oCan combine to form an organic linker optionally comprising one or more heteroatoms; in one embodiment, the two R's on the different A, B and C rings_oCombine to form a heteroatom bridge selected from-O-and-S-, thereby forming a six-membered fused ring; r on the same ring_oAnd R_mOr R on the same ring_mAnd R_pMay combine to form aliphatic fused rings or aromatic fused rings, any of which may contain heteroatoms; on 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 on at least two of rings A, B and C_oAnd R_mThe radicals are hydrogen; in some embodiments, all R on rings A, B and C_oAnd R_mThe radicals are hydrogen; preferably each R_pIndependently selected from hydrogen, — OR¹and-NR¹R²(ii) a Not more than two, preferably not more than one R_pIs hydrogen, preferably all R_pAre not hydrogen; more preferably at least one, preferably two, most preferably all three R_pis-NR¹R²(ii) a In some embodiments, one or even both of rings A, B and C may be independently selected C comprising one or two heteroatoms independently selected from O, S and N₃–C₉Heteroaryl ring substitution, said C₃–C₉Heteroaryl rings are optionally substituted with one or more independently selected R⁵Substituted by groups; g is independently selected from hydrogen, deuterium, C₁-C₁₆Alkoxides, phenoxides, bisphenolates, nitrites, nitriles, alkylamines, imidazoles, arylamines, polyalkylene oxides, halides, alkylsulphides, arylsulphides 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, and 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-membered ring or moreA ring, optionally comprising one or more rings selected from-O-NR¹⁵and-S-additional heteroatoms.

In the structures of formulae (CII) and (CIII), the variables 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 moieties, — c (o) R¹、─C(O)OR¹、─C(O)NR¹R²(ii) a And each R²²And R²³Independently selected from hydrogen, alkyl and substituted alkyl.

In the structure of formula (CIV), R³⁰Ortho OR para to the bridging amine moiety 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、─P(O)₂R¹、─P(O)(OR¹)₂、─P(O)(OR¹)O^-and-P (O)^-)₂(ii) a Wherein subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0; -NR³⁴R³⁵In ortho or para position to the bridging amine moiety, 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)OR¹and-C (O) R¹(ii) a When g is 2 to 4, any two adjacent R³¹The groups may combine to form five or more membered fused rings, wherein no more than two atoms in the fused ring may be nitrogen atoms.

In the structure of formula (CV), 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 subscript n is an integer of 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 subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0; r⁴⁴is-C (O) R¹、─C(O)NR¹R²and-C (O) OR¹。

In the formulae (I) to (V) and (C)I) In the structure of (CV) to (CV), 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, wherein the monomer molecular weight is in the range of 28 to 500, preferably 43 to 350, even more preferably 43 to 250, wherein the organic group may be partially substituted with one or more additional leuco colorant(s) conforming to the structure of formula I to V. In one aspect, R⁴Selected from the group consisting of alkylene oxides (polyethers), oxyalkylene oxides (polyesters), oxyalkylene amines (polyamides), epichlorohydrin, quaternized epichlorohydrin, alkylene amines, hydroxyalkylene, acyloxyalkylene, carboxyalkylene, alkoxycarbonylalkylene, and sugars. Where any leuco colorant comprises R having three or more contiguous monomers⁴In the case of a group, that leuco colorant is defined herein as a "polymeric leuco colorant". Those skilled in the art know that the nature of a compound with respect to any of a number of characteristic attributes (e.g., solubility, partitioning, deposition, removal, staining, etc.) is related to the placement, identity, and number of the contiguous monomers incorporated therein. Thus, the layout, identity and number of said contiguous monomers may be adjusted by the person skilled in the art in order to change any specific property in a more or less predictable manner.

In the structures of formulae (CI) to (CV), R¹、R²And R³Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R⁴。R⁴Is an alkylene oxide moiety as described above.

Furthermore, in the structures of formulae (CI) to (CV), any charge present in any of the foregoing groups is balanced with an appropriately independently selected internal or external counterion. Suitably 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 preferred among these being 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, glycolate, aminoacetate, methylaminoacetate, dichloroand trichloroacetate, 2-chloropropionate, 2-hydroxypropionate, glycolate, thioglycolate, thioacetate, phenoxyacetate, pivalate, valerate, palmitate, acrylate, oxalate, malonate, crotonate, succinate, citrate, methylene-bis-thioglycolate, ethylene-bis-iminoacetate, sulfate, aminosulfate, nitrate, dihydrogenphosphate, hydrogenphosphate, hydrogencarbonate, carbonate, methosulfate, acetate, chloroacetate, thioglycolate, glycolate, acrylate, oxalate, malonate, crotonate, succinate, citrate, methylene-bis-thioglycolate, ethylene, Nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate, chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate, indoleacetate, chlorobenzenesulfonate, benzenesulfonate, toluenesulfonate, biphenylsulfonate and chlorotoluenesulfonate. It is clear to one of ordinary skill in the art that different counterions can be used in place of those listed above.

Thus, in one aspect, the leuco compound is a triarylmethane leuco compound of formula (CI)

Wherein the ratio of formula (CI) to its oxidized form is at least 1: 3; wherein each individual R on each of rings A, B and C_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、─(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)^-)₂(ii) a Wherein subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0; wherein R is on 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(ii) a Wherein G is independently selected from hydrogen, deuterium, C₁-C₁₆Alkoxides, phenoxides, bisphenolates, 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 alkylene oxide moiety; and wherein any charge present in the compound is in equilibrium with an appropriately independently selected internal or external counterion.

In one aspect, preferred leuco compounds include those conforming to the structure of formula (CVI),

wherein each R⁴Independently selected from H, methyl, ethyl, ((CH)₂CH₂O)_a(C₃H₆O)_b) H and mixtures thereofAn agent; preferably at least one R⁴The radical being ((CH)₂CH₂O)_a(C₃H₆O)_b) H; wherein each subscript a is independently an integer of 1 to 100, each subscript b is independently an integer of 0 to 50, and wherein all R⁴The sum of all independently selected a integers in the group does not exceed 100, and all R' s⁴The sum of all independently selected b integers in the group is no more than 50. Preferably at least two R⁴The groups are selected from methyl and ethyl, most preferably at least one N in the structure (CVI) is replaced by two R's selected from methyl and ethyl, preferably methyl⁴And (4) substituting the group.

In another aspect, highly preferred leuco compounds include those conforming to the structure of formula (CVII),

wherein each subscript c is independently 0, 1 or 2, preferably each c is 0 or 1, more preferably the two independently selected values of c are the same; each R⁴Independently selected from H, Me, Et, ((CH)₂CH₂O)_a(C₃H₆O)_b) H and mixtures thereof; preferably, each R⁴Is ((CH)₂CH₂O)_a(C₃H₆O)_b) H, wherein each subscript a is independently an integer of from 1 to 50, more preferably from 1 to 25, even more preferably from 1 to 20, 1 to 15, 1 to 10, 1 to 5, or even 1 to 2; each subscript b is independently an integer of 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 colorants is no more than 100, more preferably no more than 80, most preferably no more than 60, 40, 20, 10, or even no more than 5, and the sum of all independently selected b integers in the leuco colorants is no more than 50, more preferably no more than 40, most preferably no more than 30, 20, or even 10. In a particularly preferred aspect, each subscript c is 1 and each R is⁴Is ((CH)₂CH₂O)_a(C₃H₆O)_b) H, each subscripta is an integer from 1 to 5, each subscript b is an integer from 1 to 5, the sum of all independently selected a integers in the leuco compound is from 4 to 10, and the sum of all independently selected b integers in the leuco colorant is from 5 to 15.

In another aspect, highly preferred leuco compounds include those conforming to the structure of formula (CVIII),

wherein R is⁸Is H or CH₃And each subscript b independently averages about 1 to 2.

In one aspect, the leuco colorants of the present invention 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. In another aspect, the surface tension value of the second colored state of the leuco colorant is 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 surface tension values of both the leuco colorant and its corresponding second colored state are greater than 45mN/m, more preferably greater than 47.5mN/m, and most preferably greater than 50 mN/m.

The leuco triarylmethane compounds described herein can be produced by any suitable synthetic method. For example, such compounds can be prepared by an acid catalyzed condensation reaction between an aromatic aldehyde and an electron rich aryl coupling agent (e.g., in an amount of about 2 molar equivalents of aryl coupling agent to 1 molar equivalent of aromatic aldehyde). The aromatic aldehyde can be any suitable compound comprising an aromatic moiety (e.g., an aryl moiety, a substituted aryl moiety, a heteroaromatic moiety, or a substituted heteroaromatic moiety) having an aldehyde group covalently attached thereto. In one aspect, the aromatic aldehyde is preferably a substituted benzaldehyde, preferably comprising a compound having the structure-OR in the para position relative to the aldehyde group¹or-NR¹R²A group of (1). In another aspect, the aromatic aldehyde is preferably a substituted benzaldehyde comprising a group-NR in the para position relative to the aldehyde group¹R²Wherein R is¹And R²Selected from hydrogen,Methyl or ethyl (more preferably methyl).

As mentioned above, the condensation reaction uses an aryl coupling agent in addition to the aromatic aldehyde. To produce leuco triarylmethane compounds, the condensation reaction typically utilizes at least two molar equivalents of aryl coupling agent per molar equivalent of aromatic aldehyde. In one aspect, two molar equivalents of the aryl coupling agent used in the reaction can be provided using a single aryl coupling agent compound. In another aspect, the reaction can be carried out using a mixture of two molar equivalents of two or more different aryl coupling agents. In this embodiment, two or more different aryl coupling agents may be used in any combination or relative proportions, so long as the mixture totals at least about two molar equivalents of aryl coupling agent per molar equivalent of aromatic aldehyde. In such embodiments, two or more different aryl coupling agents may differ, for example, in the number and/or nature of substituents attached to the aryl moiety. In one aspect, the reaction may utilize a first aryl coupling agent comprising a first oxyalkylene group or polyoxyalkylene moiety having a first distribution of oxyalkylene groups and a second aryl coupling agent comprising a second oxyalkylene group or polyoxyalkylene moiety having a second distribution of oxyalkylene groups different from the first distribution. For example, in one aspect, the first aryl coupling agent may comprise an oxyalkylene moiety comprised of an oxirane group, such as AC-I below, and the second aryl coupling agent may comprise a polyoxyalkylene moiety comprised of an oxirane group and a glycidoxy group, such as AC-II below.

Wherein subscripts a, b, c, and d are independently selected from an integer of 0 to 5; the sum of a and b of the coupling agents selected from the group consisting of AC-I and AC-II is from 2 to 10, and the sum of c and d in AC-II is from 2 to 10. In a more particular aspect, the sum of a and b of the coupling agents selected from AC-I and AC-II is from 2 to 5, and the sum of c and d in AC-II is from 2 to 5. In one embodiment, the sum of subscripts a and b in AC-I is 2 or 3; and the sum of subscripts a and b in AC-II is 2 or 3, and the sum of subscripts c and d in AC-II is 1 to 5, preferably 2 to 4, or even 2 to 3. The coupling agents AC-I and AC _ II may be combined in any ratio as long as the amount of coupling agent used is sufficient to provide at least two molar equivalents relative to the equivalents of aromatic aldehyde used in the acid-catalyzed condensation reaction to produce the leuco compound.

In one aspect, for example, one equivalent of p-N, N-dimethylbenzaldehyde is condensed with at least two molar equivalents of a mixture of aryl coupling agents AC-I and AC-II shown above, wherein for the aryl coupling agent AC-I, the sum of subscripts a and b is 2 or 3, preferably 2, and wherein preferably a and b are each 1; wherein for the aryl coupling agent AC-II, the sum of subscripts a and b is 2 or 3, preferably 2, and wherein preferably a and b are each 1, and the sum of subscripts c and d is, on average, about 2.5 to 3.0, and wherein at least one of c or d is 1.

One of ordinary skill in the art will recognize that when two or more different aryl coupling agents are used in the preparation of the leuco compounds herein, the intended product resulting from this reaction will comprise a leuco compound comprising a non-different (non-distintint) coupling agent (for as many different coupling agents as possible) as well as a cross-coupled leuco compound comprising a mixture of the aryl coupling agents used. For example, when prepared using two different aryl coupling agents a and B used in substantially equimolar amounts, the product distribution (excluding any perturbation due to reactivity differences) will include about 25% of the leuco compound containing the two a coupling agents, 25% of the leuco compound containing the two B coupling agents, and 50% of the leuco compound containing one a coupling agent and one B coupling agent.

Exemplary leuco compositions can be prepared according to the general methods described below for compositions in which the aryl aldehyde corresponds to Ar-C (O) H, but are readily adaptable.

The four-necked flask was equipped with an overhead stirrer, condenser, temperature controller, heating mantle and nitrogen inlet tube. Then, about 2 moles of the aryl coupling agent or mixture of aryl coupling agents are added to the flask and heated to about 65-71 ℃. During heating, about 1 mole of Ar-C (O) H and a catalytic amount (about 0.4 mole) of urea pre-dissolved in a small amount of water were added. After the above chemicals were mixed, about 1.2 moles of hydrochloric acid (in the form of hydrochloric acid) was added dropwise to control the temperature below 90-100 ℃. After addition of hydrochloric acid, the reaction was stirred at 95-100 ℃ for about 7 hours.

Various methods can be used to recover the leuco colorants synthesized by the above-described methods. One method is to neutralize the reaction product to a pH of about 9 and remove the water by rotary evaporation under reduced pressure. The resulting viscous mass is diluted with an organic solvent, such as isopropanol, and filtered to remove inorganic salts. The organic solvent was evaporated to give the final product.

In another embodiment, the present invention provides a leuco composition obtained by the steps of: (i) providing one molar equivalent of an aromatic aldehyde, (ii) providing about two molar equivalents of an aryl coupling agent or a mixture of aryl coupling agents, wherein at least one aryl coupling agent comprises a covalently bound alkylene oxide or polyoxyalkylene moiety, wherein the alkylene oxide or polyoxyalkylene moiety comprises at least one ethylene oxide group and at least one propylene oxide group, (iii) combining the aromatic aldehyde and the one or more aryl coupling agents in a suitable reaction vessel, (iv) adding 0.01 to 0.5 equivalents of urea, (v) adding technical grade hydrochloric acid to achieve a pH between about 0 and 3, (vi) heating the mixture between 60 ℃ and 120 ℃ for 2 hours to 12 hours, (vii) adjusting the pH to at least about 7, and (viii) separating at least a portion of the salt formed upon neutralization from the liquid product; wherein the leuco composition comprises at least one leuco compound comprising a leuco portion and an alkylene oxide portion covalently bonded to the leuco portion, wherein the alkylene oxide portion comprises at least one ethylene oxide group and at least one propylene oxide group. In one such embodiment, the leuco compound has the structure of formula (CVII) above, wherein at least one independently selected subscript b has a value of at least 1.

The amount of leuco colorant used in the laundry care compositions of the present invention may be any level suitable to achieve an increase in the whiteness index (WI CIE) of a white fabric or textile. In one aspect, the laundry care composition comprises a leuco colorant in an amount from about 0.0001 wt.% to about 1.0 wt.%, preferably from 0.0005 wt.% to about 0.5 wt.%, even more preferably from about 0.0008 wt.% to about 0.2 wt.%, most preferably from 0.004 wt.% to about 0.1 wt.%.

In another aspect, the laundry care composition comprises a leuco colorant in an amount of from 0.0025 to 5.0 milliequivalents/kg, preferably from 0.005 to 2.5 milliequivalents/kg, even more preferably from 0.01 to 1.0 milliequivalents/kg, most preferably from 0.05 to 0.50 milliequivalents/kg, where the unit of milliequivalents/kg refers to the milliequivalents per kg of leuco portion in the laundry composition for a leuco colorant comprising more than one leuco portion, the number of milliequivalents is related to the number of millimoles of the leuco colorant by the formula (millimoles of leuco colorant) × (number of milliequivalents of leuco portion/millimoles of leuco colorant) to the number of millimoles of leuco colorant in the case of only one leuco portion per leuco colorant.

