ES2355763T3 - COMPOSITION FOR CARE IN CLOTHING WASHING INCLUDED BY A WHITENING AGENT FOR CELLULOSTIC SUBSTRATES. - Google Patents

Abstract

This invention relates to laundry care compositions including but not limited to liquid and/or powder laundry detergent formulations and rinse added fabric softening (RAFS) compositions that comprise such whitening agents, for cellulosic substrates. The whitening agents are comprised of at least two components: at least one chromophore component comprising triphenylmethane colorant, and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. The whitening agents are further characterized by having a dispersion component value of the Hansen Solubility Parameter of less than or equal to about 17 MPa 0.5 .

Description

TECHNICAL FIELD

This invention relates to novel compositions for the care in the washing of clothes comprising bleaching agents for cellulosic substrates. The bleaching agents comprise at least two components: at least one chromophore component and at least one polymer component. Suitable chromophores components generally produce fluorescence in blue, red, violet, or purple when exposed to ultraviolet light, or can absorb light to reflect these same shades. The bleaching agents are also characterized by having a dispersion component value of the Hansen solubility parameter less than or equal to approximately 17 MPa0.5. These bleaching agents may be ideal for use in 15 laundry care compositions including, but not limited to, liquid and / or powder laundry detergent formulations and fabric softener compositions to be added during rinsing ( RAFS).

BACKGROUND OF THE INVENTION 20

The use of bleaching agents, whether optical brighteners or bluffing agents, in textile applications is well known in the state of the art. As textile substrates age, their color tends to fade or yellow due to exposure to light, air, dirt and natural degradation of the fibers that comprise the substrates. Therefore, the purpose of the bleaching agents is generally to visually brighten these textile substrates and counteract the attenuation of the color and the yellowish color of the substrates. Typically, bleaching agents may be present in laundry detergents, fabric softeners, or rinse aids and are therefore applied to textile substrates during the washing process. However, it is important that the bleaching agents exert the function of brightening the treated textile substrates without undesirably staining the textile substrates. 5

Cellulosic substrates, in particular, tend to have a yellow hue after exposure to light, air, and / or dirt. This yellowish color is often difficult to remove by normal washing procedures. As a result, there is a need for improved bleaching agents that are capable of removing the yellowish color presented by aging cellulosic substrates. Using such improved bleaching agents can prolong the life of textile substrates such as clothing, table linen, etc. fifteen

The present invention offers advantages over patents US-4,137,243, US-5,039,782 and patent application publication number US-2005/0288206, since this invention takes advantage of compounds having a lower Hansen solubility parameter or equal to approximately 17 MPa0.5 and emitting 20 light with wavelengths in the range of blue, red, violet, purple, or combinations thereof, when exposed to ultraviolet light (or absorb light to produce the same shades ) to neutralize the yellowish color of cellulosic substrates. These compounds exert their function, ideally, as bleaching agents for cellulosic substrates and can be incorporated into laundry detergent formulations for use by consumers during the washing process. EPO 006 271 A1 describes fabric softener compositions comprising a nonionic detergent, a cationic fabric softener, detergency builder additives, a nonionic optical brightener and, preferably, a discoloration inhibitor.

SUMMARY OF THE INVENTION

This invention relates to novel compositions for laundry care comprising bleaching agents for cellulosic substrates. The bleaching agents comprise at least two components: at least one chromophore component and at least one polymer component. Suitable chromophores components generally produce fluorescence in blue, red, violet, or purple when exposed to ultraviolet light, or can absorb light to reflect these same shades. The bleaching agents are also characterized by having a dispersion component value of the Hansen solubility parameter less than or equal to approximately 17 MPa0.5. This invention also relates to compositions for laundry care including, but not limited to, liquid and / or powder laundry detergent formulations and fabric softener compositions to be added during rinsing (RAFS) comprising said bleaching agents. twenty

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a graphical representation of values of the dispersion component of the Hansen solubility parameter versus CIELab b * values for various bleaching agents after 1 rinse cycle. 25

DETAILED DESCRIPTION

As used herein, "cellulosic substrates" is intended to include any substrate comprising at least a majority, by weight, of cellulose. Cellulose can be found in wood, cotton, linen, 30 jute and hemp. Cellulosic substrates may be present in the form of powders, fibers, pulp and articles formed from powders, fibers 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 5 textile articles, such as fabrics. Items formed from pasta include paper.

As used herein, the term "laundry care composition" includes, unless otherwise indicated, granulated, powdered, liquid, gel, paste type washing agents in pill form and / or scales and / or tissue treating compositions.

As used herein, the term "tissue treating composition" includes, unless otherwise indicated, fabric softening compositions, compositions for improving tissue properties, compositions for providing tissue freshness and combinations of the same. Such compositions may, although not necessarily, be compositions to be added during rinsing. twenty

It will be understood herein that articles that include "the", "a", when used in a claim, refer to one or more of what is claimed or described.

As used herein, the expressions "include", "includes" and "included" should be understood as non-limiting.

The test methods described in the test methods section of this report should be used to determine the respective values of the parameters of the applicants' inventions.

Unless otherwise indicated, all levels of the component or composition refer to an active part of that component or composition, and are excluding impurities, for example, residual solvents or by-products, which may be present in commercial sources. of 5 said components or compositions.

All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated with respect to the total composition unless otherwise indicated. 10

It should be understood that each maximum numerical limitation given throughout this specification includes any lower numerical limitation, as if these lower numerical limitations were expressly indicated herein. All the minimum limit values mentioned 15 throughout this specification will include any upper limit value, as if said upper limit values were expressly written herein. Each interval mentioned throughout this specification will include any smaller interval 20 comprised in a corresponding greater interval, as if said smaller intervals were expressly written herein.

Mention of any document should not be considered as an acceptance that it is part of the state of the art with respect to the present invention.

The bleaching agents of the present invention may be dyes, pigments, or polymeric dyes comprising a chromophore constituent and a polymeric constituent. The chromophore constituent is characterized by emitting or absorbing wavelength in the range of blue, red, violet, purple, or combinations thereof, when exposed to light. Preferably, the chromophore constituent has an absorbance spectrum value of about 520 nanometers to about 640 nanometers in water and, more preferably, from about 570 nanometers to about 610 nanometers in water. 5 Preferably, the chromophore constituent has an emission spectrum value of about 400 nanometers to about 480 nanometers in water.

Examples of suitable polymeric constituents include polyoxyalkylene chains having multiple repetitive units. Preferably, the polymeric constituents include polyoxyalkylene chains having from 2 to about 20 repetitive units and, more preferably, from 2 to about 10 or even from about 4 to about 6 repetitive units. Non-limiting examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

The bleaching agent used in the present invention may be characterized by the following structure:

in which R1 and R2 can be selected, independently of each other, from:

a) [(CH2CR'HO) x (CH2CR "HO) and H]

 wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; wherein R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + 5 and ≤ 5; where y ≥ 1; and where z = 0 to 5;

b) R1 = alkyl, aryl, or arylalkyl and R2 = [(CH2CR'HO) x (CH2CR "HO) and H]

 wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; in which R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y ≤ 10; where y ≥ 1; and where z = 0 to 5;

c) R1 = [CH2CH (OR3) CH2OR4] and R2 = [CH2CH (O R3) CH2O R4]

 wherein R3 is selected from the group consisting of 15 H, (CH2CH2O) zH, and mixtures thereof; and in which z = 0 to 10;

 wherein R4 is selected from the group consisting of (C1-C16) alkyl, aryl groups, and mixtures thereof; and 20

d) the amine addition product of styrene oxide, glycidylmethyl ether, isobutylglycidyl ether, isopropylglycidyl ether, t-butylglycidyl ether, 2-ethylhexylidethyl ether and glycidylhexadecyl ether, followed by the addition of 1 to 10 units of alkylene oxide. 25

A preferred bleaching agent of the present invention may be characterized by the following structure:

wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; wherein R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and 5 mixtures thereof; in which x + y ≤ 5; in which y ≥ 1; and where z = 0 to 5.

Another characteristic of the bleaching agent used in the present invention is its affinity for cellulosic material. The affinity can be determined quantitatively using the 10 dispersion force component of the Hansen solubility parameter. The Hansen solubility parameter is a three component measurement system that includes a dispersion force component (δd), a hydrogen bond component (δh), and a polar component (δp). The Hansen solubility parameter "δ" is derived from the fact that the total cohesive energy, which is the energy required to break all cohesive bonds, is the combination of dispersion forces (d), molecular dipole forces ( p), and hydrogen bonding forces (h) according to the following equation:

δ2 = δd2 + δp2 + δh2. (one)

Dispersion forces are weak attractive forces between non-polar molecules. The magnitude of these forces depends on the polarizability of the molecule and the Hansen dispersion solubility parameter, δd, typically increases with the increasing volume (and size) of the molecule, all other properties being approximately equal. The "δp" parameter increases with the increasing polarity of the molecule. 5

Hansen solubility parameters are calculated at 25 ° C with ChemSW Molecular Modeling Pro v.6.1.9 software that uses an unpublished property algorithm that is based on values published in Allan F.M. Handbook of Solubility Parameters and Other Parameters. Barton (CRC Press, 1983) for 10 solvents obtained experimentally by Hansen. All values of the Hansen solubility parameter indicated herein are in units of MPa0.5 (square root of mega Pascals). Hansen initially determined the solvent solubility parameter for polymer solutions. Although the calculation of the Hansen solubility parameter has been successfully applied to a wide variety of applications such as, for example, solubility of biological materials, identification of pigments, fillers and fibers, etc., it has not been adapted so far to polymeric dyes. twenty

Therefore, for the effective bleaching agents of the present invention, it is preferable that the dispersion force component of the Hansen solubility parameter, δd, be less than or equal to about 17 and, more preferably, less than or equal to about 15. It may also be desirable that the dispersion force component of the Hansen solubility parameter be from about 12 to about 17 and, more preferably, from about 12 to about 15.

While the affinity of the bleaching agent for cellulosic material seems to show a great correlation with the Hansen solubility dispersion component parameter, the invention is not limited to the use of δd. Other molecular descriptors that are directly or indirectly related to δd were also considered, such as polarizability, turning radius, molecular volume and Jurs descriptors based on partial atomic charges represented on the surface area accessible to the solvent. However, the quality of the adjustment of these univariate correlations of affinity with these descriptors was not as marked as with δd.

Without intending to impose any theory, it is believed that the affinity of the bleaching agents for cellulose substrates may be due to the forces of Van der Waals, the attractive forces that exist between electrically neutral molecules located very close to each other. It is also postulated that if the cellulose substrate comprises porous regions, the bleaching agent, or parts thereof, can be physically trapped in the pores of the cellulose, depending on the size of the molecule compared to the pore diameter. This physical entrapment can provide some level of durability to protect the bleaching agent from being easily removed from the cellulose substrate when exposed to washing or rinsing.

