JP5122583B2 - Laundry care composition comprising a whitening agent for a cellulose substrate - 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

The present invention relates to a novel whitening agent for cellulose substrates. The brightener is composed of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally emit blue, red, violet or purple fluorescence when exposed to ultraviolet light, or can absorb and reflect these same hues. This brightener is further characterized by having a dispersion term value with a Hansen solubility parameter of about 17 MPa ^0.5 or less. These brighteners may be ideal for use in laundry care compositions including but not limited to liquid and / or powder laundry detergent formulations and rinse added fabric softener (RAFS) compositions.

  The use of brighteners, either optical brighteners or bluing agents, in fabric applications is well known in the prior art. As fabric ages, fabric substrates tend to fade or yellow due to light, air, dirt and natural degradation of the fibers contained in the substrate. Thus, the purpose of brighteners is generally to make these fabric substrates visually brighter and lessen the effects of substrate fading and yellowing. Typically, brighteners can be found in laundry detergents, softeners or rinse aids and are therefore applied to the fabric substrate during the laundry process. However, it is important that the whitening agent function to lighten the treated textile substrate without causing undesirable stains on the textile substrate.

  Cellulose substrates in particular have a tendency to exhibit a yellow phase after exposure to light, air and / or dirt. It is often difficult to reverse this yellowing by normal washing procedures. As a result, there is a need for an improved whitening agent that can remove the yellowing that cellulose substrates exhibit due to aging. Use of such improved brighteners may extend the useful life of fabric substrates such as clothing, table linen and the like.

The present invention is a compound having a Hansen Solubility Parameter of about 17 MPa ^0.5 or less, and when exposed to ultraviolet light to neutralize the yellowing of a cellulose substrate, the blue, red, violet U.S. Pat. Nos. 4,137,243, 5,039,782, and compounds that emit light at wavelengths in the range of color, purple, or combinations thereof (or absorb to produce the same color) Offers advantages over US Patent Application Publication No. 2005/0288206. These compounds ideally act as brighteners for cellulose substrates and can be incorporated into laundry detergent formulations for consumer use during the laundry process.

The present invention relates to a novel whitening agent for cellulose substrates. The brightener is composed of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally emit blue, red, violet or purple fluorescence when exposed to ultraviolet light, or can absorb and reflect these same hues. The brightener is further characterized by having a dispersion term value with a Hansen solubility parameter of about 17 MPa ^0.5 or less. The present invention also relates to laundry care compositions that include, but are not limited to, liquid and / or powder laundry detergent formulations including such brighteners and rinse-added fabric softener (RAFS) compositions.

Graphic representation of the dispersion term value of the Hansen solubility parameter versus the CIELab b ^* value for various brighteners after one rinse cycle.

  As used herein, “cellulose substrate” is intended to encompass any substrate that contains at least a majority of cellulose by weight. Cellulose can be found in wood, cotton, linen, jute and linen. The cellulose substrate may be in the form of powder, fiber and pulp and in the form of an article formed from the powder, fiber and pulp. Cellulose fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate) and mixtures thereof. Articles formed from cellulose fibers include fabric articles such as woven fabrics. Articles formed from pulp include paper.

  As used herein, the term “laundry care composition” refers to detergents and / or fabric treatments in the form of granules, powders, liquids, gels, pastes, bars and / or flakes unless otherwise indicated. Includes the composition.

  As used herein, the term “fabric treatment composition” encompasses fabric softening compositions, fabric enhancing compositions, fabric freshening compositions and combinations thereof, unless otherwise indicated. Such a composition may be a rinse addition type composition, but it need not be.

  As used herein, articles including “the”, “a” and “an” are understood to mean one or more of what is claimed or described when used in the claims. The

  As used herein, the terms “include”, “includes” and “including” are used to refer to , Not intended to be limiting.

  In order to determine the values of the parameters of Applicants' invention, the test method disclosed in the test method section of the present application should be used.

  Unless otherwise stated, all concentrations of an ingredient or composition are with respect to the active portion of the ingredient or composition, and impurities that may be present in commercial sources of such ingredient or composition, such as residual solvents or by-products Things are excluded.

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

  Any given maximum numerical limitation throughout this specification should be understood to include all smaller numerical limitations as if the lower numerical limitations were expressly set forth herein. Any minimum numerical limitation described throughout this specification includes any numerical limitation as if it were expressly set forth herein, as if such higher numerical limitation was expressly set forth herein. Any numerical range stated throughout this specification should be explicitly stated in this specification, any numerical range that falls within such a wider numerical range, as if all such numerical ranges were narrower. It is included as if it were.

  All documents cited are incorporated by reference herein in the relevant part, but the citation of any document should not be construed as an admission that it is prior art with respect to the present invention.

  The brightener of the present invention may be a dye, pigment or polymeric colorant that includes a chromophore component and a polymeric component. The chromophore component is characterized by emitting or absorbing wavelengths in the range of blue, red, violet, purple or combinations thereof when exposed to light. The chromophore component preferably exhibits an absorption spectrum value of about 520 nanometers to about 640 nanometers in water, more preferably about 570 nanometers to about 610 nanometers in water. The chromophore component preferably exhibits an emission spectral value of about 400 nanometers to about 480 nanometers.

  Examples of suitable polymeric components include polyoxyalkylene chains having a plurality of repeating units. The polymeric component preferably includes a polyoxyalkylene chain having from 2 to about 20 repeat units, more preferably from 2 to about 10, and even from about 4 to about 6 repeat units. Non-limiting examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide, and mixtures thereof.

The brightener of the present invention has the following structure:
Wherein R ₁ and R ₂ are a) [(CH ₂ CR′HO) _x (CH ₂ CR ″ HO) _y H].
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O). _z H and selected from the group consisting of these, x + y ≦ 5, y ≧ 1, and z = 0-5),
b) R ₁ = alkyl, aryl or arylalkyl and R ₂ = [(CH ₂ CR′HO) _x (CH ₂ CR ″ HO) _y H]
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O). _z H and selected from the group consisting of these, x + y ≦ 10, y ≧ 1, z = 0-5),
c) R ₁ = [CH ₂ CH ₂ (OR ₃ ) CH ₂ OR ₄ ] and R ₂ = [CH ₂ CH ₂ (OR ₃ ) CH ₂ OR ₄ ]
Wherein R ₃ is selected from the group consisting of H, (CH ₂ CH ₂ O) _z H and mixtures thereof, z = 0-10.
R ₄ is selected from the group consisting of (C ₁ -C ₁₆ ) alkyl, aryl groups and mixtures thereof), and
d) R1 and R2 are independently selected from styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether and amino addition products of glycidyl hexadecyl ether. Furthermore, it can be independently selected from those to which 1 to 10 alkylene oxide units are added.

Preferred brighteners of the present invention have the following structure:
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ Selected from the group consisting of CH ₂ O) _z H and mixtures thereof, x + y ≦ 5, y ≧ 1, and z = 0-5.

Another feature of the brightener of the present invention is its affinity for cellulosic materials. Affinity can be measured quantitatively using the dispersive power term of the Hansen solubility parameter. The Hansen solubility parameter is a three-term measurement system that includes a dispersion force term (δ _d ), a hydrogen bond term (δ _h ), and a polarity term (δ _p ). The Hansen solubility parameter “δ” is the total cohesive energy, which is the energy required to break all cohesive bonds:
δ ² = δ _d ² + δ _p ² + δ _h ² . (1)
Derived from the fact that it is a combination of the dispersion force (d), the molecular dipole force (p) and the hydrogen bond force (h).

Dispersion force is a weak attraction between nonpolar molecules. The absolute value of these forces depends on the polarizability of the molecule, and the dispersion Hansen solubility parameter δ _d typically increases as the volume (and size) of the molecule increases if all other properties are approximately equal. . The parameter “δ _p ” increases as the polarity of the molecule increases.

For the solvent experimentally obtained by Hansen, Alan F. et al. M.M. Unpublished, based on values published in Barton, Allan FM “The Handbook of Solubility Parameters and Other Parameters” (CRC Press, 1983) The Hansen Solubility parameters are calculated at 25 ° C. with ChemSW's Molecular Modeling Pro v. 6.1.9 software package using the proprietary algorithm. All values of the Hansen solubility parameters reported herein are expressed in units of MPa ^0.5 (megapascal square root). Hansen originally measured the solubility parameter of the solvent for the polymer solution. While the Hansen solubility parameter calculation method has been successfully applied to a wide range of applications such as biological material solubility, pigment, filler and fiber characterization, it has been applied to polymeric colorants. There wasn't.

Therefore, for the effective whitening agent of the present invention, the dispersive power term δ _d of the Hansen solubility parameter is preferably about 17 or less, more preferably about 15 or less. It is also desirable that the dispersive power term of the Hansen solubility parameter is from about 12 to about 17, more preferably from about 12 to about 15.

Affinity brightener for cellulose material is very closely correlated with Hansen dispersion term parameters, the present invention is not limited to the use of [delta] _d. [delta] _d and directly or indirectly related to other molecules descriptors, for example, polarizability, radius of gyration, and Joule descriptors based on partial atomic charges mapped on the molar volume and solvent accessible area also Be considered. However, the affinity is fit in univariate correlation with these descriptors was not as good as when the [delta] _d.