The leuco compositions of the present invention may comprise other compounds in addition to the one or more leuco compounds, one or more antioxidant compounds, and one or more solvents described above. For example, the leuco composition may contain up to about 2% by weight of a salt (e.g., sodium chloride or sodium sulfate), unreacted starting materials used in the preparation of one or more leuco compounds, impurities resulting from side reactions of those starting materials, and leuco compounds or degradation products of such impurities. Specific non-limiting examples of such materials include compounds of the formulae (DI) - (DV)

In the structures of formulae (DI) - (DV), R¹⁰¹And R¹⁰²Independently selected from hydrogen, alkyl (e.g., methyl) and oxyalkylene groups. The oxyalkylene groups can contain any suitable number of oxyalkylene repeating units (e.g., ethylene oxide and/or propylene oxide), such as described above for the leuco compositionsThe leuco compound present in (a). R¹⁰¹And R¹⁰²Such oxyalkylene groups of (a) may be independently selected from hydrogen, CH ═ CH₂、-CH₂-CH＝CH₂、-CH＝CH-CH₃、-CH₂-CHO、-CH(CH₃)-CHO、-CH₂-CO-CH₃、-CH₂-COOH、-CH(CH₃)-COOH、-CH₂-CH₂Cl、-CHCl-CH₃、-CH₂-CH₂-CH₂Cl、-CH₂-CHCl-CH₃and-CHCl-CH₂-CH₃Is blocked. Furthermore, the radical R¹⁰¹And R¹⁰²Can be combined to form a structure-CH₂CH₂─O─CH₂CH₂-a group which, together with the nitrogen atom, forms a morpholine ring. Other compounds that may be present in the leuco compositions include compounds of the formulae (DVI) - (DIX)

Each aryl moiety of the compounds of formula (DVI) - (DIX) may independently be unsubstituted or, usually, be nitro or have the structure-NR at the para-position¹⁰¹R¹⁰²Wherein R is¹⁰¹And R¹⁰²Independently selected from the above groups. Additional compounds that may be present in the leuco compositions include compounds containing the compound having the structure-NR, typically in the para position relative to the hydroxyl group¹⁰¹R¹⁰²Phenols and aminophenols of the group (b), wherein R¹⁰¹And R¹⁰²Independently selected from the above groups. The leuco compositions may also contain compounds of formulae (DX) and (DXI)

In the structures of (DX) and (DXI), the aryl moiety and the cyclohexadienyl moiety may be unsubstituted or, in general, nitro at the para-position or have the structure-NR¹⁰¹R¹⁰²Wherein R is¹⁰¹And R¹⁰²Independently selected from the above radicalsAnd (4) clustering. The leuco compositions may also contain condensation products of certain of the above-mentioned compounds, for example compounds of formula (DXII)

As noted above, the leuco compositions may also contain a colored (e.g., oxidized) form of one or more leuco compounds present in the composition. In the case of triarylmethane leuco colorants, the oxidized form of the triarylmethane leuco colorant (which contains a central carbonium ion) may form an adduct with an anion present in the leuco composition, such as the anions described above, as charge-balancing counterions suitable for use with one or more of the leuco compounds.

The unreacted starting materials and impurities described above can be present in the leuco composition in any suitable amount. Preferably, these materials and impurities are present in the leuco composition in relatively small amounts, which do not adversely affect the performance of the leuco colorant(s) to any substantial extent. Excluding inorganic salts, unreacted starting materials and water, in a preferred embodiment, the impurities are present in an amount of less than 10 wt.%, preferably less than 5 wt.%, and more preferably less than 2 wt.%, relative to the active leuco compound.

The leuco composition may comprise any suitable number of leuco compounds as described above. In addition, the leuco compositions can comprise any suitable solvent in addition to one or more leuco compounds. In one aspect, the leuco composition comprises a solvent selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, poly (ethylene glycol), poly (propylene glycol), copolymers of ethylene oxide and propylene oxide, and mixtures thereof. In another aspect, the leuco composition comprises a solvent selected from the group consisting of poly (ethylene glycol), poly (propylene glycol), copolymers of ethylene oxide and propylene oxide, the nonionic surfactants disclosed below, and mixtures thereof. In a preferred embodiment, the leuco composition is dissolved in a poly (ethylene glycol) such as PEG200 prior to incorporation into the laundry care composition.

In one aspect, the leuco composition comprises an antioxidant compound in addition to one or more leuco compounds and any suitable solvent that may be present the antioxidant compound is useful in stabilizing the composition and reducing the amount of leuco compounds prematurely converted to a second color state in the composition any suitable antioxidant compound may be used in one aspect the antioxidant compound is selected from hindered phenols (e.g., BHT, irganox 1135, irganox1076, irganox 1010, irganox 1330, and irganox 1035), aromatic amines and derivatives thereof (e.g., irganox5057), α -, β -, γ -, -tocopherols, auxinols, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignin sulfonic acid and salts thereof, 6-hydroxy-2, 5,7, 8-tetramethylchroman-2-carboxylic acid (Trolox)^TM)1, 2-Benzisothiazolin-3-one (Proxel GX L)^TM) Benzofuran or benzopyran derivatives, for example sold by Milliken and Company, Spartanburg, USA

HP136 and AOX-1), tocopherol sorbate, butylated hydroxybenzoic acid and salts thereof, gallic acid and alkyl esters thereof, uric acid and salts and alkyl esters thereof, sorbic acid and salts thereof, dihydroxy fumaric acid and salts thereof, aromatic amines (e.g.

5057) And mixtures thereof. In the case where the antioxidant is a liquid that is miscible with the leuco composition, the antioxidant may act as a solvent or co-solvent.

The leuco compositions of the present invention should be stored and transported in a closed container to prevent contamination by dust, moisture or other foreign matter. Preferably, the leuco compositions are stored and transported in airtight containers. The transport vessel may be constructed of a material having a low oxygen permeability coefficient P, where P ═ (amount permeated) (film thickness)/(surface area) (time) (pressure drop across the membrane) in units of [ cm [^3.cm]/[cm^2.s.(cmHg)]. From which P x10 a suitable container may be formed¹⁰A material composition of less than 10, more preferably less than 5, most preferably less than 2 at 30 ℃. This limits the exposure of the material to oxygen and limits the conversion of the leuco compound to the second colored state during storage and transportation.

The containers may be made of bulk cargo in tank wagons, bails, drums, glass jars, or cylinders of any suitable size, most preferably the containers are made of stainless Steel or HDPE the containers may be open-ended containers or sealed-mouth containers stainless Steel containers may be unlined or optionally lined with any suitable coating (e.g., epoxy or epoxy-phenolic coatings). some containers may contain at least one drain valve, and the containers are preferably ruggedized, stackable and DOT/UN certified

SM 6、

SM 13、

SM 15、

SM EX、

SM L p optionally, the HDPE container can contain additives for protecting the contents from ultraviolet and visible light, for example

SM L P handbag, etc. additionally, HDPE containers may contain a mixture of the same formed by EVOAn H-barrier or additional protection provided by the Dualprotect system available from the Sch ü tz packaging system.

As explained above, the leuco compositions of the present invention are relatively stable, requiring no special shipping or packaging requirements. For example, the material need not be packaged under an inert atmosphere or transported under climate control 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 such materials or other less stable materials under anoxic atmospheres, cold temperatures, or both. One method of creating an oxygen deficient atmosphere 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 the vessel and backfilling the vessel with an inert gas. When purging, the purge time should be at least three times longer, and more preferably five times longer, than the time required to fill the headspace in the vessel. During purging or backfilling, the internal pressure should be near atmospheric pressure, or slightly above atmospheric pressure. The preferred internal pressure range is 0.5 to 2 atmospheres, more preferably 0.8 to 1.5 atmospheres, and most preferably 0.95 to 1.2 atmospheres. One skilled in the art will recognize that the ideal pressure is the value under the conditions encountered during purging or backfilling, and that as the temperature changes, the gas pressure will change, approximately 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 before or after packaging.

For any container in which the present leuco compositions or even less stable materials are 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%, which in turn limits 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 colored state. Furthermore, a container design that minimizes the surface area of the interface between the material and the headspace is generally preferred. For this reason, transporting the material by means of restricting the movement of the material within the container reduces the time-averaged surface area and may contribute to an improved stability of the material (especially of materials comprising leuco compounds of slightly lower stability).

As mentioned above, the material of the invention is stable enough 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 temperatures for storing and transporting chemicals range from-30 ℃ to 60 ℃, more preferably from-10 ℃ to 50 ℃, most preferably from 0 ℃ to 35 ℃.

Additional protection of the product, such as an oxygen scavenger located in a film, pouch (sachet), or by direct incorporation into the packaging material, may be used to maintain an oxygen-depleted atmosphere within the container.

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

The above leuco compounds and compositions are believed to be suitable for use in the treatment of textile materials (e.g., domestic laundry processes). In particular, it is believed that the leuco compound will 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 compounds may be converted into colored compounds by applying suitable chemical or physical triggers that convert the leuco compounds into their colored form. For example, when a leuco compound is oxidized to an oxidized compound, the leuco compound may be converted to its colored form. By selecting the appropriate leuco moiety, the leuco compound can be designed to impart a desired hue to the textile material upon conversion of the leuco compound into its colored form. For example, leuco compounds which, when converted into their colored form, assume a blue hue can be used to counteract yellowing of textile materials which typically occurs as a result of the passage of time and/or repeated washing. Accordingly, in other embodiments, the present invention provides laundry care compositions comprising the above-described leuco compounds, as well as domestic methods for treating textile materials (e.g., methods for washing laundry or clothes).

Preferably, the leuco compound, upon conversion to its second color state, provides the fabric with a hue at 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 may be determined as further detailed herein with respect to deposition of the leuco moiety on the cotton substance relative to the cotton substance without any leuco moiety present.

As noted above, in a second embodiment, the present invention provides a laundry care composition comprising a laundry care ingredient and a leuco composition as described herein. The laundry care composition may comprise any suitable leuco composition or combination of leuco compositions described herein. The laundry care composition may comprise any suitable laundry care ingredient. Laundry care ingredients suitable for use in the present invention are described in detail below.

Laundry care compositions

The laundry care composition may comprise other suitable adjuncts which may be incorporated in whole or in part in some aspects. The adjunct may be selected according to the intended function of the laundry care composition. The first composition may comprise an adjuvant. In some aspects, in the case of a multi-compartment unit dose article, the adjuvant may be part of a non-first (e.g., second, third, fourth, etc.) composition that is enclosed in a compartment separate from the first composition. The non-first composition may be any suitable composition. The non-first composition may be in the form of a solid, liquid, dispersion, gel, paste, or mixture thereof. When the unit dose comprises a plurality of compartments, the leuco colorant may be added to one or both or even all of the compartments, or the leuco colorant may be present in one or both or even all of the compartments. In one embodiment, the leuco colorant is added to a larger compartment, resulting in a lower concentration, which may minimize any problems related to potential contact staining. On the other hand, concentrating the antioxidant with the leuco colorant in a smaller volume compartment may result in a higher local concentration of the antioxidant, which may provide enhanced stability. Thus, as will be appreciated by those skilled in the art, the location and amount of the leuco colorant can be selected by the formulator based on the desired properties of the unit dose.

Auxiliary agent

The laundry care composition may comprise a surfactant system. The laundry care composition may comprise from about 1 wt% to about 80 wt%, or from 1 wt% to about 60 wt%, preferably from about 5 wt% to about 50 wt%, more preferably from about 8 wt% to about 40 wt% of the laundry care composition of a surfactant system.

Surfactant (b): suitable surfactants include anionic, nonionic, cationic, zwitterionic and amphoteric surfactants and mixtures thereof. Suitable surfactants may be linear or branched, substituted or unsubstituted, and may be derived from petrochemical materials or biological materials. Preferred surfactant systems comprise both anionic and nonionic surfactants, preferably in a weight ratio of 90:1 to 1: 90. In some cases, it is preferred that the weight ratio between anionic surfactant and nonionic surfactant is at least 1:1. However, ratios below 10:1 may be preferred. When present, the total surfactant content level is preferably from 0.1 wt% to 60 wt%, from 1 wt% to 50 wt%, or even from 5 wt% to 40 wt% of the subject composition.

Anionic surfactant: anionic surfactants include, but are not limited to: those surface-active compounds which comprise an organic hydrophobic group containing typically 8 to 22 carbon atoms or typically 8 to 18 carbon atoms in their molecular structure, and at least one water-solubilizing group, which is preferably selected from the group consisting of sulfonates, sulfates and carboxylates to form water-soluble compounds. Typically, the hydrophobic group comprises a C8-C22 alkyl, or acyl group. The surfactant is used in the form of a water-soluble salt, and the salt-forming cation is typically selected from sodium, potassium, ammonium, magnesium and a single ion, with the sodium cation typically being selected.

The anionic surfactant and adjuvant anionic co-surfactant of the present invention may be present in the acid form and the acid form may be neutralized to form a surfactant salt which is desirable for use in the detergent compositions of the present invention. Typical reagents for neutralization include metal counterion bases, for example hydroxides such as NaOH or KOH. Other preferred agents for neutralizing the anionic surfactant of the invention in its acid form and adjunct anionic surfactants or co-surfactants include ammonia, amines, oligoamines 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. The amine neutralization may be carried out to all or a partial extent, for example, a portion of the anionic surfactant mixture may be neutralized with sodium or potassium, and a portion of the anionic surfactant mixture may be neutralized with an amine or alkanolamine.

Suitable sulfonate surfactants include methyl ester sulfonate, α -olefin sulfonate, alkyl benzene sulfonate, especially alkyl benzene sulfonate, preferably C_10-13Suitable alkyl benzene sulfonates (L AS) may be obtained by sulfonating a commercially available linear alkyl benzene (L AB), preferably obtained in the above manner suitable L AB includes low (low) 2-phenyl L AB, such AS that sold under the trade name Sasol

Those supplied, or under the trade name Petresa

Other suitable L AB include high (high) 2-phenyl L AB, such as that sold under the trade name Sasol

Suitable anionic surfactants are alkyl benzene sulfonates obtained by DETA L catalyzed processes, although other synthetic routes such AS HF may also be suitable.

Suitable sulphate surfactants include alkyl sulphates, preferably C_8-18Alkyl sulfates, or predominantly C₁₂An alkyl sulfate.

Preferred sulphate surfactants are alkyl alkoxylated sulphates, preferably alkyl ethoxylated sulphates, preferably C_8-18Alkyl alkoxylated sulfates, preferably C_8-18Alkyl ethoxylated sulfates; preferably, the average degree of alkoxylation of the alkyl alkoxylated sulphate is from 0.5 to 20, preferably from 0.5 to 10; preferably, the alkyl alkoxylated sulphate is C with an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3_8-18Alkyl ethoxylated sulfates. The alkyl alkoxylated sulfates may have a broad alkoxy distribution or a peaked (peaked) alkoxy distribution.

The alkyl sulfates, alkyl alkoxylated sulfates and alkyl benzene sulfonates may be linear or branched, including 2-alkyl substituted or unsubstituted mid-chain branched types, and may be derived from petrochemical or biological materials. Preferably, the branching group is an alkyl group. Typically, the alkyl group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, cycloalkyl, and mixtures thereof. One or more alkyl branches may be present on the main hydrocarbon chain of one or more of the starting alcohols used to produce the sulfated anionic surfactants used in the detergents of the invention. Most preferably, the branched sulfated anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof.

Commercially available sulfates include those based on Neodol alcohol from Shell, L ial-Isalchem and Safol from Sasol, natural alcohols from Procter & Gamble Chemicals.

Other suitable anionic surfactants include alkyl ether carboxylates comprising a C10-C26 linear or branched, preferably C10-C20 linear, most preferably C16-C18 linear alkyl alcohol and 2 to 20, preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. Acid forms or salt forms, such as sodium or ammonium salts; and the alkyl chain may contain a cis or trans double bond. The alkyl ether carboxylic acid can be obtained from Kao

Huntsman

And Clariant

And (4) obtaining.

Nonionic surfactant: suitable nonionic surfactants are selected from: c₈-C₁₈Alkyl ethoxylates, e.g. from Shell

A nonionic surfactant; c₆-C₁₂Alkylphenol alkoxylates, wherein preferably the alkoxylate units are ethylene oxide units, propylene oxide units, or mixtures thereof; c₁₂-C₁₈Alcohol and C₆-C₁₂Condensates of alkylphenols with ethylene oxide/propylene oxide block polymers, e.g. from BASF

An alkyl polysaccharide, preferably an alkyl polyglycoside; a methyl ester ethoxylate; polyhydroxy fatty acid amides; ether-terminated poly (oxyalkylated) alcohol surfactants; and mixtures thereof.

Suitable nonionic surfactants are alkyl polyglycosides and/or alkyl alkoxylated alcohols.

Suitable nonionic watchesThe surfactant comprises an alkyl alkoxylated alcohol, preferably C_8-18Alkyl alkoxylated alcohols, preferably C_8-18An alkyl ethoxylated alcohol; preferably, the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10; preferably, the alkyl alkoxylated alcohol is C with an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7_8-18An alkyl ethoxylated alcohol. In one aspect, the alkyl alkoxylated alcohol is C with an average degree of ethoxylation of from 7 to 10_12-15An alkyl ethoxylated alcohol. The alkyl alkoxylated alcohol may be linear or branched, and may be substituted or unsubstituted. Suitable nonionic surfactants include those available under the trade name

Those available from BASF.

Cationic surfactant: suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulfonium compounds, and mixtures thereof.

Preferred cationic surfactants are quaternary ammonium compounds having the general formula:

(R)(R₁)(R₂)(R₃)N⁺X^-

wherein R is a linear or branched, substituted or unsubstituted C_6-18Alkyl or alkenyl moieties, R₁And R₂Independently selected from methyl or ethyl moieties, R₃Is a hydroxyl, hydroxymethyl, or hydroxyethyl moiety, X is an anion that provides charge neutrality, preferred anions include: a halide, preferably chloride; a sulfate salt; and a sulfonate salt.