The bleaching agent described herein is incorporated into a laundry care composition including, but not limited to, laundry detergents and tissue care compositions. Said compositions comprise one or more of said bleaching agents and an ingredient for laundry care. The bleaching agent can be added to cellulose substrates using a variety of application techniques. For application to textile substrates containing cellulose, the bleaching agent is preferably included as an additive in the laundry detergent. Therefore, the application to the cellulose-containing textile substrate actually occurs when a consumer adds laundry detergent to a clothes washer. Similarly, RAFS compositions are typically added to the rinse cycle, which takes place after the detergent solution has been used and replaced by the rinse solution in typical washing processes. For application to cellulosic paper substrates, the bleaching agent may be added to the paper pulp mixture prior to the formation of the final paper product. 10

Compositions for laundry care that include laundry detergents may be in solid or liquid form, included in gel form. The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.

The bleaching agent may be present in the laundry detergent composition in an amount of about 0.0001% to about 10% by weight of the composition, more preferably from about 0.0001% to about 5% by weight of the composition and, even more preferably, from about 0.0001% to about 1% by weight of the composition.

The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one embodiment, the laundry detergent composition comprises, by weight, from about 5% to about 90% of the surfactant and, more specifically, from about 5% to about 70% of the surfactant and, even more specifically, about 30 5% to about 40%. The surfactant may comprise anionic, nonionic, cationic, hybrid ion and / or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.

Suitable anionic surfactants useful in the present invention may comprise any of the types of conventional type anionic surfactant typically used in liquid detergent products. These include alkylbenzenesulfonic acids and their salts, as well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Illustrative anionic surfactants are the alkali metal salts of alkylbenzenesulfonic acids C.sub. 10-16, preferably alkylbenzenesulfonic acids C.sub. 11-14. Preferably the alkyl group is linear and said linear alkylbenzenesulfonates are known as "LAS". Alkylbenzenesulfonates, and especially LAS, are well known in the art. Such surfactants and their preparation are described, for example, in patents US-2,220,099 and US-2,477,383. Especially preferred are sodium and potassium straight chain alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is about 11 to 14. A sodium C11-C14 LAS, p. eg, C12, is a specific example of such surfactants.

Another illustrative type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkylether sulfates or polyethoxylated alkyl sulfates, are those corresponding to the formula: R'-O- (C2H4O) n-SO3M in which R 'is a C8-C20 alkyl group, n is approximately 1 to 20, and M is a salt-forming cation. In a specific embodiment, R 'is C10-C18 alkyl, n is about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R 'is a C12-C16, n is about 1 to 6 and M is sodium.

The alkylene ether sulfates will generally be used in the form of mixtures comprising various R 'chain lengths and various degrees of ethoxylation. Often such mixtures will also inevitably contain some non-ethoxylated alkyl sulfate materials, that is, surfactants of the above ethoxylated alkyl sulfate formula wherein n = 0. Non-ethoxylated alkyl sulfates can also be added separately to the compositions of this invention and used as such or in any anionic surfactant component that may be present. Specific examples of non-alkoxylated alkyl ether sulfate surfactants, e.g. eg, non-ethoxylated, are those produced by the sulfation of C8-C20 higher fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROSO3-M + in which R is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water soluble cation. In specific embodiments, R is a C10-C15 alkyl and M is alkali metal, more specifically, R is C12-C14 and M is sodium.

Non-limiting, specific examples of anionic surfactants useful in the present invention include: a) C11-C18 alkylbenzenesulfonates (LAS); b) C10-C20 primary, branched chain and random alkyl sulfates (AS); c) secondary alkyl sulfates (2,3) C10-C18 having formulas (I) and (II): wherein M, in formulas (I) and (II), is hydrogen or a cation that provides charge neutrality and all M units, whether associated with either a surfactant or an adjuvant ingredient, can be a hydrogen atom or a cation, depending on the way isolated by the technician or the relative pH of the system in which it is used. the compound, including, non-limiting examples of preferred cations, sodium, potassium, ammonium and mixtures thereof, and x is an integer that is at least about 7, preferably at least about 9, and y is an integer with a value of at least 8, preferably at least about 9; d) C10-C18 alkyl alkoxysulfates (AE.sub.xS) where, preferably, x is 1-30; e) C10-C18 alkyl alkoxycarboxylates preferably comprising 1-5 5 ethoxy units; f) medium chain branched alkyl sulfates as discussed in US Pat. Nos. 6,020,303 and 6,060,443; g) branched medium chain alkylalkoxysulfates as discussed in US-6,008,181 and US-6,020,303; h) modified alkylbenzenesulfonate (MLAS) as discussed in WO 10 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00 / 23549, and WO 00/23548 .; i) methyl ester sulphonate (MES); and j) alpha-olefin sulfonate (AOS).

Suitable non-ionic surfactants useful in the present invention may comprise any of types 15 of conventional non-ionic surfactants typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Non-ionic surfactants that are normally liquid are preferred for use in the liquid detergent products of the present invention.

Nonionic surfactants suitable for use in the present invention include nonionic alcohol alkoxylate surfactants. Alcohol alkoxylates are materials that correspond to the general formula: R1 (CmH2mO) nOH in which R125 is a C8-C16 alkyl group, m is from 2 to 4, and n is in the range of about 2 to 12. Preferably, R1 is an alkyl group that may be primary or secondary comprising from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcohol will also be ethoxylated materials containing from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) 5 in the range of about 3 to 17. More preferably, the HLB of this material will be in the range from about 6 to 15, most preferably from about 8 to 15. Alkoxylated non-ionic fatty alcohol surfactants have been marketed under the trade names Neodol and Dobanol of Shell Chemical Company.

Another suitable type of nonionic surfactant useful in the present invention comprises amine oxide surfactants. Amine oxides are materials often referred to in the art as "semipolar" nonionics. The amine oxides 15 have the formula: R (EO) x (PO) and (BO) zN (O) (CH2R ') 2.qH2O. In this formula, R is a relatively long chain hydrocarbyl radical that can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms and is, more preferably, C12- primary alkyl. C16 R 'is a short chain moiety, preferably selected from hydrogen, methyl and --CH2OH. When x + y + z is different from 0, EO is ethyleneoxy, PO is propyleneoxy and BO is butyleneoxy. Amine oxide type surfactants are illustrated by C12-14 alkyldimethylamine oxide. 25

Non-exclusive examples of non-ionic surfactants include: a) C12-C18 alkylethoxylates such as, for example, Shell NEODOL® non-ionic surfactants; b) C6-C12 alkyl phenolalkoxylates in which the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) condensation products of C12-C18 alcohol and C6-C12 alkylphenol with ethylene oxide / propylene oxide block polymers such as, for example, BASF Pluronic®; d) C14-C22, BA medium chain branched alcohols, as discussed in US-6,150,322; e) C14-C22 medium chain branched alkoxy alkoxylates, where x is 1-30, as discussed in US-6,153,577, US-6,020,303 and US-6,093,856; f) 5 alkylpolysaccharides, as described in US Patent 4,565,647, issued to Llenado, published on January 26, 1986; specifically, alkyl polyglycosides, as described in US Pat. Nos. 4,483,780 and 4,483,779; g) fatty acid polyhydroxyamides, as described in US Pat. Nos. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) poly (oxyalkylated) alcohol surfactants terminally protected with ether groups, as described in US Pat. Nos. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactant component may comprise combinations of anionic and non-ionic surfactants. When this is the case, the weight ratio of anionic surfactant to non-ionic surfactant will typically be in the range of 10:90 to 20 90:10, more typically from 30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which may have up to 26 carbon atoms. Additional examples include a) 25 alkoxylated quaternary ammonium surfactants (AQA) as discussed in US Pat. No. 6,136,769; b) dimethylhydroxyethyl quaternary ammonium, as described in US-6,004,922; c) polyamine cationic surfactants, as described in WO 98/35002, WO 98/35003, WO 98/35004, WO 30 98/35005, and WO 98/35006; d) cationic ester surfactants, as described in US Patents 4,228,042, US 4,239,660, US 4,260,529 and US 6,022,844; and e) amine-type surfactants, as described in US Pat. Nos. 6,221,825 and WO 00/47708, specifically propyldimethylamine amide (APA).

Non-limiting examples of hybrid ion surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or quaternary ammonium derivatives, quaternary phosphonium or tertiary sulfonium compounds. See US Patent 3,929,678, issued to Laughlin et al., Published December 30, 1975 in column 19, line 38 through column 22, line 48 for 10 examples of hybrid ion surfactants; betaine, including alkyldimethyl betaine and cocodimethylamidopropyl betaine, C8 to C18 amine oxides (preferably C12 to C18) and sulfo and hydroxybetaine such as, for example, N-alkyl-N, N-dimethylamino-1-propane sulfonate where the alkyl group can be C8 to C18, preferably C10 to C14.

Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of secondary and heterocyclic tertiary amines in which the aliphatic radical may be a straight or branched chain. One of the aliphatic substituents comprises at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one comprises a water-soluble anionic group, for example carboxy, sulphonate, sulfate. 25 See US Patent 3,929,678, issued to Laughlin et al., Published December 30, 1975, column 19, lines 18-35 for examples of ampholytic surfactants.

As indicated, the compositions may be in solid form, both in the form of a pill and solids in the form of 30 particles, including non-exclusive, particles, scales, or the like, or the compositions may be in liquid form. Liquid detergent compositions comprise an aqueous non-surfactant liquid carrier. Generally, the amount of the aqueous non-surfactant liquid vehicle employed in the compositions of the present invention will be effective in solubilizing, suspending or dispersing the components of the composition. For example, the compositions may comprise, by weight, from about 5% to about 90%, more specifically from about 10% to about 70% and, even more specifically, from about 20% to about 70% of the aqueous non-surfactant liquid carrier . 10

The most cost-effective type of aqueous non-surfactant liquid vehicle is, of course, water itself. Therefore, the aqueous non-surfactant liquid vehicle component will generally comprise mostly, or in its entirety, water. While other types of water-miscible liquids such as, for example, 15 alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally added to liquid detergent compositions as auxiliary or stabilizing solvents, for the purposes of In the present invention, the use of said miscible liquids in water should be minimized to control the cost of the composition. Therefore, the aqueous liquid carrier component of the liquid detergent products of the present invention will generally comprise water present in concentrations ranging from 5% to 90%, more preferably from 20% to 70%, by weight of the composition. 25

The detergent compositions may also contain bleaching agents. Suitable bleaching agents include, for example, sources of hydrogen peroxide, such as those described in detail in Encyclopedia of Chemical Technology, 4th ed. (1992, John Wiley & Sons), vol. 30 4, p. 271-300 “Bleaching Agents (Survey)” by Kirk Othmer incorporated herein. These sources of hydrogen peroxide include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.