  Without being bound by theory, the whitening agent's affinity for cellulose substrates is attributed to van der Waals forces, an attractive force that exists between electrically neutral molecules in close proximity to each other. Is believed to be able to. It is also self-evident that if the cellulose substrate consists of a porous region, the brightener or part thereof can be physically caught in the cellulose pores depending on the molecular diameter compared to the pore diameter. The This physical capture provides a degree of resistance and protects the brightener from being easily removed from the cellulosic substrate upon washing or rinsing.

  The brighteners described herein may be incorporated into laundry care compositions, including but not limited to laundry detergents and fabric care compositions. Such compositions comprise one or more of the above brighteners and laundry care ingredients. Various application techniques can be used to add the brightener to the cellulose substrate. For application to cellulose-containing fabric substrates, whitening agents are preferably included as additives in laundry detergents. Thus, application to a cellulose-containing fabric substrate actually occurs when the consumer adds laundry detergent to the washing machine. Similarly, the RAFS composition is typically added in a rinse cycle after the detergent solution is used in a typical laundry process and replaced with a rinse solution. For application to the cellulosic paper substrate, the brightener may be added to the paper pulp mixture prior to formation of the final paper product.

  Laundry care compositions including laundry detergents can include solid or liquid forms, including gel forms. The laundry detergent composition includes a sufficient amount of surfactant to provide the desired cleaning properties.

  The brightener is about 0.0001% to about 10% by weight of the composition in the laundry detergent composition, more preferably about 0.0001% to about 5% by weight of the composition, more preferably about 0.0001%. It can be present in an amount from% to about 1% by weight.

  The laundry detergent composition includes a sufficient amount of surfactant to provide the desired cleaning properties. In one embodiment, the laundry detergent composition comprises from about 5% to about 90% by weight surfactant, more specifically from about 5% to about 70% by weight surfactant, and even more specifically. About 5% to about 40% by weight of a surfactant. Surfactants may include anionic, nonionic, cationic, zwitterionic and / or amphoteric surfactants. In more specific embodiments, the detergent composition includes an anionic surfactant, a nonionic surfactant, or a mixture thereof.

  Suitable anionic surfactants useful herein can also include any type of conventional anionic surfactant typically used in liquid detergent products. These include alkyl benzene sulfonic acids and their salts, as well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Typical anionic surfactants are C10-16 alkyl benzene sulfonic acids, preferably alkali metal salts of C 11-14 alkyl benzene sulfonic acids. Preferably the alkyl group is linear and such linear alkyl benzene sulfonates are known as “LAS”. Alkylbenzene sulfonates, especially LAS, are well known in the art. Such surfactants and their preparation are described, for example, in US Pat. Nos. 2,220,099 and 2,477,383. Particularly preferred are sodium and potassium linear linear alkylbenzene sulfonates having an average number of carbon atoms in the alkyl group of about 11-14. Sodium _C 11 _{-C 14,} for _example, C 12, LAS is a specific example of such surfactants.

Another representative type of anionic surfactant includes ethoxylated alkyl sulfate surfactants. Such materials are also known as alkyl ether sulfates or alkyl polyethoxylate sulfates and correspond to the following formula: R′—O— (C ₂ H ₄ O) _n —SO ₃ M, where , R ′ is a C ₈ -C ₂₀ alkyl group, n is about 1-20, and M is a salt-forming cation. In specific embodiments, R ′ is C ₁₀ -C ₁₈ alkyl, n is about 1-15, and M is sodium, potassium, ammonium, alkyl ammonium, or alkanol ammonium. In a more specific embodiment, R ′ is C ₁₂ -C ₁₆ , n is about 1-6, and M is sodium.

Alkyl ether sulfates are generally used in the form of mixtures containing various R ′ chain lengths and various degrees of ethoxylation. Often such mixtures will also necessarily contain some non-ethoxylated alkyl sulfate material, ie a surfactant where the ethoxylated alkyl sulfate formula, where n = 0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of the present invention and used as or in any anionic surfactant component that may be present. Specific examples of non-alkoxylated, such as non-ethoxylated, alkyl ether sulfate surfactants are those prepared by sulfation of higher C ₈ -C ₂₀ aliphatic alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROSO ₃ has -M ^+, wherein, R is typically a linear _C 8 _{-C 20} hydrocarbyl group, a straight-chain or branched And M is a water-solubilizing cation. In specific embodiments, R is _C 10 _{-C 15} alkyl, M is an alkali metal, more specifically, R is _C 12 _{-C 14,} M is sodium.

Specific non-limiting examples of anionic surfactants useful herein include: a) C ₁₁ -C ₁₈ alkyl benzene sulfonate (LAS), b) C ₁₀ -C ₂₀ primary branched and random alkyl. sulfates (AS), c) formula (I) and _(C 10 _{-C 18} secondary with II) (2,3) alkyl sulfates (wherein (I) M in and (II) is hydrogen or charge Cations that impart neutrality, whether all M units are related to surfactants or auxiliary components, in forms or systems where compounds isolated by those skilled in the art are used. Depending on the relative pH, it can be either a hydrogen atom or a cation, non-limiting examples of preferred cations include sodium, potassium, ammonium and mixtures thereof, where x is small Least about 7, preferably at least about 9 integer, y is at least 8, preferably at least about 9 _{integer), d) C} 10 _{~C 18} alkyl alkoxy sulfates (AExS) (wherein, preferably x is 1 to 30), e) preferably contain 1-5 ethoxy _units, C 10 _{-C 18} alkyl alkoxy carboxylates, f) U.S. Patent No. 6,020,303 No. and the first 6,060, Medium chain branched alkyl sulfate as discussed in 443, g) medium chain branched alkyl as discussed in US Pat. Nos. 6,008,181 and 6,020,303 Alkoxysulfate, h) PCT International Publication Nos. 99/05243, 99/05242, 99/05244, 99/05082, 99/05084, 99/05241, 99/07656, 00/23549, and 00/23548, modified alkylbenzene sulfonates (MLAS), i) methyl esters Sulfonate (MES) as well as j) α-olefin sulfonate (AOS).

  Suitable nonionic surfactants useful herein can include any type of conventional nonionic surfactants commonly used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Nonionic surfactants that are normally liquid are preferred for use in the liquid detergent products herein.

Suitable nonionic surfactants for use herein include alcohol alkoxylate nonionic surfactants. The alcohol alkoxylate has the general formula: R ¹ (C _m H _2m O) _n OH, where R ¹ is a C _{8 to} C ₁₆ alkyl group, m is 2 to 4, and n is about 2 to 12 Is a substance according to (range). R ¹ may be primary or secondary and is preferably an alkyl group containing about 9-15 carbon atoms, more preferably about 10-14 carbon atoms. In one embodiment, the alkoxylated fatty alcohol is also an ethoxylated material containing about 2-12 ethylene oxide moieties per molecule, more preferably about 3-10 ethylene oxide moieties per molecule.

  Alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will often have a hydrophilic-lipophilic balance (HLB) in the range of about 3-17. More preferably, the HLB of this material will be in the range of about 6-15, most preferably about 8-15. Alkoxylated fatty alcohol nonionic surfactants are marketed by Shell Chemical Company under the trade names Neodol and Dobanol.

Another type of suitable nonionic surfactant useful herein includes amine oxide surfactants. Amine oxide is a material often referred to in the art as a “semipolar” nonionic material. The amine oxide has the formula: R (EO) _x (PO) _y (BO) _z N (O) (CH ₂ R ′) ₂ .qH ₂ O. In this formula, R is a relatively long chain hydrocarbon moiety which may be saturated or unsaturated, linear or branched and contains 8 to 20 carbon atoms, preferably 10 to 16 carbon atoms. It can contain, more preferably primary alkyl of _C 12 _{-C 16.} R ′ is a short-chain moiety, preferably selected from hydrogen, methyl and —CH ₂ OH. When x + y + z is different from 0, EO is ethyleneoxy, PO is propyleneoxy, and BO is butyleneoxy. Amine oxide surfactants are exemplified by C _12-14 alkyl dimethyl amine oxides.

Non-limiting examples of nonionic surfactants include: a) C ₁₂ -C ₁₈ alkyl ethoxylates such as NEODOL® nonionic surfactant from Shell, b) C ₆ -C ₁₂ alkyl phenol alkoxylates (where alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units), C ₁₂ with ethylene oxide / propylene oxide block polymers such as Pluronic (Pluronic) (registered trademark) from c) BASF -C ₁₈ alcohol and _C 6 _{-C 12} alkyl phenol condensates, d) U.S. Pat. _C 14 _{-C 22} chain branched alcohols, such as discussed in No. 6,150,322, BA, e) US Pat. 6,153,577, 6,020,303 and 6,093,85 C ₁₄ -C ₂₂ medium chain branched alkyl alkoxylates as discussed in US Pat. No. 6, BAE _x (where x is 1-30), f) US Pat. No. 4,565,647 (Leonard) (Llenado), published 26 January 1986), as discussed in US Pat. Nos. 4,483,780 and 4,483,779. G) as discussed in US Pat. No. 5,332,528, PCT International Publication Nos. 92/06162, 93/19146, 93/19038 and 94/09099. H) ether end-capped groups as discussed in US Pat. No. 6,482,994 and PCT WO 01 / 42,408. Poly (oxyalkylated) alcohol surfactants.