The fabric care compositions of the present invention may contain 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 cationic surfactant. For the purposes of the present invention, cationic surfactants include those which can provide fabric care benefits. Non-limiting examples of useful cationic surfactants include: fatty amines, imidazoline quaternary materials and quaternary ammonium surfactants, preferably N, N-bis (stearoyl-oxy-ethyl) N, N-dimethylammonium chloride, N-bis (tallow-oxy-ethyl) N, N-dimethylammonium chloride, N-bis (stearoyl-oxy-ethyl) N- (2-hydroxyethyl) N-methylammonium methylsulfate; 1,2 bis (stearoyl-oxy) 3 trimethylammonium chloropropane; dialkylene dimethyl ammonium salts such as dicyabean oil dimethyl ammonium chloride (dicyabean dimethyl ammonium chloride), di (hard) tallow dimethyl ammonium chloride dicyabean oil dimethyl ammonium methyl sulfate; 1-methyl-1-stearamidoethyl-2-stearyl imidazoline methylsulfate; 1-tallowaminoethyl-2-tallowimidazoline; n, N "-dialkyldiethylenetriamine; a reaction product of N- (2-hydroxyethyl) -1, 2-ethylenediamine or N- (2-hydroxyisopropyl) -1, 2-ethylenediamine and glycolic acid esterified 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 (PGE), 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 herein.

Amphoteric and zwitterionic surfactants: suitable amphoteric or zwitterionic surfactants include amine oxides and/or betaines. 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 linear or mid-branched alkyl moieties. Typical linear amine oxides include water-soluble amine oxides containing one R1C 8-18 alkyl moiety and 2R 2 and R3 moieties selected from C1-3 alkyl and C1-3 hydroxyalkyl groups. Preferably, the amine oxide is characterized by the formula R1-N (R2) (R3) O, wherein R1 is C8-18 alkyl, and R2 and R3 are selected from methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. The linear amine oxide surfactants may include, inter alia, linear C10-C18 alkyldimethylamine oxides and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxides.

Other suitable surfactants include betaines, such as alkyl betaines, alkyl amido betaines, amidozoliniumbetaines, sulfobetaines (INCI Sultaines), and phosphobetaines.

Leuco colorant diluents

Another class of ingredients in the leuco colorant compositions can be diluents and/or solvents. The purpose of the diluent and/or solvent is generally, but not limited to, improving the flow of the leuco colorant and/or reducing the viscosity of the leuco colorant. Although water is generally the preferred diluent and/or solvent in view of its low cost and non-toxicity, other solvents may also be used. Preferred solvents are low cost and low hazard solvents. Examples of suitable solvents include, but are not limited to, ethylene glycol, propylene glycol, glycerol, alkoxylated polymers such as polyethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene oxide, and mixtures thereof,

The polymers are generally characterized by a cloud point with water, which can help separate the product from water to remove unwanted water soluble impurities examples of ethylene oxide and propylene oxide copolymers include, but are not limited to, the P L URONIC series of BASF polymers and Dow's TERGITO L^TMA series of polymers. These polymers may also act as nonionic surfactants when the leuco colorant composition is incorporated into a laundry care composition.

The laundry care compositions described herein may also comprise one or more of the following non-limiting ingredients: fabric care benefit agents (benefit agents); washing the enzyme; depositing an auxiliary agent; a rheology modifier; a builder; a chelating agent; a bleaching agent; a decolorizing agent; a bleach precursor; a bleaching aid; a bleach catalyst; flavors and/or flavor microcapsules; zeolite loaded with a flavorant; starch encapsulated accord (starch encapsulated concord); a polyglycerol ester; a whitening agent; a pearlescent agent; an enzyme stabilizing system; scavengers including dye fixatives for anionic dyes, for anionic surfacesComplexing agents for the active agents and mixtures thereof; fluorescent whitening agents or fluorescent whitening agents; polymers, including but not limited to soil release polymers and/or soil suspension polymers; a dispersant; defoaming agents; a non-aqueous solvent; a fatty acid; suds suppressors, such as silicone suds suppressors; a cationic starch; a foam dispersant; a direct dye; a colorant; an opacifying agent; an antioxidant; hydrotropes such as toluene sulfonate, cumene sulfonate and naphthalene sulfonate; color spot (color spot); pigmented beads, spheres or extrudates; a clay softener; an antibacterial agent. Additionally or alternatively, the composition may comprise a surfactant, a quaternary ammonium compound and/or a solvent system. The quaternary ammonium compound can be present in a fabric enhancer composition, such as a fabric softener, and comprises a quaternary ammonium cation which is of the structure NR₄ ⁺Wherein R is an alkyl or aryl group

Shading dyes

The composition may comprise additional fabric shade modifiers. Suitable fabric shading agents include dyes, dye-clay conjugates, and pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of: dyes falling within the color index (c.i.) classification of direct blue, direct red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet, and basic red, or mixtures thereof. Preferred dyes include alkoxylated azothiophene, solvent violet 13, acid violet 50 and direct violet 9.

An aesthetic colorant. The composition may comprise one or more aesthetic colorants (aesthetical colorants). Suitable aesthetic colorants include dyes, dye-clay conjugates, pigments, and

polymeric colorants (Milliken and Company, Spartanburg, South Carolina, USA). In one aspect, suitable dyes and pigments include small molecule dyes and polymeric dyes. The aesthetic colorant may include at least one chromophore component selected from the group consisting of: acridines, anthraquinones, azines, acridines,Azo, benzodifuran, benzodifuranone, carotenoid, coumarin, cyanine blue, diaza hemicyanine blue, diphenylmethane, formazan

Hemicyanine blue, indigoids, methane, methine, naphthalimide, naphthoquinone, nitro, nitroso, oxazine, phenothiazine, phthalocyanines (e.g., copper phthalocyanine), pyrazoles, pyrazolones, quinolones, stilbenes, styryl, triarylmethanes (e.g., triphenylmethane), xanthene, and mixtures thereof.

In one aspect of the invention, aesthetic colorants include

Blue AH, AH,

Blue BB,

Blue 275,

Blue 297,

Blue BB, cyan 15,

Green color 101,

Orange 272,

255 portions of orange,

Pink AM,

Pink AMC,

Pink ST,

Purple 129,

Purple L S,

Purple 291,

Yellow FT,

Blue Buf,

Pink AM,

Pink PV, acid blue 80, acid blue 182, acid red 33, acid red 52, acid violet 48, acid violet 126, acid blue 9, acid blue 1, and mixtures thereof.

An encapsulate. The composition may include an encapsulating material. In one aspect, an encapsulate comprises a core, a shell having inner and outer surfaces, wherein the shell encapsulates the core. The core may comprise any laundry care aid, although typically the core may comprise a material selected from: a fragrance; a whitening agent; a hue adjusting dye; an insect repellent; a silicone; a wax; a seasoning; a vitamin; a fabric softener; skin protectants (in one aspect, paraffin); an enzyme; an antibacterial agent; a bleaching agent; sensates (sensates); and mixtures thereof; and the housing may comprise a material selected from the group consisting of: polyethylene; a polyamide; polyvinyl alcohol, optionally containing other comonomers; polystyrene; a polyisoprene; a polycarbonate; a polyester; a polyacrylate; polyamide plastics (in one aspect, the polyamide plastics may include polyureas, polyurethanes, and/or polyurea urethanes; in one aspect, the polyureas may include polyoxymethylene ureas and/or melamine formaldehydes); a polyolefin; polysaccharides (in one aspect, the polysaccharides may include alginate and/or chitosan); gelatin; shellac; an epoxy resin; a vinyl polymer; an insoluble aqueous inorganic substance; a silicone; and mixtures thereof.

Preferred encapsulates include perfume. Preferred enclosures include a housing, which may include melamine formaldehyde and/or cross-linked melamine formaldehyde. Other preferred capsule bodies include polyacrylate based shells. Preferred encapsulates comprise a core material and a shell, the shell being disclosed as at least partially surrounding the core material. At least 75%, 85% or even 90% of the encapsulates may have a break strength of 0.2Mpa to 10Mpa and a benefit agent leakage of 0% to 20%, or even less than 10% or 5%, based on the total initial encapsulated benefit agent. Preferably, at least 75%, 85% or even 90% of the encapsulates may have: (i) a particle size of 1 micron to 80 microns, 5 microns to 60 microns, 10 microns to 50 microns, or even 15 microns to 40 microns, and/or (ii) at least 75%, 85%, or even 90% of the encapsulates may have a particle wall thickness of 30nm to 250nm, 80nm to 180nm, or even 100nm to 160 nm. The formaldehyde scavenger may be used with the encapsulate, for example in a capsule slurry and/or added to the composition before, during or after the encapsulate is added to the composition. Can be prepared by following the USPA 2008/0305982A 1; and/or USPA2009/0247449a 1. Alternatively, suitable capsules can be purchased from Appleton Papers inc.

In a preferred aspect, the composition may comprise a deposition aid, preferably in addition to the encapsulate. Preferred deposition aids are selected from cationic polymers and nonionic polymers. Suitable polymers include cationic starch, cationic hydroxyethyl cellulose, polyvinyl alkyl formaldehydes, locust bean gum, mannan, xyloglucan, tamarind gum, polyethylene terephthalate, and polymers containing dimethylaminoethyl methacrylate, optionally with one or more monomers selected from acrylic acid and acrylamide.

And (3) a perfume. Preferred compositions of the present invention include a perfume. Typically, the composition comprises a perfume comprising one or more perfume raw materials selected from the group described in WO 08/87497. However, any perfume that can be used in laundry care compositions can be used. A preferred method of incorporating perfume into the compositions of the present invention is by encapsulating the perfume particles with water soluble hydroxyl compounds or melamine-formaldehyde or modified polyvinyl alcohol.

Malodor reducing materials

The laundry compositions of the present disclosure may comprise malodor reducing materials. The material is capable of reducing or even eliminating the perception of one or more malodours. These materials can be characterized by a calculated malodor reduction value ("MORV") calculated according to the test method shown in WO 2016/049389.

As used herein, "MORV" is a calculated malodor reduction value for a subject material. The MORV of a material indicates the ability of the material to reduce or even eliminate the perception of one or more malodours.

The detergent compositions of the present disclosure may comprise a total of from about 0.00025% to about 0.5%, preferably from about 0.0025% to about 0.1%, more preferably from about 0.005% to about 0.075%, most preferably from about 0.01% to about 0.05%, by weight of the composition, of one or more malodor reducing materials. The laundry composition may comprise from about 1 to about 20 malodor reducing materials, more preferably from 1 to about 15 malodor reducing materials, most preferably from 1 to about 10 malodor reducing materials.

One, some or each of the malodor reducing materials may have a MORV of at least 0.5, preferably from 0.5 to 10, more preferably from 1 to 10, most preferably from 1 to 5. One, some, or each of the malodor reducing materials may have a universal MORV defining all MORV values >0.5 for the malodor tested as described herein. The sum of the malodor reducing materials may have a Blocker Index (Blocker Index) of less than 3, more preferably less than about 2.5, even more preferably less than about 2, and still more preferably less than about 1, and most preferably about 0. The sum of the malodor reducing materials may have an average blocker index of about 3 to about 0.001.

In the laundry compositions of the present disclosure, the malodor reducing material may have a Fragrance Fidelity Index (Fragrance Fidelity Index) of less than 3, preferably less than 2, more preferably less than 1, and most preferably about 0 and/or an average Fragrance Fidelity Index of from 3 to about 0.001. As the scent fidelity index decreases, the malodor reducing materials provide less and less scent impact while continuing to counteract the malodor.

The detergent compositions of the present disclosure may include a perfume. The weight ratio between the parts of malodor reducing composition to the parts of fragrance may be from about 1:20,000 to about 3000:1, preferably from about 1:10,000 to about 1,000:1, more preferably from about 5,000:1 to about 500:1, most preferably from about 1:15 to about 1:1. As the ratio between the malodor reducing composition and the perfume fraction tightens, the malodor reducing material provides less and less odor impact while continuing to counteract the malodor.

Danning (Chinese character of 'Danning')

The detergent compositions of the present disclosure may include tannins. Tannins are secondary metabolites of polyphenols of higher plants or galloyl esters and their derivatives, in which the galloyl moiety or derivative is linked to a variety of polyol, catechin and triterpenoid cores (gallotannins, ellagitannins and complex tannins), or they are oligomeric and polymeric proanthocyanidins (proanthocyanidis) that can have interflavan coupling and substitution patterns (condensed tannins). The detergent composition of the present disclosure may include a tannin selected from the group consisting of gallotannins, ellagitannins, complex tannins, condensed tannins, and combinations thereof.

A polymer. The composition may include one or more polymers. Examples are optionally modified carboxymethylcellulose, poly (ethyleneglycol-pyrrolidone), poly (ethylene glycol), poly (vinyl alcohol), poly (ethylenealkylpyridine-N-oxide), poly (ethylenealkylimidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

The composition may include one or more amphiphilic wash polymers. The polymers have a balance of hydrophilicity and hydrophobicity such that they remove grease particles on fabrics and surfaces. Suitable amphiphilic alkoxylated grease wash polymers include a core structure and a plurality of alkoxylate groups attached to the core structure. These may include alkoxylated polyalkyleneimines, especially ethoxylated polyethyleneimines or polyethyleneimines, having an inner polyethylene oxide block and an outer polypropylene oxide block. Typically, these may be incorporated in the compositions of the present invention in an amount of from 0.005 to 10% by weight, typically from 0.5 to 8% by weight.

The composition may include modified hexamethylenediamine. The modification of the hexamethylenediamine comprises: (1) one or two alkoxylation modifications are made per nitrogen atom of hexamethylenediamine. The alkoxylation modification comprises substituting a hydrogen atom on a nitrogen atom of hexamethylenediamine with a (poly) alkyleneoxy chain having an average of about 1 to about 40 alkoxy moieties per modification, wherein the terminal alkoxy moieties of the alkyleneoxy chain are terminated with hydrogen, C1-C4 alkyl, sulfate, carbonate, or mixtures thereof; (2) one substitution of the C1-C4 alkyl moiety and one or two alkoxylation modifications are made per hexamethylene diamine nitrogen atom. (ii) an alkoxylation modification comprising replacing a hydrogen atom with a (poly) alkyleneoxy chain having an average of about 1 to about 40 alkoxy moieties per modification, wherein the terminal alkoxy moieties of the alkyleneoxy chain are terminated with hydrogen, C1-C4 alkyl, or mixtures thereof; or (3) combinations thereof

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, may be used to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815. 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. "backbone" of said side chains with polyacrylate"ester-linked to provide a" comb "polymer-type structure. The molecular weight may vary, but is typically in the range of about 2000 to about 50,000. The alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

Another suitable carboxylate polymer is a copolymer comprising: (i) from 50 to less than 98 weight percent structural units derived from one or more monomers including a carboxyl group; (ii) from 1 wt% to less than 49 wt% structural units derived from one or more monomers including a sulfonate moiety; (iii)1 to 49% by weight of structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by the formulae (I) and (II):

formula (I):

wherein, in the formula (I), R₀Represents a hydrogen atom or CH₃Group, R represents CH₂Radical, CH₂CH₂A group or a single bond, X represents a number from 0 to 5, with the proviso that when R is a single bond, X represents a number from 1 to 5, and R₁Is a hydrogen atom or C₁To C₂₀An organic group;

formula (II)

Wherein, in the formula (II), R₀Represents a hydrogen atom or CH₃Group, R represents CH₂Radical, CH₂CH₂A group or a single bond, X represents 0 to 5, and R₁Is a hydrogen atom or C₁To C₂₀An organic group.

It may be preferred that the polymer has a weight average molecular weight of at least 50kDa, or even at least 70 kDa.

Other suitable polymers include amphiphilic graft copolymers. Preferred amphiphilic graft copolymers include: (i) a polyethylene glycol backbone; and (ii) at least one pendant group selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, and mixtures thereof. A preferred amphiphilic graft copolymer is Sokalan HP22 supplied by BASF. Other suitable polymers include random graft copolymers, preferably polyvinyl acetate grafted polyethylene oxide copolymers having a polyethylene oxide backbone and a plurality of polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is preferably about 6000 and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 ethylene oxide units. Typically, these are incorporated in the compositions of the present invention in an amount of from 0.005 to 10% by weight, more typically from 0.05 to 8% by weight.

The composition may include one or more soil release polymers. Examples include soil release polymers having a structure defined by one of the following formulas (VI), VII), or (VIII):

(VI)-[(OCHR¹-CHR²)_a-O-OC-Ar-CO-]_d

(VII)-[(OCHR³-CHR⁴)_b-O-OC-sAr-CO-]_e

(VIII)-[(OCHR⁵-CHR⁶)_c-OR⁷]_f

wherein:

a. b and c are 1 to 200;

d. e and f are 1 to 50;

ar is 1, 4-substituted phenylene;

sAr is SO substituted at position 5₃1, 3-substituted phenylene substituted with Me;

me is L i, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, where alkyl is C₁-C₁₈Alkyl or C₂-C₁₀Hydroxyalkyl, or mixtures thereof;

R¹、R²、R³、R⁴、R⁵and R⁶Independently selected from H or C₁-C₁₈N-alkyl or iso-alkyl; and

R⁷is straight or branched C₁-C₁₈Alkyl, or straight chainOr branched C₂-C₃₀Alkenyl, or cycloalkyl having 5 to 9 carbon atoms, or C₈-C₃₀Aryl, or C₆-C₃₀An arylalkyl group.