Preferred sources of hydrogen peroxide for use in the present invention may be any suitable source, including hydrogen peroxide itself. For example, perborate can be used in the present invention, e.g. eg, sodium perborate (any hydrate but preferably monohydrates or tetrahydrates), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide. Also useful are available sources of oxygen such as persulfate bleach (eg, OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any suitable source of hydrogen peroxide can also be used.

A suitable percarbonate bleach comprises dry particles having an average particle size in the range of about 500 micrometers to about 1,000 micrometers; without more than about 10% by weight of said particles having a size less than about 200 micrometers and not more than about 10% by weight of said particles having a size greater than about 1,250 micrometers. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants. Percarbonate is marketed by various companies such as FMC, Solvay or Tokai Denka.

The compositions of the present invention may also comprise as a bleaching agent a chlorinated bleaching material. These agents are well known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC"). However, chlorinated bleaches are less preferred for compositions comprising enzymes.

(a) Bleach activators - Preferably, the peroxy bleach component in the composition is formulated with an activator (peracid precursor). Activator 5 is present at levels of about 0.01%, preferably about 0.5%, more preferably about 1% to about 15%, preferably about 10%, more preferably about 8%, by weight of the composition. A bleach activator as used in the present invention is any compound that, when used in conjunction with a source of hydrogen peroxide, results in the in situ production of the peracid corresponding to the bleach activator. Different non-limiting examples of activators are described in US Pat. Nos. 5,576,282; US-4,915,854 and US-15 4,412,934. See also US-4,634,551 for other typical bleach and activators useful in the present invention.

Preferred activators are selected from the group consisting of tetraacetylethylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, 20 benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenobenzene (CBS10), phenobenzene (CBS10), phenobenzene (CBS10) , benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolysable esters and mixtures thereof and, most preferably, benzoylcaprolactam and benzoylvalerolactam. Especially preferred bleach activators in the pH range of about 8 to about 11 are those selected that have an OBS or VL leaving group.

Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS), sodium salt of 4- [N- (nonaoyl) aminohexanoyloxy] -benzenesulfonate (NACA-OBS), an example of which is described in the patent. US 5,523,434, dodecanoyloxybenzenesulfonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C11-OBS with unsaturation at position 10) and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in US 5,998,350, issued to Burns et al .; US 5,698,504, granted to Christie et al .; US 5,695,679, granted to Christie et al .; US 5,686,401, granted to Willey et al .; US 5,686,014, issued to Hartshorn et al .; US 5,405,412, granted to Willey et al .; US 5,405,413, granted to Willey et al .; US-5,130,045, granted to 10 Mitchel et al .; and US-4,412,934, granted to Chung et al., and the pending patent application with serial number 08 / 064,564.

In the present invention, generally, the molar ratio of the peroxygen source (such as AvO) to the bleach activator is in the range of at least 1: 1, 15 preferably from about 20: 1, more preferably from about 10: 1 at about 1: 1, preferably at about 3: 1.

Substituted quaternary bleach activators may also be included. The present compositions for laundry washing preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP, preferably a quaternary substituted percarboxylic acid or a quaternary substituted peroxyimidic acid); more preferably, the first. The 25 preferred QSBA structures are described in more detail in US 5,686,015, issued to Willey et al .; US 5,654,421, issued to Taylor et al .; US 5,460,747, Gosselink et al .; US 5,584,888, granted to Miracle et al .; 5,578,136, issued to Taylor et al. 30

Very preferred bleach activators useful in the present invention are substituted with amide as described in US Pat. Nos. 5,698,504, US 5,695,679 and US 5,686,014, each cited hereinbefore. Examples of precursors of said bleach activators include: 6-octanamidocaproyl oxybenzenesulfonate, 6-nonanamidocaproyl oxybenzenesulfonate, 6-decanamidocaproyl oxybenzenesulfonate 5 and mixtures thereof.

Other useful activators are described in US 5,698,504; US 5,695,679; and US 5,686,014, each of which is cited herein above, and in US 4,966,723, granted to Hodge et al. These activators include benzoxazine type activators 10, for example, a C6H4 ring to which a moiety is attached at positions 1,2 - C (O) OC (R1) = N-.

Nitriles such as, for example, acetonitriles and / or nitriles of ammonium and other nitriles containing quaternary nitrogen, and another class of activators that are useful in the present invention. Non-limiting examples of said nitrile bleach activators are described in US 6,133,216; US 3,986,972; US 6,063,750; US 6,017,464; US 5,958,289; US 5,877,315; US 5,741,437; US 5,739,327; US-5,004,558; and in EP-790 244, EP-775 127, EP-1 017 773, EP-1 017 776; and in WO 20 99/14302, WO 99/14296, WO96 / 40661.

Depending on the activator and the specific application, good bleaching results can be obtained from bleaching systems having a pH in use of about 6 to about 13 and, preferably, about 25 to 9.0 to about 10.5. Typically, for example, activators with electron scavenging moieties are used for almost neutral or subneutral pH ranges. Alkalis and buffering agents can be used to guarantee said pH. 30

Acyl lactam-type activators, as described in US-5,698,504, US-5,695,679 and US-5,686,014, each cited above herein, are very useful in the present invention, especially acyl caprolactams (see, for example, WO 94-28102 A) and acyl valerolactams (see US 5,503,639, granted to Willey et al.).

(b) Organic peroxides, especially 5-diacyl peroxides - These are widely illustrated in Encyclopedia of Chemical Technology of Kirk Othmer, vol. 17, John Wiley and Sons, 1982 on pages 27-90 and, especially, on pages 63-72, all incorporated by reference herein. If a diacyl peroxide is used, it will preferably be one that exerts a minimal adverse impact on tissue care, including color care.

(c) Metal containing bleach catalysts - The compositions and methods of the present invention may also optionally include metal containing bleach catalysts, preferably bleach catalysts containing manganese and cobalt.

One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation with defined bleach catalytic activity 20 (such as, for example, copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations) , an auxiliary metal cation having little or no catalytic activity of the bleach (such as zinc or aluminum cations), and a sequestrant having stability constants defined for the catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid , ethylenediaminetetra acid (methylene phosphonic acid) and water soluble salts thereof. Such catalysts are described in US 4,430,243, granted to Bragg. 30

Manganese metal complexes - If desired, the compositions of the present invention can be catalyzed by a manganese compound. These compounds and their levels of use are well known in the art and include, for example, the manganese-based catalysts described in US Pat. Nos. 5,576,282; US 5,246,621; US 5,244,594; US 5,194,416; and US 5,114,606; and European patent applications 5 Nos. 549.271 A1; 549,272 A1; 544,440 A2; and 544,490 A1. Preferred examples of these catalysts include MnIV2 (uO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF6) 2, MnIII2 (uO) 1 (u-OAc) 2 (1,4, 7-Trimethyl-1,4,7-triazacyclononane) 2 (ClO4) 2, MnIV4 (uO) 6 (1,4,7-triazacyclononane) 4 (ClO4) 4, MnIIIMnIV4 (uO) 1 (u-10 OAc) 2 - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO4) 3, MnIV (1,4,7-trimethyl-1,4,7-triazacyclononane) - (OCH3) 3 (PF6) , and mixtures thereof. Other metal-based bleach catalysts include those described in US-4,430,243 and US-5,114,611. The use of manganese with various complex ligands to improve bleaching is also described in the following patents: US-4,728,455; US 5,284,944; US 5,246,612; US 5,256,779; US 5,280,117; US 5,274,147; US 5,153,161; and US 5,227,084.

Cobalt metal complexes - The cobalt bleach catalysts useful in the present invention are known and are described, for example, in US Pat. Nos. 5,597,936; 5,595,967; and US 5,703,030; and in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg Bioinorg Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful in the present invention are cobalt pentamine acetate salts having the formula [Co (NH3) 5OAc] Ty, wherein "OAc" represents an acetate moiety and "Ty" is an anion and, especially, cobalt pentamine acetate chloride, [Co (NH3) 5OAc] Cl2; as well as 30 [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2 (herein "PAC").

These cobalt catalysts are readily prepared by known methods, such as those described in US 6,302,921; US 6,287,580; US 6,140,294; US 5,597,936; 5,595,967; and US 5,703,030; in the Tobe article and in the references cited therein and in US-5 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), p. 461-3; Inorg Chem., 18, 1497-1502 (1979); Inorg Chem., 21, 2881-2885 (1982); Inorg Chem., 18, 2023-2025 (1979); Inorg Synthesis, 173-176 (1960); 10 and Journal of Physical Chemistry, 56, 22-25 (1952).

Transition metal complexes of macropolycyclic rigid ligands - The compositions of the present invention may also suitably include as a bleach catalyst a transition metal complex of a macropolycyclic rigid ligand. The amount used is a catalytically effective amount, suitably of about 1 ppb or more, for example up to about 99.9%, more typically of about 0.001 ppm or more, preferably of about 0.05 ppm to about 500 ppm ( in 20 where "ppb" means parts per billion by weight and "ppm" means parts per million by weight).

The transition metal bleach catalysts of macrocyclic rigid ligands that are suitable for use in the compositions of the invention may, in general, include known compounds that meet the definition herein as well as, more preferably, any of the multiple Novel compounds expressly designed for the present uses of laundry and are illustrated in a non-limiting manner by any of the following:

 Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese (II) hexadecane

 Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese (II) hexadecane

 Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (II)

 Hexafluorophosphate 5

 Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexafluorophosphate hexafluorophosphate (II)

 Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6,6,2] hexadecane

 Manganese Hexafluorophosphate (III) 10

 Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (II)

 Tetrafluoroborate

 Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane 15

 Manganese Hexafluorophosphate (III)

 Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (III)

 Hexafluorophosphate

 Dichloro-5,12-di-n-butyl-1,5,8,12-20 tetraazabicyclo [6.6.2] hexadecane

 Manganese (II)

 Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (II)

 Dichloro-5-n-butyl-12-methyl-1,5,8,12-25 tetraazabicyclo [6.6.2] hexadecane

 Manganese (II)

 Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane

 Manganese (II) 30

 Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane

 Manganese (II).

As a practical measure, and not exclusively, the compositions and methods herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the composition comprising a fluid. lipophilic and a bleaching system and, preferably, will provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm and, most preferably, from about 0.1 ppm to about 5 ppm , of the bleach catalyst species in the composition comprising a lipophilic fluid and a bleaching system.