  In the laundry detergent compositions herein, the detersive surfactant component may comprise a combination of anionic and nonionic surfactant materials. In this case, the weight ratio of anionic to nonionic is typically in the range of 10:90 to 90:10, more typically 30:70 to 70:30.

  Cationic surfactants are well known in the art, and non-limiting examples of these include quaternary ammonium surfactants that can have up to 26 carbon atoms. Additional examples include: a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in US Pat. No. 6,136,769, b) discussed in US Pat. No. 6,004,922. Dimethylhydroxyethyl quaternary ammonium such as c) PCT International Publication Nos. 98/35002, 98/35003, 98/35004, 98/35005 and 98/35006 D) U.S. Pat. Nos. 4,228,042, 4,239,660, 4,260,529 and 6,022, which are discussed in US Pat. Cationic ester surfactants as discussed in US Pat. No. 844 and e) as discussed in US Pat. No. 6,221,825 and PCT International Publication No. 00/47708. Amino surfactants as are, specifically include dimethylamine (APA).

Non-limiting examples of dipolar surfactants include secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives or quaternary ammonium compounds, quaternary phosphonium compounds or quaternary surfactants. Derivatives of tertiary sulfonium compounds are mentioned. For examples of bipolar surfactants, see US Pat. No. 3,929,678 (Laughlin et al., Issued Dec. 30, 1975), 19th line, 38th line to 22nd line, 48th line. dimethyl betaine and coco amidopropyl _betaine, C 8 _{-C 18} (preferably _C 12 _{-C 18)} betaines include amine oxides and sulfo and hydroxy betaines, such as alkyl group _C 8 _{-C 18,} preferably _{C 10} it can be a -C ₁₄ N- alkyl -N, include N- dimethylamino-1-propane sulfonate.

  Non-limiting examples of amphoteric surfactants include secondary or tertiary amine aliphatic derivatives or heterocyclic secondary and tertiary amine aliphatic derivatives, where the aliphatic radical is linear or It can be branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one is an anionic water-soluble group such as carboxy, sulfonate. , Including sulfate. For examples of amphoteric surfactants, see US Pat. No. 3,929,678 (Laughlin et al., Issued December 30, 1975), 19th line, lines 18-35.

  As noted above, the composition may be in solid form, either in tablet form or in particulate form consisting of particles or flakes, etc., and the composition may be in liquid form. The liquid detergent composition includes an aqueous non-surfactant liquid carrier. In general, the amount of aqueous non-surfactant liquid carrier used in the compositions herein is effective to solubilize, suspend or disperse the composition components. For example, the composition has an aqueous non-surfactant activity of from about 5% to about 90%, more specifically from about 10% to about 70% and even more specifically from about 20% to about 70% by weight. A liquid carrier may be included.

  The most cost effective type of aqueous non-surfactant liquid carrier is, of course, water itself. Thus, the aqueous non-surfactant liquid carrier component will generally consist, if not entirely, of water. Conventionally, other types of water-compatible liquids such as alkanols, diols, other polyols, ethers and amines have been added to liquid detergent compositions as cosolvents or stabilizers for the purposes of the present invention. The use of such water-compatible liquids should be minimized to reduce composition costs. Therefore, the aqueous liquid carrier component of the liquid detergent compositions herein generally comprises from about 5% to about 90%, more preferably from about 20% to about 70% by weight of the composition.

  The detergent composition may also contain a bleaching agent. Suitable bleaching agents include, for example, “Kirk Othmer's Encyclopedia of Chemical Technology” (4th edition, 1992, John Wiley & Sons, Volume 4, 271-300) Hydrogen peroxide sources as described in detail in "Bleaching Agents (Survey)" (incorporated herein). These hydrogen peroxide sources include various forms of sodium perborate and sodium percarbonate, and include various coated and modified forms of these compounds.

  A preferred hydrogen peroxide source for use herein can be any convenient source, such as hydrogen peroxide itself. For example, perborate (eg sodium perborate (any hydrate but preferably monohydrate or tetrahydrate), sodium carbonate hydrogen peroxide or the corresponding percarbonate, pyrophosphate Sodium hydrogen peroxide, urea hydrogen peroxide or sodium peroxide can be used herein, such as persulfate bleach (for example, OXONE from DuPont) A source of oxygen is also useful, sodium perborate monohydrate and sodium percarbonate being particularly preferred, and any convenient mixture of hydrogen peroxide sources can be used.

  Suitable percarbonate bleaching agents include dry particles having an average particle size in the range of about 500 micrometers to about 1,000 micrometers, with no more than about 10% by weight of the particles being less than about 200 micrometers, About 10% by weight or less of the particles are greater than about 1,250 micrometers. If desired, the percarbonate can be coated with silicates, borates or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC (FMC), Solvay and Tokai Denka.

  The composition of the present invention may also contain a chlorine-type bleachable material as a bleaching agent. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate (“NaDCC”). However, chlorine type bleaches are less preferred for compositions containing enzymes.

  (A) Bleach activator-Preferably, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The activator is present in a concentration from about 0.01%, preferably from about 0.5%, more preferably from about 1% by weight of the composition, up to about 15%, preferably about 10%. %, More preferably at a concentration of up to about 8% by weight. As used herein, a bleach activator is any compound that, when used in conjunction with hydrogen peroxide, leads to the in situ generation of a peracid whose source corresponds to the bleach activator. Various non-limiting examples of activators are described in US Pat. Nos. 5,576,282, 4,915,854, and 4,412,934. See also US Pat. No. 4,634,551 for other typical bleaches and activators useful herein.

Preferred activators are tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate ( PhBz), decanoyl oxybenzene sulphonate _(C 10 -OBS), benzoyl valerolactam (BZVL), octanoyl oxybenzenesulfonate _(C 8 -OBS), the group consisting of over-hydrolyzable (perhydrolyzable) esters and mixtures thereof Most preferred are benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of about 8 to about 11 are selected from those having OBS or VL leaving groups.

Preferred hydrophobic bleach activators include nonanoyloxybenzene sulfonate (NOBS); 4- [N- (nonanoyl) aminohexanoyloxy] -benzenesulfonic acid sodium salt (NACA-OBS) (US Pat. No. 5,523). examples of those described in JP 434); dodecanoyl oxybenzene sulphonate (LOBS or _C 12 -OBS); 10- undecenyl UDOBS or _C 11 -OBS with unsaturation alkanoyloxy benzene sulphonate (10th); Decanoyloxybenzoic acid includes, but is not limited to.

  Preferred bleach activators are US Pat. Nos. 5,998,350 (Burns et al.), 5,698,504 (Christie et al.), And 5,695,679 (Christy et al.). No. 5,686,401 (Willey et al.), No. 5,686,014 (Hartshorn et al.), No. 5,405,412 (Wiley et al.), No. 5,405,413 (Wiley et al.), 5,130,045 (Mitchel et al.) And 4,412,934 (Chung et al.) And co-pending patent applications No. 08 / 064,564, all of which are incorporated herein by reference.

  In the present invention, the molar ratio of peroxygen source as available oxygen (AvO) to bleach activator is generally from at least 1: 1, preferably from about 20: 1, more preferably from about 10: 1. From up to about 1: 1, preferably up to about 3: 1.

  Quaternary substituted bleach activators may also be included. The laundry composition preferably comprises a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP, preferably a quaternary substituted percarboxylic acid or quaternary. Secondary substituted peroxyimidic acid), preferably the former. Preferred QSBA structures are US Pat. Nos. 5,686,015 (Willey et al.), 5,654,421 (Taylor et al.), 5,460,747 (Gosselink). Et al., 5,584,888 (Miracle et al.) And 5,578,136 (Taylor et al.), All of which are incorporated herein by reference. Yes.

  The highly preferred bleach activators useful herein are U.S. Pat. Nos. 5,698,504, 5,695,679 and 5,686, each previously cited herein. Amide substitution, as described in US Pat. Preferred examples of such bleach activators include (6-octaneamidocaproyl) oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene sulfonate, and the like. Of the mixture.

Other useful activators are US Pat. Nos. 5,698,504, 5,695,679, and 5,686,014, each of which is previously cited herein. No. 4,966,723 (Hodge et al.). These activators include benzoxazine-type activators such as C ₆ H ₄ rings in which the —C (O) OC (R ¹ ) ═N— moiety is attached to the 1,2-position.

  Nitriles such as acetonitrile and / or ammonium nitriles and other quaternary nitrogen-containing nitriles are another class of activators useful herein. Non-limiting examples of such nitrile bleach activators are U.S. Patent Nos. 6,133,216, 3,986,972, 6,063,750, 6,017,464. 5,958,289, 5,877,315, 5,741,437, 5,739,327, 5,004,558 and European Patent 790244. No. 775127, No. 1017773, No. 1017776 and PCT International Publication Nos. 99/14302, 99/14296, No. 96/40661, all of which are referred to Is incorporated herein by reference.

  Depending on the activator and the exact application, good bleaching results can be obtained from a bleach system having a pH of about 6 to about 13, preferably about 9.0 to about 10.5, in use. Typically, an activator having an electron withdrawing moiety is used in an approximately neutral or sub-neutral pH range. Alkalis and buffers can be used to maintain such a pH.

