carboxylate dyes

专利摘要:
"CARBOXYLATE DYES" This application refers to carboxylate dyes suitable for use in tissue protection compositions and tissue treatment.
公开号:BR112014023153B1
申请号:R112014023153-2
申请日:2013-03-19
公开日:2021-02-23
发明作者:Gregory S. Miracle；Eduardo Torres
申请人:Milliken & Company；The Procter & Gamble Company；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to carboxylate dyes suitable for use in laundry compositions and in the treatment of fabrics. BACKGROUND OF THE INVENTION
[002] As textile substrates age, their color tends to fade or yellow due to exposure to light, air, soil and the natural degradation of the fibers that comprise the substrates. To counteract this unwanted effect, laundry detergent manufacturers incorporate shading dyes into their products. The purpose of shading dyes is typically to neutralize the fading and yellowing of textile substrates by providing a blue-violet tint to the washed fabrics, reducing the visual impact of yellowing. There are several descriptions of shading dyes in detergents. However, formulating detergent compositions with shading dyes is challenging: not only do the compositions need to give the product a good look, they also need to deposit the shading dyes evenly on the fabrics during the treatment step and provide a consistent shade to the product. throughout the product life cycle. SUMMARY OF THE INVENTION
[003] This invention relates to a laundry composition comprising between 0.00001% by weight to 0.5% by weight of a carboxylate dye that has the formula 1 structure:

[004] where D is a dye portion selected from benzodifurans, methines, triphenylmethanes, naphthalimides, pyrazoles, naphthoquinines, anthraquinones and mono- and di-azo dyes and mixtures thereof, azo dyes being particularly preferred, but DH compound preferably has a maximum extinction coefficient greater than about 1000 liters / mol / cm at Àmax in the wavelength range from 400 nm to 750 nm in methanol solution, preferably a maximum extinction coefficient between about 20,000 to about 100,000 liters / mol / cm at Àmax in the wavelength range from about 540 nm to about 630 nm and most preferably a maximum extinction coefficient between about 20,000 to about 65,000 liters / mol / cm at Àmax in the wavelength range from about 560 nm to about 610 nm; and
[005] L is an organic bonding group which preferably has a molecular weight of 14 to 1000 Daltons or 14 to 600 or 28 to 300, preferably consisting essentially only of C, H and optionally additionally O and / or N and na sequence of bonds starting from the carbonyl carbon of the group C (O) OM and ending in the dye portion, any groups - (Ca (O) -Ob) - are incorporated such that the oxygen atom Ob is found before of the carbonyl Ca carbon, preferably L is a C1-20 alkylene chain which optionally has ether (-O-) and / or ester and / or amine bonds in it, the chain being optionally substituted, for example, with - OH, -CN, -NO2, -SO2CH3, -Cl, -Br; and M is any suitable counterion, typically a hydrogen, sodium or potassium ion.
[006] In one aspect of the invention, L can comprise Formula 2:

[007] The present invention also comprises a method of treating a textile, the method comprising the steps of (i) treating a textile with an aqueous solution comprising an adjunct for protecting clothing and between 1 ppb to 500 ppm of a dye carboxylate; and (ii) rinsing and drying the textile, the carboxylate dye comprising a dye that has a Formula 1 structure above. DETAILED DESCRIPTION OF THE INVENTION DEFINITIONS
[008] As used herein, the term "alkoxy" is intended to include C1-C8 alkoxy and polyoxy alkoxy derivatives that have repeated units such as butylene oxide, glycidol oxide, ethylene oxide or propylene oxide.
[009] As used herein, unless otherwise specified, the terms "alkyl" and "coated alkyl" are intended to include the C1-C18 alkyl groups and, in another aspect, C1-C6 alkyl groups.
[0010] As used herein, unless otherwise specified, the term "aryl" is intended to include groups C3-C12 aryl.
[0011] As used herein, unless otherwise specified, the term "arylalkyl" is intended to include the C1-C18 alkyl groups and, in another aspect, C1-C6 alkyl groups.
[0012] The terms "ethylene oxide", "propylene oxide" and "butylene oxide" can be shown here by their typical designations "EO", "PO" and "BO", respectively.
[0013] As used herein, the term "laundry composition" includes, unless otherwise indicated, washing agents of the granular, powder, liquid, gel, paste, unit dose, bar-shaped and / or flake and / or fabric treatment compositions, including, but not limited to fabric washing products, fabric softening compositions, fabric improving compositions, fabric renewing compositions and other care and care products maintenance of fabrics and their combinations. Such compositions can be pre-treatment compositions for use before a washing step or it can be a rinse added to the compositions, as well as cleaning aids, such as bleaching additives and / or "stain remover" or pre-treatment compositions or products loaded with substrate such as softener towels added to the dryer.
[0014] As used herein, the term "detergent composition" is a subgroup of compositions for the protection of clothing and includes, but is not limited to, products for washing fabrics. Such compositions can be a pre-treatment composition for use prior to a washing step or it can be a rinse added to the compositions, as well as cleaning aids, such as bleach and stain remover or pre-treatment additives.
[0015] As used herein, "cellulosic substrates" are intended to include any substrate that comprises at least the majority by weight of cellulose. Cellulose can be found in wood, cotton, linen, jute and hemp. Cellulosic substrates can be in the form of powders, fibers, pulp and articles formed by powders, fibers and pulp. Cellulosic fibers include, without limitation, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacate) and mixtures thereof. Articles formed from cellulose fibers include textile articles such as fabrics. Articles formed from the pulp include paper.
[0016] As used here, the term "maximum extinction coefficient" is intended to describe the molar extinction coefficient at the maximum absorption wavelength (also referred to here as maximum wavelength), in the range between 400 nanometers to 750 nanometers.
[0017] As used here, "average molecular weight" of thiophene azo carboxylate dyes is reported as an average molecular weight, as determined by their molecular weight distribution: as a consequence of their manufacturing process, the thiophenine azo dyes carboxylates described herein may contain a distribution of repeating units in their polymeric portion.
[0018] The test methods described in the Test Methods Section of this application should be used to determine the respective parameter values of the inventors of the applicants.
[0019] As used herein, the articles "one" and "one", when used in a claim, are understood to mean one or more than claimed or described.
[0020] As used here, the terms "include / include" and "including" are intended not to be limiting.
[0021] As used here, the term "solid" includes products in granular form, powder, bar and tablet.
[0022] As used herein, the term "fluid" includes liquid, gel, paste and gas product forms.
[0023] Unless otherwise noted, all levels of components or compositions are in reference to the active portion of that component or composition and exclude impurities, for example, residual solvents or by-products, which may be present in commercially available sources. such components or compositions.
[0024] All percentages and proportions are calculated by weight, unless otherwise stated. All percentages and proportions are calculated based on the total composition, unless otherwise stated. DYE
[0025] Suitable dyes are selected from the group comprising carboxylate dyes that have the structure of Formula 1:

[0026] where D is a dye portion selected from benzodifurans, methines, triphenylmethanes, naphthalimides, pyrazoles, naphthoquinines, anthraquinones and mono- and di-azo dyes and mixtures thereof, azo dyes being particularly preferred, but DH compound preferably has a maximum extinction coefficient greater than about 1000 liters / mol / cm at Àmax in the wavelength range from 400 nm to 750 nm in methanol solution, preferably a maximum extinction coefficient between about 20,000 to about 100,000 liters / mol / cm at Àmax in the wavelength range from about 540 nm to about 630 nm and most preferably a maximum extinction coefficient between about 20,000 to about 65,000 liters / mol / cm at Àmax in the wavelength range from about 560 nm to about 610 nm; and
[0027] L is an organic bonding group which preferably has a molecular weight of 14 to 1000 Daltons or 14 to 600 or 28 to 300, preferably consisting essentially only of C, H and optionally additionally O and / or N and na sequence of bonds starting from the carbonyl carbon of the group C (O) OM and ending in the dye portion, any groups - (Ca (O) -Ob) - are incorporated such that the oxygen atom Ob is found before of the carbonyl Ca carbon, preferably L is a C1-20 alkylene chain which optionally has ether (-O-) and / or ester and / or amine bonds in it, the chain being optionally substituted, for example, with - OH, -CN, -NO2, -SO2CH3, -Cl, -Br; and M is any suitable counterion, typically a hydrogen, sodium or potassium ion.
[0028] In one aspect of the invention, L can comprise Formula 2:

[0029] As examples of L, there may be mentioned ethylene, tri-methylene, tetramethylene, hexamethylene, isopropylene, decamethylene, hexamethylene and - (CH2CH2O) n-CH2-, where n is between 1 to 9.
[0030] In a preferred embodiment, the carboxylate dye comprises the structure of Formula 3:

[0031] where R is a C1-20 chain, or C2-12 alkyl optionally having ether (-O-) and / or ester and / or amide bonds, the chain being optionally substituted, for example, by -OH- , -CN, -NO2, -SO2CH3, -Cl, -Br; R1 and R2 are selected independently and can be hydrogen, but are preferably selected independently from groups that remove electrons such as -CN, - NO2, -SO2CH3, -Cl, -Br; Z is an electron removing group preferably selected from cyano, sulfamoyl, N: N-diethylsulfamoyl, N-ethylsulfamoyl, trifluoromethyl, ethylsulfonyl, nitro, N-methylsulfamoyl, chlorine, bromine, more preferably Z is nitro; Y is hydrogen, (C1-4) lower alkoxy, halogen, -NHCOR, preferably H, CH3, -Cl; X is hydrogen, (C1-4) lower alkoxy and halogen, preferably H, methoxy, ethoxy and -Cl.
[0032] As examples of (C1-4) alkyl and / or (C1-4) lower alkoxy radicals, methyl, ethyl, n-propyl and n-butyl, ethoxy and methoxy can be mentioned. As examples of substituted lower (C1-4) alkyl radicals represented by R, hydroxy lower alkyl such as β-hydroxyethyl, cyano lower alkyl such as β-cyanoethyl, lower alkoxy lower alkyl such as β- (met0- or ethoxy-) ethyl and x-methoxypropyl, aryl lower alkyl such as benzyl and β-phenylethyl, lower alkoxycarbonyl lower alkyl such as β-methoxycarbonylethyl, and lower alkyl acyloxyl such as β-acetoxyethyl.
[0033] The dye can comprise a Formula 4 dye, in which the groups Z, R, X, Y and L are as defined above:

[0034] In one aspect of the invention, the composition is in the form of a unit dose laundry composition in a single or multiple compartment.
[0035] In an additional aspect, the carboxylate dye can have the structure:

[0036] where A is an aromatic moiety, preferably an aromatic moiety without sulfonic acid, selected from the group consisting of substituted carbocyclic or substituted heterocyclic moieties; X is selected independently from the group consisting of H, R6, OR6, Cl, Br, and mixtures thereof, wherein R6 is selected independently from the group consisting of H, C1-C4 alkyl and mixtures thereof; each of R10 and R11 is independently selected from H and C1-C16 alkyl or alkenyl; preferably at least one of R10 and R11 is H, more preferably both are H; M is H or a charge-balance cation and L is an organic bonding group that preferably has a molecular weight between 14 to 1000 Daltons or 14 to 600 or 14 to 300, preferably consisting essentially of C, H and optionally additionally O and / or N. R1 and R2 are selected independently and can be any suitable substituent that has one or more carbon atoms and that will fulfill the objectives of the present invention. Typical of such substituents that can be coupled to the dye radical are hydroxyalkylenes, polymeric epoxides, such as polyalkylene oxides and their copolymers. Polymeric substitutes are in a preferred aspect. In this regard, the polyalkylene oxides and their copolymers that can be used to provide the dye of the present invention are, without limitation, polyethylene oxides, polypropylene oxides, polybutylene oxides, polyethylene oxide copolymers, polyethylene oxides polypropylene, polybutylene oxides, and other copolymers including block copolymers, in which the majority of polymeric substituents are polyethylene oxide, polypropylene oxide and / or polybutylene oxide. In addition, such substituents generally have an average molecular weight in the range between 44 to about 2500, preferably from about 88 to about 1400, but should not be so limited.
[0037] In a Formula 5 modality, R1 and R2 can be selected such that:
[0038] - R1 and R2 can be independently selected from [(CH2CR'HO) x (CH2CR "HO) yH] where R 'is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures of these ; where R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y <10, preferably <5; where y> 1; and where z = 0 to 5;
[0039] - R1 = C1-12 alkyl, C6-10 aryl, C7-C22 aryl alkyl, and R2 = [(CH2CR'HO) x (CH2CR "HO) yH] where R 'and R" are as defined above ; where x + y <20, preferably <10; where y> 1; and where z = 0 to 5;
[0040] - R1 and R2 are independently selected from the group consisting of C1-C12 linear or branched alkyl optionally comprising one or more moieties of ether, ester, cyano, or amide, C6-10 aryl, C7-C22 aryl alkyl optionally comprising one or more portions of ether, ester, cyano, or amide, and Formula 6:

[0041] in which each R3 is selected from the group consisting of phenyl and CH2OR5; each R4 is selected from the group consisting of H, C1-C4 alkyl, and mixtures thereof; preferably R4 is H or methyl, even more preferably H; wherein q is an integer between 0 to 50, preferably 1-25, even more preferably 1-10; and wherein each R5 is selected from the group consisting of C1-C16 linear or branched alkyl, C6-C14 aryl C7-C16 aryl alkyl; preferably R5 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, phenyl, benzyl, 2 -phenylethyl, naphthyl and their mixtures;
[0042] In another form of Formula 5, R1 and R2 can be selected such that:
[0043] - R1 and R2 can be selected independently from the group consisting of H, C6H11, or optionally substituted C2 - C12 alkyl chains which optionally have ether (O-) or ester linkages in them, the chain being optionally substituted with Cl , Br, OH, CN, NO2, SO2CH3, and mixtures thereof, provided that no more than one of R1 and R2 is H;
[0044] - R1 is CH2CH2R7 and R2 is CH2CH2R8 and R7 and R8 are selected independently from the group consisting of: H, CN, OH, C6H5, -OCOR9 and -COOR9, where each of R9 is selected independently among : aryl and alkyl, preferably C6H5 or C10H7 aryl or C1 - C8 alkyl.
[0045] In a preferred embodiment of the carboxylate dye, group A in Formula 5 is an aromatic carbocyclic moiety without Formula 7 sulfonic acid below:

[0046] where the asterisk indicates the point of coupling of the aromatic carbocyclic moiety without sulfonic acid to the azo nitrogen of Formula 5. Z, G1 and G2 are independently selected from H, Cl, Br, I, CN, NO2, SO2CH3 and mixtures of these, preferably Z is NO2.
[0047] In a preferred embodiment of the present invention, the bleaching agent is represented by Formula 8:

[0048] where A, X, R1 and R2 are as defined for Formula 5 above; Y is an organic radical represented by Formula 9

[0049] where M is H or a cation that balances the charge; the index m is 0, 1, 2 or 3; the index n is 0, 1, 2 or 3; the sum of m + n is 1, 2 or 3; each R12 is independently selected from the group consisting of H and C1-C18 alkyl, C2-C18 alkenyl, C7-C18 aryl or alkylaryl, and C6-C10 aryl, said R12 groups optionally comprising one or more ether and / or hydroxyl moieties . In certain preferred embodiments, at least one of R12 is not H.
[0050] In another aspect, the bleaching agent of the present invention can be characterized by the following structure:

[0051] Non-limiting examples of carboxylate dyes suitable for use in the present invention are illustrated in structures (a) to (d) below:


[0052] wherein each R12 is independently selected from the group consisting of H and C1-C18 alkyl, C2-C18 alkenyl, C7-C18 arylalkyl or alkylaryl, and C6-C10 aryl, said R6 groups optionally comprising one or more ether or hydroxyl portions. It may be preferable that R12 is not H.
Particularly preferred anhydrides suitable for use in creating the Y portion of the present invention include, but are not limited to the following: 3- (2-buten-1-yl) dihydro-2,5-furandione; 3- (2-hexen-1-yl) dihydro-2,5-furandione; dihydro-3- (2-octen-1-yl) -2,5-furandione; dihydro-3- (2,7-octadien-1-yl) -2,5-furandione; dihydro-3- (2-nonen-1-yl) -2,5-furandione; 3- (2-decen-1-yl) dihydro-2,5-furandione; 3- (2E) -2-dodecen-1-ildihydro-2,5-furandione; dihydro-3- (2-tetradecen-1-yl) -2,5-furandione; 3- (2-hexadecen-1-yl) dihydro-2,5-furandione; dihydro- 3- (2-octadecen-1-yl) -2,5-furandione; 3-hexyldihydro-3-methyl-2,5-furandione; 3-hexyldihydro-2,5-furandione; dihydro-3- (phenylmethyl) -2,5-furandione; 3-decildihydro-2,5-furandione; dihydro-3,3-dimethyl-2,5-furandione; 3-ethyldihydro-2,5-furandione; dihydro-3- (2-propen-1-yl) - 2,5-furandione; dihydro-3-octyl-2,5-furandione; dihydro-3-methyl-2,5-furandione; 3-dodecyldihydro-2,5-furandione; dihydro-3-phenyl-2,5-furandione; and dihydro-2,5-furandione.
[0054] Such suitable anhydrides can be obtained from one or more of the following: Sigma-Aldrich, St. Louis, MO 63178; City Chemical LLC, West Haven, CT 06516; Ryan Scientific, Inc., Mt. Plea-sant, SC 29465; TCI America, Portland, OR 97203; Aurora Fine Che-micals LLC, San Diego, CA 92126; Accel Pharmtech, LLC, East Brunswick, NJ 08816; ABI Chem, Munich, Germany; BOC Sciences, Shirley, NY 11967; ChemSampCo, Inc., Dallas, TX 75220; Accel Pharmtech, LLC, East Brunswick, NJ, 08816; and Reagent World, Inc., Ontario, CA 91761.
[0055] Other carboxylate dyes suitable for use in the present invention include, but are not limited to, those shown below, where R12 is as defined above:









[0056] It may be preferable that R12 is not H. DYE SYNTHESIS EXAMPLES

[0057] CI Dispersed Violet 55 (also known as Dispersed Red 65) is converted to Dye 1 using the hydrolysis procedure described in EP 2085434 A1, Example 11, followed by the formation of the sodium salt through treatment with NaH in THF (or treatment with Na2CO3 in water). The product is isolated as sodium salt.

[0058] CI Disperse Blue 148 is converted to Dye 2 using the hydrolysis procedure described in EP 2085434 A1, Example 6. The product is isolated as the sodium salt.

[0059] CI Disperse Blue 85 is converted to Dye 3 using the sequential alkylation and hydrolysis procedures described in EP 2085434 A1, Examples 5 and 6, respectively. The product is isolated as sodium salt.

[0060] CI Disperse Blue 12 is converted to Dye 5 using the sequential alkylation and hydrolysis procedures described in EP 2085434 A1, Examples 5 and 6, respectively. The product is isolated as sodium salt.

[0061] CI Disperse Blue 13 is converted to Dye 6 using the sequential alkylation and hydrolysis procedures described in EP 2085434 A1, Examples 5 and 6, respectively. The product is isolated as sodium salt.

[0062] CI Disperse Blue 24 is converted to Dye 7 using the sequential alkylation and hydrolysis procedures described in EP 2085434 A1, Examples 5 and 6, respectively. The product is isolated as sodium salt.

[0063] Dye 8 'is prepared according to the procedure described in US Patent No. 3,793,305, Example 4, except that N- (2-cyanoethyl) -NN-hexyl-m-toluidine is used in place of N - (2-cyanoethyl) -N-ethyl-m-toluidine. Dye 8 'is converted to Dye 8 according to the procedure described in Example 1 above.

[0064] Dye 9 is prepared according to the sequence described in Example 8, except that N- (2-cyanoethyl) -N-decyl-m-toluidine is used in place of N- (2-cyanoethyl) - N-ethyl-m-toluidine.

[0065] Dye 10 'is prepared according to the procedure described in the Journal of the Society of Dyers and Colourists, 1984, 100 (10), 316-19, except that 3 - [(N-hexyl-N-phenyl) amino] ethyl propionate is used in place of N-ethyl-N-2- (methoxycarbonyl) ethylaniline. Dye 10 is prepared from Dye 10 'using the hydrolysis procedure described in EP 2085434 A1, Example 6. The product is isolated as the sodium salt.

[0066] Dye 11 is prepared according to Example 1 of GB 1,428,395 using 3 - [(N-hexyl-N-phenyl) amino] propionic acid in place of N-ethyl-N- (β-carboxyethyl ) -m-toluidine.

[0067] Dye 12 is prepared according to Example 1 of GB 1,428,395 using 3 - [(N-hexyl-N-phenyl) amino] propionic acid in place of N-ethyl-N- (β-carboxyethyl ) -m-toluidine.

[0068] Dye 13 is prepared according to the procedures described in WO 2011/17719 A2 using 15- (3-methylphenyl) -3,6,9,12-tetraoxa-15-azatetracosan-1-ol, which is prepared according to the procedure described in WO 2011/017719 A2 for the preparation of 15- (3-methylphenyl) -3,6,9,12-tetraoxa-15-azaheptadecan-1-ol, except that N-ethyl- m-toluidine is replaced by N-octyl-m-toluidine. Dye 13 'is converted to Dye 13 using the sequential alkylation and hydrolysis procedures described in EP 2085434 A1, Examples 5 and 6, respectively. The product is isolated as sodium salt.

[0069] N, N-diethyl 1,3-benzenediamine (available from BOC Sciences, Shirley, NY, 11967) is acylated with dihydro-3- (2-octen-1-yl) - 2,5- furandione (available from TCI America Fine Chemicals, Portland, OR, 97203) according to the general procedure described in US Patent No. 3,943,120, Column 10, Instruction 3 for providing Compound IV coupling below (largest regioisomer shown).

[0070] A small amount of impurities that result from the attack of the amino group on the most impeded carbonyl of the anhydride is expected. This impurity can be removed or it can be charged forward resulting in a small amount of a second reflective dye from the smaller regioisomer being present with the larger regimen indicated. Dye C ', the precursor to Dye C, is prepared according to the procedure described for the preparation of I.1 in Dyes and Pigments 1994 24 (3), p. 207, Section 2.1, replacing p-nitroaniline with 2-bromo-4-nitro-6-cyanoaniline and replacing dye I.2 with Compound IV above, followed by optional neutralization to obtain the sodium salt.

[0071] Dye C is prepared according to the procedure described for the preparation of dye I.9 in Dyes and Pigments 1994 24 (3), p. 207, replacing dye I.2 with Dye C '.
[0072] Dye C can be represented by Formula 11 below:

[0073] where R7 and R8 are each H and R12 is oct-2-en-1-yl. Other dyes according to this Formula can be readily prepared, for example, by replacing dihydro-3- (2-octen-1-yl) - 2,5-furandione with any preferred anhydride as described above or by replacing N, N-diethyl 1,3-benzene diamine by any other suitable 1,3-benzene diamine.
[0074] 1,3 suitable benzene diamines to replace N, N-diethyl 1,3-benzenediamine include, but are not limited to N1-butyl-N1- propyl-1,3-benzenediamine; N1-ethyl-N1- [2- (1-methylethyloxy) ethyl] -1,3-benzenediamine; 5 - [(3-aminophenyl) ethylamino] -pentanonitrile; 3 - [(3-aminophenyl) (2-methoxyethyl) amino] -propanonitrile; 4 - [(3-aminophenyl) propylamino] -butanonitrile; N- (3-aminophenyl) -N-ethyl-β-alanine, methyl ester; N1- (3-methoxypropyl) -N1-propyl-1,3-benzenediamine; 3- [(3-aminophenyl) ethylamino] -N-methylpropanamide; N1-ethyl-N1- (3-methoxypropyl) -1,3-benzenediamine; N1- (3,3-dimethylbutyl) -N1-ethyl-1,3-benzenediamine; N1- (2-methoxyethyl) -N1-propyl-1,3-benzenediamine; N1- ethyl-N1-pentyl-1,3-benzenediamine; N1-ethyl-N1- (2-phenylethyl) -1,3-benzenediamine; N1- (2-phenylethyl) -N1-propyl-1,3-benzenediamine; N1- ethyl-N1-octyl-1,3-benzenediamine; 4 - [(3-aminophenyl) ethylamino] butanoic acid, methyl ester; N1- [2- (3-methylbutoxy) ethyl] - N1-propyl-1,3-benzenediamine; 1 N1-heptyl-N1-propyl-, 3-benzenediamine; N1-ethyl-N1-heptyl-1,3-benzenediamine; N1-ethyl-N1- [2- (3-methylbutoxy) ethyl] -1,3-benzenediamine; N1-ethyl-N1- (3-phenylpropyl) -1,3-benzenediamine; 5 - [(3-aminophenyl) propylamino] pentanonitrile; N1- (2-methoxyethyl) -N1- (3-methoxypropyl) -1,3-benzenediamine; N1- (2-ethoxyethyl) - N1-propyl-1,3-benzenediamine; 3 - [(3-aminophenyl) ethylamino] propanonitrile; N1-ethyl-N1- (2-methoxyethyl) -1,3-benzenediamine; 4-ethoxy-N3, N3-diethyl-1,3-benzenediamine; N1-ethyl-N1- propyl-1,3-benzenediamine; N1-butyl-N1-ethyl-1,3-benzenediamine; 4-chloro-N3, N3-diethyl-1,3-benzenediamine; N1, N1-dipropyl-1,3-benzenediamine; N1, N1-dibutyl-1,3-benzenediamine; N1, N1-bis (2-methoxyethyl) -1,3-benzenediamine; 2,2 '- [(3-aminophenyl) imino] bis-ethanol, 1,1'-dibenzoate; 4 - [(3-aminophenyl) ethylamino] butanonitrile; N3, N3-diethyl-4-methoxy-1,3-benzenediamine, and mixtures thereof.
[0075] 1,3-benzene diamines suitable for substituting N, N-diethyl 1,3-benzene diamine include, but are not limited to, α, α '- [[(3-aminophenyl) imino] di-2,1-ethanediyl ] bis [w-hydroxy] poly (oxy-1,2-ethanediyl), prepared according to US 5,135,972, Column 28, lines 25-45; N1- methyl-N1- (phenylmethyl) -1,3-benzenediamine; N1- (2-methoxyethyl) -N1-methyl-1,3-benzenediamine; 7-amino-3,4-dihydro-1 (2H) -quinoline ethanol; 4-chloro-N3, N3-dimethyl-1,3-benzenediamine; 4-chloro-N3, N3-dipropyl-1,3-benzenediamine; 4-chloro-N3, N3-diethyl-1,3-benzenediamine; N- (3-aminophenyl) -N-methyl glycine, methyl ester; 4-methyl-3- (4-morpholinyl) benzenamine; 4-methoxy-3- (4-morpholinyl) benzenamine; N1, N1- dipropyl-1,3-benzenediamine; 1-ethyl-1,2,3,4-tetrahydro-7-quinolinamine; N1, N1-dibutyl-1,3-benzenediamine; 3,4-dihydro-4-propyl-2H-1,4-benzoxazin-6-amine; N1, N1-bis (2-methoxyethyl) -1,3-benzenediamine; 4-methoxy-N3, N3-dimethyl-1,3-benzenediamine; 2,2 '- [(3-aminophenyl) imino] bis-ethanol; 2,2 '- [(5-amino-2-methoxyphenyl) imino] bis-ethanol; N3, N3-diethyl-4-methyl-1,3-benzenediamine; N3-ethyl-N3,4-dimethyl-1,3-benzenediamine; 2 - [(3-aminophenyl) ethylamino] acetonitrile; 4 - [(3-aminophenyl) ethylamino] butanenitrile; 6-amino-2,3-dihydro-4H-1,4-benzoxazine-4-ethanol; N1, N1-bis (phenylmethyl) -1,3-benzenediamine; N1, N1-diethyl-1,3-benzenediamine; N3, N3,4-trimethyl-1,3-benzenediamine; N3, N3-diethyl-4-methoxy-1,3-benzenediamine; N1, N1-dimethyl-1,3-benzenediamine; and mixtures of these.
[0076] Such suitable 1,3-benzenodiamines can be obtained from one or more of the following: Sigma-Aldrich, St. Louis, MO 63178; City Chemical LLC, West Haven, CT 06516; Ryan Scientific, Inc., Mt. Pleasant, SC 29465; TCI America, Portland, OR 97203; Aurora Fine Chemicals LLC, San Diego, CA 92126; Accel Pharmtech, LLC, East Brunswick, NJ 08816; ABI Chem, Munich, Germany; BOC Sciences, Shirley, NY 11967; ChemSampCo, Inc., Dallas, TX 75220; Accel Pharmtech, LLC, East Brunswick, NJ, 08816; and Reagent World, Inc., Ontario, CA 91761.
[0077] The carboxylate dye can be incorporated into the composition as a mixture of reaction products formed via the organic synthesis used: such a reaction mixture will typically comprise a mixture of formula I dyes and, often, in addition, products side reaction reactions and / or small amounts of unreacted starting materials. Although it may be preferred to remove impurities other than dyes as defined in Formula I, it may not be necessary, such that the reaction product mixture can be used directly in a composition according to the invention.
[0078] Typically, the carboxylate dye or mixture of dyes of formula I will be present in the composition in an amount between 0.00001 to 5% by weight of the composition, more generally in an amount from 0.0001 to 1% by weight or 0.5% by weight of the composition.
[0079] When the dye is first formed in a premix, for example, a particle or a concentrated liquid for incorporation into the composition, the dye can be present at a level of 0.001 or up to 0.01 or more, up to an amount 2% by weight or 10% by weight based on the weight of a premix.
[0080] The compositions of the present invention typically comprise, in addition to the dye, one or more adjunct materials for care of clothes. SUBJECT MATERIALS TO CARE FOR CLOTHING
[0081] Suitable adjuncts can be, for example, to assist or intensify performance in cleaning, for the treatment of the substrate to be cleaned, for example, by softening or revitalizing or to modify the aesthetics of the composition as is the case with perfumes, co -rantes, shading dyes for non-woven or similar. Suitable adjunct materials include, but are not limited to surfactants, builders, chelating agents, agents that inhibit dye transfer, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersing agents, soil clay removing / anti-redeposition agents, rinse aid, foam suppressants, dyes, toning dyes, perfumes, perfume release systems, elastifying agents of structure, fabric softeners, vehicles, hydrotropes, processing aids, solvents, additional dyes and / or pigments, some of which are discussed in more detail below. In addition to the description below, suitable examples of such other adjuncts and usage levels are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 which are incorporated by reference.
[0082] Additional Fabric Toning Agents. While it is not preferred to incorporate additional fabric shading dyes, in addition to the aza thiophene dye, the composition may comprise one or more additional fabric toning agents. Suitable fabric toning agents include dyes, dye-clay conjugates and pigments. Suitable dyes include those that deposit more on cotton textiles compared to deposition on synthetic textiles such as polyester and / or nylon. Suitable additional dyes include those that are deposited on synthetic fibers such as polyester and / or nylon compared to cotton. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes that fall within the Color Index (CI) classification of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue , Basic Violet and Basic Red or their mixtures. Examples of small molecule dyes include those selected from the group consisting of the Color Index (Society of Dyers and Colorists, Bradford, UK) numbers Violet Direct 9, Violet Direct 35, Violet Direct 48, Violet Direct 51, Violet Direct 66, Violet Direct 99, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 43, Acid Violet 43 , Acid Red 52, Acid Violet 49, Acid Violet 50, Direct Blue 15, Direct Blue 17, Direct Blue 25, Direct Blue 40, Direct Blue 45, Direct Blue 75, Direct Blue 80, Direct Blue 80, Blue Straight 90 and Straight Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66 , Basic Blue 75, Basic Blue 159, small molecule dyes selected from the group comprising nsiste in Color Index (Society of Dyers and Colourists, Bradford, UK) numbers Acid Violet 17, Acid Violet 43, Acid Red 52, Acid Red 73, Acid Red 88, Acid Red 150, Direct Blue 25, Direct Blue 29, Blue Direct 45, Direct Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71. Small molecule dyes Direct Violet may be preferred. Dyes selected from the group consisting of Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Direct Blue 29, Direct Blue 113 and their mixtures may be preferred.
[0083] Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing covalently linked chromogens (dye-polymer conjugates) and polymers with copolymerized chromogens in the polymer framework and mixtures of these and polymeric dyes selected from the group consisting in background dyes for fabric sold under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA) Violet CT, dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers which comprise a selected portion of the group consisting of a hydroxyl portion, a primary amine portion, a secondary amine portion, a thiol portion and mixtures thereof. In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® (Milliken, Spartanburg, South Carolina, USA) Violet CT, carboxymethyl cellulose (CMC) conjugated to a reactive blue, reactive violet or green dye reactive improvement such as CMC conjugated with CI Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the trade name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated polymeric triphenyl methane dyes, alkoxylated polymer dyes of thiophene, and mixtures of these. Preferred additional toning dyes include the bleaching agents found in WO 08/87497 A1. These bleaching agents can be characterized by the following structure (IV):

[0084] where R1 and R2 can be selected independently from:
[0085] - [(CH2CR'HO) x (CH2CR "HO) yH], where R 'is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; where R" is selected the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y <5; where y> 1; and where z = 0 to 5;
[0086] - R1 = alkyl, aryl or aryl alkyl and R2 = [(CH2CR'HO) x (CH2CR "HO) yH]
[0087] wherein R 'is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; where 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
[0088] - R1 = [CH2CH (OR3) CH2OR4] and R2 = [CH2CH (O R3) CH2O R4]
[0089] wherein R3 is selected from the group consisting of H, (CH2CH2O) zH, and mixtures thereof; and where z = 0 to 10
[0090] wherein R4 is selected from the group consisting of (C1- C16) alkyl, aryl groups, and mixtures thereof; and
[0091] - wherein R1 and R2 can be independently selected from an amino addition product of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether, 2-ethylhexylgicidyl ether and glycidylhexadecyl ether, if -guided by the addition of between 1 to 10 alkylene oxide units.
[0092] An additional preferred fabric toning agent that can be incorporated into the compositions of the invention can be characterized by the following structure (IV):

[0093] wherein R 'is selected from the group consisting of H, CH3, CH2O (CH2CH2O) zH, and mixtures thereof; where R "is selected from the group consisting of H, CH2O (CH2CH2O) zH, and mixtures thereof; where x + y <5; where y> 1; where z = 0 to 5.
[0094] A preferred additional toning dye can be characterized by the following structure (V):