(d) Bleach reinforcing compounds - The compositions of the present invention may comprise one or more bleach reinforcing compounds. Bleach reinforcing compounds provide greater bleaching efficiency in low temperature applications. Bleach boosters act in conjunction with conventional peroxygen bleach sources to provide greater bleaching efficiency. This is usually achieved by the formation in situ of an active oxygen transfer agent such as a dioxyran, an oxaciridine or an oxaciridinium. Alternatively, previously formed dioxirans, oxaciridines and oxaciridins can be used.

Among the bleach reinforcing compounds suitable for use in accordance with the present invention are cationic imines, hybrid ion imines, anionic imines and / or polyionic imines having a net charge of about 30 +3 to about -3, and mixtures from the same. These imine bleach reinforcing compounds of the present invention include those of the general structure:

 5

wherein R1-R4 may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.

Among the preferred bleach booster compounds 10 are the hybrid ion bleach boosters described in US 5,576,282 and US 5,718,614. Other bleach reinforcing compounds include cationic bleach enhancers described in US 5,360,569; US 5,442,066; US 5,478,357; US 15,370,826; US 5,482,515; US 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.

The peroxygen sources are well known in the art and the peroxygen source employed in the present invention may comprise any of these well-known sources, including peroxygenated compounds as well as compounds which, under conditions of use by the consumer, provide an amount effective in situ peroxygen. The peroxygen source may include a source of hydrogen peroxide, the in situ formation of a perennial anion by the reaction of a source of hydrogen peroxide with a bleach activator, previously formed peracid compound or mixtures of suitable peroxygen sources . Logically, one skilled in the art will recognize that other sources of peroxygen can be used without thereby abandoning the scope of the invention. Bleach reinforcing compounds, when present, are preferably employed together with a peroxygen source in the bleach systems of the present invention. 5

(e) Pre-formed peracids - Pre-formed peracids are also suitable as bleaching agents. The previously formed peracid compound, as used herein, is any convenient compound that is stable and which, under conditions of use by the consumer, provides an effective amount of peracid or peracid anion. The previously formed peracid compound may be selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in US 5,576,282 issued to Miracle et al.

A class of suitable organic peroxycarboxylic acids have the general formula:

 twenty

wherein R is an alkylene or substituted alkylene group containing from 1 to about 22 carbon atoms or a substituted phenylene or phenylene group, Y is hydrogen, halogen, alkyl, aryl, -C (O) OH or -C (O ) OOH.

Organic peroxyacids suitable for use in the present invention may contain one or two peroxy groups and may be aliphatic or aromatic. If the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:

wherein Y may be, for example, H, CH3, CH2Cl, C (O) OH or C (O) OOH; n is an integer from 0 to 20. If the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

 10

where Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C (O) OH or C (O) OOH.

Typical monoperoxy acids useful in the present invention include alkyl and aryl peroxyacids such as:

(i) peroxybenzoic acid and peroxybenzoic acid substituted with ring, that is, peroxy-a-naphthoic acid, monoperoxyxtalic acid (magnesium hexahydrate salt) and o-carboxybenzamidoperoxyhexanoic acid (sodium salt);

(ii) aliphatic, substituted aliphatic acids and arylalkyl monoperoxy acids, e.g. eg, peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-octylsuccinoyl) aminoperoxycaproic acid (SAPA) and N, N-phthaloylaminoperoxyproic acid (PAP); 25

(iii) amidoperoxy acids, that is, peroxysuccinic acid (NAPSA) or peroxyandipic acid (NAPAA) monononylamide.

Typical diperoxy acids useful in the present invention include alkyl diperoxyacids and aryl diperoxy acids such as:

(i) 1,12-diperoxy-dodecanedioic acid;

(ii) 1,9-diperoxyazelaic acid;

(iii) diperoxybrasilic acid; diperoxisebacic acid and diperoxyisophthalic acid;

(iv) 2-decyldiperoxybutane-1,4-dioic acid;

(v) 4,4'-sulfonylbisperoxybenzoic acid.

Such bleaching agents are described in US-4,483-781, granted to Hartman, and in US-4,634,551, granted to Burns and 10 col .; European Patent Application 0,133,354 to Banks et a and US-4,412,934, granted to Chung et al. Sources also include 6-nonylamino-6-oxoperoxicaproic acid as described in US 4,634,551, issued to Burns et al. Persulfate-type compounds, such as OXONE, commercially manufactured by E.I. DuPont de Nemours de Wilmington, DE, USA It can also be used as a suitable source of peroxymonosulfuric acid. PAP is described in, for example, US-5,487,818; US 5,310,934; US 5,246,620; US 5,279,757 and US 5,132,431. twenty

(f) Photobleaching agents - The photobleaching agents suitable for use in the treating compositions of the present invention include, but are not limited to, the photobleaching agents described in US Pat. Nos. 4,217,105 and US 5,916,481. 25

(g) Enzymatic bleaching - Enzymatic systems can be used as bleaching agents. Hydrogen peroxide may also be present by adding an enzymatic system (i.e., an enzyme and a substrate thereof) that is capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing process. These enzymatic systems are described in patent application EP-537 381.

The compositions and methods of the present invention can use alternative bleaching systems such as, for example, ozone, chlorine dioxide and the like. Ozone bleaching can be achieved by introducing, in the solution to be contacted with the tissues, ozone-containing gas with an ozone content of about 20 to about 300 g / m3. The gas: liquid ratio in the solution should be maintained at approximately 1: 2.5 to approximately 1: 6. US 5,346,588 describes a process for the use of ozone as an alternative to conventional bleaching systems. 10

The detergent compositions of the present invention may also include any number of additional optional ingredients. These include components of a conventional laundry detergent composition such as, for example, non-dye dyes, detersive detergent builders, enzymes, enzyme stabilizers (such as, for example, propylene glycol, boric acid and / or borax), soaps suppressants, dirt suspensions, soil release agents, other beneficial agents for tissue care, pH regulators, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, inhibiting agents of the transfer of dyes, opacifying agents, optical brighteners, perfumes and coloring agents. The various optional ingredients for detergent compositions, if present in the compositions of the present invention, should be used at the concentrations employed, in a conventional manner, to give rise to their desired contribution to the composition or the washing operation. Frequently, the total amount of said optional ingredients for the detergent composition may be in the range of about 0.01% to about 50%, more preferably from about 0.1% to about 30%, by weight of the composition.

The liquid detergent compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, bleaching agent and other optional optional ingredients, some of which may normally be in solid form, which have been combined with the normally liquid components of the composition such as, for example, ethoxylated non-ionic liquid alcohol, the aqueous liquid carrier and other optional ingredients, usually any liquid. Said solution, dispersion or suspension will be of an acceptable stable phase and will typically have a viscosity in the range of about 100 to 600 cps, more preferably, about 150 to 400 cps. For the purposes of this invention, the viscosity is measured with a Brookfield LVDV-II + viscometer that uses a # 21 axis.

The liquid detergent compositions of the present invention can be prepared by combining the components thereof in any order that is convenient and mixing, e.g. eg, by stirring, the resulting combination of components to form a stable phase liquid detergent composition. In a preferred process for preparing said compositions, a liquid matrix is formed containing at least a major proportion, and preferably practically all, of the liquid components, e.g. eg, non-ionic surfactant, the 25 non-surfactant liquid vehicles and other optional liquid components, the liquid components being intimately mixed by shear agitation to obtain this liquid combination. For example, rapid stirring with a mechanical stirrer can be used in a useful manner. While stirring is maintained with shear, virtually all surfactants and ingredients can be added in solid form. Stirring of the mixture is continued and, if necessary, can be increased at this stage to form a solution or a uniform dispersion of insoluble solid phase particles within the liquid phase. Once some or all of the materials in solid form have been added to this stirred mixture, the particles of the enzyme material to be included are incorporated, e.g. eg, enzyme pellets. As a variation of the method of preparing the composition described hereinbefore, one or more of the solid components may be added to the stirred mixture as an aqueous solution or suspension of premixed particles with a minor part of one or more of the components. liquids After the addition of all the components of the composition, stirring of the mixture is continued for a period of time sufficient to form the compositions having the required viscosity and phase stability characteristics. This often involves agitation for a period of approximately 30 to 60 minutes.

In an alternative embodiment to form the liquid detergent compositions, the bleaching agent 20 is first combined with one or more liquid components to form a bleaching agent premix, and this bleaching agent premix is added to a formulation of the composition that it contains a substantial part, for example more than 50% by weight, more specifically, more than 70% by weight and, even more specifically, more than 90% by weight, of the other components of the laundry detergent composition. For example, in the methodology described above, both the bleaching agent premix and the enzyme component are added in a final stage of component additions. In another embodiment, the bleaching agent is encapsulated before the addition to the detergent composition, the encapsulated bleaching agent is suspended in a structured liquid, and the suspension is added to a formulation of the composition containing a substantial part of the rest of the components of the laundry detergent composition.

As mentioned above, the detergent compositions may be in solid form. Suitable solid forms include tablets and compositions in the form of particles, for example, granulated particles or scales. Various techniques for forming detergent compositions in such solid forms are well known in the art and can be used in the present invention. In one embodiment, for example when the composition is in the form of a granulated particle, the bleaching agent is provided in the form of particles, optionally including additional, but not all, components of the laundry detergent composition. The particulate bleaching agent is combined with one or more solids in the form of additional particles containing a remaining component of the laundry detergent composition. In addition, the bleaching agent, optionally including additional components, but not all, of the laundry detergent composition, can be provided in encapsulated form, and the encapsulated bleaching agent is combined with particulate solids containing a substantial remainder of components of the laundry detergent composition. 25

The compositions of this invention, prepared as described hereinbefore, can be used to form aqueous wash solutions for use in tissue washing. Generally, an effective amount of said compositions is added to the water, preferably in an automatic washing machine 30 for conventional fabric washing, to form said aqueous washing solutions. Then, the aqueous wash solution formed in this way is brought into contact, preferably with stirring, with the tissues to be washed therewith. An effective amount of the liquid detergent compositions of the present invention added to water to form aqueous wash solutions may comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous wash solution. More preferably, about 1,000 to 3,000 ppm of the detergent compositions of the present invention will be provided in aqueous wash solution. 10

Fabric care compositions / Fabric softener compositions to add during rinsing

In another specific embodiment, the bleaching agents used in the present invention can be included in a tissue care composition. The fabric care composition 15 may comprise at least one bleaching agent and a fabric softening composition to be added during rinsing ("RAFS;" also known as fabric conditioning compositions to be added during rinsing). Examples of softener compositions 20 to be added during the typical rinse can be found in provisional patent application US-60/687582, filed October 8, 2004. The fabric softener compositions to be added during the rinse of the present invention may comprise ( a) active fabric softening substance and (b) a thiazolium type dye. The fabric softener composition to be added during rinsing may comprise from about 1% to about 90% by weight of the FSA, more preferably, from about 5% to about 50% by weight of the FSA. The bleaching agent may be present in the fabric softening composition to be added during rinsing in an amount of about 0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to about 30 ppm.