  Acyl lactam activators as described in US Pat. Nos. 5,698,504, 5,695,679 and 5,686,014, each of which is previously cited herein. , In particular acyl caprolactam (see, eg, PCT Publication No. 94-28102 A) and acyl valerolactam (US Pat. No. 5,503,639 (Willey, incorporated herein by reference)). ) Et al) is very useful herein.

  (B) Organic peroxides, especially diacyl peroxides—these are “Kirk Othmer, Encyclopedia of Chemical Technology” (1982, John Wiley & Sons, No. 1). Vol. 17, pages 27-90, especially pages 63-72), all of which are incorporated herein by reference. If diacyl peroxide is used, this is preferably one that minimizes adverse effects on fabric care such as color care.

  (C) Metal-containing bleach catalysts-The compositions and methods of the present invention can also optionally include metal-containing bleach catalysts, particularly manganese and cobalt-containing bleach catalysts.

  One class of metal-containing bleach catalysts has limited bleach catalyst activity transition metal cations (eg, copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations), little or no bleach catalyst activity Auxiliary metal cations (eg zinc or aluminum cations) and sequestering agents with limited stability constants for catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and these A catalyst system comprising a water-soluble salt of Such a catalyst is disclosed in U.S. Pat. No. 4,430,243 (Bragg).

Manganese Metal Complex—If desired, the compositions herein can be catalyzed by manganese compounds. Such compounds and concentrations used are well known in the art, for example, U.S. Pat. Nos. 5,576,282, 5,246,621, 5,244,594, 194,416 and 5,114,606 and European Patent Application Publication Nos. 549,271 A, 549,272 A1, 544,440 A2 and 544,490 A1 And manganese-based catalysts. Preferred examples of these catalysts include Mn ^IV ₂ (u—O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (u _{-O) 1 (u-OAc)} 2 (1,4,7- _{^{trimethyl-1,4,7-triazacyclononane) 2 (ClO 4) 2,}} Mn IV 4 (u-O) 6 (1,4 , ^{_{7-triazacyclononane) 4 (ClO 4) 4,}} Mn III Mn IV 4 (u-O) 1 (u-OAc) 2- (1,4,7- trimethyl-1,4,7-triaza Cyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metallic bleach catalysts include those disclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance the bleaching effect is also described in US Pat. Nos. 4,728,455, 5,284,944, 5,246,612, No. 5,256,779, No. 5,280,117, No. 5,274,147, No. 5,153,161 and No. 5,227084.

Cobalt Metal Complexes—Cobalt bleach catalysts useful herein are known and are described, for example, in US Pat. Nos. 5,597,936, 5,595,967, and 5,703,030, and M.C. L. Tobe, ML “Base Hydrolysis of Transition-Metal Complexes” (“Adv. Inorg. Bioinorg. Mech. ), 1983, Volume 2, pages 1 to 194). The most preferred cobalt bleach catalyst useful herein is cobalt pentaamine acetate having the formula [Co (NH ₃ ) ₅ OAc] T _y , where “OAc” represents the acetate moiety and “T _y ” Is an anion, especially cobalt pentaamine acetate chloride, [Co (NH ₃ ) ₅ OAc] Cl ₂ ; and [Co (NH ₃ ) ₅ OAc] (OAc) ₂ ; [Co (NH ₃ ) ₅ OAc] ( _{PF 6) 2; [Co (} NH 3) 5 OAc] (SO 4); [Co (NH 3) 5 OAc] (BF 4) 2; and _{[Co (NH 3) 5 OAc} ] (NO 3) 2 ( In this specification, “PAC”).

  These cobalt catalysts are, for example, U.S. Patent Nos. 6,302,921, 6,287,580, 6,140,294, 5,597,936, 5,595, 967 and 5,703,030; and the Tobe paper and references cited therein; and US Pat. No. 4,810,410, “Journal of Chemical Education (J. Chem. Ed.) "(1989) 66 (12) 1043-45; L. Jolly, WL "The Synthesis and Characterization of Inorganic Compounds" (Prentice-Hall, 1970) pages 461-3; "Inorganic Chemistry ( Inorg. Chem.) (1979), 1849-1502; “Inorganic Chemistry” (1982) 21, 2881-2885; “Inorganic Chemistry” (1979) 18, 2023-2025 Taught in “Inorg. Synthesis” (1960) 173-176; and “Journal of Physical Chemistry” (1952) 56-22-25; Are readily prepared by known procedures such as

  Macropolycyclic Rigid Ligand Transition Metal Complex—The composition herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand as a bleach catalyst. The amount used is a catalyst effective amount, suitably 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm to about 500 ppm ( However, “ppb” indicates one billionth by weight, and “ppm” indicates one millionth by weight.

Macrocyclic rigid ligand transition metal bleach catalysts suitable for use in the present invention can include known compounds broadly consistent with the definitions herein, and more preferably of the present invention. Any of the novel compounds explicitly designed for laundry and laundry applications can be included, including:
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)
Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)
Diaqua-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)
Hexafluorophosphate Diaqua-5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) hexafluorophosphate aquo-hydroxy-5,12-dimethyl-1,5 , 8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (III) hexafluorophosphate diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II)
Tetrafluoroborate dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (III) hexafluorophosphate dichloro-5,12-diethyl-1,5,8 , 12-tetraazabicyclo [6.6.2] hexadecane manganese (III)
Hexafluorophosphate Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II)
Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane Manganese (II)
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane Manganese (II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane Manganese (II)
Explicitly specified by any of the above.

  As a practical matter, but not by way of limitation, the compositions and methods herein provide active bleach catalyst species on the order of at least 100 million parts in a composition comprising a lipophilic fluid and a bleach system. Preferably 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 bleach catalyst species and the lipophilic fluid and Provided in a composition comprising a bleach system.

  (D) Bleach-enhancing compounds—The compositions herein may comprise one or more bleach-enhancing compounds. Bleach enhancing compounds provide an enhanced bleaching effect when applied at low temperatures. Bleach enhancers act in conjunction with conventional peroxygen bleach sources to provide enhanced bleaching effects. This is usually accomplished by forming an active oxygen transfer agent such as dioxirane, oxaziridine or oxaziridinium in situ. Alternatively, preformed dioxirane, oxaziridine and oxaziridinium may be used.

Bleach enhancing compounds suitable for use in accordance with the present invention include cationic imines, zwitterionic imines, anionic imines and / or polyionic imines having a net charge of about +3 to about -3 and mixtures thereof There is. These imine bleach enhancing compounds of the present invention include their general structure:
Wherein R ^{1 to} R ⁴ are hydrogen or an unsubstituted or substituted radical selected from the group consisting of a phenyl radical, an aryl radical, a heterocyclic radical, an alkyl radical, and a cycloalkyl radical Good.

  Preferred bleach enhancing compounds include zwitterionic bleach enhancing agents and are described in US Pat. Nos. 5,576,282 and 5,718,614. Other bleach enhancing compounds include U.S. Pat. Nos. 5,360,569, 5,422,066, 5,478,357, 5,370,826, and 5,482. , 515 and 5,550,256 and PCT International Publication Nos. 95/13351, 95/13352, and 95/13353.

  Peroxygen sources are well known in the art, and peroxygen sources employed in the present invention include peroxygen compounds and compounds that provide an effective amount of peroxygen in situ under consumer use conditions, etc. Any of these known sources can be included. Peroxygen source is hydrogen peroxide source, in situ formation of peracid anion by reaction of hydrogen peroxide source and bleach activator, pre-formed peracid compound or suitable peroxygen source Can be included. Of course, those skilled in the art will recognize that other sources of peroxygen can be employed without departing from the scope of the present invention. Bleach enhancing compounds, if present, are preferably employed in conjunction with a peroxygen source in the bleach system of the present invention.

  (E) Pre-formed peracids-Pre-formed peracids are also suitable as bleaching agents. A preformed peracid as used herein is any convenient compound that is stable and provides an effective amount of peracid or peracid anion under consumer use conditions. . The preformed peracid compound can be selected from the group consisting of percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. Examples of these compounds are described in US Pat. No. 5,576,282 (Miracle et al.).

One class of suitable organic percarboxylic acids is of the general formula:
Wherein R is an alkylene or substituted alkylene group containing 1 to 22 carbon atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, —C (O) OH or -C (O) OOH.

Organic peroxyacids suitable for use in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic. When the organic percarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:
Where Y can be, for example, H, CH ₃ , CH ₂ Cl, C (O) OH, or C (O) OOH, and n is an integer from 0-20. When the organic percarboxylic acid is aromatic, the unsubstituted peracid has the general formula:
Where Y can be, for example, hydrogen, alkyl, alkyl halogen, halogen, C (O) OH, or C (O) OOH.

Exemplary monoperoxyacids useful herein include:
(I) peroxybenzoic acid and ring-substituted peroxybenzoic acid, such as peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and o-carboxybenzamide peroxyhexanoic acid (sodium salt),
(Ii) Aliphatic, substituted aliphatic and arylalkyl monoperoxy acids such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-octylsuccinoyl) Aminoperoxycaproic acid (SAPA) and N, N-phthaloylaminoperoxycaproic acid (PAP),
(Iii) Amidoperoxyacids, for example alkyl and arylperoxyacids such as monononylamides of either peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA).