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, SRN300 and SRN325 supplied by Clariant.

The composition may also include one or more cellulosic polymers, including cellulosic polymers selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses. Preferred cellulosic polymers are selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methylcarboxymethyl cellulose, and mixtures thereof. In one aspect, the carboxymethyl cellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000Da to 300,000 Da.

Soil release polymer: the composition may include a soil release polymer. Suitable soil release polymers have a structure defined by one of the following formulas (I), (II), or (III):

(I)-[(OCHR¹-CHR²)_a-O-OC-Ar-CO-]_d

(II)-[(OCHR³-CHR⁴)_b-O-OC-sAr-CO-]_e

(III)-[(OCHR⁵-CHR⁶)_c-OR⁷]_f

wherein:

a. b and c are 1 to 200;

d. e and f are 1 to 50;

ar is 1, 4-substituted phenylene;

sAr is SO substituted at position 5₃1, 3-substituted phenylene substituted with Me;

me is L i, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium,trialkylammonium or tetraalkylammonium in which the alkyl group is C₁-C₁₈Alkyl or C₂-C₁₀Hydroxyalkyl, or mixtures thereof;

R¹、R²、R³、R⁴、R⁵and R⁶Independently selected from H or C₁-C₁₈N-alkyl or iso-alkyl; and

R⁷is straight or branched C₁-C₁₈Alkyl, or straight or branched C₂-C₃₀Alkenyl, or cycloalkyl having 5 to 9 carbon atoms, or C₈-C₃₀Aryl, or C₆-C₃₀An arylalkyl group.

Suitable soil release polymers are available from Clariant and Clariant

Series of polymers sold, e.g.

SRN240 and

SRA 300. Other suitable soil release polymers are available from Solvay corporation

Series of polymers sold, e.g.

SF2 and

Crystal。

known polymeric soil release agents, hereinafter "SRA" or "SRA's", may optionally be used in the detergent compositions of the present invention. If used, the SRA will typically comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight of the composition.

Preferred SRAs typically have hydrophilic segments that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments that deposit on the hydrophobic fibers and remain adhered thereto through the completion of wash and rinse cycles, thereby serving as anchors for the hydrophilic segments. This may make stains generated after treatment with SRA easier to clean in later washing procedures.

SRAs may include, for example, various charged, e.g., anionic or even cationic (see U.S. patent No.4,956,447) monomeric units, as well as uncharged monomeric units, and structures may be linear, or even star-shaped, they may include end-capping moieties that are particularly effective in controlling molecular weight or altering physical or surface-active properties, structure and charge distribution may be tailored to suit different fiber or textile types, as well as various detergent or detergent additive products.

Carboxylate polymer: the composition may include a carboxylate polymer, such as a maleate/acrylate random copolymer or a polyacrylate homopolymer. Suitable carboxylate polymers include: polyacrylate homopolymers having a molecular weight of 4,000Da to 9,000 Da; and a maleate/acrylate random copolymer having a molecular weight of from 50,000Da to 100,000Da, or from 60,000Da to 80,000 Da.

Alternatively, these materials may include polyacrylates having one ethoxy side chain per 7-8 acrylate units. The sideThe chain has the formula- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2 to 3 and n is 6 to 12. The side chains are ester-linked to the polyacrylate's "backbone" to provide a "comb" polymer-type structure. The molecular weight may vary, but is typically in the range of about 2000 to about 50,000. The alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

Another suitable carboxylate polymer is a copolymer comprising: (i) from 50 to less than 98 weight percent structural units derived from one or more monomers including a carboxyl group; (ii) from 1 wt% to less than 49 wt% structural units derived from one or more monomers including a sulfonate moiety; (iii)1 to 49% by weight of structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by the formulae (I) and (II):

formula (I):

wherein, in the formula (I), R₀Represents a hydrogen atom or CH₃Group, R represents CH₂Radical, CH₂CH₂A group or a single bond, X represents a number from 0 to 5, with the proviso that when R is a single bond, X represents a number from 1 to 5, and R₁Is a hydrogen atom or C₁To C₂₀An organic group;

formula (II)

Wherein, in the formula (II), R₀Represents a hydrogen atom or CH₃Group, R represents CH₂Radical, CH₂CH₂A group or a single bond, X represents 0 to 5, and R₁Is a hydrogen atom or C₁To C₂₀An organic group.

It may be preferred that the polymer has a weight average molecular weight of at least 50kDa, or even at least 70 kDa.

The carboxylate-based polymer may be advantageously used at a concentration of from about 0.1% to about 7% by weight of the compositions herein. Suitable polymeric dispersants include carboxylate polymers such as maleate/acrylate random copolymers or polyacrylate homopolymers. Preferably, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 daltons to 9,000 daltons, or a maleate/acrylate copolymer having a molecular weight of 60,000 daltons to 80,000 daltons. Polymeric polycarboxylates and polyethylene glycols may also be used. The polyalkylene glycol-based graft polymer may be prepared from a polyalkylene glycol-based compound and a monomer material, wherein the monomer material includes a carboxyl group-containing monomer and optionally other monomers. Optional other monomers not classified as carboxyl-containing monomers include sulfonic acid group-containing monomers, amino group-containing monomers, allylamine monomers, quaternized allylamine monomers, N-vinyl hydrocarbyl monomers, hydroxyl group-containing monomers, vinyl hydrocarbyl aryl monomers, isobutylene monomers, vinyl acetate monomers, salts of any of these salts, derivatives of any of these salts, and mixtures thereof. While not intending to be limited by theory, it is believed that the polymeric dispersant enhances the overall performance of the detergent builder by crystal dispersion inhibition, particulate soil release peptization, and anti-redeposition when used in combination with other builders (including lower molecular weight polycarboxylates). Examples of polymeric dispersants can be found in U.S. patent No. 3,308,067, and european patent applications No. 66915, EP193,360, and EP193,360.

Alkoxylated polyamine-based polymer: the composition may include alkoxylated polyamines. Such materials include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and sulfated versions thereof. Polypropoxylated derivatives are also included. Various amines and polyalkyleneimines can be alkoxylated to varying degrees and optionally further modified to provide the benefits described above. One useful example is the ethoxylation of 600g/mol polyethyleneimine core to 20 EO groups per NH and is available from BASF corporation.

Useful alkoxylated polyamine-based polymers include alkoxy groups(ii) an alkoxylated polyethyleneimine type, wherein the alkoxylated polyalkyleneimine has a polyalkyleneimine core with one or more side chains of the polyalkyleneimine core bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has the empirical formula (I), i.e. (PEI)_a-(EO)_b-R₁Wherein a is the average number average Molecular Weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine_PEI) And in the range of from 100 to 100,000 daltons, wherein b is the average degree of ethoxylation of the one or more side chains of the alkoxylated polyalkyleneimine, and is in the range of from 5 to 40, and wherein R₁Independently selected from hydrogen, C₁-C₄Alkyl groups and combinations thereof.

Other suitable alkoxylated polyalkyleneimines include those wherein the alkoxylated polyalkyleneimine has a polyalkyleneimine core with one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has the empirical formula (II), i.e. (PEI)_o-(EO)_m(PO)_n-R₂Or (PEI)_o-(PO)_n(EO)_m-R₂Wherein o is the average number average Molecular Weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine_PEI) And in the range of 100 to 100,000 daltons, wherein m is the average degree of ethoxylation in the one or more side chains of the alkoxylated polyalkyleneimine is in the range of 10 to 50, wherein n is the average degree of propoxylation in the one or more side chains of the alkoxylated polyalkyleneimine is in the range of 1 to 50, and wherein R is₂Independently selected from hydrogen, C₁-C₄Alkyl groups and combinations thereof.

Amphiphilic graft copolymer: amphiphilic graft copolymers may also be used according to the present invention. Particularly useful polymers include polymers having (i) a polyethylene glycol backbone; and (ii) at least one pendant moiety selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, and mixtures thereof, may also be used in the present invention. Suitable polyethylene glycol polymers includeA random graft copolymer comprising: (i) a hydrophilic backbone comprising polyethylene glycol; (ii) a hydrophobic side chain selected from: c₄-C₂₅Alkyl, polypropylene, polybutene, saturated C₁-C₆Vinyl alkyl esters of monocarboxylic acids, C of acrylic or methacrylic acid₁-C₆Alkyl esters and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone may be in the range of 2,000Da to 20,000Da, or 4,000Da to 8,000 Da. The molecular weight ratio between the polyethylene glycol backbone and the polyvinyl acetate side chains may be in the range of 1:1 to 1:5, or 1:1.2 to 1: 2. The average number of grafting sites per ethylene oxide unit may be less than 1 or less than 0.8, the average number of grafting sites per ethylene oxide unit may be in the range of 0.5 to 0.9, or the average number of grafting sites per ethylene oxide unit may be in the range of 0.1 to 0.5, or 0.2 to 0.4. A suitable polyethylene glycol polymer is Sokalan HP 22. Suitable polyethylene glycol polymers are described in WO 08/007320.

Cellulose polymer: cellulose polymers may be used according to the invention. Suitable cellulose polymers are selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses, sulfoalkyl celluloses, more preferably from carboxymethyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000Da to 300,000 Da.

Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, for example as described in WO 09/154933.

The consumer product of the present invention may further comprise one or more cellulosic polymers, including cellulosic polymers selected from the group consisting of alkyl celluloses, alkylalkoxy alkyl celluloses, carboxyalkyl celluloses, and alkylcarboxyalkyl celluloses. In one aspect, the cellulosic polymer is selected from the group consisting of carboxymethyl cellulose, methyl fiberCellulose, methylhydroxyethyl cellulose, methylcarboxymethylcellulose and mixtures thereof. In one aspect, the carboxymethyl cellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000Da to 300,000 Da. An example of a carboxymethyl cellulose polymer is that manufactured by CPKelko corporation

GDA commercially available carboxymethyl cellulose, hydrophobically modified carboxymethyl cellulose, such as from CPKelco

Alkyl ketene dimer derivatives of carboxymethyl cellulose commercially available as SH1, or from CPKelco

V block carboxymethyl cellulose commercially available.

Cationic polymer: cationic polymers may be used according to the invention. Suitable cationic polymers will have a cationic charge density of at least 0.5meq/gm, in another embodiment at least 0.9meq/gm, in another embodiment at least 1.2meq/gm, in yet another embodiment at least 1.5meq/gm, but in one embodiment also less than 7meq/gm, and in another embodiment less than 5meq/gm at the pH at which the composition is intended to be used, which is typically in the range of pH 3 to pH 9, and in one embodiment in the range of pH 4 to pH 8. Herein, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. Such suitable cationic polymers will typically have an average molecular weight of from 10,000 to 1,000 million, in one embodiment from 50,000 to 5 million, and in another embodiment from 100,000 to 3 million.

Suitable cationic polymers for use in the compositions of the present invention contain cationic nitrogen-containing moieties, such as quaternary ammonium or cationic protonated amino moieties. Any anionic counterions can be used in conjunction with the cationic polymers so long as the polymers remain soluble in water, in the composition, or in coacervates of the composition, and so long as the counterions are physically and chemically compatible with the essential components of the composition or do not otherwise unduly impair product performance, stability, or aesthetics. Non-limiting examples of such counterions include halides (e.g., chloride, fluoride, bromide, iodide), sulfate, and methyl sulfate.

Non-limiting examples of such polymers are described in Estrin, Crosley and Haynes, edited by CTFA Cosmetic ingredient dictionary, 3 rd edition (The American society of cosmetics, toiletries, and perfumes, The Columbia Texas Washington (1982)).

Particularly effective cationic polymers that can be used according to the present invention include, wherein the cationic polymer comprises a polymer selected from the group consisting of: cationic cellulose, cationic guar gum, poly (acrylamide-co-diallyldimethylammonium chloride), poly (acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly (acrylamide-co-methacrylamidopropyl-pentamethyl-1, 3-propen-2-ol-ammonium dichloride), poly (acrylamide-co-N, N-dimethylaminoethyl acrylate) and quaternized derivatives thereof, poly (acrylamide-co-N, N-dimethylaminoethyl methacrylate) and quaternized derivatives thereof, poly (acrylamide-methacrylamidopropyltrimethylammonium chloride), Poly (acrylamide-methacrylamidopropyltrimethylammonium chloride-co-acrylic acid), poly (diallyldimethylammonium chloride-co-acrylic acid), poly (ethylmethacrylate-co-oleylmethacrylate-co-diethylaminoethylmethacrylate) and quaternized derivatives thereof, poly (ethylmethacrylate-co-dimethylaminoethylmethacrylate) and quaternized derivatives thereof, poly (hydroxypropylacrylate-co-methacrylamidopropyltrimethylammonium chloride) and quaternized derivatives thereof, poly (hydroxyethylacrylate-co-dimethylaminoethylmethacrylate) and quaternized derivatives thereof, poly (methacrylamide-co-dimethylaminoethylacrylate) and quaternized derivatives thereof, poly (acrylamide-co-dimethylaminoethylacrylate) and quaternized derivatives thereof, poly (methacrylamido-co-dimethylaminoethylmethacrylate) and quaternized derivatives thereof, poly (methacrylamido-co-dimethylaminoeth, Poly (methacrylate-co-methacrylamidopropyltrimethylammonium chloride), poly (vinylalkylformamide-co-acrylic acid-co-diallyldimethylammonium chloride), poly (vinylalkylformamide-co-diallyldimethylammonium chloride), poly (vinylalkylpyrrolidone-co-acrylamide-co-vinylalkylimidazole) and quaternized derivatives thereof, poly (vinylalkylpyrrolidone-co-dimethylaminoethylmethacrylate) and quaternized derivatives thereof, poly (vinylalkylpyrrolidone-co-methacrylamide-co-vinylalkylimidazole) and quaternized derivatives thereof, poly (vinylalkylpyrrolidone-co-vinylalkylimidazole), Polyethyleneimine, and including quaternized derivatives thereof and mixtures thereof

Other suitable cationic polymers for use in the composition include polysaccharide polymers, cationic guar derivatives, quaternary nitrogen-containing cellulose ethers, synthetic polymers, etherified cellulose, guar and starch copolymers. When used, the cationic polymers herein may be soluble in the composition or may be soluble in a complex coacervate phase formed in the composition from the cationic polymer and anionic, amphoteric and/or zwitterionic surfactant components described above. Complex coacervates of the cationic polymer can also be formed with other charged materials in the composition.

Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418, 3,958,581, and U.S. publication No. 2007/0207109A 1.

Dye Transfer Inhibition (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 a polymeric dye transfer inhibiting agent in addition to the specified dye 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-vinyl pyrrolidone and N-vinyl benzimidazole, polyvinyl oxazolidone and polyvinyl imidazole, or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, Chromabond S-400, available from Ashland Aqualon corporation,Chromabond S-403E and Chromabond S-100, and Sokalan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59, available from BASF,

HP 56K、

HP 66. The dye control agent may be selected from (i) sulfonated phenol/formaldehyde polymers; (ii) a urea derivative; (iii) a polymer of ethylenically unsaturated monomers, wherein the polymer is molecularly imprinted with a dye; (iv) fibers comprised of a water-insoluble polyamide, wherein the fibers have an average diameter of no greater than about 2 μm; (v) a polymer obtainable by polymerizing a benzoxazine monomer compound; and (vi) combinations thereof. Other suitable DTIs are described in WO 2012/004134. When present in the subject composition, the dye transfer inhibiting agent may be present at a concentration of from 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.

Other water-soluble polymers: examples of water soluble polymers include, but are not limited to, polyvinyl alcohol (PVA), modified PVA; polyvinylpyrrolidone; PVA copolymers, such as PVA/polyvinylpyrrolidone and PVA/polyvinylamine; partially hydrolyzed polyvinyl acetate; polyoxyalkylenes such as polyethylene oxide; polyethylene glycol; (ii) acrylamide; acrylic acid; cellulose, alkyl celluloses, such as methyl cellulose, ethyl cellulose, and propyl cellulose; a cellulose ether; cellulose esters; a cellulose amide; polyvinyl acetate; polycarboxylic acids and salts; a polyamino acid or peptide; a polyamide; polyacrylamide; maleic/acrylic acid copolymers; polysaccharides, including starch, modified starch; gelatin; an alginate; xyloglucan, other hemicellulose polysaccharides including xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan and galactoglucomannan; and natural gums such as pectin, xanthan and carrageenan, locust bean gum, acacia, tragacanth; and combinations thereof

Non-limiting examples of amines include, but are not limited to, ether amines, cyclic amines, polyamines, oligomeric amines (e.g., triamines, diamines, pentylamines, tetramines), or combinations thereof. The compositions described herein can include an amine selected from the group consisting of oligoamines, etheramines, cyclic amines, and combinations thereof. In some aspects, the amine is not an alkanolamine. In some aspects, the amine is not a polyalkyleneimine.