In one embodiment of the invention, the fabric softening active substance (hereinafter "FSA") is a quaternary ammonium compound suitable for softening tissues in a rinse stage 5. In one embodiment, the FSA is formed from a reaction product of a fatty acid and an amino alcohol, obtaining mixtures of compounds of the monoester, diester type and, in one embodiment, of the triester type. In another embodiment, the FSA comprises one or more softening quaternary ammonium compounds such as, but not limited to, a monoalkyl quaternary ammonium compound, a diamido type quaternary compound and a diester type quaternary ammonium compound, or A combination of them.

In one aspect of the invention, the FSA comprises a composition of quaternary ammonium compound of the diester type (hereinafter "DQA"). In certain embodiments of the present invention, compositions of DQA-type compounds also encompass a description of FSA of diamide type and FSA with a mixture of amido and ester linkages, as well as the 20 diester linkages mentioned above, all named herein. as DQA.

A first type of DQA ("DQA (1)") suitable as FSA in the CFSC of the present invention includes a compound comprising the formula:

{R4-m - N + - [(CH2) n - Y - R1] m} X-

wherein each R substituent is hydrogen, a C1-C6 short chain, preferably a C1-C3 alkyl or hydroxyalkyl group, e.g. Eg, methyl (more preferred), ethyl, propyl, hydroxyethyl, and the like, poly (C2-3 alkoxy), preferably polyethoxy group, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4, preferably 2; each Y is -O- (O) C-, -C (O) -O-, -NR-C (O) -, or -C (O) -NR- and it is acceptable that each Y be the same or different ; the sum of carbons in each R1, plus one, when Y is -O- (O) C- or -NR-C (O) -, is C12-C22, preferably 5 C14-C20, each R1 being a hydrocarbyl group, or substituted hydrocarbyl; it is acceptable that R1 is unsaturated or saturated and branched or linear and, preferably, is linear; it is acceptable that each R1 be the same or different and, preferably, they are the same; and X- can be any anion compatible with softener, preferably chloride, bromide, methylsulfate, ethyl sulfate, sulfate, phosphate, and nitrate, more preferably, chloride or methylsulfate. Preferred DQA type compounds are typically prepared by reacting alkanolamines such as, for example, MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that typically result from such reactions include N, N-di (acyl-oxyethyl) -N, N-dimethylammonium chloride or N, N-di (acyl-oxyethyl) -N, N-methylhydroxyethylammonium chloride wherein the acyl group is derived from animal, unsaturated and polyunsaturated fats, fatty acids, 20 p. eg, tallow, hardened tallow, oleic acid, and / or partially hydrogenated fatty acids, derived from vegetable oils and / or partially hydrogenated vegetable oils such as, for example, canola oil, safflower oil, peanut oil, sunflower oil , corn oil, soybean oil, coniferous oil, 25 rice bran oil, palm oil, etc.

Non-limiting examples of saturated fatty acids are listed in US 5,759,990, in column 4, lines 45-66. In one embodiment, the FSA comprises other active substances in addition to DQA (1) or DQA. In another additional embodiment, FSA 30 comprises only DQA (1) or DQA and is exempt or virtually free of any other quaternary ammonium compound or other active substances. In another additional embodiment, the FSA comprises the precursor amine that is used to produce the DQA.

In another aspect of the invention, the FSA comprises a compound, identified as DTTMAC, which comprises the formula:

 5

[R4-m - N (+) - R1m] A-

wherein each m is 2 or 3, each R1 is a C6-C22, preferably C14-C20, but without more than one being less than about C12 and the other being at least about 16, 10 hydrocarbyl, or substituted hydrocarbyl substituent , preferably C10-C20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also sometimes referred to as "alkylene"), most preferably C12-C18 alkyl or alkenyl, and branched or unbranched. In one embodiment, the iodine (IV) index of the FSA is about 1 to 70; each R is H or a C1-C6 short chain, preferably C1-C3 alkyl or hydroxyalkyl group, e.g. eg, methyl (more preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R2O) 2-4H, where each R2 is a C1-6 alkylene group; and A- is an anion 20 compatible with softener, preferably chloride, bromide, methylsulfate, ethyl sulfate, sulfate, phosphate, or nitrate; more preferably, chloride or methylsulfate.

Examples of these FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as, for example, disebodimethylammonium methylsulfate and disebodimethylammonium methylsulfate. Examples of commercial dialkylenedimethylammonium salts that can be used in the present invention are dihydrogenated sebodimethylammonium chloride and disebodimethylammonium chloride, marketed by Degussa under the trade names Adogen® 442 and Adogen® 470 respectively. In one embodiment, the FSA comprises other active substances in addition to the DTTMAC. In another additional embodiment, the FSA comprises only DTTMAC compounds and is exempt or virtually free of any other quaternary ammonium compound or other active substances.

In one embodiment, the FSA comprises an FSA described in 5 Patent Publication No. US-2004/0204337 A1, published October 14, 2004, granted to Corona et al., In paragraphs 30-79. In another embodiment, the FSA is one described in Patent Publication No. US 2004/0229769 A1, published on November 18, 2005, granted to Smith and 10 col., In paragraphs 26-31; or US Patent 6,494,920, in column 1, line 51 et seq. detailing an "esterquat" or a quaternized fatty acid triethanolamine ester salt.

In one embodiment, the FSA is chosen from at least one of the following: diseboilloxyethyldimethylammonium chloride, dihydrogenated seboyloxyethyldimethylammonium chloride, disebodimethylammonium chloride, diseboyloxyethyldimethylammonium methylsulfate, seboyloxyethyldimethylammonium dihydroxy dimethyl dihydroxy dihydroxy dihydroxy dihydroxymethyl chloride combinations .

In one embodiment, the FSA may also include compositions of amide-containing compounds. Examples of compounds comprising diamide may include, but are not limited to, methyl bis bis (seboamidoethyl) -2-25 hydroxyethylammonium sulfate (marketed by Degussa under the trade names Varisoft 110 and Varisoft 222). An example of an amide-ester-containing compound is N- [3- (stearoylamino) propyl] -N- [2- (stearoyloxy) ethoxy) ethyl)] - N-methylamine. 30

Another specific embodiment of the invention provides a fabric softening composition to be added during rinsing which further comprises a cationic starch. Cationic starches are described in US-2004/0204337 A1. In one embodiment, the fabric softener composition to be added during rinsing comprises from about 0.1% to about 7% cationic starch by weight of the fabric softener composition. In one embodiment, the cationic starch is National Starch HCP401.

Ingredients suitable for laundry care

The laundry care ingredients of the non-limiting list illustrated below are suitable for use in the laundry care compositions of the present invention, for example, to contribute to or improve efficacy, for the treatment of the substrate to be cleaned, or to modify the aesthetic properties of the composition as with perfumes, dyes, dyes or the like. It is understood that said ingredients are additional to the components mentioned above for any particular embodiment. The total amount of said adjuvants can range from about 0.1% to about 50%, or even from about 1% to about 30%, by weight of the composition for care in laundry.

The precise nature of these additional components and, the levels at which they are incorporated, will depend on the physical form of the composition and the nature of the operation for which it will be used. The laundry care ingredients include, but are not limited to, polymers, for example, cationic polymers, surfactants, detergency builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, inhibitors for the removal / antiredeposition of clay stains, brighteners, suds suppressors, dyes, perfume systems and additional perfume delivery, elasticizing agents the structure, fabric softeners, vehicles, hydrotropes, process aids and / or pigments. In addition to the following description, 5 suitable examples of other adjuvants of this type and levels of use are found in patents US 5,576,282, US 6,306,812 B1 and US 6,326,348 B1.

As discussed, the ingredients for laundry care are not essential for compositions 10 for laundry care of applicants. Thus, certain embodiments of the applicants' compositions do not contain one or more of the following adjuvant materials: bleach activators, surfactants, detergency builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, and Enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, agents for the removal / anti-redeposition of dirt and clay, brighteners, suds suppressors, 20 dyes, additional perfume and perfume delivery systems, structure elasticizing agents , fabric softeners, vehicles, hydrotropes, process improvers and / or pigments. However, when one or more adjuvants are present, this one or more adjuvants may be present as described below:

Surfactants - The compositions according to the present invention may comprise a surfactant or surfactant system in which the surfactant can be selected from nonionic and / or anionic and / or cationic and / or ampholytic and / or hybrid ion and / or non-surfactant surfactants semipolar ionic The surfactant is typically present at a level of about 0.1%, about 1%, or even about 5% by weight of the cleaning compositions at about 99.9%, at about 80%, at about 35%, or even about 30% by weight of the cleaning compositions. 5

Detergency builder additives - The compositions of the present invention may comprise one or more detergency builder additives or detergent builder additive systems. When present, the compositions will typically comprise at least about 1% of 10 detergent builder additive, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, of said builder additive of detergency. Detergent-enhancing additives include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates, 15 alkali metal silicates, alkaline earth metal and alkali metal carbonates, aluminosilicate type detergency builders, polycarboxylate, hydroxypolycarboxylate ether, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-20 trisulfonic acid and carboxymethyloxysuccinic acid, various alkali metal, ammonium and substituted ammonium poly salts (acetic acids) such as, for example, ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as, for example, melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

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

Dye Transfer Agents-5 The compositions of the present invention may also include one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-10 oxide polymers, N-vinyl pyrrolidone and N-vinylimidazole copolymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. When present in the compositions of the present invention, dye transfer inhibitors are present at levels of about 0.0001%, about 0.01%, about 0.05% by weight of the cleaning compositions to about 10%, about 2%, or even about 1%, by weight of the cleaning compositions.

Dispersants - The compositions of the present invention may also contain dispersant. Suitable water-soluble organic materials are homopolymeric or copolymeric acids or their salts, wherein the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by no more than two carbon atoms. 25

Enzymes - The compositions may comprise one or more detergent enzymes that provide advantages of cleaning capacity and / or tissue care. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, 30 lipases, phospholipases, esterases, cutinases, pectinases, queratanases, reductases, oxidases, phenoxidases, lipoxygenases, ligninases, pulses, peas , malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and amylases, or mixtures thereof. A typical combination is a combination of conventional applicable enzymes such as protease, lipase, cutinase and / or cellulase together with amylase.

Enzyme stabilizers - Enzymes for use in the compositions, for example, detergents, can be stabilized by various techniques. The enzymes used in the present invention can be stabilized by the presence of water-soluble sources of calcium and / or magnesium ions in the finished compositions that provide such ions to enzymes.