Exemplary diperoxy acids useful herein include:
(I) 1,12-diperoxide decanedioic acid,
(Ii) 1,9-diperoxyazeline acid,
(Iii) diperoxybrassic acid, diperoxysebacic acid and diperoxyisophthalic acid,
(Iv) 2-decyldiperoxybutane-1,4-dioic acid,
(V) 4,4′-sulfonylbisperoxybenzoic acid The following alkyldiperoxyacids and aryldiperoxyacids are mentioned.

  Such bleaches are disclosed in U.S. Pat. Nos. 4,483,781 (Hartman) and 4,634,551 (Burns et al.), European Patent Application No. 0,133,354 ( Banks et al.) And U.S. Pat. No. 4,412,934 (Chung et al.). Sources also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Pat. No. 4,634,551 (Burns et al.). For example, E.I. in Wilmington, Delaware. I. Persulfate compounds such as OXONE commercially produced by E.I. DuPont de Nemours can also be employed as a suitable source of peroxymonosulfuric acid. PAP is disclosed in, for example, US Pat. Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757, and 5,132,431. It is disclosed.

  (F) Photobleaching agents—Photobleaching agents suitable for use in the treatment compositions of the present invention include those described in US Pat. Nos. 4,217,105 and 5,916,481. An agent is mentioned, but it is not limited to these.

  (G) Enzymatic bleach-enzyme systems may be used as bleaching agents. Hydrogen peroxide may also be present, by adding an enzyme system (ie, enzyme and substrate) that can generate hydrogen peroxide at the beginning or during the cleaning and / or rinsing process. Such an enzyme system is disclosed in European Patent Application No. 91202655.6 (filed Oct. 9, 1991).

The compositions and methods of the present invention may utilize alternative bleaching systems such as ozone and chlorine dioxide. Bleaching with ozone can be achieved by introducing an ozone-containing gas having an ozone content of about 20 to about 300 g / m ³ into the solution in contact with the fabric. The “gas: liquid” ratio in the solution should be maintained from about 1: 2.5 to about 1: 6. US Pat. No. 5,346,588 describes a process for the use of ozone as an alternative to conventional bleaching systems, which is incorporated herein by reference.

  The detergent composition of the present invention may include any number of additional optional ingredients. These include non-tinting dyes, detergency builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and / or borax), foam inhibitors, soil suspending agents, soil release. Agents, other fabric care benefit agents, pH adjusters, chelating agents, smectite clays, solvents, hydrophiles and phase stabilizers, structuring agents, dye transfer inhibitors, opacifiers, optical brighteners, fragrances and colorants Conventional laundry detergent composition components such as A variety of optional detergent composition ingredients, when present in the compositions herein, should be utilized at the concentrations conventionally used to provide their desired contribution to the composition or laundry operation. is there. Often the total amount of any such detergent composition components will range from about 0.01% to about 50%, more preferably from about 0.1% to about 30% by weight of the composition. Can do.

  Liquid detergent compositions are in the form of aqueous solutions, uniform dispersions or suspensions of surfactants, brighteners and some other ingredients, some of which may normally be in solid form, Combined with conventional liquid composition components such as non-ionic liquid alcohol ethoxylates, aqueous liquid carriers and any other normal liquid optional components. Such solutions, dispersions or suspensions are phase stable and typically about 0.1 Pa.s. s (100 cps) to 0.6 Pa.s. s (600 cps), more preferably about 0.15 Pa.s. s (150 cps) to 0.4 Pa.s. It has a viscosity in the range of s (400 cps). For purposes of this invention, viscosity is measured with a Brookfield LVDV-II + viscometer using a # 21 spindle.

  The liquid detergent compositions herein can be prepared by combining the compositions in any convenient order and mixing the resulting combination of ingredients, for example by stirring, to provide a phase stable liquid detergent composition Form. In a preferred method of preparing such a composition, including, for example, at least a major portion, preferably substantially all, of a nonionic surfactant, a non-surfactant liquid carrier and any other liquid component, A liquid matrix is formed with liquid components that are thoroughly mixed by subjecting the combination to shear agitation. For example, it may be useful to use high speed stirring with a mechanical stirrer. While any shear agitation is maintained, virtually any anionic surfactant and all of the solid form components can be added. Stirring of the mixture can be continued and increased if necessary to form a solution or homogeneous dispersion of insoluble solid particulate matter within the liquid phase. After some or all of the solid form material is added to the stirred mixture, particles of any enzyme material to be included, such as the enzyme prill, are incorporated. As a variation of the composition preparation method described above, one or more solid components may be added to the stirred mixture as a solution or slurry of particles premixed with a minor component portion of one or more liquid components. After all composition components have been added, stirring of the mixture is continued for a time sufficient to form a composition having the necessary viscosity and phase stability characteristics. Often this involves agitation for about 30-60 minutes.

  In an alternative embodiment for forming a liquid detergent composition, the brightener is first combined with one or more liquid ingredients to form a brightener premix, the brightener premix comprising a substantial portion. For example, greater than 50% by weight, more specifically greater than 70% by weight, and more specifically greater than 90% by weight, to a composition formulation containing the remainder of the laundry detergent composition. For example, in the method described above, both the brightener premix and the enzyme component are added at the final stage of component addition. In a further embodiment, the brightener is encapsulated before being added to the detergent composition, and the encapsulated brightener is suspended in a structured liquid, Added to the composition formulation containing a substantial portion of the remaining components of the laundry detergent composition.

  As noted before this, the detergent composition may be in solid form. Suitable solid forms include tablet forms and particulate forms such as granular particles or flakes. Various techniques for forming such solid form detergent compositions are well known in the art and may be used herein. In one embodiment, for example, where the composition is in the form of particulate particles, the brightener is provided in particulate form, which optionally includes additional but not all ingredients of the laundry detergent composition. To do. The brightener particles are combined with one or more additional particles that contain the remaining components of the laundry detergent composition. Further, the brightener optionally includes additional but not all ingredients of the laundry detergent composition and may be provided in an encapsulated form, wherein the brightener encapsulation is a laundry detergent composition. In combination with particles containing a substantial balance of the components.

  The compositions of the present invention prepared as described above can be used to form aqueous cleaning solutions for use in fabric laundering. In general, to form such an aqueous laundry solution, an effective amount of such a composition is added to water, preferably water in a conventional fabric laundry automatic washing machine. The aqueous cleaning solution thus formed is then contacted with the fabric to be washed, preferably under agitation. An effective amount of a liquid detergent composition herein added to water to form an aqueous laundry solution includes an amount sufficient to form a 500-7,000 ppm composition in the aqueous cleaning solution. It's okay. More preferably, 1,000 to 3,000 ppm of the detergent composition will be provided in the aqueous cleaning solution herein.

Fabric Care Composition / Rinse-Adding Fabric Softening Composition In another specific embodiment, the brightener of the present invention may be included in a fabric care composition. The fabric care composition may consist of at least one brightener and a rinse-added fabric softening composition ("RAFS", also known as a rinse-added conditioning composition). An example of a typical rinse added softening composition can be found in US Provisional Patent Application No. 60/687582 (filed Oct. 8, 2004). The rinse-added fabric softening composition of the present invention may comprise (a) a fabric softening activator and (b) a thiazolium dye. The rinse-added fabric softening composition may comprise from about 1 wt% to about 90 wt% FSA, more preferably from about 5 wt% to about 50 wt% FSA. The brightener may be present in the rinse-added fabric softening composition in an amount from 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 (hereinafter “FSA”) is a quaternary ammonium compound suitable for softening the fabric in the rinsing process. In one embodiment, FSA is formed from the reaction product of a fatty acid and an aminoalcohol, resulting in mono-, di- and triester compounds in one embodiment. In another embodiment, the FSA is one or more flexible, such as, but not limited to, monoalky quaternary ammonium compounds, diamide quaternary compounds and diester quaternary ammonium compounds or combinations thereof. Containing quaternary ammonium compounds.

  In one aspect of the invention, the FSA comprises a diester quaternary ammonium (hereinafter “DQA”) compound composition. In certain embodiments of the present invention, the composition of the DQA compound also includes diamide FSAs and mixed amide and ester linkages, as well as the types of FSAs having the aforementioned diester linkages, all of which are described herein. This is called DQA.

A first type of DQA (“DQA (1)”) suitable as FSA in this CFSC has the formula:
^{_{{R 4-m -N + -}} [(CH 2) n -Y-R 1] m} X -
Wherein each R substituent is hydrogen, a short chain C ₁ -C ₆ , preferably a C ₁ -C ₃ alkyl or hydroxyalkyl group such as methyl (most preferred), ethyl, propyl, such as hydroxyethyl, poly (C _{2 to 3} alkoxy) are either 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 each Y is the same. Or the sum of carbons in each R ¹ (plus one when Y is —O— (O) C— or —NR—C (O) —) is C ₁₂ -C ₂₂ , preferably a _C 14 _{-C 20,} each ^{R 1} is hydrocarbyl or substituted hydrocarbyl And a, R ¹ may be unsaturated or saturated and branched or straight chain, preferably straight-chain, each R ¹ may also be the same or different, preferably these same X ⁻ is any softener compatible anion, preferably chloride ion, bromide ion, methyl sulfate ion, ethyl sulfate ion, sulfate ion, phosphate ion or nitrate ion, more preferably chloride ion. Alternatively, methyl sulfate ion can be used, and chloride ion or methyl sulfate ion is more preferable. Preferred DQA compounds are typically prepared by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials typically obtained from such reactions include N, N-di (acyl-oxyethyl) -N, N-dimethylammonium chloride or N, N-di (acyl-oxyethyl) -N, N -Methyl hydroxyethylammonium methyl sulfate, wherein the acyl group is derived from animal fats, unsaturated and polyunsaturated fatty acids such as tallow, hardened tallow, oleic acid and / or partially hardened fatty acids, vegetable oils and Also derived from partially hardened vegetable oils such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil and the like.