Examples of suitable oligoamines include tetraethylenepentamine, triethylenetetramine, diethylenetriamine, and mixtures thereof.

Ether amine: the detergent compositions described herein may include an ether amine. The detergent composition may contain from about 0.1% to about 10%, from about 0.2% to about 5%, or from about 0.5% to about 4%, by weight of the composition, of an etheramine.

The weight average molecular weight of the ether amines of the present disclosure can be less than about 1000 grams/mole, or from about 100 grams/mole to about 800 grams/mole, or from about 200 grams/mole to about 450 grams/mole, or from about 290 grams/mole to about 1000 grams/mole, or from about 290 grams/mole to about 900 grams/mole, or from about 300 grams/mole to about 700 grams/mole, or from about 300 grams/mole to about 450 grams/mole. The weight average molecular weight of the ether amines of the present invention can be from about 150 g/mole, or from about 200 g/mole, or from about 350 g/mole, or from about 500 g/mole, to about 1000 g/mole, or to about 900 g/mole, or to about 800 g/mole.

Alkoxylated phenol compound: the detergent compositions of the present disclosure may include an alkoxylated phenol compound. The alkoxylated phenol compound may be selected from the group consisting of alkoxylated polyarylphenol compounds, alkoxylated polyalkylphenol compounds, and mixtures thereof. The alkoxylated phenol compound may be an alkoxylated polyarylphenol compound. The alkoxylated phenol compound may be an alkoxylated polyalkylphenol compound.

The alkoxylated phenol compound may be present in the wash composition at a concentration of from about 0.2% to about 10%, or from about 0.5% to about 5%, by weight of the wash composition.

The alkoxylated phenol compound may have a weight average molecular weight of between 280 and 2880.

Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases (malanases), β -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.

Protease preferably, the composition comprises one or more proteases. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisin (ec 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, the suitable protease may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the above-mentioned suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases or/and trypsin-type proteases. Examples of suitable neutral or alkaline proteases include:

(a) subtilisins (EC3.4.21.62), including those derived from Bacillus, for example Bacillus lentus (Bacillus lentus), Bacillus alkalophilus (B.alkalophilus), Bacillus subtilis (B.subtilis), Bacillus amyloliquefaciens (B.amyloliquefaciens), Bacillus pumilus (Bacillus pumilus) and Bacillus gibsonii (Bacillus gibsonii) as described in U.S. Pat. No. 6,312,936B1, U.S. Pat. No. 3,760,025, U.S. Pat. No. 3/021867.

(b) Trypsin-type or chymotrypsin-type proteases, such as proteases (e.g. porcine-or bovine-derived trypsin), including the Fusarium protease described in WO 89/06270 (Fusarium protease) and chymotrypsin derived from cellulomonas (Cellumonas) described in WO 05/052161 and WO 05/052146.

(c) Metalloproteinases, including those derived from Bacillus amyloliquefaciens (Bacillus amyloliquefaciens) as described in WO 07/044993A 2.

Preferred proteases include those derived from Bacillus gibsonii (Bacillus gibsonii) or Bacillus lentus (Bacillus L entus).

Suitable commercially available proteases include Novozymes A/S, Denmark

Liquanase

Savinase

And

the protease sold is under the trade name of Jencology enzyme preparations, USA (Genencor International)

Purafect

Purafect

And Purafect

Commercially available protease, sold under the trade name Solvay Enzymes

And

commercially available proteases, i.e., those commercially available from Henkel/Kemira, namely B L AP (see FIG. 29 of US 5,352,604, SEQ ID NO: B L, B L AP having the following mutants S99D + S101R + S103A + V104I + G159S (hereinafter referred to as B L AP), B L AP R (B L AP having S3L + V4L + V199L + V205L + 36217D), B L AP X (B L AP having S3L + V4L + V205L) and B L AP F L (B L AP having S3L + V4L + A194L + V205L + L D) -all from Henkel/Kemira, and KAP from Kao (Bacillus subtilis) having S256A 36230 + S L).

Suitable α -amylases include α -amylases of bacterial or fungal origin, including chemically or genetically modified mutants, preferred alkaline α -amylases are derived from strains of Bacillus, such as Bacillus licheniformis (Bacillus licheniformis), Bacillus amyloliquefaciens (Bacillus amyloliquefaciens), Bacillus stearothermophilus (Bacillus stearothermophilus), Bacillus subtilis (Bacillus subtilis), or other Bacillus, such as Bacillus NCIB 12289, NCIB 12512, NCIB12513, DSM 9375(USP 7,153,818) DSM 12368, DSMZ No. 12649, KSM AP1378(WO 97/00324), SMK36, or KSM K38(EP 1,022,334), preferred amylases include:

(a) variants described in WO 94/02597, WO 94/18314, WO96/23874 and WO 97/43424, in particular variants having substitutions in one or more of the following positions relative to the enzyme listed as SEQ ID No.2 in WO 96/23874: 15. 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.

(b) Variants described in USP 5,856,164 and WO99/23211, WO 96/23873, WO00/60060 and WO06/002643, in particular variants having one or more substitutions at the following positions relative to the AA560 enzyme listed as SEQ ID No.12 in WO 06/002643:

26. 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably also containing the deletion of D183 and G184.

(c) Variants exhibiting at least 90% identity with SEQ ID No.4 in WO06/002643, the wild-type enzyme from bacillus SP722, in particular variants having deletions at positions 183 and 184 and the variant described in WO00/60060 incorporated herein by reference.

(d) Variants exhibiting at least 95% identity to a wild-type enzyme from bacillus 707 (SEQ ID NO:7 in US6,093,562), in particular variants comprising one or more of the following mutants M202, M208, S255, R172 and/or M261 preferably the amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and/or R172Q particularly preferred are amylases comprising M202L or M202T mutants.

(e) The variant described in WO 09/149130, preferably exhibits at least 90% identity with SEQ ID NO:1 or SEQ ID NO:2 in WO 09/149130, i.e.the wild-type enzyme from Bacillus stearothermophilus (Geobacillus stearthermophilus) or a truncated form thereof.

Suitable commercially available α -amylases include

TERMAMYL

STAINZYME

And

(Novozymes A/S, Denmark Baggevir),

AT 9000Biozym Biotech TradingGmbH Wehlistrasse 27b A-1200Wien Austria、

OPTISIZE HT

And PURASTAR

(Jencology Engineers, USA, California Axis Palo Alto (Palo Alto)) and

(Kao, Tokyo, central area-Dingmu Konfo Komat city 14-10, zip code: 103-8210). In one aspect, suitable amylases include

And STAINZYME

And mixtures thereof.

A lipase. Preferably, the present invention comprises one or more lipases, including "first cycle lipases", such as the lipases described in US patent 6,939,702B1 and US PA 2009/0217464. The preferred lipase is first wash (first-wash) lipase. In one embodiment of the invention, the composition comprises a first wash lipase. The lipase included in the first-wash lipase is a polypeptide having the following amino acid sequenceAnd the polypeptide: (a) at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109; (b) a neutral or negatively charged amino acid on the surface of the three-dimensional structure included in 15A of E1 or Q249 is substituted with a positively charged amino acid, as compared to the wild-type lipase; (c) peptide addition including the C-terminus; and/or (d) comprises an N-terminal peptide addition, and/or (e) satisfies the following constraints: i) comprising a negative amino acid at position E210 of the wild-type lipase; ii) comprises a negatively charged amino acid in a region corresponding to positions 90-101 of the wild-type lipase; iii) comprises a neutral or negative amino acid at a position corresponding to N94 or the wild-type lipase and/or has a negative or neutral net charge in the region corresponding to positions 90-101 of the wild-type lipase. Preferred are variants of wild-type lipases from thermomyces lanuginosus, comprising one or more of the T231R and N233R mutants. The wild-type sequence is 269 amino acids (amino acids 23-291) from Swissprot accession number Swiss-Prot O59952 (derived from Thermomyces lanuginosa Bombycis (Humicola lanuginosa)). Preferred lipases will include those under the trade name

And

and

a lipase sold.

Other preferred enzymes include microbial-derived endoglucanases exhibiting endo- β -1, 4-glucanase activity (e.c.3.2.1.4), endogenous bacterial polypeptides including members of the genus bacillus having a sequence at least 90%, 94%, 97% and even 99% identity to the amino acid sequence SEQ ID NO:2 in US7,141,403B2, and mixtures thereof

And

(VenoNurse company (Novozymes A/S), Denmark Bagsvir).

Pectate lyase. Other preferred enzymes include those under the trade name

Pectate lyases sold under the trade name

(all from Novozymes A/S, Denmark Baggevir) and

(Jencology, USA) enzyme preparation company (Genencor International) USA California axis Palo Ordoo (Palo Alto)) sold mannanase.

A nuclease. The composition may 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. A functional fragment or moiety refers to a moiety in a nuclease that catalyzes cleavage of phosphodiester bonds in the DNA backbone, and thus is a region of the nuclease protein that retains catalytic activity. Thus, it includes truncated but functional forms of enzymes and/or variants and/or derivatives and/or homologues whose functionality is maintained.

Preferably, the nuclease is a dnase, preferably selected from the group consisting of class e.c.3.1.21.x, wherein x ═ 1,2, 3, 4,5, 6, 7,8, or 9; e.c.3.1.22.y, wherein 1,2, 4 or 5; e.c.3.1.30.z, wherein z is 1 or 2; any of e.c.3.1.31.1 and mixtures thereof.

A bleaching agent. The composition may preferably include one or more bleaching agents. Suitable bleaching agents in addition to the bleach catalyst include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, and mixtures thereof. Generally, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% of the bleaching agent or mixture of bleaching agents, by weight of the subject composition. Examples of suitable bleaching agents include:

(1) photobleaches such as sulfonated zinc phthalocyanines, sulfonated aluminum phthalocyanines, xanthene dyes, thioxanthones, and mixtures thereof;

(2) preformed peracid: suitable preformed peracids include, but are not limited to, those selected from preformed peroxyacids or salts thereof, typically percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, e.g.

And mixtures thereof.

A particularly preferred peroxy acid is phthalimido-peroxy-alkanoic acid, especially-phthalimido-peroxy hexanoic acid (PAP). Preferably, the melting point of the peroxyacid or salt thereof is in the range of 30 ℃ to 60 ℃.

(3) Sources of hydrogen peroxide, such as inorganic perhydrate salts, include alkali metal salts, such as the sodium salt of perborate (usually monohydrate or tetrahydrate), percarbonate, persulfate, perphosphate, persilicate salts and mixtures thereof. When used, inorganic perhydrate salts are normally present in amounts ranging from 0.05% to 40% or from 1% to 30% by weight of the total fabric and home care product and are normally incorporated in such fabric and home care products in the form of a crystalline solid which may be coated. Suitable coatings include inorganic salts, such as alkali metal silicates, carbonates or borates or mixtures thereof, or organic materials, such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and

(4) bleach activators having R- (C ═ O) -L, wherein R is an alkyl group, optionally a branched alkyl group, having 6 to 14 carbon atoms or 8 to 12 carbon atoms when the bleach activator is hydrophobic and less than 6 carbon atoms or even less than 4 carbon atoms when the bleach activator is hydrophilic, and L is a leaving group.

(5) Suitable bleach catalysts include, but are not limited to, iminium cations and polyions, iminium zwitterions, modified amines, modified amine oxides, N-sulfonylimines, N-phosphonoimines, N-acylimines, thiadiazodioxides, perfluoroimines, cyclic sugar ketones and α amino ketones and mixtures thereof one particularly preferred catalyst is an acylhydrazone-type catalyst, such as 4- (2- (2- ((2-hydroxyphenylmethyl) methylene) hydrazino) -2-oxoethyl) -4-methylchloride.

(6) The composition may preferably include a catalytic metal complex. One preferred type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation having defined bleach catalytic activity, such as a copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cation.

The compositions herein can be catalyzed, if desired, by means of manganese compounds. Such compounds and concentrations used are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S.5,576,282. In some embodiments, no other source of oxidant is present in the composition, and molecular oxygen from the air provides the source of oxidation.

Cobalt bleach catalysts useful in the present invention are known and described in, for example, U.S.5,597,936, U.S.5,595,967.

When present, the hydrogen peroxide/peracid and/or bleach activator source is typically present in the composition in an amount of from about 0.1 wt.% to about 60 wt.%, from about 0.5 wt.% to about 40 wt.%, or even from about 0.6 wt.% to about 10 wt.%, based on the fabric and home care product. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracids or precursors thereof.

Typically, the source of hydrogen peroxide and the bleach activator will be combined. The amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio between available oxygen (from the peroxide source) and peracid is from 1:1 to 35:1, or even from 2:1 to 10: 1. If formulated as a liquid detergent, the peroxide source and activator may be formulated at low pH, usually 3-5, with a pH jump system such as borate/sorbitol.

The laundry care compositions of the present invention may be particularly useful in chlorinated waters, such as those typically found in most household supplies. Alternatively, the leuco agent containing system may be used in combination with other bleaching sources, such as electrolysis, and may be used in an auto-dosing system.

A builder. Preferably, the composition may comprise one or more builders or builder systems. When a builder is used, the compositions of the present invention will typically comprise at least 1%, 2% to 60% builder. It may be preferred that the composition comprises a low concentration of phosphate and/or zeolite, for example 1 to 10 or 5 wt%. The composition may even be substantially free of a strong builder; by substantially free of a potent adjuvant is meant that the zeolite and/or phosphate are "not deliberately added". Typical zeolite builders include zeolite a, zeolite P and zeolite MAP. A typical phosphate builder is sodium tripolyphosphate.

A chelating agent. 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 hydroxamic acids, aminocarboxylates, aminophosphonates, succinates, salts thereof, and mixtures thereof. Non-limiting examples of suitable chelating agents suitable for use in the present invention include ethylenediaminetetraacetate, N- (hydroxyethyl) ethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine hexaacetate, diethylenetriaminepentaacetate, ethanoldiglycine, ethylenediaminetetra (methylenephosphonate), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), ethylenediaminedisuccinic acid ammoniumsalt (EDDS), hydroxyethylenedimethylenephosphonic acid (HEDP), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), salts thereof, and mixtures thereof. Other non-limiting examples of chelating agents for use in the present invention can be found in U.S. patent nos. 7445644, 7585376, and 2009/0176684a 1. Other suitable chelating agents for use herein are the commercial DEQUEST series of chelating agents, as well as those from Monsanto, Dupont and Nalco, Inc. Other suitable chelating agents include pyridyl N-oxide types.

A fluorescent whitening agent. Preferably, the composition comprises one or more fluorescent whitening agents. Commercially available optical brighteners useful in the present invention may be classified in subgroups, which include, but are not limited to, derivatives of: stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine blue, dibenzothiophene-5, 5-dioxide, pyrrole, five-and six-membered ring heterocycles, and other miscellaneous agents. Particularly preferred whitening agents are selected from: sodium 2 (4-phenylethenyl-3-sulfophenyl) -2H-naphthalenol [1, 2-d ] triazole, disodium 4,4 '-bis { [ ((4-anilino-6- (N-methyl-N-2 hydroxyethyl) amino 1,3, 5-triazin-2-yl) ] amino } -2-2-disulfonate, disodium 4,4' -bis { [ ((4-anilino-6-morpholino-l, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 'disulfonate, and disodium 4,4' -bis (2-sulfophenylethynyl) biphenyl other examples of such brighteners are disclosed in "Production and use of fluorescent whitening Agents" (The Production and approval of brightening Agents) ", zahradnik, published by John willy & Sons, new york (1982). Specific non-limiting examples of fluorescent whitening agents that can be used in the compositions of the present invention are the whitening agents identified in U.S. Pat. No.4,790,856 and U.S. Pat. No. 3,646,015.

Preferred whitening agents have the following structure:

suitable optical brightener concentrations include from a lower concentration of about 0.01 wt%, from about 0.05 wt%, from about 0.1 wt% or even from about 0.2 wt% to an upper concentration of 0.5 wt% or even 0.75 wt%.

In one aspect, the whitening agent may be loaded onto the clay to form particles.

Preferred brighteners are wholly or predominantly (typically at least 50 wt%, at least 75 wt%, at least 90 wt%, at least 99 wt%) α -crystalline form a highly preferred brightener comprises c.i. fluorescent brightener 260, preferably having the structure:

this is particularly useful because it dissolves well in cold water, for example below 30 ℃ or 25 ℃ or even 20 ℃.

An enzyme stabilizer. The composition may preferably include an enzyme stabilizer. Any conventional enzyme stabilizer may be used, for example, by the presence of a water-soluble source of calcium and/or magnesium ions in finished fabrics and home care products that provide these ions to the enzyme. In case of an aqueous composition comprising a protease, a reversible protease inhibitor, such as a boron compound comprising borate or preferably 4-formylphenyl boronic acid, phenyl boronic acid and derivatives thereof, or compounds such as calcium formate, sodium formate and 1, 2-propane diol may be added to further improve stability.