Catalytic Metal Complexes - Applicant compositions may include complexes of catalytic metals. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as, for example, copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, a 20 auxiliary metal cation having little or no catalytic activity of the bleach, such as zinc or aluminum cations, and a sequestrant having defined stability constants for catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, acid ethylenediaminetetra (methylene phosphonic) and water soluble salts thereof. Such catalysts are described in US 4,430,243.

If desired, the compositions of the present invention can be catalyzed by a manganese compound. These compounds and their levels of use are well known in the art and include, for example, the manganese-based catalysts described in US 5,576,282.

The cobalt bleach catalysts useful in the present invention are known and are described, for example, in US 5,597,936 and US 5,595,967. These cobalt 5 catalysts are readily prepared by methods known as those described, for example, in US 5,597,936 and US 5,595,967.

The compositions of the present invention may also suitably include a transition metal complex of a rigid macropolyclic ligand, abbreviated as "MRL." At practical level 10, and not exclusively, the compositions and cleaning processes of the present invention can be adjusted to provide at least one part per hundred million of the MRL species of the beneficial agent to the aqueous wash solution. , and can provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm or even from about 0.1 ppm to about 5 ppm of the MRL to the wash solution.

Preferred transition metals in the catalysts 20 of the transition metal bleach of the present invention include manganese, iron and chromium. Preferred MRLs in the present invention are a special type of ultra-rigid ligand with crosslinked bridges such as 5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexa-decane. 25

Suitable transition metal MRLs are readily prepared by methods known as those described, for example, in WO 00/32601 and US-6,225,464.

Examples

The following examples are provided to further illustrate the novel bleaching agents of the present invention; however, they should not be considered as limiting the invention as defined in the appended claims thereto. In fact, it will be apparent to the person skilled in the art that various modifications and variations can be made to this invention without abandoning the scope or spirit of the invention. All 5 parts and percentages offered in these examples are by weight, unless otherwise indicated. All Hansen solubility parameter values provided herein are in units of MPa0.5.

Sample preparation and test methods 10

A. Sample preparation

Each sample is prepared by adding 0.5 grams of bleaching agent (0.1% by weight of the cellulosic substrate) to a solution containing 3 grams of laundry detergent (laundry detergent AATCC) 15 and 500 ml of water at room temperature. The absorbance for each dye load is corrected to ensure the same amount of color units. The formulation is then combined with 50 grams of cellulose powder (marketed by Aldrich) and the mixture is stirred for 10 minutes. Then, the mixture is filtered to separate the cellulose particles from the liquid and the cellulose particles are allowed to air dry. The color of both the cellulose particles and the liquid is measured using a Gretag Macbeth Color Eye 7000A spectrophotometer, as described above. 25

The cellulose particles are then placed in a container containing 500 ml of running water and stirred for 10 minutes. The mixture is filtered to separate the cellulose particles from the liquid, and the cellulose particles are allowed to air dry again. Color 30 of both the cellulose particles and the liquid is measured using the Gretag Macbeth Color Eye 7000A spectrophotometer. A control sample containing untreated cellulose particles (without added bleaching agent) is also prepared.

The bleaching agents shown in Tables 1A and 1B are prepared as described in the present invention and subject to various parameters. 5 All violet dyes are synthesized according to the procedure described in US-4,912,203, granted to Kluger et al. Also note that ethylene oxide, propylene oxide and butylene oxide are shown below with their typical designation of "EO," "PO" and "BO," respectively. The average length and composition of the polymer components of the bleaching agents in Tables 1A and 1B is obtained from the formula: (Block 1 + Block 2 + Block 3) / (number of chains). For example, the average structure of Violet thiophene_5EO consists of a chromophore of 15 thiophene with 2 chains in nitrogen, one equal to 3EO and one equal to 2EO. In all polymeric components there are chain protecting groups present.

Table 1A - Identification of bleaching agents of the invention

 Example #

 Sample identification Block 1 Block 2 Block 3 No. of chains Chain guard groups

 Example 1

 Violet thiophene_3EO 3 EO - - 2 OH

 Example 2

 Violet thiophene_5EO 5 EO - - 2 OH

 Example 3

 Violet thiophene_10EO 10 EO - - 2 OH

 Example 4

 Violet thiophene_2EO_6PO 2 EO 6 PO - 2 OH

 Example 5

 Violet thiophene_5EO_5PO 5 EO 5 PO - 2 OH

 Example 12

 Violet thiophene_glycidol (CH2CHOHCH2OH) 2 - - 2 OH

 Example 13

 Violet thiophene_glycidol_5EO (a) (CH2CHOHCH2O-) 2 5 EO - 2 OH

(a) EO groups are added to the terminal OH group.

Table 1B - Identification of bleaching agents of the invention

 Example #

 Sample identification Alkyl / aryl Block 1 Block 2 Block 3 No. of chains Chain protecting groups

 Example 18

 Thiophene Violet N-ethyl, N-glycidyl CH2CH3 (CH2CHOHCH2OH) - - 2 OH

 Example 19

 Thiophene Violet N-ethyl, 5EO CH2CH3 5EO - - 1 OH

 Example 20

 Violet thiophene N, N-bisglycidyl-t-butyl ether 5 EO - (CH2CH (O-) CH2OC (CH3) 3) 2 5EO - 2 OH

 Example 21

 Violet thiophene N, N-bisglycidyl do / tetradecyl ether 5 ethoxylate - (CH2CH (O-) CH2OC11,13 H22,26CH3) 2 5EO - 2 OH

 Example 22

 Violet thiophene N, N-bisglycidylisopropyl ether 5 ethoxylate - (CH2CH (O-) CH2OCH (CH3) 2) 2 - - 2 OH

 Example 23

 Violet thiophene N, N-bisglycidyl-n-butyl ether 5 ethoxylate - (CH2CH (O-) CH2OCH2CH2CH2CH3) 2 - - 2 OH

 Example 24

 Violet thiophene N-benzyl, 5-ethoxylated CH2C6H5 5EO - - 1 OH

(a) EO groups are added to the terminal OH group.

 5

B. Whiteness calculation: CIELab b * and Ganz and CIE whiteness indices

The whiteness index (“WI”) is a qualitative assessment of the color that is calculated by a formula that includes three components of color measurement - hue, saturation, and 10 luminosity - that is expressed by an index relative to a standard white value . Several whiteness formulas can be used to measure whiteness in cellulose derived substrates. Two common formulas are the Ganz whiteness indices and the CIE. The Ganz whiteness index is expressed by the formula: 15 WI = (D * Y) + (P * x) + (Q * y) + C, where Y, x and y are colorimetric values and D, P, Q and C They are parameters of the formula. The CIE whiteness is expressed by the formula: WI = Y- (800 * x) - (1,700 * y) + 813.7, where Y, x and y are colorimetric values. More information is available in the Rolf Griesser publication, Ciba-Geigy Ltd, "Whiteness and Tint", June 1993.

The surface color of an article can be quantified using a series of measurements - L *, a *, and b * - generated by measuring the samples, using a spectrophotometer. The equipment used for this test is a Gretag Macbeth Color Eye 7000A spectrophotometer. The computer program used is "Color imatch." "L" is a measure of the amount of white or 10 black in a sample; higher "L" values indicate a lighter color sample. A measure of the amount of red or green in a sample is determined by "a *" values. A measure of the amount of blue or yellow in a sample is determined by "b *" values. The lower b * values (plus 15 negatives) indicate more blue in a sample.

Another additional measure of the relative color of a substrate is DE CMC. DE CMC is a measure of the whole color difference for all uniform color spaces, where DE CMC represents the magnitude of the difference between a color and a reference (in this case, a pure white standard). The higher the CMC value, the more pronounced the color difference. In other words, lower CMC values represent colors closer to white. The Gretag Macbeth Color Eye 7000A spectrometer calculates CMC values based on the 25 wavelength and reflectance data for each sample.

C. Calculation of molecular properties

The average structure of each bleaching agent of the invention is drawn with the Material Studio molecular modeling software (commercialized by Accelrys, Inc.). 30 Each geometric shape of the structure is optimized by minimizing its energy with the Forcite module using the semi-empirical universal force field and the Qeq load allocation system. The N = N bond of the diazo dyes is calculated at ~ 1,270-1,275 Angstrom compared to the average N = N bond distance of 1.25 Angstrom. These values are slightly lower than those provided by Liu Jun-na et al., That is, 5 ~ 1.3 Angstrom, which are calculated for diphenyl diazo type dyes with Gaussian 98 software and method B3LYP / 6-311G ( Liu Jun-na, Chen Zhi-rong, and Yuan Shen-feng, Journal of Zhejiang University Science, 6B (6), 2005, pp. 584-589).

After the optimization of the geometry of all 10 structures, various descriptors are calculated. The descriptors can be categorized into the following categories: 1. Structural, 2. Functional, 3. Energy, 4. Topological, 5. Spatial, and 6. Thermodynamic.

All descriptors are calculated using the QSAR module of the 15 Material Studio software, except for the total number of EO and PO groups on the chromophore, the Hansen solubility parameter (Solubility_parameter), and the hydrophilic-lipophilic equilibrium number (MW_HLB). The last two parameters are calculated with ChemSW Molecular Modeling Pro software. The 20 descriptors are analyzed as potential predictors of the affinity of the bleaching agent towards the cellulosic substrate. Table 2 summarizes some of the test parameters that are used to characterize the bleaching agents of the present invention. 25

Table 2 - Summary of test parameters

 Descriptor Symbol

 Test Name Definition

 Hansen solubility parameter, δ

 Total Hansen Solubility (Hildebrand) δ2 = δ2 dispersion + δ2polar + δ2-H sum of solubility components for dispersion, polarity, and hydrogen bonding forces, respectively

 FPSA1 (Jurs Descriptor)

 Fractional positive surface area Sum of the solvent accessible surface area of all positively charged atoms divided by the total molecular surface area accessible to the solvent

 RPSA (Jurs Descriptor)

 Relative polar surface area Total polar surface area divided by the total molecular surface area accessible to the solvent

 Turn radius

 Parameter that characterizes the size of any shape (Σmi ri2 / Σmi) 0.5, where mi = mass of the element i, ri = distance of the element from the center of mass

 Magnitude of the dipole moment

 The magnitude of the dipole moment from the set of spatial descriptors Σqi ri, where qi = partial atomic load, ri = distance

 Polarizability

 Sum of atomic polarizabilities relative tendency of the electron cloud of a molecule to deform with respect to its normal shape due to the presence of an ion or near dipole

Test Results

Test 1: Whiteness test determined according to CIELab b * values and Ganz whiteness index

Examples 1 to 13 are subjected to whiteness test to determine the CIELab b * values and the Ganz whiteness index values ("Ganz WI"). Table 3 shows the test results. The lower CIELab b * values (more negative) and higher Ganz WI positive values indicate that the treated cellulose particles have a greater bluish or bleaching effect.