  Non-limiting examples of suitable fatty acids are listed in US Pat. No. 5,759,990, 4th row, lines 45-66. In one embodiment, the FSA includes other active agents in addition to DQA (1) or DQA. In yet another embodiment, the FSA comprises only DQA (1) or DQA and is free or substantially free of any other quaternary ammonium compound or other active agent. In yet another embodiment, the FSA comprises a precursor amine that is used to produce DQA.

In another aspect of the invention, the FSA has the formula:
^{_{[R 4-m -N (+}} ) -R 1 m] A -
Wherein each m is 2 or 3 and each R ¹ is C ₆ -C ₂₂ , preferably C ₁₄ -C ₂₀ (but less than about C ₁₂ ) the is 1 or less, the other is at least about 16) hydrocarbyl, or substituted hydrocarbyl substituent, preferably also be referred to as C ₁₀ -C ₂₀ alkyl or alkenyl ( "alkylene", a polyunsaturated alkyl Including unsaturated alkyl), most preferably C ₁₂ -C ₁₈ alkyl or alkenyl, branched or unbranched. In one embodiment, the iodine number (IV) of FSA is about 1-70, and each R is H or a short chain C ₁ -C ₆ , preferably a C ₁ -C ₃ alkyl or hydroxyalkyl group such as methyl ( Most preferred), such as ethyl, propyl and hydroxyethyl, such as benzyl or (R ² O) _2-4 H, each R ² is a C _1-6 alkylene group, A ⁻ is a softener compatible anion, preferably It is chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate or nitrate, more preferably chloride or methyl sulfate.

  Examples of these FSAs include dialkyl dimethyl ammonium salts and dialkylene dimethyl ammonium salts, such as ditallow dimethyl ammonium and ditallow dimethyl ammonium methyl sulfate. Examples of commercially available dialkylenedimethylammonium salts that can be used in the present invention include di-hydrogenated tallowdimethylammonium chloride and ditallowdimethylammonium chloride (Adogen® 442 and Adgen® 470, respectively). (Available from Degussa). In one embodiment, the FSA includes other active agents in addition to DTTMAC. In yet another embodiment, the FSA includes only the DTTMAC compound and is free or essentially free of any other quaternary ammonium compound or other active agent.

  In one embodiment, the FSA comprises the FSA described in U.S. Patent Application Publication No. 2004/0204337 A1 (Corona et al., Published Oct. 14, 2004, paragraphs 30-79). In another embodiment, the FSA is disclosed in U.S. Patent Application Publication No. 2004/0229769 A1 (Smith et al., Published November 18, 2005, paragraphs 26-31) or U.S. Pat. No. 6,494,920 ( 1st line, see line 51 and below), specifically “ester quats” or quaternized fatty acid triethanolamine ester salts.

  In one embodiment, the FSA is ditallow oil oxyethyl dimethyl ammonium chloride, dihydrogenated tallow oil oxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallow oil oxyethyl dimethyl ammonium methyl sulfate, dihydrogen tallow oil oxy. It is selected from at least one of ethyl dimethyl ammonium chloride, dihydrogenated tallow oil oxyethyl dimethyl ammonium chloride, or combinations thereof.

  In one embodiment, the FSA may also include a composition of amide-containing compounds. Examples of compounds containing diamide include methyl-bis (tallowamidoethyl) -2-hydroxyethylammonium methyl sulfate (available under the trade names Varisoft 110 and Balisoft 222 from Degussa) Good but not limited to them. An example of an amide ester-containing compound is N- [3- (stearoylamino) propyl] -N- [2- (stearoyloxy) ethoxy) ethyl)]-N-methylamine. Another specific embodiment of the present invention provides a rinse-added fabric softening composition further comprising cationic starch. Cationic starch is disclosed in U.S. Patent Application Publication No. 2004/0204337 A1. In one embodiment, the rinse-added fabric softening composition comprises from about 0.1% to about 7% cationic starch by weight of the fabric softening composition. In one embodiment, the cationic starch is HCP401 from National Starch.

Suitable Laundry Care Ingredients Although not essential for the purposes of the present invention, the non-limiting list of laundry care ingredients exemplified below is suitable for use in a laundry care composition, eg, assisting or improving performance. In order to modify the aesthetics of the composition, such as for the treatment of substrates to be cleaned or when using fragrances, colorants and dyes, etc. Good. It is understood that such components are in addition to the components listed above for any particular embodiment. The total amount of such adjuvants may range from about 0.1% to about 50% or even from about 1% to about 30% by weight of the laundry care composition.

  The exact nature of these additional ingredients and the concentration at which they are incorporated will depend on the physical form of the composition and the nature of the work to be used. Suitable laundry care ingredients include polymers such as cationic polymers, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic agents, bleach activators, polymers. Dispersants, clay soil removal / anti-redeposition agents, brighteners, foam suppressants, dyes, additional perfumes and perfume delivery systems, structural elasticizers, softeners, carriers, hydrophiles, processing aids and / or Examples include, but are not limited to, pigments. In addition to the disclosure below, suitable examples and concentrations of such other adjuvants are disclosed in US Pat. Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1. Which are incorporated by reference.

  As noted above, laundry care ingredients are not essential to Applicants' cleaning and laundry care compositions. Accordingly, certain embodiments of Applicants' compositions include the following auxiliary substances: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, Catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, foam inhibitors, dyes, additional perfumes and perfume delivery systems, structural elasticizers, softeners, carriers, hydrophiles, Does not contain one or more processing aids and / or pigments. However, when one or more adjuvants are present, the one or more adjuvants may be present as described in detail below.

  Surfactant-The composition according to the invention can comprise a surfactant or a surfactant system, the surfactant being a nonionic and / or anionic and / or cationic surfactant and / or amphoteric. And / or can be selected from bipolar and / or semipolar nonionic surfactants. The surfactant is typically from about 0.1%, from about 1% or even from about 5% by weight of the cleaning composition to about 99.9% by weight of the cleaning composition, about 80%. It is present in a concentration of up to about 50%, up to about 35% or even up to about 30%.

  Builders—The compositions of the present invention can include one or more detergent builders or builder systems. When present, the composition typically comprises at least about 1% by weight builder or about 5% or 10% to about 80%, 50% or even 30% by weight builder. . Builders include polyphosphates such as alkali metal, ammonium and alkanol ammonium salts, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders, polycarboxylate compounds, ether hydroxy polycarboxylates, maleic anhydride Of various polyacetic acids such as copolymers of ethylene with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid Alkali metal, ammonium and substituted ammonium salts thereof, as well as merit acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and these It includes polycarboxylate such as soluble salts but not limited thereto.

  Chelating Agents—The compositions herein may also optionally contain one or more copper, iron and / or manganese chelating agents. When used, the chelating agent is generally from about 0.1% to about 15% by weight of the composition herein, or even from about 3.0% to about 15% by weight of the composition herein. Configure.

  Anti-transfer agents—The compositions of the present invention may also include one or more anti-transfer agents. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinyl oxazolidone and polyvinyl imidazole or mixtures thereof. Not. When present in the compositions herein, the dye transfer inhibitor is present from about 0.0001% to about 0.01% to about 0.05% by weight of the cleaning composition. It is present at a concentration of up to about 10%, up to about 2% or even up to about 1%.

  Dispersants—The compositions of the present invention can also include a dispersant. Suitable water-soluble organic materials are homopolymer or copolymer acids or salts thereof, of which the polycarboxylic acid has at least two carboxyl groups separated by no more than two carbon atoms from each other. May include.

  The enzyme-composition can include one or more detersive enzymes that provide a cleaning performance effect and / or a fabric care effect. Examples of suitable enzymes include hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, Examples include, but are not limited to, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase and amylase or mixtures thereof. A typical combination is a mixture of conventional applicable enzymes such as protease, lipase, cutinase and / or cellulase combined with amylase.

  Enzyme stabilizers—Enzymes for use in compositions, such as detergents, can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of a water-soluble source of calcium and / or magnesium ions in the final composition that provides calcium and / or magnesium ions to the enzyme.

  Catalytic metal complexes-Applicants' compositions may include catalytic metal complexes. One type of metal-containing bleaching catalyst is a bleaching catalyst, such as a transition metal cation of limited bleaching catalytic activity, such as a cation of copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese, a cation of zinc or aluminum Sequestrates with defined stability constants for auxiliary metal cations with little or no activity and catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) And a catalyst system containing these water-soluble salts. Such a catalyst is disclosed in US Pat. No. 4,430,243.

  If desired, the compositions herein can be catalyzed with manganese compounds. Such compounds and concentrations used are well known in the art and include, for example, manganese-based catalysts disclosed in US Pat. No. 5,576,282.

  Cobalt bleach catalysts useful herein are known and are described, for example, in US Pat. Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as those taught in US Pat. Nos. 5,597,936 and 5,595,967.