A solvent system. The solvent system in the composition of the invention may be a solvent system containing only water, or a mixture of organic solvents containing no water or preferably water.

Organic solvent

The composition may optionally include an organic solvent. Suitable organic solvents include C_4-14Ethers and diethers, glycols, alkoxylated glycols, C₆-C₁₆Glycol ethers, alkoxylated aromatic alcohols, aliphatic branched alcohols, alkoxylated straight chain C₁-C₅Alcohol, straight chain C₁-C₅Alcohol, amine, C₈-C₁₄Alkyl and cycloalkyl hydrocarbons and halogenated hydrocarbons and mixtures thereof. Preferred organic solvents include 1, 2-propanediol, 2, 3-butanediol, and,Ethanol, glycerol, ethoxylated glycerol, dipropylene glycol, methyl propylene glycol, and mixtures thereof. Other lower alcohols, C1-C4 alkanolamines, such as monoethanolamine and triethanolamine, may also be used. The solvent system may, for example, be absent from the anhydrous solid embodiments of the present invention, but more typically is present at a concentration of from about 0.1% to about 98%, preferably at least about 1% to about 50%, more typically from about 5% to about 25%, or from about 1% to about 10%, by weight of the liquid detergent composition of the organic solvent. These organic solvents may be used in combination with water or without water.

Structuring the liquid: in some embodiments of the invention, the composition is in the form of a structured liquid. The structured liquid may be internally structured whereby 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), for example to act as a thickener. The composition may comprise a structurant, preferably from 0.01 wt% to 5 wt%, from 0.1 wt% to 2.0 wt% structurant. Examples of suitable structurants are found in US2006/0205631A1, US2005/0203213A1, US7294611, US 6855680. The structuring agent is generally selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulose-based materials, microfibrillar cellulose, hydrophobically modified alkali swellable emulsions, such as Polygel W30(3 vsig), biopolymers, xanthan gum, gellan gum, hydrogenated castor oil, derivatives of hydrogenated castor oil, such as non-ethoxylated derivatives thereof and mixtures thereof, and specifically from the group consisting of hydrogenated castor oil, derivatives of hydrogenated castor oil, microfibrillar cellulose, hydroxy functional crystalline materials, long chain fatty alcohols, 12-hydroxystearic acid, clays and mixtures thereof. One preferred structuring agent is described in U.S. patent No. 6,855,680, which defines in detail suitable hydroxy-functional crystalline materials. Hydrogenated castor oil is preferred. Some structurants have a linear architecture with a variety of aspect ratios. Another preferred structurant is cellulose-based and can be derived from a number of sources including biomass, wood pulp, citrus fiber, and the like.

The compositions of the present invention may include high melting point fatty compounds. The high melting point fatty compounds useful in the present invention have a melting point of 25 ℃ or higher and are selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. Such low melting compounds are not intended to be included in this section. Non-limiting examples of high melting point compounds can be found in the fifth edition international cosmetic ingredient dictionary 1993 and the second edition CTFA cosmetic ingredient handbook 1992. When present, the high melting point fatty compound is preferably included in the composition at a concentration of from 0.1% to 40%, preferably from 1% to 30%, more preferably from 1.5% to 16%, from 1.5% to 8% by weight of the composition, in view of providing improved conditioning benefits such as smooth feel during application to wet hair, soft and moist feel on dry hair.

A cationic polymer. The compositions of the present invention may include a cationic polymer. The concentration of the cationic polymer in the composition is generally in the range of 0.05% to 3%, in another embodiment in the range of 0.075% to 2.0%, and in yet another embodiment in the range of 0.1% to 1.0%. Suitable cationic polymers will have a cationic charge density of at least 0.5meq/gm, in another embodiment at least 0.9meq/gm, in another embodiment at least 1.2meq/gm, in yet another embodiment at least 1.5meq/gm, but in one embodiment also less than 7meq/gm, and in another embodiment less than 5meq/gm at the pH at which the composition is intended to be used, which is typically in the range of pH 3 to pH 9, and in one embodiment in the range of pH 4 to pH 8. Herein, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. Such suitable cationic polymers will typically have an average molecular weight of from 10,000 to 1,000 million, in one embodiment from 50,000 to 5 million, and in another embodiment from 100,000 to 3 million.

Suitable cationic polymers for use in the compositions of the present invention contain cationic nitrogen-containing moieties, such as quaternary ammonium or cationic protonated amino moieties. Any anionic counterions can be used in conjunction with the cationic polymers so long as the polymers remain soluble in water, in the composition, or in coacervates of the composition, and so long as the counterions are physically and chemically compatible with the essential components of the composition or do not otherwise unduly impair product performance, stability, or aesthetics. Non-limiting examples of such counterions include halides (e.g., chloride, fluoride, bromide, iodide), sulfate, and methyl sulfate.

Non-limiting examples of such polymers are described in Estrin, Crosley and Haynes, edited by CTFA Cosmetic ingredient dictionary, 3 rd edition (The American society of cosmetics, toiletries, and perfumes, The Columbia Texas Washington (1982)).

Other suitable cationic polymers for use in the composition include polysaccharide polymers, cationic guar derivatives, quaternary nitrogen-containing cellulose ethers, synthetic polymers, etherified cellulose, guar and starch copolymers. When used, the cationic polymers herein may be soluble in the composition or may be soluble in a complex coacervate phase formed in the composition from the cationic polymer and anionic, amphoteric and/or zwitterionic surfactant components described above. Complex coacervates of the cationic polymer can also be formed with other charged materials in the composition.

Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418, 3,958,581, and U.S. publication No. 2007/0207109A 1.

A non-ionic polymer. The compositions of the present invention may include a nonionic polymer as a conditioning agent. Polyalkylene glycols having a molecular weight greater than 1000 are useful in the present invention. Effective are nonionic polymers having the general formula:

wherein R is⁹⁵Selected from the group consisting of H, methyl and mixtures thereof.

A conditioning agent, particularly a silicone, may be included in the composition. The conditioning agents useful in the compositions of the present invention generally comprise water-insoluble, water-dispersible, nonvolatile liquids that form emulsified liquid particles. Suitable conditioning agents for use in the compositions are those that are generally characterized as silicones (e.g., silicone oils, cationic silicones, silicone rubbers, high refractive silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty esters), or combinations thereof, or that otherwise form liquid dispersed particles in the aqueous surfactant matrix herein. The conditioning agent should be physically and chemically compatible with the essential components of the composition and should not otherwise unduly impair product stability, aesthetics or performance.

The concentration of the modulator in the composition should be sufficient to provide the desired modulating benefit. The concentration may vary with the conditioner, the desired conditioning performance, the average size of the conditioner particles, the type and concentration of other components, and other similar factors.

The concentration of silicone modifier is typically in the range of about 0.01% to about 10%. Non-limiting examples of suitable silicone conditioning agents and optional suspending agents for silicones are described in U.S. reissue patent No. 34,584; U.S. Pat. nos. 5,104,646, 5,106,609, 4,152,416, 2,826,551, 3,964,500, 4,364,837, 6,607,717, 6,482,969, 5,807,956, 5,981,681, 6,207,782, 7,465,439, 7,041,767, 7,217,777; united states patent application nos. 2007/0286837a1, 2005/0048549a1, 2007/0041929a 1; british patent No. 849,433; DE 10036533, which are incorporated herein by reference in their entirety; silicone chemistry and technology, new york: academic press (1968); general electric silicone rubber product data tables SE 30, SE 33, SE 54 and SE 76; silicon compounds, PetrarchSystems, Inc. (1984); and John Wiley & Sons, Inc. (1989), encyclopedia of Polymer science and engineering, Vol.15, 2 nd edition, page 204-308.

And (3) organic conditioning oil. The compositions of the present invention may also include as a conditioning agent from about 0.05% to about 3% of at least one organic conditioning oil, alone or in combination with other conditioning agents such asSilicones (as described herein) are used in combination. Suitable conditioning oils include hydrocarbon oils, polyolefins, and fatty esters. Sanitising Agents the compositions of the present invention may also include components which provide hygiene and/or malodour benefits, for example zinc ricinoleate, thymol, quaternary ammonium salts such as

Polyethyleneimine (e.g. from BASF)

) And one or more of zinc complexes, silver and silver compounds thereof, particularly compounds designed for slow release of Ag + or nanosilver dispersions.

And (4) probiotics. The composition may comprise a probiotic, for example as described in WO 2009/043709.

A foam booster. If high foaming is desired, the composition may preferably include a foam booster. A suitable example is the incorporation of C preferably at a concentration of 1% to 10%₁₀-C₁₆Alkanolamides or C₁₀-C₁₄An alkyl sulfate. C₁₀-C₁₄Monoethanol and diethanol amides illustrate a typical class of such suds boosters. It is also advantageous to use such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines described above. If desired, water-soluble magnesium and/or calcium salts, for example MgCl, can be added, usually at concentrations of 0.1% to 2%₂、MgSO₄、CaCl₂、CaSO₄Etc. to provide additional foam and enhance oil removal performance.

And (4) a foam inhibitor. Compounds for reducing or inhibiting foam formation may be incorporated into the compositions of the present invention. Suds suppressors can be particularly important in the so-called "heavy-duty wash process" described in U.S. patent nos. 4,489,455 and 4,489,574, as well as in front-loading washing machines. A variety of materials can be used as suds suppressors and suds suppressors are well known to those skilled in the art. See, for example, Kock-Osmo chemical university, volume 7, page 430-447 (John Wiley & Sons, 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 monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearyl ketone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point below about 100 ℃, silicone suds suppressors, and secondary alcohols. Particularly effective silicone suds suppressors are based on diphenyl-containing silicones.

A silicone suds suppressor. It is generally used in amounts up to 2.0% by weight of the detergent, although higher amounts may be used.

A pearling agent. Pearlescent agents as described in WO2011/163457 may be incorporated into the compositions of the present invention.

Pearlescent agents can be crystalline or glassy solids, transparent or translucent compounds that reflect and refract light to produce a pearlescent effect. Typically, pearlescent agents are crystalline particles that are insoluble in the composition in which they are incorporated. Preferably, the pearlescent agent has the shape of a sheet or sphere. The particle size of the pearlescent agent is typically less than 200 microns, preferably less than 100 microns, more preferably less than 50 microns. The inorganic pearlescent agent includes aluminosilicate and/or borosilicate. Preferred are aluminosilicates and/or borosilicates, preferably silica, metal oxides, oxychloride coated aluminosilicates and/or borosilicates, which have been treated to have a very high refractive index. More preferred inorganic pearlescent agents are mica, even more preferred is titanium dioxide treated mica, such as BASF Mearlin Superfine.

The composition may comprise from 0.005% to 3.0%, preferably from 0.01% to 1% by weight of pearlescent agent, based on the weight of the composition of 100% active pearlescent agent. The pearlescent agent may be organic or inorganic. The composition may include organic and/or inorganic pearlescent agents.

Organic pearling agent:

when the composition includes an organic pearlescent agent, the organic pearlescent agent is included at an active concentration of 0.05% to 2.0% by weight, preferably 0.1% to 1.0% by weight, based on 100% active organic pearlescent agent composition weight. Suitable organic pearlescent agents include monoesters and/or diesters of alkylene glycols, such as ethylene glycol distearate.

Inorganic pearlescent agent:

in another embodiment, the composition may also include an inorganic pearlescent agent. When the composition includes an inorganic pearlescent agent, the inorganic pearlescent agent is included at an active concentration of 0.005% to 1.0% by weight, preferably 0.01% to 0.2% by weight, based on 100% active inorganic pearlescent agent composition weight.

Suspended particles

In one embodiment, the composition further comprises a plurality of suspended particles at a concentration of about 0.01% to about 5% by weight, alternatively about 0.05% to about 4% by weight, alternatively about 0.1% to about 3% by weight. Examples of suitable suspended particles are provided in U.S. patent No. 7,169,741 and U.S. patent publication No. 2005/0203213, the disclosures of which are incorporated herein by reference. These suspended particles may comprise a liquid core or a solid core. A detailed description of these liquid core and solid core particles, as well as preferred particle size, particle shape, particle density and particle fracture strength, is described in U.S. patent application No. 12/370,714, the disclosure of which is incorporated herein by reference.

In a preferred embodiment, the particles may be in any discrete and visually distinguishable form of matter, including but not limited to (deformable) pellets, encapsulates, polymer particles such as plastics, metals (e.g. foil materials, flakes, glitters), (interference) pigments, minerals (salts, rocks, pebbles, lava, glass/silica particles, talc), plant materials (e.g. pits or seeds, plant fibers, stalks, stems, leaves or roots), solids, liquid crystals, and the like. Different particle shapes are possible, from spherical to flat.

In one embodiment, the suspended particles may be gas bubbles or air bubbles. In this embodiment, each bubble may have a diameter of about 50 microns to about 2000 microns, and may be present at a concentration of about 0.01% to about 5% by volume of the composition, or about 0.05% to about 4% by volume of the composition, or about 0.1% to about 3% by volume of the composition.

Light-shading agent

In one embodiment, the composition may further comprise an opacifying agent.

As used herein, an "opacifier" is a substance added to a material to opacify the subsequent system. In a preferred embodiment, the sunscreen agent is Acusol available from Dow Chemicals. Acusol opacifier is provided in liquid form at a certain percent solids content. Acusol sunscreen is provided having a pH in the range of 2.0 to 5.0 and a particle size in the range of 0.17 to 0.45 um. In a preferred embodiment, AcusolOP303B and 301 may be used.

In yet another embodiment, the sunscreen may be an inorganic sunscreen. Preferably, the inorganic sunscreen may be TiO₂ZnO, talc, CaCO₃And combinations thereof. The composite sunscreen-microsphere material is readily formed at a preselected specific gravity, and thus the material has little tendency to segregate.

Hydrotrope: the composition may optionally include a hydrotrope in an effective amount of about 0% to 15%, or about 1% to 10%, or about 3% to about 6%, so that the composition is compatible in water. Hydrotropes suitable for use in the present invention include anionic hydrotropes, particularly sodium xylene sulfonate, potassium xylene sulfonate and ammonium xylene sulfonate; sodium, potassium and ammonium tosylates; sodium, potassium and ammonium cumene sulfonates and mixtures thereof, as disclosed in U.S. Pat. No. 3,915,903.

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% to 0.08% by weight. Mixtures of antioxidants may be used.

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

One class of antioxidants used in the present invention are alkylphenols having the general formula:

wherein R is C₁-C₂₂Straight or branched alkyl, preferably methyl or branched C₃-C₆Alkyl radical, C₁-C₆Alkoxy, preferably methoxy; r₁Is C₃-C₆A branched alkyl group, preferably a tert-butyl group; x is 1 or 2. Hindered phenol compounds are a preferred type of alkylated phenol having this formula. A preferred hindered phenol compound of this type is 3, 5-di-tert-butyl-4-hydroxytoluene (BHT).

Additionally, the antioxidants used in the compositions may be selected from the group consisting of α -, β -, gamma-, -tocopherols, auxins, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and salts thereof, and mixtures thereof it is noted that the auxins (1, 2-dihydro-6-ethoxy-2, 2, 4-trimethylquinoline) are made from Raschig^TMRaluquin, Inc^TMName selling.

Another type of antioxidant that may be used in the composition is 6-hydroxy-2, 5,7, 8-tetramethylchromane-2-carboxylic acid (Trolox)^TM) And 1, 2-benzothiazolin-3-one (Proxel GX L)^TM)。

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

wherein R is₁And R₂Each independently is alkyl, or R₁And R₂May be taken together to form C₅-C₆A cyclic hydrocarbyl moiety; b is absent or CH₂；R₄Is C₁-C₆An alkyl group; r₅Is hydrogen or-C (O) R₃Wherein R is₃Is hydrogen or C₁-C₁₉An alkyl group; r₆Is C₁-C₆An alkyl group; r₇Is hydrogen or C₁-C₆An alkyl group; x is-CH₂OH or-CH₂A, wherein A is a nitrogen-containing unit, a phenyl group or a substituted phenyl group. Preferred nitrogen-containing a units include amino, pyrrolidinyl, piperidinyl, morpholino, piperazine and mixtures thereof.

In one aspect, the most preferred type of antioxidant for use in the composition is 3, 5-di-tert-butyl-4-hydroxytoluene (BHT), α -, β -, gamma-, -tocopherol, 1, 2-benzothiazolin-3-one (Proxel GX L)^TM) And mixtures thereof.

The detergent compositions of the present invention may also contain an antimicrobial agent. 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 also quaternary ammonium salts, such as benzethonium chloride, and quaternary ammonium compounds having inorganic or organic counterions, such as bromine, carbonates or other moieties, including dialkyl dimethyl ammonium carbonate, and antimicrobial amines, such as Chlorhexidine Gluconate (chlorexidine Gluconate), PHMB (polyhexamethylene biguanide), salts of biguanides, substituted biguanide derivatives, organic salts containing quaternary ammonium compounds or inorganic salts containing quaternary ammonium compounds or mixtures thereof.