Table 3 - Whiteness test results determined according to CIELab b * values and Ganz whiteness index

 Sample

 CIELab color value b * Ganz whiteness value value

 Post cleared 1 Post cleared 1

 Control

 2.66 54.34

 Example 1

 -7.57 144.11

 Example 2

 -9.28 162.21

 Example 3

 -5.34 118.09

 Example 4

 -6.58 135.30

 Example 5

 -4.12 107.80

 Example 12

 -9.37 162.00

 Example 13

 -5.94 126.34

The test results indicate that Example 2, which contained 5 repetitive units of ethylene oxide, and Example 12, which contained a glycidol unit, gave the best results under these test conditions. The data 5 show a relatively linear correlation between the CIELab b * color values and the Ganz WI values. A linear regression adjustment for all points has a regression value of R2 = 0.988.

Test 2: Measurement of CIELab b * values and values of the 10 dispersion component of the Hansen solubility parameter

Examples 1 to 13 are tested for the CIELab b * values and the dispersion component values of the Hansen solubility parameter. Note that Examples 1 to 13 contain a violet thiophene chromophore. Examples 18 to 15 24 are tested for the value of the dispersion component of the Hansen solubility parameter only.

Table 4 shows the results of the test. The more negative CIELab b * values indicate that the treated cellulose particles have a greater bluish or bleaching effect. “N / A” indicates that there is no data available

Table 4 - CIELab values b * measured and dispersion component values Hansen solubility parameter

 Sample

 CIELab color value b * Value of the dispersion component of the Hansen solubility parameter (MPa0.5)

 Post cleared 1 Post cleared 1

 Control

 2.66 25.4

 Example 1

 -7.57 14.9

 Example 2

 -9.28 14.8

 Example 3

 -5.34 16.6

 Example 4

 -6.58 17.9

 Example 5

 -4.12 18.4

 Example 12

 -9.37 14.1

 Example 13

 -5.94 12.7

 Example 18

 N / A 16.3

 Example 19

 N / A 16.7

 Example 20

 N / A 15.8

 Example 21

 N / A 16.6

 Example 22

 N / A 16.0

 Example 23

 N / A 16.2

 Example 24

 N / A 17.0

The test result shows a relatively linear correlation between the bluish parameter, CIELab b *, and the value of the dispersion component of the Hansen solubility parameter. The color value b * decreases (i.e., the bluish efficiency increases) linearly as δd decreases.

A linear regression adjustment for all points has a regression value of R2 = 0.763. The regression line has the following equation: 10

b_blueing = 0.9704 * δd - 22.468 (2)

Test 3: prediction of CIELab values b * Based on the values of the dispersion component of the Hansen solubility parameter 15

Examples 1-5 are first used to guide a model based on the value of the dispersion component of the Hansen solubility parameter. The CIELab b * value is calculated for these examples using Equation 3, as shown below, which uses the value of the dispersion component obtained after 1 rinse cycle:

b_blueing = 1.0014 * δd - 23.02 (3) 5

This equation is very similar to Equation 2, which is derived using all the examples. The model represented by Equation 3 is validated with the experimental compounds in Examples 11-14. Equation 3 is used to generate predictions 10 for the CIELab b * value of the molecules of Examples 11-14 (test molecules) before synthesizing these molecules and testing them for bleaching efficiency. The predicted CIELab b * values obtained from Equation 3 are compared with the previously measured values obtained with the Gretag Macbeth Color Eye 7000A spectrophotometer. The percentage difference between the measured b * color values and the predicted b * color values is also determined.

The values of the dispersion component and the predicted CIELab b * values are also determined for comparative Examples 1 and 2. Comparative Example 1 is a blue polymeric anthraquinone dye described in Example III of USPN-4,127,243, granted to Farmer Comparative Example 2 is Basic Violet 3, as described in Table 2 of application publication no. US-2005/0288206, granted to Sadlowski et al. 25

The test results are provided in Table 5 and in Figure 1. "N / A" indicates that no data is available.

Table 5 - Predicted CIELab b * values based on the values of the dispersion component Hansen solubility parameter after rinsing 1

 Example #

 Value of the dispersion component of the Hansen solubility parameter (MPa0.5) CIELab b * predicted value CIELab b * measured value Difference between predicted and measured CIELab b * values (%)

 Control

 25.4 N / A 2.66 N / A

 Example 1

 14.9 -8.1 -7.57 6.6

 Example 2

 14.8 -8.2 -9.28 -13.2

 Example 3

 16.6 -6.4 -5.34 17.0

 Example 4

 17.9 -5.1 -6.58 -29.9

 Example 5

 18.4 -4.6 -4.12 10.6

 Example 12

 14.1 -8.9 -9.37 -4.9

 Example 13

 12.7 -8.7 -8.25 5.2

 Comparative Example 1

 21.3 -1.7 N / A N / A

 Comparative Example 2

 19.5 -3.5 N / A N / A

 5

The compounds (Violet thiophene_5EO_COCH3) and Example 12 (Violet thiophene_glycidol) are synthesized and tested to verify that the model can explain the effects of the functionality of the protected ends of the polymer chain. The compound of Example 12 has four hydroxyl groups, while bleaching agents with EO or PO end groups have only 2 hydroxyl groups. Violet thiophene_5EO_COCH3 is about the same size as Example 12, but acetate protecting groups are less polar than OH groups. fifteen

Figure 1 provides a graphical representation of the data. The phrase "thiophene violet" is indicated as "violet" and "triphenylmethane" is indicated as "TPM" in Figure 1. The dots represent the measured CIELab b * color values. The solid line represents Equation 3, which is the predicted data. The linear correlation between the color value b * and δd suggests that, the smaller the molecule, the greater the deposition on cellulose powder. The size of the bleaching agent compound may influence its ability to access and diffuse in the pores of the cellulose powder. In addition, the bleaching agents that have a more polar protective group in the chains of the molecule, or the bleaching agents that have a greater number of polar terminal groups, have greater bluish efficacy. Calculations 10 also show that bleaching agents containing triphenylmethane are preferred bleaching agents.

Illustrative detergent formulations

Formulations 1a - 1l: Liquid detergent formulations

Tables 6A and 6B provide examples of liquid detergent formulations that include at least one bleaching agent of the present invention. The formulations are shown in Table 6A as Formulations 1a-1f and, in Table 6B, as Formulations 1h-1l.

 twenty

Table 6A - Liquid detergent formulations comprising the bleaching agent of the invention

 Ingredient

 1a 1c 1d 1f5

 % by weight% by weight% by weight% by weight

 sodium alkyl ether sulfate

 14.4% 9.2%

 linear alkylbenzenesulfonic acid

 4.4% 12.2% 5.7% 22.0%

 alkylethoxylate

 2.2% 8.8% 8.1% 18.0%

 amine oxide

 0.7% 1.5%

 citric acid

 2.0% 3.4% 1.9% 1.6%

 fatty acid

 3.0% 8.3% 16.0%

 protease

 1.0% 0.7% 1.0% 2.5%

 amylase

 0.2% 0.2% 0.3%

 lipase

       0.2%

 borax

 1.5% 2.4% 2.9%

 calcium and sodium formate

 0.2%

 formic acid

          1.1%

 ethoxylated amine polymers

 1.8% 2.1% 3.2%

 sodium polyacrylate

 sodium polyacrylate copolymer

       0.6%

 DTPA1

 0.1% 0.9%

 DTPMP2

    0.3%

 EDTA3

 fluorescent whitening agent

 0.15% 0.2% 0.12% 0.2%

 ethanol

 2.5% 1.4% 1.5%

 propanediol

 6.6% 4.9% 4.0% 15.7%

 sorbitol

       4.0%

 ethanolamine

 1.5% 0.8% 0.1% 11.0%

 sodium hydroxide

 3.0% 4.9% 1.9%

 sodium cumensulfonate

    2.0%

 silicone soaps suppressant

    0.01%

 fragrance

 0.3% 0.7% 0.3% 0.6%

 Example 2 Table 1

 0.013% 0.005% 0.003% 0.001%

 Water

 Rest Rest Rest Rest

 100.0% 100.0% 100.0% 100.0%

Table 6B - Liquid detergent formulations comprising the bleaching agent of the invention

 Ingredient

 1h 1i 1j 1l6

 % by weight% by weight% by weight% by weight

 sodium alkyl ether sulfate

 14.4% 9.2%

 linear alkylbenzenesulfonic acid

 4.4% 12.2% 5.7% 22.0%

 alkylethoxylate

 2.2% 8.8% 8.1% 18.0%

 amine oxide

 0.7% 1.5%

 citric acid

 2.0% 3.4% 1.9% 1.6%

 fatty acid

 3.0% 8.3% 16.0%

 protease

 1.0% 0.7% 1.0% 1.7%

 amylase

 0.2% 0.2% 0.6%

 lipase

       0.2% 0.2%

 borax

 1.5% 2.4% 2.9%

 calcium and sodium formate

 0.2%

 formic acid

          1.1%

 ethoxylated amine polymers

 1.8% 2.1% 3.2%

 sodium polyacrylate

 sodium polyacrylate copolymer

       0.6%

 DTPA1

 0.1% 0.9%

 DTPMP2

    0.3%

 EDTA3

 fluorescent whitening agent

 0.15% 0.2% 0.12% 0.2%

 ethanol

 2.5% 1.4% 1.5%

 propanediol

 6.6% 4.9% 4.0% 15.7%

 sorbitol

       4.0%

 ethanolamine

 1.5% 0.8% 0.1% 11.0%

 sodium hydroxide

 3.0% 4.9% 1.9%

 sodium cumensulfonate

    2.0%

 silicone soaps suppressant

    0.01%

 fragrance

 0.3% 0.7% 0.3% 0.6%

 Example 15 Table 1

 Example 2 Table 1

 0.01% 0.02% 0.003% 0.012%

 opacifying9

 0.5%

 Water

 Rest Rest Rest Rest

 100.0% 100.0% 100.0% 100.0%

Footnotes for Formulations 1a-l:

1 diethylenetriaminepentaacetic acid, sodium salt

2 diethylenetriaminopentakismethylenephosphonic acid, sodium salt

3 ethylenediaminetetraacetic acid, sodium salt

4 non-dye dye used to adjust the color of formula 5

5 compact formula, packaged as a unit dose in polyvinyl alcohol film

6 alkoxylated anthraquinone dye with clarification efficiency> 10 and removal by washing 30% -85%

7 alkoxylated thiophene dye with tinting efficiency> 10 and 10 removal by washing 30% -85%

8 triphenylmethane dye with tinting efficiency> 10 and removal by washing 30% -85%