  The compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand (abbreviated “MRL”). As a practical matter, but not by way of limitation, the compositions and cleaning methods herein may be tailored to provide a benefit agent MRL species on the order of at least one hundred million in aqueous cleaning media. And MRL can be set in the cleaning solution 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.

  Preferred transition metals in the transition metal bleach catalyst include manganese, iron and chromium. A preferred MRL herein is a specific type of ultra-rigid ligand that is bridged, such as 5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane.

  Suitable transition metal MRLs are readily manufactured by known procedures, such as those taught in PCT International Publication No. 00/32601 and US Pat. No. 6,225,464.

The following examples are provided to further illustrate the novel brighteners of the present invention, which should be construed as limiting the invention as defined in the appended claims. is not. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. All parts and percentages given in these examples are by weight unless otherwise indicated. All values of the Hansen solubility parameter reported herein are expressed in units of ^0.5 MPa.

Sample Preparation and Test Methods A. Sample Preparation 0.5 grams of brightener (0.1% by weight based on the weight of the cellulose substrate) in a solution containing 3 grams of powdered laundry detergent (AATCC powder laundry detergent) and 500 mL of room temperature water. Each sample is prepared by adding. Correct each colorant load for absorbance to ensure equal color units. The blend is then combined with 50 grams of cellulose powder (available from Aldrich) and the mixture is stirred for 10 minutes. Next, the mixture is filtered to separate the cellulose particles from the liquid, and the cellulose particles are allowed to air dry. As described above, both cellulose particles and liquid are measured for color using a Gretag Macbeth Color Eye 7000A spectrometer.

  Next, the cellulose particles are placed in a container containing 500 mL of tap water and stirred for 10 minutes. The mixture is filtered to separate the cellulose particles from the liquid and the cellulose particles are again air dried. Using a Gretag Macbeth Color Eye 7000A spectrometer, both cellulose particles and liquid are measured again for color. A control sample is also prepared containing untreated cellulose particles (no brightener added).

The brighteners shown in Tables 1A and 1B are prepared as described herein and tested for various parameters. All violet colorants are synthesized according to the procedure disclosed in US Pat. No. 4,912,203 (Kluger et al.). Note that ethylene oxide, propylene oxide, and butylene oxide are indicated below by their typical notations "EO", [PO], and [BO], respectively. The average length and composition of the polymeric components of the brighteners of Tables 1A and 1B are obtained by the following formula: (Block 1 + Block 2 + Block 3) / (Number of chains). For example, the average structure of violet thiophene_5EO (Violet thiophene-5EO) consists of a thiophene chromophore having two chains on nitrogen, one corresponding to 3EO and one corresponding to 2EO. Chain caps are present on all polymeric components.
(A) Add EO group to terminal OH group.
(A) Add EO group to terminal OH group.

B. Whiteness Calculation: CIELab b ^* values and Ganz and CIE Whiteness Index The Whiteness Index ("WI") includes three components of color measurement-Hue, Saturation and Lightness-and is a standard It is an evaluation of the suitability of color calculated by an expression that also serves as an index of white value. Several whiteness formulas can be used to measure the whiteness of cellulosic substrates. Two common formulas are the Ganz Whiteness Index and the CIE Whiteness. The Ganz whiteness index is represented by the following formula: WI = (D × Y) + (P × x) + (Q × y) + C, where Y, x and y are colorimetric values, D, P, Q and C are formula parameters. CIE whiteness is represented by the following formula: WI = Y− (800 × x) − (1700 × y) +813.7, where Y, x and y are colorimetric values. Further information is available from the publication Rolf Griesser (Ciba-Geigy Ltd) "Whiteness and Tint" (June 1993).

A series of measurements -L ^* , a ^* and b ^* -obtained by measuring a sample using a spectroscopic analyzer may be used to quantify the surface color of the article. The instrument used for this test is a Gretag Macbeth Color Eye 7000A spectrometer. The software program used is “Color imatch”. “L” is a measure of the amount of white or black in the sample, with a higher “L” value indicating a lighter color sample. The measured value of the amount of red or green in the sample is measured by the “a ^* ” value. A measure of the amount of blue or yellow in the sample is measured with a “b ^* ” value, and a lower (more negative) b ^* value indicates that there is more blue in the sample.

  Yet another measure for the relative color of the substrate is DE CMC. DE CMC is a measure of the overall color difference for the entire uniform color space, and DE CMC represents the absolute value of the difference between the color and the reference color (in this case, the pure white standard). The higher the DE CMC value, the more obvious the color difference. In other words, a smaller DE CMC value represents a color closer to white. The Gretag Macbeth Color Eye 7000A spectrophotometer calculates DE CMC values for each sample based on wavelength and reflectance data.

C. Calculation of molecular properties Material Studio molecular modeling software (available from Accelrys, Inc.) derives the average structure of each of the brighteners of the present invention. The shape of each structure is optimized by a Forcite module using a semi-empirical universal force field and a charge balance method (Qeq) charge configuration system. In contrast to the average N = N bond distance of 1.25 angstroms, the N = N bond of the diazo colorant is calculated to be about 1.270-1.275 angstroms. These values are calculated for the diphenyldiazo dye by the Gaussian 98 software package and the B3LYP / 6-311G method (Liu, Jun-na et al. (Liu, Jun -na), Chen, Zhi-rong and Yuan, Shen-feng “Journal of Zhejiang University Science” (6B (6), 2005) 584-589), i.e. slightly shorter than about 1.3 angstroms.

  After the shape optimization of the entire structure, various descriptors are calculated. Descriptors are in the following categories: Structure, 2. Function, 3. Energy, 4. 4. Topological, Space and 6. It can be classified into thermodynamics.

Except for the total number of EO and PO groups on the chromophore, the Hansen solubility parameter (Solubility-parameter) and the hydrophilic-lipophilic balance value (MW_HLB), all descriptors are software) QSAR module, the latter two parameters are calculated by ChemSW's Molecular Modeling Pro software, with descriptors as potential predictors of the affinity of brighteners for cellulose substrates. Table 2. Table 2 summarizes some of the test parameters used to characterize the brighteners of the present invention.

Test Results Test 1: CIELab the ^{b *} values and Ganz (Ganz) whiteness of whiteness test CIELab measured by index ^{b *} values and Ganz (Ganz) whiteness index ( "Ganz WI") values in order to measure Examples 1-14 and Reference Examples 15-17 are tested for whiteness. The test results are shown in Table 3. Lower (more negative) CIELab b ^* values and higher Gantz WI values indicate that the treated cellulose particles are developing a greater bluing or whitening effect.

The test results show that Example 2 containing 5 ethylene oxide repeat units and Example 12 containing 1 glycidol unit perform best under these test conditions. The data reveals a relatively linear correlation between CIELab b ^* values and Gantz WI values. A linear regression that fits all data points has a regression value of R ² = 0.988.

Test 2: In order to measure the variance term value of ^{b *} values and Hansen parameters measured CIELab the dispersion term value of ^{b *} values and Hansen parameters CIELab, Test Examples 1-14 and Reference Examples 15 to 17 To do. Note that Examples 1-14 contain a violet thiophene chromophore, while Reference Examples 15-17 contain a triphenylmethane colorant. Examples 18-25 are tested to measure only the dispersion term value of the Hansen solubility parameter.

The test results are shown in Table 4. Larger negative CIELab b ^* values indicate that the treated cellulose particles are developing a greater bluing or whitening effect. “N / A” indicates that data is not available.

The test results reveal that there is a relatively linear correlation between the bluing parameter, CIELab b ^* value and the Hansen solubility parameter dispersion term value. The color value b ^* decreases linearly (ie, the bluing effect increases) as δ _d decreases.

Linear regression fits all data points and has a regression value of R ² = 0.763. The regression line has the following equation:
b_blue tinting = 0.9704 × δ _d −22.468 (2)
Test 3: CIELab b ^* Value Prediction Based on Hansen Solubility Parameter Dispersion Term Value Examples 1-10 and Reference Examples 15-17 are first used to train a model based on the Hansen solubility parameter dispersion term value. . CIELab b ^* values are calculated for these examples using Equation 3 below, which utilizes the dispersion term value obtained after one rinse cycle:
b_blue tinting = 1.0014 × δ _d −23.02 (3)
This equation is very similar to Equation 2 and is derived using all examples. The model represented by Equation 3 is also valid for Examples 11-14. Using Equation 3, the CIELab b ^* values for the molecules of Examples 11-14 are predicted before these molecules are synthesized and tested for whitening effects. The CIELab b ^* predicted value obtained from Equation 3 is compared to the measurements previously obtained from the Gretag Macbeth Color Eye 7000A spectrometer. Also determine the percentage difference between the b ^* measured color value and the b ^* predicted color value.

For Comparative Examples 1 and 2, the dispersion term value and CIELab b ^* predicted value are also measured. Comparative Example 1 is a blue polymeric anthraquinone dye disclosed in Example III of US Pat. No. 4,127,243 (Farmer). Comparative Example 2 is Basic Violet 3 disclosed in Table 2 of US Patent Application Publication No. 2005/0288206 (Sadlowski et al.).

The test results are shown in Table 5 and FIG. “N / A” indicates that data is not available.