And (6) packaging. Any conventional packaging can be used and the packaging can be completely or partially transparent so that the consumer can see the color of the laundry care composition, which can be provided or produced by the color of the dyes necessary for the present invention. The ultraviolet absorbing compound may be included in part or all of the packaging.

When in liquid form, the laundry care compositions of the present invention may be aqueous (typically above 2 wt% or even above 5 or 10 wt% total water, up to 90 wt% or up to 80 wt% or 70 wt%) or non-aqueous (typically below 2 wt% total water). Typically, the compositions of the present invention will be in the form of an aqueous solution or homogeneous dispersion or suspension of the surfactant, the shading dye and certain optional other ingredients, some of which may be in a generally solid form that has been combined with the generally liquid components of the composition, such as the nonionic liquid alcohol ethoxylate, the aqueous liquid carrier and any other generally liquid optional ingredients. The solution, dispersion or suspension will be acceptably phase stable. When in liquid form, the laundry care compositions of the invention preferably have a viscosity at 20s-1 and 21 ℃ of from 1 to 1500 cps (1-1500 mPas), more preferably from 100 to 1000cps (100-. The viscosity can be determined by conventional methods. The viscosity can be measured using an AR 550 rheometer from taimeters using a steel plate spindle with a diameter of 40mm and a gap size of 500 μm. High shear viscosity at 20s-1 and low shear viscosity at 0.05-1 can be obtained by scanning at a logarithmic shear rate from 0.1-1 to 25-1 over 3 minutes at 21 ℃. The preferred rheology described therein can be achieved using an internally present detergent ingredient configuration or by using an external rheology modifier. More preferably, laundry care compositions, such as detergent liquid compositions, have a high shear rate viscosity of from about 100 to 1500 cps, more preferably from 100 to 1000 cps. The unit dose laundry care compositions, e.g., detergent liquid compositions, have a high shear rate viscosity of 400cps to 1000 cps. Laundry care compositions such as laundry softening compositions typically have a high shear rate viscosity of from 10cps to 1000, more preferably from 10cps to 800cps, most preferably from 10cps to 500 cps. The dishwashing hand composition has a high shear rate viscosity of from 300cps to 4000cps, more preferably from 300cps to 1000 cps.

The liquid compositions, preferably laundry care compositions herein, may be prepared by bringing together the components thereof in any convenient order and by mixing, e.g. agitating, the resulting component compositions to form a phase stable liquid laundry care composition. In the process of making the composition, a liquid matrix is formed that contains at least a major proportion, or even substantially all, of the liquid components, such as the nonionic surfactant, the non-surface active liquid carrier, and other optional liquid components, and the liquid components are thoroughly mixed by subjecting the liquid composition to shear agitation. For example, rapid stirring may be performed using a mechanical stirrer. Substantially all of any anionic surfactant and ingredients in solid form may be added while maintaining shear agitation. The mixture is continued to be stirred and, if necessary, at this point stirring is increased to form a solution or homogeneous dispersion of the insoluble solid phase particles in the liquid phase. After some or all of the material in solid form is added to the stirred mixture, any particles of enzyme material, such as enzyme particles, that are to be included are incorporated. As a variant of the above composition preparation process, one or more solid components may be added to the stirred mixture as a solution or slurry of particles premixed with a small amount of one or more liquid components. After all composition components are added, the mixture is continued to be stirred for a period of time to form a composition having the necessary viscosity and phase stability characteristics. Typically, this requires about 30 to 60 minutes of stirring.

The leuco colorants of the present invention have been found to be suitable for use in liquid laundry care compositions having a wide pH range. 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. Furthermore, the leuco colorants of the present invention have 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.

And (4) a bag. In a preferred embodiment of the invention, the composition is provided in the form of a unitized dose (unitary dose) which is in the form of a tablet, or preferably in the form of a liquid/solid (optionally particulate)/gel/paste within a water-soluble film known as a pouch or sachet. The composition may be enclosed in a single compartment pouch or a multi-compartment pouch. Multi-compartment bags are described in more detail in EP- ｃA-2133410. When the composition is present in a multi-compartment pouch, the composition of the invention may be present in one or two or more compartments, and thus the dye may be present in one or more compartments, optionally in all compartments. Non-opacifying dyes or pigments or other aesthetic materials may also be used in one or more compartments. In one embodiment, the composition is present in a single compartment of a multi-compartment pouch.

Preferred membrane materials are polymeric materials. As is known in the art, film materials may be obtained, for example, by casting, blow molding, extrusion or blown extrusion of polymeric materials. Preferred polymers, copolymers or derivatives thereof suitable for use as the pouch material are selected from the group consisting of polyvinyl alcohols, polyvinyl pyrrolidones, polyoxyalkylenes, acrylamides, acrylic acids, celluloses, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamides, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatin, natural gums such as xanthan and carrageenan. More preferred polymers are selected from the group consisting of polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and most preferably from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymers and Hydroxypropylmethylcellulose (HPMC) and combinations thereof. Preferably, the content of polymer, e.g. PVA polymer, in the bag material is at least 60%. The polymer may have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000, still more preferably from about 20,000 to 150,000. Mixtures of polymers may also be used as bag materials. Depending on the application of the compartment or bag and the required requirements, it may be beneficial to control the mechanical and/or dissolution properties of the compartment or bag. Suitable mixtures include, for example, mixtures in which one polymer has a higher water solubility than the other polymer and/or in which one polymer has a higher mechanical strength than the other polymer. Also suitable are mixtures of polymers having different weight average molecular weights, for example PVA or copolymers thereof having a weight average molecular weight of about 10,000-40,000, preferably about 20,000, and mixtures of PVA or copolymers thereof having a weight average molecular weight of about 100,000 to 300,000, preferably about 150,000. Also suitable herein are polymer blend compositions, for example comprising hydrolytically degradable and water soluble polymer blends, such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35% by weight polylactide and about 65% to 99% by weight polyvinyl alcohol. Preferred for use herein are polymers that are hydrolyzed from about 60% to about 98%, preferably from about 80% to about 90%, to improve the dissolution characteristics of the material.

Naturally, different membrane materials and/or different thicknesses of the membrane may be used in the manufacture of the compartments of the present invention. The benefit of choosing different membranes is that the resulting compartments may exhibit different solubility or release characteristics.

The most preferred membrane materials are PVA membranes known under MonoSol trade designations M8630, M8900, H8779, PVA membranes described in US patent nos. US 6166117 and US 6787512, and PVA membranes with corresponding solubility and deformability.

The film material herein may also include one or more additive components. For example, it may be beneficial to add a plasticizer, such as glycerin, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures thereof. Other additives include functional detergent additives to be delivered to the wash water, such as organic polymeric dispersants and the like.

In solid form. As mentioned above, the laundry care composition may be in solid form. Suitable solid forms include tablets and granular forms such as granules, flakes or sheets. Various techniques for forming such solid form detergent compositions are well known in the art and may be used herein. In one aspect, for example when the composition is a granular particle, the leuco colorant is provided in the form of a particle, optionally including additional but not all components of the laundry detergent composition. The colorant particle is combined with one or more additional particles which comprise the remaining components of the laundry detergent composition. Furthermore, the colorant, optionally including other but not all components of the laundry care composition, may be provided in an encapsulated form and the sunscreen dye encapsulate is combined with a particle containing a substantial balance of the components of the laundry care composition.

The application method is disclosed. The compositions of the present invention prepared as described above may be used to form aqueous laundering/treatment solutions for use in the laundering/treatment of fabrics. Typically, an effective amount of such compositions is added to water to form the aqueous laundering solution, for example, in a conventional fabric automatic washing machine. The aqueous washing solution thus formed is then brought into contact with the fabric to be washed/treated, usually under agitation. An effective amount of the liquid detergent compositions herein added to water to form an aqueous wash solution may comprise sufficient to form from about 500ppm to 7,000ppm of the composition in an aqueous wash solution, or from about 1,000 to 3,000ppm of the laundry care compositions herein will be provided in an aqueous wash solution.

Typically, the wash liquor is formed by contacting the wash care composition with wash water such that the concentration of the wash care composition in the wash liquor is from above 0g/l to 5g/l, alternatively from 1g/l to 4.5g/l, alternatively to 4.0g/l, alternatively to 3.5g/l, alternatively to 3.0g/l, alternatively to 2.5g/l, alternatively to 2.0g/l, alternatively to 1.5 g/l. The process of washing fabrics or textiles may be carried out in a top loading or front loading automatic washing machine, or may be used in a hand wash laundry application. In these applications, the concentration of the wash liquor and laundry detergent composition formed in the wash liquor is that of the main wash cycle. The volume of wash liquor is determined without including any water input in the optional rinse step.

The wash liquor may comprise 40 litres or less of water, or 30 litres or less of water, or 20 litres or less of water, or 10 litres or less of water, or 8 litres or less of water, or even 6 litres or less of water. The wash liquor may comprise from above 0 to 15 litres, or from 2 to 12 litres, or even to 8 litres of water. Usually 0.01kg to 2kg of fabric per litre of wash liquor is dosed to the wash liquor. Typically from 0.01kg, or 0.05kg, or 0.07kg, or 0.10kg, or 0.15kg, or 0.20kg, or 0.25kg of fabric per litre of wash liquor is dosed into the wash liquor. Optionally, 50g or less, or 45g or less, or 40g or less, or 35g or less, or 30g or less, or 25g or less, or 20g or less, or even 15g or less, or even 10g or less of the composition is contacted with water to form a wash liquor. The compositions are typically used at concentrations of about 500ppm to about 15,000ppm in solution. When the wash solvent is water, the water temperature is typically in the range of about 5 ℃ to about 90 ℃, and when the location includes fabric, the water to fabric ratio is typically about 1:1 to about 30: 1. Typically, the pH of the wash liquor comprising the laundry care composition of the invention is from 3 to 11.5.

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; the surface or fabric is then optionally washed and/or rinsed, and optionally a drying step.

Drying of the surface or fabric may be accomplished by any of the usual methods employed 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 certain aspects also to synthetic fabrics, such as polyester and nylon, and to 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 of cellulosic fibers, for example, polycotton fabrics. The pH of the solution is typically 7 to 11, more typically 8 to 10.5. The composition is typically used at a concentration of 500ppm to 5,000ppm in solution. The water temperature is typically from about 5 ℃ to about 90 ℃. The water to fabric ratio is typically from about 1:1 to about 30: 1.

Thus, in a third embodiment, the present invention provides a method of treating a textile, preferably comprising the steps of (i) treating the textile with an aqueous solution comprising a leuco composition as described herein, (ii) optionally rinsing the textile, and (iii) drying the textile in one aspect, the present invention provides a method of treating a textile, comprising the steps of (i) treating the textile with an aqueous solution comprising a leuco composition as described herein, the aqueous solution comprising from 10ppb to 5000ppm of at least one leuco compound and from 0.0 g/L to 3 g/L of a surfactant, (ii) optionally rinsing, and (iii) drying the textile.

Test method

The fabric swatches used in the test methods herein (fabric swatch) were obtained from Testfabrics, inc. of WestPittston, pa 100% cotton, 403 (cut to 2 inches × 2 inches) and/or 464 (cut to 4 inches × 6 inches), and an unbleached multi-fiber fabric, specifically 41 (5cm × 10 cm).

All reflectance spectra and color measurements of the dry textile sample pieces, including L, a, b, K/S and whiteness index (WICIE) values, were measured using one of four spectrophotometers, (1) Konica-Minolta 3610D reflectance spectrophotometer (Konica Minolta Sensing America, Inc., Ramsey, N.J.; D65 illumination, 10 ℃ viewer, no UV included), (2) L abScan XE reflectance spectrophotometer (Hunter L abs, Reston, Virginia, U.S.; D65 illumination, 10 ℃ viewer, no UV included), (3)

7000A (GretagMacbeth, New Windsor, N.Y., USA; lamp D65, UV-free), or (4) Color i7 spectrophotometer (X-rite, Inc., Rapids, Mich., USA; lamp D65, UV-free).

Upon irradiation of the fabric, unless otherwise indicated, the designated dried fabric was exposed to 0.77W/m irradiance of 420nm in an Atlas Xenon face-Ometer Ci3000+ (Atlas Material Testing Technology, MountProspec, Ill.) for²In simulated sunlight of (2), the Atlas Xenon Fade-Ometer Ci3000+ is equipped with an S-type borosilicate internal filter (part number 20277300) andexternal filters (part number 20279600) set at a maximum cabinet temperature of 37 ℃, a maximum blackboard temperature of 57 ℃ (BPT blackboard geometry) and 35% RH (relative humidity). Unless otherwise specified, irradiation is continuous for a specified duration.

I. Method for determining efficiency of leuco conjugates in wash solutions

Cotton swatches were washed twice prior to use with a zero brightener heavy-duty liquid laundry detergent (1.55 g/L in aqueous solution) at 49 ℃ to decorticate (strip) the cotton swatches (464 formula) in a solvent (preferably ethanol) selected from ethanol or 50:50 ethanol: water to make a concentrated stock solution of each of the leuco compositions to be tested.

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

A base wash liquor was prepared by dissolving a zero brightener AATCC heavy-duty liquid laundry detergent (5.23 g/1.0L) in deionized water, four stripped cotton swatches were weighed together and placed in a 250m L conical flask (Erlenmeyer flask) with two 10mm glass spheres, a total of three such flasks were prepared for each wash liquor to be tested, the leuco conjugate storage solution was metered into the base wash liquor to obtain a laundry detergent with the desired 2.00 × 10^-6equivalent/L leuco conjugate wash concentration.

An aliquot of this wash liquor sufficient to provide a liquor to fabric ratio (weight ratio, w/w) of 10.0:1.0 was placed into each of three 250m L Erlenmeyer flasks 1000gpg of the hardness stock solution was dosed into each flask to achieve a final wash hardness of 6gpg (3:1Ca: Mg).

The flasks were placed on a model 75 hand shaker (wrisat action shaker) (burell Scientific, inc., p. pa., usa) and stirred at maximum setting for 12 minutes, then The wash liquor was removed by aspiration, rinse water (0gpg) was added at a volume comparable to The amount of wash liquor used, 1000gpg of a hardness stock solution was metered into each flask to achieve a final wash hardness of 6gpg (3:1Ca: Mg), then stirred for an additional 4 minutes, The rinse liquor was removed by aspiration, then cotton swatches were Spin dried (Mini counter top Spin Dryer), The L autonomic, nashou, NH) for 1 minute, then placed in a food dehydrator set at 135 ° F, dried in The dark for 2 hours after this drying procedure, The swatches could be stored in dark for different times before measuring fabric properties or by exposure to light in The dark.

The method used must be able to measure the benefits of the leuco compound in each case since the habits of consumers vary significantly around the world, one such condition is exposure to light after drying some leuco compounds do not exhibit as much benefit under dark storage as under light storage, and therefore each leuco compound must be tested under both sets of conditions to determine the best benefit.

A. Dark conditions after drying

The L, a, b and whiteness index (WI CIE) values for the cotton fabric were measured at times t 0, 6, 24 and 48 hours after the end of the two hour drying time the average of the 12 swatches generated for each leuco colorant (three flasks, 4 swatches per flask) was calculated to give sample values of L, a, b and WI CIE for each time t.

The above steps were repeated in order to obtain control treated L x, a x, b x and whiteness index (WI CIE) values, except that (1) a control base wash was prepared using an AATCC heavy duty liquid laundry detergent with zero brightener (5.23 g/1.0L) in deionized water, (2) the values measured after the drying period for the 12 control-generated sample sheets were averaged to give sample values of L x, a x, b x and WI CIE, and the control value of t 0 was also used as the control value of t6, 24 and 48 hours.

Based on the data collected at each time point t, the leuco colorant efficiency (L CE) of the leuco colorant in the laundry care formulation was calculated 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 laundered with an AATCC heavy-duty liquid laundry detergent with zero brightener) and sample (i.e., fabric laundered with a laundry care formulation containing a leuco colorant), respectively, used to calculate L CE_tThe values of (c) are those at the corresponding time points t (0, 6, 24 or 48 hours).

The WI CIE values of the 12 coupons generated for each wash (three flasks with 4 coupons per flask) were averaged and the change in whiteness index at wash was calculated using the following equation:

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

Laundry care formulations (Δ WI)_sample) And AATCC HD L (delta WI) with zero whitening agent_control) The values that would be separated. The change in whiteness between the two formulations is given by the formula:

ΔWI＝ΔWI_sample–ΔWI_control

B. light condition after drying

The designated cotton fabric 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 were measured on the sample after each exposure period the calculation of L CE and Δ WI values for each exposure time point was as described in method i.a. above and the L CE and Δ WI values for the sample and control laundry care formulations were set to the maximum values from the set of exposure times listed.