[0095] This dye is typically a mixture of compounds that have an average of 3 to 10 EO groups, preferably 5 EO groups per molecule;
[0096] Additional shading dyes are those described in USPN 2008 34511 A1 (Unilever). A preferred agent is "Solvent Violet 13".
[0097] Suitable clay dye conjugates include clay dye conjugates selected from the group comprising at least one cationic / basic dye and smectite clay and mixtures thereof. In another aspect, suitable clay dye conjugates include clay dye conjugates selected from the group consisting of a cationic / basic dye selected from the group consisting of CI Yellow Basic 1 to 108, CI Orange Basic 1 to 69, CI Red Basic 1 to 118, CI Basic Violet 1 to 51, CI Blue Basic 1 to 164, CI Green Basic 1 to 14, CI Brown Basic 1 to 23, CI Black Basic 1 to 11, and a clay selected from the group consisting of clay Montmorillonite, Hectorite clay, Saponite clay and their mixtures. In yet another aspect, suitable clay dye conjugates include clay dye conjugates selected from the group consisting of: Montmorillonite Basic Blue conjugate B7 CI 42595, Montmorillonite Basic Blue conjugate B9 CI 52015, Montmorillonite Basic Violet V3 CI 42555 , Montmorillonite Green Basic conjugate G1 CI 42040, Montmorillonite Red Basic conjugate Red R1 CI 45160, Montmorillonite CI Basic Black 2 conjugate, Basic Blue Hectorite conjugate B7 CI 42595, Basic Blue Hectorite conjugate B9 CI 52015, Violet Hectorite conjugate Basic V3 CI 42555, Basic Green Hectorite conjugate G1 CI 42040, Basic Red Hectorite conjugate R1 CI 45160, Basic Black Hectorite CI basic Black 2, Basic Blue Saponite conjugate B7 CI 42595, Basic Blue Saponite conjugate B9 CI 52015, conjugate, Basic Saponite Conjugate V3 CI 42555, Basic Saponite Conjugate G1 CI 42040, Red Basic Saponite conjugate R1 C.I. 45160, Black Saponite conjugate C.I. Basic 2 and mixtures thereof.
[0098] Suitable pigments include pigments selected from the group consisting of flavantrone, indantrone, chlorinated indanthrone containing 1 to 4 chlorine atoms, pyrantrone, dichloropyrantrone, monobromodichloropyrantrone, dibromodichloropyrantrone, tetrabromopyrantro- na, perylene-3,4 diimide, 9,10-tetracaboxy, in which the imide groups can be unsubstituted or substituted by a C1-C3-alkyl or phenyl or heterocyclic radical and in which the phenyl and heterocyclic radicals can additionally carry substituents that do not confer solubility in water, amides of anthrapyrimidonocarboxylic acid, violantrone, isoviolantrone, dioxazin pigments, copper phthalocyanine that can contain up to 2 chlorine atoms per molecule, copper polychloro-phthalocyanine or copper polychromyclo-phthalocyanine containing up to 14 bromine atoms per molecule and mixtures of these. Particularly preferred are Blue Pigments 15 to 20, especially Blue Pigment 15 and / or 16. Other suitable pigments include those selected from the group consisting of Ultramarine Blue (CI Pigment Blue 29), Ultramarine Violet (CI Pigment Violet 15) and mixtures of these. Suitable toning agents are described in more detail in US 7,208,459 B2, WO2012 / 054835, WO2009 / 069077, WO2012 / 166768.
[0099] Encapsulated. The composition can comprise an encapsulated one. In one aspect, an encapsulated shell comprises a core, a shell that has an internal and external surface, said shell encapsulating said core. The core can comprise any clothing protection adjunct, although typically the core can comprise material selected from the group consisting of perfumes; rinse aid; dyes; insect repellents, silicones; waxes; flavoring; vitamins; tissue softening agents; agents for care of the skin in one aspect, paraffins; antibacterial agents; bleaches; sensitizers; and mixtures of these; and said shell may comprise a material selected from the group consisting of polyethylenes; polyamides; polyvinyl alcohols, optionally containing other co-monomers; polystyrenes; polyisoprene; polycarbonates; polyesters; polyacrylates; aminoplasts, in one aspect said aminoplast comprises polyureas, polyurethane and / or polyureaurethane, in one aspect said polyurea can comprise polyoxymethylurea and / or methylamine formaldehyde; polyolefins; polysaccharides, in one aspect the polysaccharide may comprise alginate and / or chitosan; gelatine. Shellac; epoxy resins; vinyl polymers; inorganic insoluble in water; silicone; and mixtures of these; Preferred encapsulates comprise perfume. Preferred encapsulates comprise a shell which may comprise melamine formaldehyde and / or melamine formaldehyde crosslinked. Preferred encapsulates comprise a core material and a shell, said shell at least partially surrounding said core material. At least 75%, 85% or up to 90% of said encapsulations can have a fracture resistance between 0.2 MPa to 10 MPa and an agent that helps leakage between 0 to 20% or even less than 10% or 5% based on the agent that aids the total initial leak. Preferred are those in which at least 75%, 85% or up to 90% of said encapsulations have (i) a particle size between 1 micron to 80 microns, 5 microns to 60 microns, from 10 microns to 50 microns or even between 15 micron to 40 micron and / or (ii) at least 75%, 85% or up to 90% of said encapsulates have a particle wall thickness between 30 nm to 250 nm, from 80 nm to 180 nm or up to 100 nm at 160 nm. Formaldehyde removers can be employed with the encapsulated, for example, in a capsule paste and / or added to a composition between, during or after the encapsulated are added to such a composition. Suitable capsules can be made following the guidelines of USPA 2008/0305982 A1; and / or USPA 2009/0247449 A1. Alternatively, suitable capsules can be purchased from Appleton Papers Inc. of Appleton, Wisconsin USA.
[00100] In a preferred aspect, the composition may comprise a deposition aid, preferably in addition to the encapsulated ones. Preferred deposition aids are selected from the group consisting of cationic and non-ionic polymers. Suitable polymers include cationic starches, cationic hydroxyethylcellulose, polyvinylformaldehyde, locust bean gum, mannans, xyloglycans, tamarind gum, polyethylene terephthalate and polymers containing dimethylaminoethyl methacrylate, optionally with one or more monomeric acids that are l-group monomers. and acrylamide.
[00101] Perfume. Preferred compositions of the invention comprise perfume. Typically, the composition comprises a perfume that comprises one or more raw perfume materials, selected from the group described in WO08 / 87497. However, any perfume useful in a clothing treatment composition can be used. A preferred method of incorporating perfume into the compositions of the invention is through an encapsulated perfume particle comprising a water-soluble hydroxyl compound or melamine-formaldehyde or modified polyvinyl alcohol. In one aspect, the en-capsule comprises (a) at least a partially water-soluble solid matrix comprising one or more water-soluble hydroxy compounds, preferably starch; and (b) a perfumed oil encapsulated by the solid matrix. In a further aspect, the perfume can be pre-complexed with a polyamine, preferably a polyethyleneimine so as to form a Schiff base.
[00102] Polymers. The composition can comprise one or more polymers. Examples are optionally modified carboxymethylcellulose, poly) vinyl-pyrrolidone), poly (ethylene glycol), poly (vinyl vinyl), poly (vinylpyridine) N-oxide, poly (vinylimidazole), polycarboxylates such as polyacrylates, acid copolymers maleic / acrylic and laurel methacrylate / acrylic acid copolymers.
[00103] The composition may comprise one or more amphiphilic cleaning polymers such as the compound having the following general structure: bis ((C2H5O) (C2H4O) n) (CH3) -N + -CxH2x-N + - (CH3) -bis ((C2H5O) (C2H4O) n), where n = between 20 to 30 and ex = between 3 to 8 or sulphated or sulphonated variants thereof. In one aspect, this polymer is sulfated or sulfonated to provide a suspended soil zwitterionic polymer.
[00104] The composition preferably comprises alkoxylated amphiphilic polymers for grease cleaning which have balanced hydrophilic and hydrophobic properties such that they remove grease particles from fabrics and surfaces. Preferred alkoxylated amphiphilic polymers for grease cleaning comprise a core structure and a plurality of alkoxylated groups coupled to that core structure. These may comprise alkoxide polyalkyleneimines, preferably having an internal polyethylene oxide block and an external propylene oxide block. Typically, these can be incorporated into the compositions of the invention in amounts between 0.005 to 10% by weight, generally between 0.5 to 8% by weight.
[00105] Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful here to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815. Chemically, these materials comprise polyacrylates that have a side-ethoxy chain for every 7 to 8 acrylate units. The side chains are of the formula - (CH2CH2O) m (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are ester bonded to the polyacrylate "frame" to provide a "comb" polymer type structure. The molecular weight may vary, but it is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarbonylates can comprise between about 0.05% to about 10% by weight of the compositions thereof.
[00106] Mixtures of co-surfactants and other adjunct ingredients are particularly suitable for use with an amphiphilic copolymer graft. Preferred amphiphilic copolymer grafts comprise (i) polyethylene glycol framework; and (ii) at least one pendant portion selected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof. A preferred amphiphilic copolymer graft is Sokalan HP22 supplied by BASF. Suitable polymers include random copolymer grafts, preferably a polyvinyl acetate copolymer grafted with polyethylene oxide that has a polyethylene oxide framework and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide framework is preferably about 6000 and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 units. of ethylene oxide. Typically these are incorporated into the compositions of the invention in amounts between 0.005 to 10% by weight, more generally between 0.05 to 8% by weight. Preferably, the composition comprises one or more carboxylate polymers, such as random maleate / acrylate copolymer or polyacrylate homopolymer. In one aspect, the carboxylate polymer is a polyacrylate homopolymer that has a molecular weight of 4000 Da to 9000 Da or 6000 Da to 9000 Da. Typically these are incorporated into the compositions of the invention in amounts between 0.005 to 10% by weight or between 0.05 to 8% by weight.
[00107] Preferably, the composition comprises one or more polymers that release dirt. Examples include dirt-releasing polymers that have a structure as defined by one of the following Formulas (VI), (VII) or (VIII): - [(OCHR1-CHR2) aO-OC-Ar-CO-] d ( VI) - [(OCHR3-CHR4) bO-OC-sAr-CO-] and (VII) - [(OCHR5-CHR6) c-OR7] f (VIII)
[00108] where:
[00109] a, b, and c are between 1 to 200;
[00110] d, e and f are between 1 to 50;
[00111] Ar is 1,4-substituted phenylene;
[00112] sAr is 1,3-substituted phenylene at position 5 with SO3Me;
[00113] Me is Li, K, Mg / 2, Ca / 2, Al; 3, ammonia, mono, di, tri or tetraalkylammonia in which the alkyl groups are C1-C18 alkyl or C2-C10 hydroxyalkyl or mixtures thereof ;
[00114] R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C18 n- or iso-alkyl; and
[00115] R7 is C1-C18 straight or branched alkyl or C2-C30 straight or branched alkenyl or a cycloalkyl group with 5 to 9 carbon atoms or a C8-C30 aryl group or a C6-C30 arylalkyl group.
[00116] Suitable dirt-releasing polymers are polymers that release polyester dirt such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6 supplied by Rhodia. Other suitable dirt-releasing polymers include Texcare polymers including Texcare SRA100, SRA300, SRN100, SRN170, S-RN240, SRN300 and SRN325 provided by Clariant. Other suitable dirt-releasing polymers are Marloquest polymers such as Marloquest SL supplied by Sasol.
[00117] Preferably, the composition comprises one or more cellulosic polymers, including those selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose. Preferred cellulosic polymers are selected from the group comprising carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. In one aspect, carboxymethyl cellulose has a degree of carboxymethyl substitution between 0.5 to 0.9 and a molecular weight between 100,000 Da to 300,000 Da.
[00118] Enzymes. Preferably, the composition comprises one or more enzymes. Preferred enzymes provide benefits in cleaning performance and / or tissue care. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, chitinases, pectinases, mannases, pectate lyases, keratinases, reductions, oxidases, phenoloxidases, lipoxygenases, lignins, lignins pullulanases, tanases, pentosanases, malanases, β-glycanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases or mixtures thereof. A typical combination is an enzyme cocktail that can comprise, for example, a protease and a lipase together with an amylase. When present in the composition, the additional enzymes mentioned above can be present at levels between about 0.00001% to about 2%, between about 0.0001% to about 1% or even between about 0.001% to about 0.5% enzyme protein by weight of the composition.
[00119] Proteases. Preferably the composition comprises one or more proteases. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such a suitable protease may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the suitable proteases mentioned above. In one aspect, the suitable protease can be a serine protease, such as an alkaline microbial protease and / or a trypsin-like protease. Examples of neutral or alkaline proteases include:
[00120] (a) subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US 6,312,936 B1. US 5,679,630. US 4,760,025. US7,262,042 and WO09 / 021867.
[00121] (b) trypsin-like or chymotrypsin-like proteases, such as trypsin (for example, of porcine or bovine origin), including the Fusarium protease described in WO 89/06270 and the chymotrypsin-derived proteases from Cellumonas described in WO 05/052161 and WO 05/052146.
[00122] (c) metalloproteases, including those derived from Bacillus amyloliquefaciens described in WO 07 / 044993A2.
Preferred proteases include those derived from Bacillus gibsonii or Bacillus lentus.
[00124] Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquana-se®, Liquanase Ultra®, Savinase Ultra®, Ovozyme® , Neutrase®, E-verlase® and Esperase® from Novozymes A / S (Denmark), those sold under the trade name of Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox ®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International, those sold under the trade names Opticlean® and Optimase® by Solvay Enzymes, those made available by Henkel / Kemira, namely BLAP (sequence shown in Figure 29 US 5,352,604 with the following mutations S99D + S101 R + S103A + V104I + G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) - all from Henkel / Kemira; and KAP (Bacillus alkalophilus subtilisin with A230V + S256G + S259N mutations) from Kao.
[00125] Amylases. Preferably, the composition can comprise an amylase. Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtisis, or other Bacillus sp., Such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36 or KSM K38 (EP 1,022,334). Preferred amylases include:
[00126] (a) the variants described in WO 94/02597, WO 94/18314, WO96 / 23874 and WO 97/43424, especially the variants with substitutions in one or more of the following positions versus the enzyme listed as SEQ ID No. 2 in WO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391 , 408 and 444;
[00127] (b) the variants described in USP 5,856,164 and WO99 / 23211, WO 96/23873, WO00 / 60060 and WO 06/002643, especially the variants with substitutions in one or more of the following positions versus the enzyme AA560 listed as SEQ ID No. 12 in WO 06/002643: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178,182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295,296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482,484, which also preferably contain the D183 * and G184 * deletions.
[00128] (c) variants that exhibit at least 90% identity with SEQ ID No. 4 in WO06 / 002643, the wild-type enzyme of Bacillus SP722, especially variants with deletions at positions 183 and 184 and the variants described in WO 00/60060, which is incorporated herein by reference.
[00129] (d) variants that exhibit at least 95% identity with the Bacillus SP707 wild type enzyme (SEQ ID NO: 7 in US 6,093,562), especially those comprising one or more of the following M202, M208 mutations , S255, R172, and / or M261. Preferably said amylases comprise one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and / or R172Q. Particularly preferred are those comprising the M202L or M202T mutations.
[00130] (e) variants described in WO 09/149130, preferably those that exhibit at least 90% identity with SEQ ID NO: 1 or SEQ ID NO: 2 in WO 09/149130, the wild type enzyme of Geobacillus stearophermophilus or a truncated version of that.
[00131] Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A / S, Bagsvaerd, Denmark ), KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZY-SIZE®, OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor International Inc., Palo Alto , California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixtures thereof.
[00132] Lipases. Preferably, the invention comprises one or more lipases, including "first cycle lipases" such as those described in U.S. Patent 6,939,702 B1 and US PA 2009/0217464. Preferred lipases are the lipases from the first wash. In one embodiment of the invention the composition comprises a first wash lipase. First wash lipases include a lipase that is a polypeptide that has an amino acid sequence that: (a) has at least 90% identity with the wild-type lipase derived from the DSM 4109 strain of Humicola lanuginosa; (b) compared to said wild-type lipase, it comprises a replacement of an electrically neutral or negatively charged amino acid on the surface of the three-dimensional structure within 15 A of E1 or Q249 with a positively charged amino acid; and (c) comprises an addition of the C-terminated peptide; and / or (d) comprises an addition of the N-terminated peptide and / or (e) meets the following limitations: i) comprises a negative amino acid at position E210 of said wild-type lipase; ii) comprises a negatively charged amino acid in the region corresponding to positions 90-101 of said wild-type lipase; and iii) comprises a neutral amino acid or a net neutral electrical charge in the region corresponding to positions 90-101 of said wild-type lipase. Thermomyces lanuginosus wild-type lipase variants which comprise one or more of the T231R and N233R mutations are preferred. The wild-type sequence is 269 amino acids (amino acids 23-291) from Swissprot, Swiss-Prot accession number O59952 (derived from Thermomyces laugugusus (Humicola lanuginosa)). Preferred lipases may include those sold under the trade names Lipex® and Lipolex® and Lipoclean®.
[00133] Endoglycanases. Other preferred enzymes include endoglucanases derived from microbes that exhibit beta-1,4-glycanase activity (EC 3.2.1.4), including a bacterial endogenous polypeptide from a member of the genus Bacillus that has a sequence of at least 90 %, 94%, 97% and up to 99% identity with the amino acid sequence of SEQ ID NO: 2 in US7.141.403B2 and mixtures thereof. Suitable endoglycanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bags- vaerd, Denmark).
[00134] Pectato Liases. Other preferred enzymes include peccary lyes sold under the trade names of Pectawash®, Petaway®, Xpect® and mannanases sold under the trade names of Mannaway® (all from Novozymes A / S, Bagsvaerd, Denmark), and Pu - rabrite® (Genencor International Inc., Palo Alto, California).
[00135] Bleaching agents. It may be preferred for the composition to comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photo-bleaches, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids and mixtures thereof. In general, when a bleaching agent is used, the compositions of the present invention can comprise between about 0.1% to about 50% or even between about 0.1% about 25% of the bleaching agent or mixtures of agents bleaches by weight of the composition in question. Examples of suitable bleaching agents include:
[00136] (1) photo-brighteners, for example, sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanines, xanthone dyes and mixtures thereof;
[00137] (2) preformed peracids: suitable preformed peracids include, but are not limited to compounds selected from the group consisting of preformed peroxyacids or their salts, typically percarboxylic salts and acids, percarbonic salts and acids , perimidic salts and acids, peroxymonosulfuric salts and acids, for example, Oxone® and mixtures thereof. Suitable examples include peroxycarboxylic acids and their salts or peroxysulfonic acids or their salts. Typical peroxycarboxylic acid salts suitable for use in this have a chemical structure that corresponds to the following chemical formula:

[00138] where: R14 is selected from alkyl, aralkyl, cycloalkyl, aryl or heterocyclic groups; the group R14 can be linear or branched, substituted or unsubstituted; having, when the peracid is hydrophobic, between 6 to 14 carbon atoms or between 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms and Y is any suitable counterion that achieves electrical charge neutrality, preferably Y is selected from hydrogen, sodium and potassium. Preferably, R14 is C6-9 straight or branched, substituted or unsubstituted alkyl. Preferably, the peroxyacid or its salt is selected from peroxyhexanoic acid, peroxyheptanoic acid, peroxycyanoic acid, peroxynonanoic acid, peroxidecanoic acid and any salt thereof or any combination thereof. Particularly preferred peroxyacids are phthalimido-peroxyalkanoic acids, in particular ε-phthalimido hexanoic acid (PAP). Preferably, the peroxyacid or its salt has a melting point in the range of 30 ° C to 60 ° C.
[00139] The preformed peroxyacid or its salt can also be a peroxysulfonic acid or its salt, which typically has the chemical structure that corresponds to the following chemical formula:

[00140] where: R15 is selected from alkyl, aralkyl, cycloalkyl, aryl or heterocyclic groups; the group R15 can be linear or branched, substituted or unsubstituted; and Z is any suitable counterion that achieves electrical charge neutrality, preferably Z is selected from hydrogen, sodium and potassium. Preferably, R15 is C4-14 straight or branched, substituted or unsubstituted alkyl, preferably C6-14 alkyl. Preferably, such bleaching components can be present in the compositions of the invention in an amount between 0.01% to 50%, most preferably between 0.1% to 20%.
[00141] (3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium perborate salts (usually mono or tetrahydrate), percarbonate, persulfate, phosphate, persilicate of mixtures of these. In one aspect of the invention, the inorganic perhydrate salts are selected from the group consisting of sodium perborate, percarbonate salts and mixtures thereof. When used, inorganic perhydrate salts are typically present in amounts between 0.05 to 40% by weight or 1 to 30% by weight of the total fabric and treatment product and are typically incorporated into such fabric and treatment products as crystalline solids that can be coated. Suitable coatings include inorganic salts such as alkali metal silicate, carbonate and borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils and fatty soaps; and
[00142] (4) bleach activators that have R- (C = O) -L, where R is an alkyl group, optionally branched that has, when the bleach activator is hydrophobic, between 6 to 14 carbon atoms or between 8 to 12 carbon atoms and when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is a starting group. Examples of suitable starting groups are benzoic acid and its derivatives - especially benzene sulfonate. Suitable bleach activators include dodecanoyl oxybenzene sulfonate, decanoyl oxybenzene sulfonate, decanoyl oxybenzoic acid or its salts, 5,5,5-trimethyl hexanoyl benzene sulfonate, tetracetyl ethylene diamine (TAED) and nonanoyloxybenzene sulfonate (NOBS). Bleach activators are also described in WO 98/17767. Although any suitable bleach activator can be employed, in one aspect of the invention the composition in question may comprise NOBS, TAED or mixtures thereof.
[00143] (5) Bleaching catalysts. The compositions of the present invention can also include one or more bleaching catalysts capable of accepting an oxygen atom from a peroxyacid and / or its salt and transferring the oxygen atom to an oxidizable substrate. Suitable bleach catalysts include, but are not limited to: imine cations and polyions; imino zwitterions; modified amines; modified amine oxides; N-sulfonyl imines; N-phosphonyl imines; N-acyl imines; thiadiazole dioxides; perfluoro-rimins; cyclic sugar ketones and alpha amino ketones and their mixtures. Suitable alpha amino ketones are, for example, as described in WO 2012/000846 A1, WO 2008/015443 A1, and WO 2008/014965 A1. Suitable mixtures are as described in USPA 2007/0173430 A1.
[00144] Without wishing to be bound by theory, the inventors believe that controlling electrophilicity and hydrophobicity in the manner described above, allows the whitening ingredient to be released substantially only in areas of the tissue that are more hydrophobic and that contain electron-rich dirt , including visible chromophores that are susceptible to bleaching by highly electrophilic oxidants.
[00145] In one aspect, the bleaching catalyst has a structure that corresponds to the general formula below:

[00146] Where R13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyladecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n -octadecyl, iso-nonyl, isodecyl, iso-tridecyl and iso-pentadecyl;
[00147] (6) The composition may preferably comprise complex metal catalysts. A preferred type of metal-containing bleach is a catalyst system comprising a transition metal cation of defined bleaching catalyst activity, such as cations of copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese, a cation of auxiliary metal that has little or no catalytic activity, such as zinc and aluminum cations and a scavenger that has defined stability constants for catalytic and auxiliary metal cations, particularly ethylenediamine tetraacetic acid, ethylenediamine tetra (methylenephosphonic) acid and its salts soluble in water. Such catalysts are described in U.S. 4,430,243.
[00148] If desired, the compositions can be catalyzed by means of a manganese compound. Such compounds and usage levels are well known in the art and include, for example, the manganese-based catalysts described in U.S. 5,576,282.
Useful cobalt bleaching catalysts are known and are described, for example, in U.S. 5,597,936; U.S. 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught, for example, in U.S. 5,597,936, and U.S. 5,595,967.
[00150] The compositions may also suitably include a transition metal complex of binders such as bispidones (WO 05/042532 A1) and / or macropolicy rigid binders - abbreviated as "MRLs". In a practical and non-limiting way, the compositions and processes of this can be adjusted to provide on the order of at least one part per hundred million of the active MRL species in the aqueous washing medium and will typically supply between about 0.005 ppm to about 25 ppm , between about 0.05 ppm to about 10 ppm or even between about 0.1 ppm to about 5 ppm of the MRL in the wash liquid.
[00151] Suitable transition metals in the present transition metal bleaching catalyst include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-1,5,8,12-tetrazabicyclo [6.6.2] hexadecane. Suitable transition metal MRLs are easily prepared by known procedures, such as those taught in WO 00/32601 and U.S. 6,225,464.
[00152] When present, the source of hydrogen peroxide / perished and / or bleaching poker is generally present in the composition in an amount between about 0.1 to about 60% by weight, between about 0.5 to about 40% by weight or even between about 0.6 to about 10% by weight based on the fabric and the treatment product. One or more hydrophobic peracids or their precursors can be used in combination with one or more hydrophilic peracids or their precursors.
[00153] Typically, the hydrogen peroxide source and bleach activator will be incorporated together. The quantities of the hydrogen peroxide source and perished or bleach activator can be selected such that the molar ratio of available oxygen (from the peroxide source) to perished is between 1: 1 to 35: 1 or even 2: 1 to 10: 1.
[00154] Surfactant. Preferably, the composition comprises a surfactant or surfactant system. The surfactant can be selected from non-ionic, anionic, cationic, amphoteric, ampholytic, amphiphilic, zwitterionic, non-ionic semi-polar surfactants and mixtures of these. Preferred surfactant systems comprise one or more anionic surfactants, most preferably in combination with a co-surfactant, most preferably a nonionic and / or amphoteric and / or zwitterionic surfactant. Preferred surfactant systems comprise both anionic and non-ionic surfactants, preferably in weight ratios between 90: 1 to 1:90. In some examples, a weight ratio of anionic to nonionic surfactant of at least 1: 1 is preferred. However, a ratio below 10: 1 may be preferred. When present, the total level of surfactant is preferably from 0.1% to 60%, from 1% to 50% or even from 5% to 40% by weight of the composition in question.
[00155] Preferably, the composition comprises an anionic detersive surfactant, preferably sulfate and / or sulfonate surfactants. Preferred examples include alkyl benzene sulfonates, alkyl sulfates and alkoxylated alkyl sulfates. Preferred sulfonates are C10-13 alkyl benzene sulphonates. Suitable alkyl benzene sulfonate (LAS) can be obtained by sulfonation of commercially available linear alkyl benzene (LAB); Suitable LAB includes 2-phenyl lower LAB such as those supplied by Sasol under the trade name of I-sochem® or those supplied by Petresa under the trade name of Petrelab®, another suitable LAB includes 2-phenyl LAB, such as those provided by Sasol under the Hyblene® trade name. A suitable anionic detersive surfactant is alkyl benzene sulfonate which is obtained by the DETAL catalyzed process, although other synthesis pathways, such as HF, may also be suitable. In one aspect, a magnesium salt from LAS is used.
Preferred sulfate detersive surfactants include alkyl sulfate, typically C8-18 alkyl sulfate or predominantly C12 alkyl sulfate. A preferred alkyl sulfate is alkoxide alkyl sulfate, preferably C8-18 alkoxide alkyl sulfate. Preferably, the alkoxy group is a deethoxylation group. Typically, alkoxylated alkyl sulfate has an average degree of alkoxy between 0.5 to 30 or 20 or between 0.5 to 10. Particularly preferred are C8-18 alkyl ethoxylated sulfates that have an average degree of ethoxylation between 0.5 to 30 10, between 0.5 to 7, between 0.5 to 5 or even between 0.5 to 3.
[00157] Alkyl sulfate, alkyl ethoxylated sulfate and alkyl benzene sulfonates can be linear or branched, substituted or unsubstituted. When the surfactant is branched, preferably the surfactant will comprise a branched medium chain sulfate or sulfonate surfactant. Preferably, the branching groups comprise C1-4 alkyl groups, typically methyl and / or ethyl groups.
[00158] Preferably, the composition comprises a nonionic detersive surfactant. Suitable non-ionic surfactants are selected from the group consisting of: C8-18 alkyl ethoxides, such as Shell's NEODOL® non-ionic surfactants; C6-12 alkyl phenol alkoxides in which the alkoxide units may be ethyleneoxy units, propyneloxyl units or a mixture thereof; condensates of C12-18 alcohol and C6-12 alkyl phenol with ethylene oxide / propylene oxide block polymers such as Pluronic® from BASF; medium chain branched C14-22 alcohols; medium chain branched C14-22 alkyl alkoxides, typically having an average degree of alkoxy between 1 to 30; alkyl polysaccharides, in one aspect, alkyl polyglycosides; polyhydroxy fatty acid amides; poly (oxyalkylated) ether alcohol surfactants; and mixtures of these.
[00159] Suitable non-ionic detersive surfactants include alkyl polyglucoside and / or an alkoxylated alkyl alcohol.
[00160] In one aspect, nonionic detersive surfactants include alkoxylated alkyl alcohols, in one aspect a C8-18 alkoxyalkyl alcohol, for example, a C8-18 alkylethoxylated alcohol, the alkoxylated alkyl alcohol may have a medium degree alkoxy between 1 to 80, preferably between 1 to 50, most preferably between 1 to 30, between 1 to 20 or between 1 to 10. In one aspect, the alkoxylated alkyl alcohol may be a C8-18 alkyl ethoxylated alcohol which has an average degree of ethoxylation between 1 to 10, between 1 to 7 or greater than 1 to 5 or between 3 to 7 or even below 3 or 2. Alkoxylated alkyl alcohol can be linear or branched and substituted or unsubstituted.
[00161] Suitable non-ionic surfactants include those with the BASF Lutensol ® trade name.
[00162] Suitable cationic detersive surfactants include alkyl pyridinium compounds, aquila quaternary ammonium compounds, aquila quaternary phosphonium compounds, aquil ternary sulfonic compounds and mixtures thereof.
[00163] Suitable cationic detersive surfactants are quaternary ammonia compounds that have the general formula: (R) (R1) (R2) (3) N + X-
[00164] Where R is a straight or branched, substituted or unsubstituted C6-18 alkyl or alkenyl moiety, R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or hydroxyethyl moiety, X is an anion which provides charge neutrality, suitable anions include: halides, for example, chloride; sulfate; and sulfonate. Suitable cationic detersive surfactants are mono- C6-18 alkyl chlorides monohydroxyethyl dimethyl quaternary ammonia. Highly suitable cationic detersive surfactants are mono- C8-10 alkyl monohydroxyethyl dimethyl quaternary ammonia, C10-12 mono-hydroxyethyl dimethyl quaternary ammonium chloride and mono- C10 alkyl mono- hydroxyethyl dimethyl quaternary ammonia.
[00165] Suitable amphoteric / zwitterionic surfactants include amine oxides and betaines.
[00166] Anionic surfactants neutralized with amine - Anionic surfactants of the present invention and adjunct anionic co-surfactants can exist in the form of an acid and said acid form can be neutralized to form a surfactant salt that is desirable for use in detergent compositions are present. Typical agents for neutralization include a metal counterion base such as hydroxides, for example, NaOH or KOH. Preferred additional agents to neutralize anionic surfactants of the present invention and adjunct anionic surfactants or co-surfactants in their acidic forms include ammonia, amines or alkanolamines. Alcanolamines are preferred. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine and other linear or branched alkanolamines known in the art; for example, highly preferred alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine or 1-amino-3-propanol. The amine neutralization can be done in a complete or partial extension, for example, part of the anionic surfactant mixture can be neutralized with sodium or potassium and part of the anionic surfactant mixture can be neutralized with amines or alkanolamines.
[00167] Builders. Preferably, the composition comprises one or more builders or a builder system. When a builder is used, the composition of the invention will typically comprise at least 1%, from 2% to 60% of builder. It may be preferred that the composition comprises low levels of phosphate salt and / or zeolite, for example, between 1 to 10 or 5% by weight. The composition may even be substantially free of a strong builder; substantially free of a strong builder means "deliberately not added" zeolite and / or phosphate. Typical zeolite builders include zeolite A, zeolite P and zeolite MAP. A typical phosphate builder is sodium tri-polyphosphate.
[00168] Chelating agent. Preferably the composition comprises chelating agents and / or inhibitors of crystal growth. Suitable molecules include copper, iron and / or manganese chelating agents and mixtures thereof. Suitable molecules include amino-carboxylates, aminophosphonates, succinates, their salts and mixtures. Non-limiting examples of chelators suitable for use in this include ethylene diaminetetraacetates, N- (hydroxyethyl) ethylene diaminotriacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraminehexacetates, diethylonetriamine-pentacetates, ethanethylsine- ), ethylenediamine disuccinate (EDDS), hydroxyethanedimethylenephosphonic acid (HEDP), methylglycinodiacetic acid (MGDA), diethylene triaminopentaacetic acid (DTPA), its salts and mixtures thereof. Other non-limiting examples of chelators for use in the present invention are found in U.S. Patent Nos. 7445644, 7585376 and 2009 / 0176684A1. Other chelating agents suitable for use in this are the DEQUEST commercial series and chelators from Monsanto, DuPont and Nalco, Inc.
[00169] Dye Transfer Inhibitors (DTI). The composition can comprise one or more agents that inhibit dye transfer. In one embodiment of the invention, the inventors have surprisingly found that compositions comprising agents that inhibit polymeric dye transfer in addition to the specified dye provide improved performance. This is surprising because these polymers prevent dye deposition. Suitable dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, N-oxide polyamine polymers, N-vinylpyrrolidone and N-vinylimidazole copolymers, polyvinyloxazolidones and polyvinylimidazois or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, Chro-maBond S-403E and Chromabond S-100 from Ashland Aqualon, and Sokanan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59, Sokalan® HP 56K , Sokalan® HP 66 from BASF. Other suitable DTIs are as described in WO2012 / 004134. When present in a composition in question, agents that inhibit dye transfer may be present at levels between about 0.0001% to about 10%, between about 0.01% to about 5% or even between about from 0.1% to about 3% by weight of the composition.
[00170] Fluorescent Brightener. Preferably the composition comprises one or more fluorescent brighteners. Optical brighteners that may be useful in the present invention can be classified into subgroups, which include, but are not limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinocyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered heterocyclic rings and other mixtures of agents. Particularly preferred brighteners are selected from: sodium 2 (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] triazole, disodium 4, 4'-bis {[(4-anilino-6- (N methyl -N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)] amino} stilbene-2-2- disulfonate, disodium 4,4'-bis {[(4-anilino-6-morpholino-1, 3,5-triazin-2-yl)] amine} stilbene-2-2 'disulfonate and disodium 4,4'-bis (2-sulfo-styryl) biphenyl. Other examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Specific non-limiting examples of optical brighteners that are useful in the present compositions are those identified in U.S. Pat. No. 4,790,856 and Pat. No. 3,646,015.
[00171] A preferred rinse aid has the structure below:

[00172] Suitable levels of fluorescent brightener include levels less than about 0.01, about 0.05, about 0.1 or up to about 0.2% by weight to levels greater than 0.5 or up to 0 , 75% by weight.
[00173] In one aspect, the rinse aid can be loaded on clay to form a particle.
Preferred brighteners are wholly or predominantly (typically at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 99% by weight) in alpha-crystalline form. A highly preferred brightener comprises a fluorescent brightener CI 260, preferably having the following structure:

[00175] This can be particularly useful as it dissolves well in cold water, for example, below 30 or 25 or even 20 ° C.
[00176] Preferably, the brighteners are incorporated into the composition in the form of micronized particulate, most preferably having an average weighted primary particle size between 3 to 30 microns, from 3 microns to 20 microns or between 3 to 10 microns.
[00177] The composition may comprise the fluorescent brightener CI 260 in beta-crystalline form and the weight ratio of: (i) fluorescent brightener CI 260 in alpha-crystalline form to (ii) a-fluorescent brightener CI 260 in beta- crystalline can be at least 0.1 or at least 0.6.
[00178] BE680847 refers to a process for making fluorescent polisher C.I. 260 in alpha-crystalline form.
[00179] Silicate salts. The composition may preferably contain silicate salts, such as sodium or potassium silicate. The composition can comprise from 0% by weight to less than 10% by weight of silicate salt, 9% by weight or 8% by weight, or 7% by weight, or 6% by weight, or 5% by weight. weight or 4% by weight or 3% by weight or up to 2% by weight and preferably between about 0% by weight or 0.5% by weight or up to 1% by weight of silicate salt. A suitable silicate salt is sodium silicate.
[00180] Dispersants. The composition may also preferably contain dispersants. Suitable water-soluble organic materials include homo or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms.
[00181] Enzyme Stabilizers. The composition may preferably comprise enzyme stabilizers. Any conventional enzyme stabilizer can be used, for example, by the presence of water-soluble sources of calcium and / or magnesium ions in the finished tissue and treatment products that provide these ions to the enzymes. In the case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a boron compound that includes borate or preferably 4-formyl phenylboronic acid, phenylboronic acid and its derivatives or compounds such as calcium formate, sodium formate and 1 , 2-propane diol can be added to improve stability.
[00182] Solvent System. The solvent system in the present compositions can be a solvent system that contains only water or mixtures of organic solvents without or preferably with water. Preferred organic solvents include 1,2-propanediol, e-tanol, glycerol, dipropylene glycol, methyl propane diol and mixtures thereof. Other lower alcohols, C1-C4 alkanolamines such as monoethanolamine and triethanolamine can also be used. Solvent systems may be absent, for example, in solid anhydrous embodiments of the invention, but more typically they are present in levels in the range of about 0.1% to about 98%, preferably at least about 1% to about 50%, more generally between about 5% to about 25%.
[00183] In some embodiments of the invention, the composition is in the form of a structured liquid. Such structured liquids can be internally structured, whereby the structure is formed by the primary ingredients (for example, surfactant material) and / or externally structure by providing a three-dimensional matrix that uses secondary ingredients (for example, polymers, clay and / or silicate material), for use, for example, as thickeners. The composition can comprise a structurant, preferably from 0.01% by weight to 5% by weight, from 0.1% by weight to 2% by weight of structurant. Examples of suitable structures are given in US2006 / 0205631A1, US2005 / 0203213A1, US7294611, US6855680. The structuring agent is typically selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulose-based materials, cellulose microfiber, hydrophobically modified alkali-modified e-mulsions such as Polygel W30 (3VSigma) , biopolymers, xanthan gum, gellan gum, hydrogenated castor oil, hydrogenated castor oil derivatives such as non-ethoxylated derivatives thereof and mixtures thereof, in particular those selected from the group of hydrogenated castor oil, hydrogenated castor oil derivatives, cellulose microfibrillar, hydroxyfunctional crystalline materials, long-chain fatty alcohols, 12-hydroxystearic acids, clays and their mixtures. A preferred structuring agent is described in US Patent No. 6,855,680 which defines suitable hydroxy-functional crystalline materials in detail. Hydrogenated castor oil is preferred. Such structuring systems have a structuring system similar to a thread that has a range of proportions. Other suitable structures and processes for making them are described in WO2010 / 034736.
[00184] The composition of the present invention may comprise a high melting bridge fatty compound. The high-melting fatty compound useful in this has a melting point of 25 ° C or higher and is selected from the group consisting of fatty alcohols, fatty acids, derived from fatty alcohol, derivatives of fatty acid and their mixtures. Such low melting point compounds are not intended to be included in this section. Non-limiting examples of compounds with a high melting point are found in the International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. When present, the high melting fat compound is included in the composition. a level of 0.1% to 40%, preferably from 1% to 30%, more preferably from 1.5% to 16% by weight of the composition, from 1.5% to 8% with a view to providing benefits of improved conditioning such as sliding sensation during application on damp hair, softness and feeling of humidity on dry hair.
[00185] Cationic Polymer. The compositions of the present invention can contain a cationic polymer. Concentrations of the cationic polymer in the composition typically range from 0.05% to 3%, in another modality from 0.075% to 2.0% and in another modality from 0.1% to 1.0%. Suitable cationic polymers will have cationic charge densities of at least 0.5 meq / gm, in another modality at least 0.9 meq / gm, in another modality at least 1.2 meq / gm, in another modality at least 1 , 5 meq / gm, but in an embodiment less than 7 meq / gm, and in another embodiment less than 5 meq / gm, at the intended use pH of the composition, whose pH will generally vary between pH 3 to pH 9, in a mode between pH 4 and pH 8. Here, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges in the polymer to the molecular weight of the polymer. The average molecular weight of such suitable cationic polymers will generally be between 10,000 and 10 million, in a modality between 50,000 and 5 million and in another modality between 100,000 and 3 million.
[00186] Cationic polymers suitable for use in the compositions of the present invention contain portions containing cationic nitrogen such as portions of quaternary ammonia or cationic protonated amino portions. Any anionic counterions can be used in association with cationic polymers as long as the polymers remain soluble in water, in the composition or in a coacervated phase of the composition and as long as the counterions are physically and chemically compatible with the essential components of the composition or that would not otherwise unnecessarily impair the performance, stability or aesthetics of the product. Non-limiting examples of such counterions include halides (eg, chloride, fluoride, bromide, iodide), sulfate and methyl sulfate.
[00187] Non-limiting examples of such polymers are described in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)).
[00188] Other cationic polymers suitable for use in the composition include polysaccharide polymers, cationic guar gum derivatives, cellulose ethers containing quaternary nitrogen, synthetic polymers, etherified cellulose copolymers, guar and starch. When used, cationic polymers are soluble in the composition or are soluble in a complex coacervate phase in the composition formed by the cationic polymer and the anionic, amphoteric and / or zwitterionic surfactant component described here previously. Complex coacervates of the cationic polymer can also be formed with other materials loaded in the composition;
[00189] Suitable cationic polymers are described in U.S. Pat. No. 3,962,418; 3,958,581; and U.S. Publication No. 2007 / 0207109A1.
[00190] Non-ionic polymer. The composition of the present invention can include a nonionic polymer as a conditioning agent. Polyalkylene glycols having a molecular weight of more than 1000 are useful here. Those with the following general formula are useful:

[00191] in which R95 is selected from the group consisting of H, methyl and their mixtures.
[00192] Conditioning agents and, in particular silicones, can be included in the composition. The conditioning agent useful in the compositions of the present invention typically comprises a water-insoluble, water-dispersible, non-volatile liquid that forms liquid, emulsified particles. Conditioning agents suitable for use in the composition are those conditioning agents generally characterized as silicones (for example, silicone oils, cationic silicones, silicone gums, highly refractive silicones and silicone resins), organic conditioning oils (for example, oils hydrocarbon, polyolefins and fatty esters) or combinations thereof or those conditioning agents which otherwise form liquid particles, dispersed in the aqueous surfactant matrix. Such conditioning agents must be physically and chemically compatible with the essential components of the composition and must not unnecessarily impair the performance, stability or aesthetics of the product.
[00193] The concentration of the conditioning agent in the composition should be sufficient to provide the desired conditioning benefits. Such concentration may vary with the conditioning agent, desired conditioning performance, average particle size of the conditioning agent, the type and concentration of other components and other similar factors.
[00194] The concentration of the silicone conditioning agent typically ranges from about 0.01% to about 10%. Non-limiting examples of silicone conditioning agents and additional silicone suspending agents are described in Pat. Re-edited U.S. No. 34,584. Pat. U.S. Nos. 5,104,646; 5,106,609; 4,152,416; 2,826,551; 3,964,500; 4,364,837; 6,607,717; 6,482,969; 5,807,956; 5,981,681; 6,207,782; 7,465,439; 7,041,767; 7,217,777; US Patent Application Nos. 2007 / 0286837A1; 2005 / 0048549A1; 2007 / 0041929A1; Pat. British No. 849,433; German Patent No. DE 10036533, which are all incorporated herein by reference; Chemistry and Technology of Silicones, New York: Academic Press (1968); General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76; Silicon Compounds, Petrarch Systems, Inc. (1984); and in the Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., Pp 204-308, John Wiley & Sons, Inc. (1989).
[00195] Organic Conditioning Oil. The compositions of the present invention can also comprise from about 0.05% to about 3% of at least one organic conditioning oil as a conditioning agent, alone or in combination with other conditioning agents, such as silicones (described herein) . Suitable conditioning oils include hydrocarbon oils, polyolefins and acidic esters. Also suitable for use in such compositions are the conditioning agents described by Procter & Gamble Company in Pat. U.S. Nos. 5,674,478 and 5,750,122. Also suitable for use are the conditioning agents described in Pat. U.S. Nos. 4,529,586. 4,507,280, 4,663,158, 4,197,865, 4,217,914, 4,381,919 and 4,422. 853.
[00196] Hygiene Agent. The compositions of the present invention may also comprise components to release benefits for hygiene and / or foul odor such as one or more of zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac®, polyethyleneine (such as BASF's Lupasol®) ) and its complexes of zinc, silver and silver compounds, especially those designed to bind Ag + slowly or silver nanodispersions.
[00197] Probiotics. The composition can comprise probiotics, such as those described in WO2009 / 043709.
[00198] Foam reinforcers. The composition may preferably comprise foam reinforcers if a large amount of foaming is desired. Suitable examples are C10-C16 alkanolamines or C10-C14 alkyl sulfates, which are preferably incorporated at levels of 1% -10%. C10-C14 monoethanol and diethanol amines illustrate a typical class of such foam boosters. The use of such foam reinforcers with highly foaming adjunct surfactants such as amine oxides, betaines and sultains noted above is also advantageous. If desired, water-soluble magnesium and / or calcium salts such as MgCl2, MgSO4, CaCl2, Ca-SO4 and the like can be added at levels of typically 0.1% to 2%, to provide additional foam and to intensify grease removal performance.
[00199] Foam suppressor. Compounds to reduce or suppress foaming can be incorporated into the compositions of the present invention. Foam suppression may be of particular importance in the so-called "high-concentration cleaning process" as described in Pat. No. 4,489,455 and 4,489,574 and in front loading type washing machines. A wide variety of materials can be used as foam suppressors and foam suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Tech-nology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples of foam suppressors include monocarboxylic fatty acids and soluble salts thereof, high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg fatty acid triglycerides), monovalent alcohol fatty acid esters, C18-C40 aliphatic ketones (e.g., stearone), N-alkylated amino triazines, waxy hydrocarbons having a melting point, preferably below about 100 ° C, silicone foam suppressants and secondary alcohols. Foam suppressors are described in Pat. U.S. Nos. 2,954,347; 4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471; 4,983,316; 5,288,431; 4,639,489; 4,749,740; and 4,798,679; 4,075,118; European patent application No. 89307851.9; EP 150,872; and DOS 2,124,526.
[00200] For any detergent compositions to be used in automatic washing machines, the foam must not form in an amount that it overflows in the washing machine. Foam suppressors, when used, are preferably present in a "foam suppressant amount". By "foam suppressant amount" is understood that the composer of the composition can select an amount of these foam controlling agents that will sufficiently control the foam to result in a low foam laundry detergent for use in automatic washing machines. The compositions will generally comprise between 0% to 10% foam suppressor. When used as foam suppressants, monocarboxylic fatty acids and their salts will typically be present in amounts up to 5% by weight of the detergent composition. Preferably, 0.5% to 3% fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are used in amounts up to 2.0% by weight of the detergent composition, although larger amounts can be used. Monostearyl phosphate foam suppressants are generally used in amounts ranging from 0.1% to 2% by weight of the composition. Hydrocarbon foam suppressors are typically used in amounts ranging from 0.01% to 5.0% by weight of the composition, although higher levels can be used. Alcohol foam suppressors are typically used in 0.2% to 3% by weight of the finished compositions.
[00201] Pearly agents. Pearlized agents as described in WO2011 / 163457 can be incorporated into the compositions of the invention.
[00202] Perfume. Preferably, the composition comprises a perfume, preferably in the range between 0.001 to 3% by weight, most preferably between 0.1 to 1% by weight. Several suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. It is common for a plurality of components of perfume are present in the compositions of the invention, for example, four, five, six, seven or more. In perfume mixes, preferably 15 to 25% are higher grades. Top grades are defined by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1995]). Preferred top notes include rose oxide, citrus oils, linaloyl acetate, linalool, dihydromyrcenol and cis-3-hexanol.
[00203] Packaging. Any conventional packaging can be used and the packaging can be totally or partially transparent so that the consumer can see the color of the product that he may have supplied or contributed to the color of the dyes essential to the invention. Compounds that absorb UV may be included in some or all of the packaging. PROCESS FOR MAKING COMPOSITIONS
[00204] The compositions of the invention can be in any useful form, as described above. They can be made by any process chosen by the formulator, non-limiting examples of which are described in the examples and in U.S. 4,990,280; U.S. 20030087791A1; U.S. 20030087790A1; U.S. 20050003983A1; U.S. 20040048764A1; U.S. 4,762,636; U.S. 6,291,412; U.S. 20050227891A1; EP 1070115A2; U.S. 5,879,584; U.S. 5,691,297; U.S. 5,574,005; U.S. 5,569,645; U.S. 5,565,422; U.S. 5,516,448; U.S. 5,489,392; U.S. 5,486.
[00205] When in liquid form, the laundry compositions can be aqueous (typically above 2% by weight or even above 5 to 10% by weight of total water, up to 90 or up to 80% by weight or 70% by weight total water) or non-aqueous (typically below 2% of the total water content). Typically the compositions of the invention will be in the form of an aqueous solution or uniform dispersion or suspension of surfactant, shading dye and certain types of other optional ingredients, some of which may normally be in solid form, which have been combined with components normally liquids of the composition, such as liquid nonionic alcohol epoxy, aqueous liquid carrier and any other optional ingredients normally liquid. Such a solution, dispersion or suspension will be in an acceptably stable phase. When in the form of a liquid, the laundry compositions of the invention have a viscosity between 1 to 1500 centipoises (1 to 1500 mPa * s), more preferably between 100 to 1000 centipoises (100-1000 mPa * s), and most preferably between 200 to 500 centipoises (200-500 mPa * s) at 20 s -1 and 21 ° C. Viscosity can be determined by conventional methods. Viscosity can be measured using a TA instruments AR 550 rheometer, using a 40 mm diameter sheet steel shaft and a gap size of 500 μm. The high shear stress at 20s-1 and the low shear stress at 0.05-1 can be obtained by scanning the logarithmic shear stress from 0.1-1 to 25-1 at the time of 3 minutes at 21 ° C. The preferred rheology described can be obtained using the existing internal structure with detergent ingredients or by using an external rheology modifier. More preferably, laundry compositions, such as liquid detergent compositions, have a high shear stress between about 100 centipoise to 1500 centipoise, more preferably between 100 to 1000 cps. Unit dose of laundry compositions, such as liquid detergent compositions, have a high shear stress between 400 to 1000 cps. Laundry compositions such as laundry softening compositions typically have a high shear stress between 10 to 1000, more preferably between 10 to 800 cps, most preferably between 10 to 500 cps. Dishwashing compositions have a shear stress of between 300 to 4000 cps, more preferably 300 to 1000 cps.
[00206] Liquid compositions, preferably liquid detergent compositions can be prepared by combining their components in any convenient order and by mixing, for example, stirring, the resulting combination of components to form a liquid detergent composition in a stable phase . In one process, for the preparation of such compositions, a liquid matrix is formed containing at least a greater proportion or even substantially all of the liquid components, for example, a non-ionic surfactant, non-surfactant liquid vehicles and other liquid components optional, with the liquid components being e-thoroughly mixed by transmitting shear agitation to that liquid combination. For example, rapid stirring with a mechanical stirrer can be usefully employed. As long as the shear stirring is maintained, substantially all of the anionic surfactants and the ingredients in solid form can be added. Stirring of the mixture is continued and if necessary can be increased at that point to form a solution or a uniform dispersion of insoluble particles in the solid phase within the liquid phase. After some or all materials in solid form have been added to this stirred mixture, particles of any enzymatic material to be included, for example, enzyme granules, are incorporated. As a variation of the composition preparation procedure described hereinabove, one or more solid components can be added to the stirred mixture as a solution or paste of premixed particles with a small portion of one or more of the liquid components. After adding the components of the composition, stirring of the mixture is continued for a period of time sufficient to form compositions that have the required viscosity and phase stability characteristics. This will often involve shaking for about 30 to 60 minutes.
[00207] In one aspect of forming liquid compositions, the dye is first combined with one or more liquid components to form a dye premix and that dye premix is added to a composition formulation that contains a substantial portion , 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 balance of the components of the laundry detergent composition. For example, in the methodology described above, both the dye premix and the enzyme component are added in a final stage of component additions. In another aspect, the dye is encapsulated prior to addition to the detergent composition, the encapsulated dye is suspended in a structured liquid, and the suspension is added to a composition formulation that contains a substantial portion of the balance of the components of the laundry detergent composition. .
[00208] Scholarships. In a preferred embodiment of the invention, the composition is provided in the form of a unified dose, in the form of a tablet or preferably in the form of a liquid / solid (optionally granules) / gel / paste kept within a water-soluble film which it is known as a pouch or pod. The composition can be encapsulated in a pouch with one or multiple compartments. Multi-compartment bags are described in more detail in EP-A-2133410. When the composition is present in a bag with multiple compartments, the composition of the invention can be in one or two or more compartments, therefore the dye can be present in one or more compartments, optionally all compartments. Non-shading dyes or pigments or other aesthetics can also be used in one or more compartments. In one embodiment, the composition is present in a single compartment of a bag with multiple compartments.
[00209] The soluble film for forming the bags is soluble or dispersible in water and preferably has a solubility / dispersibility in water of at least 50%, preferably at least 75% or even at least 95% as measured by the method described here after using a glass filter with a maximum pore size of 20 microns:
[00210] 50 grams ± 0.1 grams of material for bag are added in a pre-weighed 400 ml beaker and 245 ml ± 1 ml of distilled water are added. This is vigorously stirred with a magnetic stirrer set to 600 rpm for 30 minutes. Then, the mixture is filtered through a folded qualitative sintered glass filter with a pore size as defined above (max. 20 microns). The water is removed from the collected filtrate by any conventional method and the weight of the remaining material is determined (which is dissolved or the dispersed fraction). Then, the percentage of solubility or dispersibility can be calculated. Preferred film materials are polymeric materials. The film material can be obtained, for example, by casting, blow molding, extrusion or blow extrusion of the polymeric material as known in the art. Polymers, copolymers or their derivatives preferred for use as bag material are selected from polyvinyl alcohols, pyrrolidine polyvinyl, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates , polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic / acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan and carrageenan gum. The most preferred polymers are selected from water-soluble acrylate polyacrylates and copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, polymethyl alcohol and most preferably polyvinyl alcohols, most preferably selected from alcohols. and hydroxypropyl methyl cellulose (HPMC) and their combinations. Preferably, the level of polymer in the material in the bag material, for example, a PVA polymer, is at least 60%. The polymer can have any weighted average molecular weight, preferably between about 1000 to 1,000,000, more preferably between about 10,000 to 300,000, even more preferably between about 20,000 to 150,000. Polymer mixtures can also be used as a bag material. This can be beneficial for controlling the mechanical and / or dissolving properties of the compartments or pouch, depending on your applications and the requirements required. Suitable mixtures include, for example, mixtures in which one polymer has greater solubility in water than another polymer and / or a polymer which has greater mechanical strength than another polymer. Also suitable are mixtures of polymers having different weighted average molecular weights, for example, a mixture of PVA or its copolymer with an average weighted molecular weight of about 10,000 to 40,000, preferably around 20,000 and of PVA or its copolymer with an average weighted molecular weight of about 100,000 to 300,000, preferably around 150,000. Polymer blend compositions are also suitable, for example, comprising mixtures of hydrolytically degradable and water-soluble polymers such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1 to 35% by weight of polylactide and about 65% to 99% by weight of polyvinyl alcohol. For use here, polymers are preferred which are hydrolyzed by about 60% to about 98%, preferably hydrolyzed by about 80% to about 90%, to improve the dissolution characteristics of the material.
[00211] Naturally, different film material and / or films of different thicknesses can be used in the production of the compartments of the present invention. A benefit in selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.
[00212] Most preferred film materials are the PVA films known under the MonoSol brand, trade reference M8630, M8900, H8779 (as described in the claimants' pending applications, ref. 44528 and 11599) and those described in US 6 166 117 and US 6 787 512 and PVA films with corresponding solubility and deformation characteristics.
[00213] The film material can also comprise one or more additive ingredients. For example, it may be beneficial to add plasticizers, for example, glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol and mixtures thereof. Other additives include functional detergent additives to be released into the wash water, for example, organic polymeric dispersants, etc. PROCESS TO MAKE THE WATER SOLUBLE BAG
[00214] Compositions of the invention in bag form can be made using any suitable equipment and method. However, multi-compartment bags are preferably made using the horizontal filling process. The film is preferably moistened, more preferably heated to increase its malleability. Even more preferably, the method also involves using a vacuum to design the film in a suitable mold. The vacuum drawing the film in the mold can be applied for 0.2 to 5 seconds, preferably 0.3 to 3 or even more preferably 0.5 to 1.5 seconds, once the film is on the horizontal portion of the surface. This vacuum can preferably be such that it provides a sub-pressure between -10 KPa and -100 KPa (-100 mbar and -1000 mbar) or even between -20 KPa and -60 KPa (-200 mbar and -600 mbar).
[00215] The molds, in which the bags are made, can have any shape, length, width and depth, depending on the required dimensions of the bags. The molds can also vary in size and shape from one to the other, if desired. For example, it may be preferred that the volume of the finished bags is between 5 and 300 ml or up to 10 and 50 ml or even 20 2 100 ml and that the sizes of the molds are accordingly adjusted.
[00216] Heat can be applied to the film in the process commonly known as thermoforming by any means. For example, the film can be heated directly by passing it through a heating element or through hot air, before feeding it over the surface or once over the surface. Alternatively, it can be indirectly heated, for example, by heating the surface or applying a heated item on the film. Preferably, most of the film is heated using an infrared light. The film is preferably heated to a temperature of 50 to 120 ° C or up to 60 to 90 ° C. Alternatively, the film can be moistened by any means, for example, directly by spraying a wetting agent (including water, solutions of the film material or plasticizers for the film material) on the film, before feeding it on. the surface or place it at once on the surface or indirectly by moistening the surface or by applying a moistened item on the film.
[00217] In the case of bags comprising powders, it is advantageous to perforate the film for several reasons: (a) to reduce the possibility of defects in the film during the formation of the bag, for example, defects in the film that can cause the film to break can be generated if the stretch of the film is very fast; (b) allowing the release of any gases derived from products contained in the bag, such as, for example, the formation of oxygen in the case of bleaching powders; and / or (c) to allow the continuous release of the perfume. In addition, when heating and / or humidification are used, perforation can be used before, during or after using the vacuum, preferably during or before applying the vacuum. It is therefore preferred that each mold comprises one or more orifices which are connected to a system that can provide vacuum through these orifices, on the film above the orifices, as described in more detail here.
[00218] Once the film has been heated / humidified, it is drawn in the appropriate mold, preferably using a vacuum. The filling of the molded film can be done by any known method for filling (mobilizing) items. The most preferred method will depend on the shape of the product and the required filling speed. Preferably, the molded film is filled by inline filling techniques. The filled, open bags are then closed using a second film by any suitable method. Preferably, this is also done while in a horizontal position and with continuous, constant movement. Preferably, the closure is done by continuously feeding a second material or film, preferably a water-soluble film, along and over the web of the open pouches and then preferably sealing the first film and the second film together, typically in the area between the molds and then between the bags.
[00219] Preferred methods for sealing include heat sealing, solvent welding and solvent or wet sealing. It is preferred that only the area that is to form the seal is treated with heat or solvent. Heat or solvent can be applied by any method, preferably over the closure of the material, preferably only in the areas that must form the seal. If solvent or wet welding or welding is used, it may be preferred that heat is also applied. Preferred wet or solvent welding / welding methods include applying the solvent selectively over the area between the molds or over the closing material, for example, by spraying or printing it on those areas and then applying pressure on these areas, to form the seal. Sealing cylinders and straps as described above (optionally also providing heat) can be used, for example.
[00220] The formed bags can then be cut by a cutting device. Cutting can be done using any known method. It may be preferred that the cut is also made continuously and preferably at a constant speed and preferably while in the horizontal position. The cutting device can, for example, be a sharp item or a heated item, whereby in the latter case, the heated item "burns" through the film / sealing area.
[00221] The different compartments of a bag with multiple compartments can be made together in a side-by-side style and consecutive bags are not cut. Alternatively, the compartments can be made separately. According to this preferred arrangement and process, grants are made according to the process that comprises the steps of:
[00222] a) forming a first compartment (as described above);
[00223] b) forming a recess within some or all of the closed compartments formed in step (a), to generate a second molded compartment superimposed above the first compartment;
[00224] c) fill and close the second compartment by means of a third film;
[00225] d) prohibit said first, second and third films; and
[00226] e) cutting the films to produce a bag with multiple compartments.
[00227] Said recess formed in step b is preferably obtained by applying a vacuum to the compartment prepared in step a).
[00228] Alternatively, the second and optionally the third compartments can be made in a separate step and then combined with the first compartment as described in our co-pending order EP 08101442.5, which is incorporated here by reference. A particularly preferred process comprises the steps of:
[00229] a) forming a first compartment, optionally using heat and / or vacuum, using a first film on a first molding machine;
[00230] b) filling said first compartment with a first composition;
[00231] c) in a second molding machine, deform a second film, optionally using heat and vacuum to make a second and, optionally, a third molded compartment;
[00232] d) fill in the second and, optionally, the third compartment;
[00233] e) seal the second and, optionally, the third compartment using a third film;
[00234] f) place the second and, optionally, the third sealed compartments on the first compartment;
[00235] g) seal the first, second and, optionally, the third compartments; and
[00236] h) cut the films to produce a bag with multiple compartments.
[00237] The first and second molding machines are selected based on their suitability to carry out the above process. The first molding machine is preferably a horizontal molding machine. The second molding machine is preferably a rotating drum molding machine, preferably located above the first molding machine.
[00238] In addition, it will be understood that by using appropriate feeding stations, it is possible to manufacture bags with multiple compartments that incorporate several different or different compositions and / or liquid, gel or paste compositions that are different or different.
[00239] Solid Form. As noted previously, laundry compositions can be in solid form. Suitable solid forms include tablets and particulate forms, for example, granulated particles, flakes or sheets. Various techniques for forming detergent compositions in such solid forms are well known and can be used here. In one aspect, for example, when the composition is in the form of a granulated particle, the dye is supplied in particulate form, optionally including additional components, but not all, of the laundry detergent composition. The particulate dye is combined with one or more additional particles that contain a balance of components of the laundry detergent composition. The dye, optionally including additional components, but not all components of the laundry detergent composition, can be supplied in an encapsulated form and the encapsulated shading dye is combined with particulates that contain a substantial balance of the components of the detergent composition for laundry. Particulate premixes suitable for the incorporation of coloring agents / benefits in laundry compositions of the invention are described, for example, in WO2010 / 084039, WO2007 / 039042, WO2010 / 022775, WO2009 / 132870, WO2009 / 087033, WO2007 / 006357 , WO2007 / 039042, WO2007 / 096052, WO2011 / 020991, WO2006 / 053598, WO2003 / 018740 and WO2003 / 018738.
[00240] Method of use. The compositions of that invention, prepared as described hereinabove, can be used to form aqueous washing / treatment solutions for use in the washing / treating of fabrics. Generally, an effective amount of such compositions is added to the water, for example, in a conventional automatic fabric washer, to form such aqueous washing solutions. The aqueous wash solution thus formed is then contacted, typically with stirring, with the fabrics to be washed / treated with it. An effective amount of the liquid detergent compositions added to the water to form aqueous washing solutions can comprise amounts sufficient to form between about 500 to 7000 ppm of composition in the aqueous washing solution or between about 1000 to 3000 ppm of the detergent compositions will be provided in the aqueous wash solution.
[00241] Typically, the washing liquid is formed by contacting the laundry composition with the washing water in such an amount, such that the concentration of the laundry composition in the washing liquid is above 0 g / l to 5 g / l, or 1 g / l, and 4.5 g / l, or 4.0 g / l, or 3.5 g / l, or 3.0 g / l, or 2.5 g / l, or up to 2.0 g / l, or up to 1.5 g / l. The fabric or textile washing method can be performed in a top-loading or front-loading automatic washing machine or it can be used in a manual wash application. In these applications, the washing liquid formed and the concentration of the laundry detergent composition in the washing liquid is that of the main washing cycle. Any water intake during any optional rinsing step is not included when the volume of the washing liquid is determined.
[00242] The washing liquid can comprise 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or up to 6 liters or less of water. The washing liquid can comprise from 0 to 15 liters, or 2 liters, and 12 liters, or up to 8 liters of water. Typically, from 0.01 kg to 2 kg of fabric per liter of washing liquid are dosed in said washing liquid. Typically 0.01 kg, or 0.05 kg, or 0.07 kg, or 0.10 kg, or 0.15 kg, or 0.20 kg, or 0.25 kg of fabric per liter of washing liquid are dosed in said washing liquid. Optionally, 50 g or less, or 45 g or less, or 40 g or less, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g or less, or up to 15 g or less, or up to 10 g or less of the composition is contacted with water to form the washing liquid. Such compositions are typically employed in concentrations between about 500 ppm to about 15,000 ppm in solution. When the washing solvent is water, the water temperature typically ranges from about 5 ° C to about 90 ° C, when the site comprises a fabric, the water-to-fabric ratio is typically between about 1: 1 to about 30: 1. Typically, the washing liquid comprising the laundry composition of the invention has a pH between 3 to 11.5.
[00243] In one aspect, such a method comprises the steps of optionally washing and / or rinsing said surface or fabric, contacting said surface or fabric with any composition described in that application, then optionally washing and / or rinsing said surface or fabric with an optional drying step.
[00244] The drying of such surfaces or fabrics can be achieved by any of the common means employed in domestic or industrial settings. The fabric can comprise any fabric capable of being washed under normal or institutional conditions of use and the invention is particularly suitable for synthetic textiles such as polyester and nylon and especially for the treatment of mixed fabrics and / or fibers comprising fabrics and / or fibers synthetic and cellulosic. Examples of synthetic fabrics are polyester, nylon and these can be present in mixtures with cellulosic fibers, for example, poly-cotton fabrics. The solution typically has a pH between 7 to 11, more generally 8 to 10.5. The compositions are typically used in concentrations from 500 ppm to 5000 ppm in solution. Water temperatures will typically range from about 5 ° C to about 90 ° C. The water to fabric ratio is typically between about 1: 1 to about 30: 1. EXAMPLES
[00245] In the following examples, the dye of formula 1 can be any dye of formula 1 or mixtures thereof, in particular any of the dyes 1 to 13 shown in the Dye Synthesis Examples above or mixtures thereof. EXAMPLES 1 TO 6
[00246] Granular laundry detergent compositions for manual washing or washing machines, typically top loading washing machines.