  To verify that the model can demonstrate the effect of the polymer chain end cap, Example 11 (violet thiophene_5EO_COCH3) and Example 12 (violet thiophene_glycidol) are synthesized and tested. Example 12 has 4 hydroxyl groups, while the brightener with EO and PO end groups has only 2 hydroxyl groups. Example 11 has approximately the same size as Example 12, but the acetate cap is less polar than the OH group.

FIG. 1 shows a graphical representation of the data. In FIG. 1, the term “violet thiophene” is indicated as “violet” and “triphenylmethane” is indicated as “TPM”. Data points represent CIELab b ^* measured color values. The solid line represents Equation 3 which is the prediction data. The linear correlation between the color values b ^* and δ _d suggests that the smaller the molecule, the stronger the adhesion on the cellulose powder. The size of the brightener compound can affect the ability of the brightener compound to approach and diffuse into the pores of the cellulose powder. In addition, brighteners with a more polar cap on the molecular chain or brighteners with more polar end groups showed a greater bluing effect. Calculations also indicate that triphenylmethane-containing brighteners are preferred brighteners.

Exemplary Detergent Formulations Formulations 1a-1l: Liquid Detergent Formulations Tables 6A and 6B provide examples of liquid detergent formulations that include at least one brightener of the present invention. Formulations are shown as Formulations 1a-1f in Table 6A and 1g-1l in Table 6B.
Footnotes for formulations 1a-1:
¹ Diethylenetriaminepentaacetic acid, sodium salt
² Diethylenetriaminepentakis methylenephosphonic acid, sodium salt
³ Ethylenediaminetetraacetic acid, sodium salt
⁴ Non-tint pickled dyes used for blending colors regulatory (non-tinting dye)
⁵ Compact formulation packaged as unit dose in polyvinyl alcohol film
⁶ Alkoxylated anthraquinone colorant having a hue efficiency greater than 10 and a wash-off rate of 30-85%
⁷ Alkoxylated thiophene colorant having a hue efficiency greater than 10 and a wash-off rate of 30-85%
⁸ Alkoxylated triphenylmethane colorant having a hue efficiency greater than 10 and a wash-off rate of 30-85%
⁹ Acusol OP301
Formulations 2a-2e: Granular detergent formulations Table 7 provides examples of powdered detergent formulations including at least one brightener of the present invention. In Table 7, the blends are shown as blends 2a to 2e.

Exemplary Fabric Care Composition Formulations 3a-3d: Liquid Fabric Care Composition Table 8 provides examples of liquid fabric care compositions that include at least one brightener of the present invention. In Table 8, a composition is shown as compounding 3a-3d.
^a N, N-di (tallow oil oxyethyl) -N, N-dimethylammonium chloride.
^b Normal maize 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 water flow having a value of 50 to 84 Cationic starch based.
^c A copolymer of ethylene oxide and terephthalate having the formula described in US Pat. No. 5,574,179, column 15, lines 1-5, wherein each X is methyl and each n Is 40, u is 4, each R ¹ is essentially a 1,4-phenylene moiety, and each R ² is essentially an ethylene, 1,2-propylene moiety or mixtures thereof.
^d Diethylenetriaminepentaacetic acid.
^e KATHON® CG available from Rohm and Haas Co.
^f Silicone defoamer available from Dow Corning Corp. under the trade name DC2310.
^g 4,4′-bis- (2-sulfostyryl) biphenyl disodium available from Ciba Specialty Chemicals.
^h Cocomethylethoxylated [15] ammonium chloride available from Akzo Nobel.

Accordingly, the present invention provides a cellulosic whitening agent comprising at least one chromophore component comprising a thiophene or triphenylmethane colorant and at least one polymeric component, the whitening agent comprising: About 17 MPa with a Hansen solubility parameter dispersion term value of ^0.5 or less. Laundry detergents containing such brighteners are also contemplated herein.

The whitening agent of the present invention includes a whitening agent for a cellulose substrate containing at least one chromophore component containing a thiophene colorant and at least one polymeric component. Construction:
Wherein R ₁ and R ₂ are
_{a) [(CH 2 CR'HO)} x (CH 2 CR "HO) y H]
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O ) Selected from the group consisting of _z H and mixtures thereof, x + y ≦ 5, y ≧ 1, z = 0-5),
b) R ₁ = alkyl, aryl or arylalkyl and R ₂ = [(CH ₂ CR′HO) _x (CH ₂ CR ″ HO) _y H]
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O ) Selected from the group consisting of _z H and mixtures thereof, x + y ≦ 10, y ≧ 1, z = 0-5)
_{c) R 1 = [CH 2} CH 2 (OR 3) CH 2 OR 4] _{and, R 2 = [CH 2 CH} 2 (OR 3) CH 2 OR 4]
Wherein R ₃ is selected from the group consisting of H, (CH ₂ CH ₂ O) _z H and mixtures thereof, z = 0-10.
R ₄ is selected from the group consisting of (C ₁ -C ₁₆ ) alkyl, aryl groups and mixtures thereof) and d) R1 and R2 are styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, An amino addition product of t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether and glycidyl hexadecyl ether can be independently selected and further independent of those adding 1 to 10 alkylene oxide units. Can be selected.

A potentially preferred whitening agent of the present invention includes a cellulosic whitening agent comprising at least one chromophore component comprising a thiophene colorant and at least one polymeric component. The agents are:
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O ( CH ₂ CH ₂ O) _z H and a mixture thereof, selected from x + y ≦ 5, y ≧ 1, and z = 0-5.

Furthermore, the present invention provides brighteners characterized by CIELab b ^* color values (“b”) and Hansen solubility parameter dispersion term values (“δ _d ”), wherein “b” and “δ _d ” Are substantially linearly correlated with each other according to the following equation: b = 1.00 (δ _d ) −23. Laundry detergents containing such brighteners are also contemplated herein.

  It is therefore considered to be an advantage of the present invention to employ a predictive model to assist in the selection of chromophore-containing compounds that are ideally suited as brighteners. The test results provided herein teach that the adhesion of the brightener on the cellulose powder can be at least partially adjusted by the size of the brightener compound and by its chain cap functionality. Has a tendency. Test results also indicate that larger molecules may be too bulky to diffuse into the pores of the cellulose powder, which may reduce the whitening effect after multiple washing and / or rinsing cycles. Also suggest.

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

Claims (12)

A laundry care composition comprising a laundry care component and a brightener, wherein the brightener is (a) at least one chromophore component comprising a thiophene colorant;
(B) at least one polymeric component;
The brightener has the following structure:
Wherein R ₁ and R ₂ are
_{a) [(CH 2 CR'HO)} x (CH 2 CR "HO) y H]
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O). _z H and selected from the group consisting of these, x + y ≦ 5, y ≧ 1, and z = 0-5),
b) R ₁ = alkyl, aryl or arylalkyl and R ₂ = [(CH ₂ CR′HO) _x (CH ₂ CR ″ HO) _y H]
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O). _z H and selected from the group consisting of these, x + y ≦ 10, y ≧ 1, z = 0-5),
c) R ₁ = [CH ₂ CH ₂ (OR ₃ ) CH ₂ OR ₄ ] and R ₂ = [CH ₂ CH ₂ (OR ₃ ) CH ₂ OR ₄ ]
Wherein R ₃ is selected from the group consisting of H, (CH ₂ CH ₂ O) _z H and mixtures thereof, z = 0-10.
R ₄ is selected from the group consisting of (C ₁ -C ₁₆ ) alkyl, aryl groups and mixtures thereof) and d) R1 and R2 are styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, t- Can be independently selected from amino addition products of butyl glycidyl ether, 2-ethylhexyl glycidyl ether and glycidyl hexadecyl ether, and further independently selected from those adding 1 to 10 alkylene oxide units. A laundry care composition that can.   The laundry care composition of claim 1, wherein the brightener comprises a polyoxyalkylene chain having 2 to 20 repeating units.   A laundry care composition according to claim 1 or 2, wherein the whitening agent comprises at least two hydroxyl groups.   4. A laundry care composition according to claim 3, wherein the hydroxyl group is a primary hydroxyl moiety.   The laundry care composition according to any one of claims 1 to 4, wherein the whitening agent comprises an alkoxylated thiophene polymeric colorant. The laundry care composition according to any one of claims 1 to 5, wherein the whitening agent has a Hansen solubility parameter dispersion term value of 17 MPa ^0.5 or less. The laundry care composition of claim 6, wherein the whitening agent has a Hansen solubility parameter dispersion term value of 12-17 MPa ^0.5 .   The laundry care composition according to any one of the preceding claims, wherein the brightener chromophore exhibits an absorption spectrum in water of 520 nanometers to 640 nanometers.   A laundry care composition according to any preceding claim, wherein the brightener chromophore exhibits an emission spectrum of 400 nanometers to 480 nanometers in water. A laundry care composition comprising a laundry care component and a whitening agent, wherein the whitening agent comprises:
(A) at least one chromophore component comprising a thiophene colorant;
(B) at least one polymeric component;
The brightener has the following structure:
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ A laundry care composition selected from the group consisting of CH ₂ O) _z H and mixtures thereof, wherein x + y ≦ 5, y ≧ 1, and z = 0-5. The laundry care composition of claim 10 , wherein the brightener comprises a polyoxyalkylene chain having 2 to 20 repeat units. The laundry care composition according to claim 11 , wherein the brightener comprises a polyoxyalkylene chain having 4 to 6 repeating units.