Method for determining relative hue angle (relative to AATCC control)

The relative hue angle that the leuco colorant imparts to cotton fabrics treated according to method I above was determined in the following manner.

a) The values of a and b were averaged for the 12 coupons in each solution and Δ a and Δ b were determined using the following equations:

Δa*＝a*_s-a*_cand Δ b ═ b-_s-b*_c

Where subscripts c and s refer to fabrics washed in a zero brightener AATCC heavy-duty liquid laundry detergent (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 both <0.25, the Relative Hue Angle (RHA) is not 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:

RHA (ATAN 2) (Δ a, Δ b), for Δ b ≧ 0

RHA 360+ ATAN2(Δ a, Δ b), for Δ b <0

The relative hue angle can be calculated for each time point at which data is collected in the evaluation under dark conditions after drying or in the evaluation under light conditions after drying. Any of these points in time may be used to satisfy the requirements of the claims.

A method of determining the surface tension values of leuco colorants and oxidized forms thereof.

The material to be tested was a leuco colorant according to the present invention, or a dye representing the second colored state of the leuco colorant (e.g., a triarylmethane dye). A total of 250 and 255mg of the material to be tested was weighed into a 4 ounce glass jar and 50.0m L deionized water (Barnstead B-PureSystems, about 17.27ohm) was added along with a magnetic stirrer (magnetic stir bar). The glass jar was capped, placed on a magnetic stir plate, and the mixture was stirred at 22.0 ℃ for 1 hour, after which stirring was stopped and the mixture was left undisturbed for 1 hour at the end of which time 10.0m L solution was drawn into a syringe which was then fitted with fiberglass fibers

Filter, filter aliquots into 20m L scintillation vials pipetted using a VWR L abMax pipettor to deliver 45.0 microliters of filtered solution to each of eight separate wells of a 96 well plate, using a Kibron DeltaThe solution was tested with an 8 tensiometer at about 22.0 ℃ and the average of 8 replicates of measurements was reported as surface tension value (in mN/m).

Example 1

A bias was determined for the leuco colorant to increase the whiteness of the aged garments relative to the whiteness of the cleaned new garments.

Tests were conducted using leuco colorants 1 and 2 to determine the extent to which the leuco compounds provide improved whiteness to consumer-derived aged cotton fabrics as well as to clean, stripped new cotton fabrics. The structures of the leuco colorants tested are shown below.

Leuco colorant 1(a + b ═ 0) and leuco colorant 2(a + b ═ 2.8; the sum of a + b ═ 5.6)

The test was performed according to method i.a. found herein on stripped cotton fabric, replacing formula 464 with formula 403. the test procedure was then re-performed as described, wherein the stripped cotton cloth was replaced with swatches cut from consumer-derived aged white T-shirt fabric (st. vincent depau 4 in × 6 in T-shirt swatches, heavy soiled; from J & R Coordinating Services, cincinnati, ohio), wherein the T-shirt swatches had L, a, b, and WI CIE values prior to washing as shown in table 1 below.

Table 1 average of consumer-derived aged cotton T-shirts before washing.

For the stripped cotton fabrics washed in the composition according to method i.a. and the consumer-derived aged white T-shirt fabrics, the change in whiteness index (Δ WI) was calculated according to the equation provided in the method, using the WI CIE values measured at 2, 24 and 48 hours after drying for the calculation in each case.

By comparing the change in whiteness index of the same fabrics washed in both detergent formulations, i.e. control (zero leuco colorant) and sample (containing leuco colorant), the change in whiteness due to the presence of leuco colorant in the wash liquor is derived; and the change in whiteness is calculated by the equation provided in the method. The results of the wash test are shown in table 2 below.

Table 2. whitening bias ratio of aged consumer cotton clothes versus clean cotton.

^a100% cotton, 403, Test Fabrics, inc.

^b100% cotton, white T-shirt from consumer.

The data in table 2 show that leuco colorants containing moieties with EO and PO oxyalkylene groups have a bias to increase the whiteness of aged consumer cotton fabrics relative to the whiteness of new clean cotton fabrics which is consistently greater than that obtained by leuco colorants containing moieties with only EO oxyalkylene units. This means that the use of such leuco colorants (e.g. 2) will provide the same whiteness benefits to aged cotton fabrics as leuco compounds having only EO oxyalkylene groups (e.g. 1) without compromising the color integrity of new cotton garments. Thus, the inventive leuco colorants of the present invention provide the consumer with a distinct advantage of efficiently depositing where they are needed (aged cotton fabrics that readily exhibit yellowing) while avoiding deposition on new clean fabrics where color adjustment is neither needed nor desired.

Example 2

Leuco colorant J (average a + b ≈ 2.5; sum of all a + b ≈ 5.0)

Various cotton fabrics (Testfabrics, Inc., West Pittston, Pa.; 100% cotton, cut to 4 inches × 6 inches) were separated into two comparable groups and tested as received, except that a second additional set of #403 swatches (CW120 cotton, cut to 4 inches × 4 inches; lot number different from the first) was stripped as described below and added to the test group, one set was washed with heavy duty liquid detergent (formulation A) using a zero leuco colorant, the other set was washed with the same detergent containing leuco colorant J (formulation B), each wash was run for 12 minutes with a 12:1 liquor to fabric ratio using a city water supply (about 6gpg, 3:1Ca: Mg) and 5,300ppm heavy duty liquid detergent formulation, the compositions of which are listed in Table 3 below, the fabrics were rinsed with a 12:1 liquor to fabric ratio for four minutes and then air dried in 48 hours at room temperature.

TABLE 3 heavy-duty liquid detergent formulations A and B

L, a, b and whiteness index (WI CIE) values of the cotton fabric were measured on dry swatches both before and at 48 hours after washing using a CM3610D spectrophotometer (Konica Minolta, Ramsey, new jersey, usa; D65 illumination, 10 ° observer, no uv included).

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

By comparing the change in whiteness index of the same type # fabrics washed in the two detergent formulations a and B, the change in whiteness due to the addition of leuco colorant J to the wash liquor is derived; and the change in whiteness is calculated by the following equation:

ΔWI_CIEΔ WI (detergent B) - Δ WI (detergent a)

The results for the fabrics are given in the table below, as Δ WI obtained_CIEThe values of (a) are arranged numerically. The fabric ID (identi) testedty) and the results are listed in table 4 below.

TABLE 4.Δ WI obtained for various standard cotton fabrics_CIEThe value of (c).

Even for such cotton cloths of the same style #, one of which had been washed twice at 49 ℃ with an AATCC heavy duty liquid laundry detergent (in 1.55 g/L aqueous solution) that had used a zero brightener before use to decorticate (giving a Δ WI CIE value of 1.93), the other unpicked (giving a Δ WI CIE value of 0.72.) this indicates that a given detergent formulation in consumer use would encounter textiles representing a wide range of possibilities, and that the manner of action of the formulation on some textiles would often be significantly different from that on other textiles.

Example 3

The fully oxidized forms of leuco colorants 1 and J from examples 1 and 2, respectively, were deposited on 403 cotton swatches through the wash cycle. As mentioned above, the oxidized form of leuco colorant J was also deposited on the above-mentioned consumer-derived aged white T-shirt fabric through the wash cycle. Fabric samples were exposed to 0.77W/m with an irradiance of 420nm in an Atlas Xenon Fade-Ometer Ci3000+ (Atlas Material Testing Technology, Mount Prospects, Ill.)²In simulated sunlight, to test the degree of photobleaching of the fabric sample; wherein the atlas xenon face-Ometer Ci3000+ is fitted with an S-type borosilicate inner filter (part number 20277300) and an outer filter (part number 20279600) set at a maximum cabinet temperature of 37 deg.C, a maximum blackboard temperature of 57 deg.C (BPT blackboard geometry) and 35% RH (relative humidity). Exposing the 403 fabric for 30 and 120 minutes continuously; consumer-derived aged white T-shirts were exposed continuously for 120 minutes. The leuco colorant J faded less than leuco colorant 1 after 30 and 120 minutes of irradiationFading. After 120 minutes, the fading of leuco colorant J was similar on clean fabrics and consumer-derived aged white T-shirts.

Example 4

This example demonstrates the preparation of a compound according to the invention having the following structure

12.45 grams of 4-acetamidobenzaldehyde and aniline-2, 4 (aniline alkoxylated with an average of 2 EO and 4 PO) were added to a three-necked round bottom flask equipped with a heating mantle, stirrer, condenser and nitrogen inlet.2.71 grams of urea was then dissolved in 18 grams of water and the solution added to the reaction after mixing 23.74 grams of concentrated HCl (37%) was slowly added to the reaction mixture while maintaining the temperature below 90 deg.C. the reaction mixture was stirred under nitrogen for 6 hours after the reaction was complete the contents of the flask were added to an excess of sodium bicarbonate solution (30 g in 600m L water). the product was extracted from the resulting mixture using ethyl acetate and washed with deionized water.

Formulation examples

The following are illustrative examples of detergent compositions according to the present disclosure and are not intended to be limiting.

Examples 3 to 9: heavy-duty liquid laundry detergent compositions.

Based on the total weight of the washing and/or treatment composition. Enzyme content levels are reported as raw materials.

Examples 10 to 20:a unit dosage composition.

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 composition is a polyvinyl alcohol-based film.

Based on the total weight of the washing and/or treatment composition. Enzyme content levels are reported as raw materials.

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

Enzyme content levels are reported as raw materials based on the total weight of the washing and/or treatment composition.

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 with an average degree of ethoxylation of 8

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

The amylase 1 is

15mg active substance/g, supplied by Novozymes

The amylase 2 is

29mg active substance/g, supplied by Novozymes

The xyloglucanase is

20mg active substance/g, supplied by Novozymes

Chelating agent 1 is diethylenetriaminepentaacetic acid

The chelating agent 2 is 1-hydroxyethane 1, 1-diphosphonic acid

Dispersin B is a glycoside hydrolase, which is reported as 1000mg active substance/g

DTI is either poly (4-vinylpyridine-1-oxide) (e.g. Chromabond)

) Or is

Poly (1-vinylpyrrolidone-co-1-vinylimidazole) (e.g., Sokalan)

)。

Dye control Agents the dye control agents according to the invention, for example

O.IN(M1)、

P(M2)、

PM (M3) or

HF(M4)

HSAS is the intermediate branching (mid-branched) disclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443

Alkyl sulfates

L AS is a carbon chain having an average aliphatic carbon chain length C₉-C₁₅Linear alkylbenzenesulfonate (H L AS is an acid)

Forms).

Leuco colorants any suitable leuco colorant or mixture thereof according to the present disclosure.

The lipase is

18mg active substance/g, supplied by Novozymes

V200 is a thiophene azo dye, supplied by Milliken

The mannanase is

25mg active substance/g, supplied by Novozymes

The nuclease is phosphodiesterase SEQ ID NO 1, which is reported as 1000mg active substance/g

The fluorescent whitening agent 1 is 4,4' -bis { [ 4-anilino-6-morpholinyl-s-triazin-2-yl radical]-amino } -2,2' -di

Disodium styrene disulfonate

The fluorescent whitening agent 2 is disodium 4,4' -bis- (2-sulfostyryl) biphenyl (sodium salt)

Fluorescent whitening agent 3 is Optiblanc from 3V Sigma

The perfume encapsulates are core shell melamine formaldehyde perfume microcapsules.

Polish enzyme is p-nitrobenzyl esterase, reported as 1000mg active substance/g

Polymer 1 is bis ((C)₂H₅O)(C₂H₄O)_n)(CH₃)-N⁺-C_xH_2x-N⁺-(CH₃) -bis ((C)₂H₅O)(C₂H₄O)

n) or sulfated or sulfonated variants thereof, wherein n-20 to 30 and x-3 to 8

Polymer 2 is Ethoxylated (EO)₁₅) Tetraethylenepentamine (IV)

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 Purafect

40.6mg active substance/g, supplied by DuPont

The structurant is hydrogenated castor oil

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".

The entire contents of each document (including any cross-referenced or related patent or application and any patent application or patent to which this application claims priority or benefit) cited herein are hereby incorporated by reference herein, unless expressly excluded or otherwise limited. Citation of any reference 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 one or more of any other references. 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.

Claims (17)

1. A leuco composition comprising at least one leuco compound comprising a leuco portion and an alkylene oxide portion covalently bonded to the leuco portion, wherein the alkylene oxide portion comprises at least one ethylene oxide group and at least one propylene oxide group.

2. The leuco composition according to claim 1, wherein said leuco moiety is selected from the group consisting of diarylmethane leuco moieties, triarylmethane leuco moieties, oxazine moieties, thiazine moieties, hydroquinone moieties, and arylaminophene moieties.

3. The leuco composition according to claim 2, wherein the leuco moiety is a triarylmethane leuco moiety.

4. The leuco composition according to any one of claims 1-3, wherein the alkylene oxide moiety comprises 1 to about 20 ethylene oxide groups and 1 to about 20 propylene oxide groups.

5. The method of any one of claims 1-4Wherein the alkylene oxide moiety is covalently bound to the leuco moiety through a nitrogen atom, the nitrogen atom and the alkylene oxide moiety together having the structure-NR¹(C₂H₄O)_n(C₃H₆O)_qH, wherein n and q are independently selected from integers of 1 to 5, and R¹Selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and alkylene oxide moieties.

6. The leuco composition of any one of claims 1-5, wherein the leuco compound comprises two alkylene oxide moieties, each alkylene oxide moiety being covalently bonded to the leuco moiety through a nitrogen atom, the nitrogen atom and the alkylene oxide moieties together having a structure

Wherein n, q, r and s are independently selected from integers of 0 to 5, the sum of n and r is 2 to 10, and the sum of q and s is 2 to 10.

7. The leuco composition according to claim 6, wherein the sum of n and r is 2 to 5, and the sum of q and s is 2 to 5.

8. The leuco composition according to any one of claims 1-7, wherein the leuco compound has the structure of formula (CI)

Wherein the ratio between formula (CI) and its oxidized form is at least 1: 3; wherein each individual R on each of rings A, B and C_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, alkarylAlkyl, substituted alkylaryl, — (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)^-)₂(ii) a Wherein subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0;

wherein G is independently selected from hydrogen, deuterium, C₁-C₁₆Alkoxides, phenoxides, bisphenolates, 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 said alkylene oxide moiety;

wherein any charge present in the compound is balanced by an appropriately independently selected internal or external counterion.

9. The leuco composition according to claim 8, wherein G is hydrogen.

10. The leuco composition according to any one of claims 1-9, wherein the leuco composition further comprises a solvent selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, poly (ethylene glycol), poly (propylene glycol), copolymers of ethylene oxide and propylene oxide, and mixtures thereof.

11. The leuco composition according to any one of claims 1-10, wherein the leuco compound is present in the composition in an amount of about 10% by weight or greater.

12. The leuco composition according to any one of claims 1-11, wherein the leuco composition further comprises an antioxidant compound.

13. The leuco composition according to claim 12, wherein the antioxidant compound is selected from the group consisting of hindered phenols, diarylamines, benzofuranones, and mixtures thereof.

14. The leuco composition according to claim 13, wherein the leuco composition comprises from about 0.01% to about 20% by weight of a hindered phenol, preferably BHT.

15. A leuco composition obtained by the steps of: (i) providing one molar equivalent of an aromatic aldehyde, (ii) providing about two molar equivalents of an aryl coupling agent or a mixture of aryl coupling agents, wherein at least one aryl coupling agent comprises a covalently bound alkylene oxide or polyoxyalkylene moiety, wherein the alkylene oxide or polyoxyalkylene moiety comprises at least one ethylene oxide group and at least one propylene oxide group, (iii) combining the aromatic aldehyde and the one or more aryl coupling agents in a suitable reaction vessel, (iv) adding 0.01 to 0.5 equivalents of urea, (v) adding technical grade hydrochloric acid to achieve a pH between about 0 and 3, (vi) heating the mixture between 60 ℃ and 120 ℃ for 2 hours to 12 hours, (vii) adjusting the pH to at least about 7, and (viii) separating at least a portion of the salt formed upon neutralization from the liquid product; wherein the leuco composition comprises at least one leuco compound comprising a leuco portion and an alkylene oxide portion covalently bonded to the leuco portion, wherein the alkylene oxide portion comprises at least one ethylene oxide group and at least one propylene oxide group.

16. The leuco composition of claim 15, wherein the leuco compound is of formula (CVII)

Wherein each subscript c is independently 0, 1 or 2, preferably each c is 1; each R⁴Independently selected from H, Me, Et, ((CH)₂CH₂O)_a(C₃H₆O)_b) H and mixtures thereof; preferably, each R⁴Is ((CH)₂CH₂O)_a(C₃H₆O)_b) H, wherein each subscript a is independently an integer of from 1 to 50, more preferably from 1 to 25, even more preferably from 1 to 20, 1 to 15, 1 to 10, 1 to 5, or even 1 to 2; each subscript b is independently an integer of 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 colorants is no more than 100, more preferably no more than 80, most preferably no more than 60, 40, 20, 10, or even no more than 5, and the sum of all independently selected b integers in the leuco colorants is at least 1 and no more than 50, more preferably no more than 40, most preferably no more than 30, 20, or even 10.

17. The leuco composition of claim 16, wherein the leuco compound is of formula (CVIII)

Wherein R is⁸Is H or CH₃And each subscript b independently averages about 1 to 2.