9 Acusol OP301

Formulations 2b - 2d: Granulated detergent formulations 15

Table 7 provides examples of granulated detergent formulations that include at least one bleaching agent of the present invention. The formulations are shown in Table 7 as Formulations 2b-2d.

 twenty

Table 7 - Granulated detergent formulations comprising the bleaching agent of the invention

 Ingredient

 2b 2c 2d

 % by weight% by weight% by weight

 Na linear alkylbenzenesulfonate

 3.3% 11.0% 3.4%

 Na alkylsulfate

 4.1% 4.0%

 Na (branched) alkyl sulfate

 9.6% 9.4%

 alkylethoxylate

    3.5%

 type A zeolite

 35.4% 26.8% 37.4%

 sodium carbonate

 22.5% 35.9% 22.3%

 sodium sulfate

    18.8% 1.0%

 sodium silicate

    2.2%

 protease

 0.2% 0.1%

 sodium polyacrylate

 1.2% 0.7% 1.0%

 carboxymethyl cellulose

    0.1%

 PEG 600

 0.5%

 PEG 4000

 2.2%

 DTPA

 0.6% 0.7%

 fluorescent whitening agent

 0.1% 0.1% 0.1%

 sodium percarbonate

 5.0%

 sodium nonanoyloxybenzenesulfonate

 5.3%

 silicone soaps suppressant

 0.02% 0.02%

 fragrance

 0.3% 0.2% 0.3%

 Example 2 Table 1

 0.006% 0.002% 0.004%

 water and others

 Rest Rest Rest

 100.0% 100.0% 100.0%

Compositions for care of illustrative fabrics 5

Formulations 3a - 3d: Compositions for the care of liquid tissues

Table 8 provides examples of liquid tissue care compositions that include at least one bleaching agent of the present invention. Compositions 10 are shown in Table 8 as Formulations 3a-3d.

Table 8 - Compositions for the care of liquid tissues comprising the bleaching agent of the invention

 Ingredients

 3a 3b 3c 3d

 active substance fabric softener

 13.70% 13.70% 13.70% 13.70%

 ethanol

 2.14% 2.14% 2.14% 2.14%

 cationic starch

 2.17% 2.17% 2.17% 2.17%

 fragrance

 1.45% 1.45% 1.45% 1.45%

 phase c stabilizing polymer

 0.21% 0.21% 0.21% 0.21%

 calcium chloride

 0.147% 0.147% 0.147% 0.147%

 DTPAd

 0.007% 0.007% 0.007% 0.007%

 conservantee

 5 ppm 5 ppm 5 ppm 5 ppm

 antiespumantef

 0.015% 0.015% 0.015% 0.015%

 Example 1 of Table 1

 30 ppm 15 ppm

 Example 2 of Table 1

    30 ppm

 Example 3 of Table 1

       30 ppm 15 ppm

 tinopal CBS-Xg

 0.2 0.2 0.2 0.2

 ethoquad C / 25h

 0.26 0.26 0.26 0.26

 Ammonium chloride

 0.1% 0.1% 0.1% 0.1%

 hydrochloric acid

 0.012% 0.012% 0.012% 0.012%

 deionized water

 Rest Rest Rest Rest

a N, N-di (sebooyloxyethyl) -N, N-dimethylammonium chloride. 5

b Cationic starch based on common corn starch or potato starch containing 25% to 95% amylose and a degree of substitution of 0.02 to 0.09, and having a viscosity measured as fluidity in water that has A value of 50 to 84.

c Copolymer of ethylene oxide and terephthalate having the formula described in US 5,574,179, in column 15, lines 1-5, where each X is methyl, each n is 40, u is 4, each R1 is Essentially 1,4-phenylene moieties, each R2 is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.

d Diethylenetriaminepentaacetic acid.

e KATHON® CG marketed by Rohm and Haas Co. 15

f Silicone antifoaming agent marketed by Dow Corning Corp. under the trade name DC2310.

g 4,4′-bis- (2-sulfoestyryl) biphenyl disodium, marketed by Ciba Specialty Chemicals.

h Ethoxylated cocomethyl ammonium chloride [15], marketed by Akzo Nobel. twenty

Therefore, the present invention provides a bleaching agent for cellulosic substrates comprising at least one chromophore component comprising a thiophene or triphenylmethane dye and at least one polymer component; wherein the bleaching agent has a value of the dispersion component of the Hansen solubility parameter of less than or equal to about 17 MPa0.5. Also contemplated in the present invention is a laundry detergent containing a bleaching agent of said characteristics.

The bleaching agent used in the present invention includes a bleaching agent for cellulosic substrates comprising at least one chromophore component 10 comprising a thiophene dye and at least one polymeric component in which the bleaching agent is characterized by the following structure:

 fifteen

in which R1 and R2 can be selected, independently of each other, from:

a) [(CH2CR'HO) x (CH2CR "HO) and H]

 wherein R ’is selected from the group consisting of 20 H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; wherein R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y ≤ 5; where y ≥ 1; and where z = 0 to 5;

b) R1 = alkyl, aryl, or arylalkyl and R2 = [(CH2CR'HO) x (CH2CR "HO) and H]

 wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; wherein R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y ≤ 10; where y ≥ 1; and where z = 0 to 5;

c) R1 = [CH2CH (OR3) CH2OR4] and R2 = [CH2CH (O R3) CH2O R4]

 wherein R3 is selected from the group consisting of H, (CH2CH2O) zH, and mixtures thereof; and where z 10 = 0 to 10;

 wherein R4 is selected from the group consisting of (C1-C16) alkyl, aryl groups, and mixtures thereof; Y

d) the amine addition product of styrene oxide, glycidylmethyl ether, isobutylglycidyl ether, isopropylglycidyl ether, t-butylglycidyl ether, 2-ethylhexylidethyl ether and glycidylhexadecyl ether, followed by the addition of 1 to 10 units of alkylene oxide.

A potentially preferred bleaching agent used in the present invention includes a bleaching agent for cellulosic substrates comprising at least one chromophore component comprising a thiophene dye and at least one polymeric component wherein the bleaching agent is characterized by the following structure: 25

wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; wherein R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and 5 mixtures thereof; where x + y ≤ 5; where y ≥ 1; and where z = 0 to 5.

Therefore, it is believed that it is an advantage of the present invention to employ the predictive model to aid in the selection of ideally suitable chromophores containing compounds as bleaching agents. The results of the tests provided herein tend to indicate that the deposition of the bleaching agent on the cellulose powder can be controlled, at least in part, by the size of the bleaching agent compound and by its group functionality. chain guard The results of the tests also suggest that the larger molecules may be too bulky to diffuse into the pores of the cellulose powder, which may decrease the bleaching effect after multiple wash and / or rinse cycles. twenty

Although particular embodiments of the present invention have been illustrated and described, it will be apparent to one skilled in the art that other changes and modifications can be made without departing from the scope of the invention. Accordingly, the following claims are intended to cover all such changes and modifications contemplated within the scope of the present invention.

Claims (15)

1. A laundry care composition comprising an ingredient for laundry care and a bleaching agent, said bleaching agent comprising: (a) at least one chromophore component comprising a thiophene dye, and (b) at least one polymer component;  wherein the bleaching agent is characterized by the following structure: 10  Where R1 and R2 can be selected, independently of each other, from: a) [(CH2CR'HO) x (CH2CR "HO) and H]  wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; wherein R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + 20 and ≤ 5; where y ≥ 1; and where z = 0 to 5; b) R1 = alkyl, aryl or arylalkyl and R2 = [(CH2CR'HO) x (CH2CR "HO) and H]  wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; in which R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y ≤ 10; where y ≥ 1; and where z = 0 to 5; c) R1 = [CH2CH (OR3) CH2OR4] and R2 = [CH2CH (O R3) CH2O R4]  wherein R3 is selected from the group consisting of 5 H, (CH2CH2O) zH, and mixtures thereof; and where z = 0 to 10;  wherein R4 is selected from the group consisting of (C1-C16) alkyl, aryl groups, and mixtures thereof; and 10 d) the amine addition product of styrene oxide, glycidylmethyl ether, isobutylglycidyl ether, isopropylglycidyl ether, t-butylglycidyl ether, 2-ethylhexylidethyl ether, and glycidylhexadecyl ether, followed by the addition of 1 to 10 alkylene oxide units. fifteen 2. The laundry care composition of claim 1, wherein the bleaching agent comprises a polyoxyalkylene chain having from 2 to about 20 repetitive units. 3. A laundry care composition according to any one of the preceding claims, wherein the bleaching agent comprises at least two hydroxyl groups, preferably said at least two hydroxyl groups are primary hydroxyl moieties. 4. A laundry care composition according to any one of the preceding claims, wherein the bleaching agent comprises an alkoxylated thiophene polymeric dye. 5. A laundry care composition according to any one of the preceding claims, wherein the bleaching agent has a dispersion component value of the Hansen solubility parameter of less than or equal to 17 MPa0.5, preferably 12 at 17 MPa0.5. 6. The laundry care composition of any one of claims 1 to 4, wherein the bleach agent chromophore has a water absorbance spectrum 5 of 520 nanometers to 640 nanometers. 7. The laundry care composition of any of claims 1 to 4, wherein the chromophore of the bleaching agent has a water emission spectrum of 400 nanometers to 480 nanometers. 10 8. A laundry care composition comprising an ingredient for laundry care and a bleaching agent, said bleaching agent comprising: (a) at least one chromophore component comprising a thiophene dye, and (b) at least one polymer component; wherein the bleaching agent has a dispersion component value of the Hansen solubility parameter less than or equal to 17 MPa0.5, preferably 12 to 17 MPa0.5. twenty 9. The laundry care composition of claim 8, wherein the bleaching agent comprises a polyoxyalkylene chain having 2 to 20 repetitive units. 10. A laundry care composition according to any one of the preceding claims, wherein the bleaching agent comprises at least two hydroxyl groups, preferably said at least two hydroxyl groups are primary hydroxyl moieties. 11. A laundry care composition according to any one of the preceding claims, wherein the bleaching agent comprises an alkoxylated thiophene polymeric dye. 12. A laundry care composition according to any one of claims 8 to 11, wherein the bleach agent chromophore has a water absorbance spectrum 5 of 520 nanometers to 640 nanometers. 13. A laundry care composition according to any one of claims 8 to 12, wherein the chromophore of the bleaching agent has a water emission spectrum of 400 nanometers to 480 nanometers. 10 14. A laundry care composition according to claim 1, wherein the bleaching agent is characterized by the following structure:  fifteen  wherein R ’is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; wherein R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y ≤ 20 5; where y ≥ 1; and where z = 0 to 5. 15. The laundry care composition of claim 14, wherein the bleaching agent comprises a polyoxyalkylene chain having 2 to 20 repetitive units, preferably 4 to 6 repetitive units.