EXAMPLES 7 TO 13
[00247] Granular laundry detergent compositions typically for front-loading automatic washing machines



[00248] Any of the above compositions is used to wash fabrics at a concentration of 7000 to 10,000 ppm in water, 20 to 90 ° C and a 5: 1 water: clothing ratio. The typical pH is around 10. The fabrics are dry. In one aspect, fabrics are actively dried using a dryer. In one aspect, the fabrics are actively dried using an iron. In another aspect, the fabrics are merely allowed to dry on a rope on which they are exposed to air and optionally to sunlight.EXAMPLES 14-20 LAUNDRY LIQUID DETERGENT COMPOSITIONS FOR HEAVY CLEANING


* Based on the total weight of the cleaning and / or treatment composition, a total of no more than 12% water EXAMPLES 21 TO 25 COMPOSITIONS IN UNIT DOSE
[00249] This Example provides several formulations for unit dose laundry detergents. Such unit dose formulations can comprise one or multiple compartments.
[00250] The following unit dose laundry detergent formulations of the present invention are provided below.

EXAMPLE 26 UNIT DOSE COMPOSITIONS IN MULTIPLE COMPARTMENTS
[00251] Multi-compartment unit dose laundry detergent formulations of the present invention are provided below. In these examples, the unit dose has three compartments, but similar compositions can be made with two, four or five compartments. The film used to encapsulate the compartments is polyvinyl alcohol.



* Other optional component agents include foam suppressants, structuring agents such as those based on hydrogenated castor oil (preferably hydrogenated castor oil, anionic premix, solvents and / or pearlized Mica aesthetic enhancer. Raw Materials and Notes for the Examples of Composition
[00252] LAS is linear alkylbenzenesulfonate that has a medium aliphatic carbon chain with C9-C15 extension supplied by Stepan, Northfield, Illinois, USA or Huntsman Corp. (HLAS is the acid form).
[00253] C12-14 dimethylhydroxyethyl ammonium chloride, supplied by Clariant GmbH, Germany.
[00254] AE3S is C12-15alkylethoxy sulfate supplied by Stepan, Northfield, Illinois, USA.
[00255] AE7 is C12-15 alcohol epoxy, with an average ethoxylation grade of 7, supplied by Huntsman, Salt Lake City, Utah, USA.
[00256] AES is C10-18alkylethoxy sulfate supplied by Shell Chemicals.
[00257] AE9 is C12-13 alcohol epoxy, with an average ethoxylation grade of 9, supplied by Huntsman, Salt Lake City, Utah, USA.
[00258] HSAS or HC1617HSAS is a medium-chain primary alkyl sulfate with an average carbon chain length of about 16-17.
[00259] Sodium tripolyphosphate is supplied by Rhodia, Paris, France.
[00260] Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK.
[00261] 1.6 R Silicate is supplied by Koma, Nestemica, Czech Republic.
[00262] Sodium carbonate is supplied by Solvay, Houston, Texas, USA.
[00263] Polyacrylate MW 4500 is supplied by BASF, Ludwigshafen, Germany.
[00264] Carboxymethyl cellulose is Finnfix® V supplied by CP Kelco, Arnhem, Netherlands.
[00265] Suitable chelators are, for example, pentacetic diethylenetrotamine acid (DTPA) supplied by Dow Chemical, Midland, Mi-chigan, USA or hydroxyethane diphosphonate (HEDP) supplied by Sofia, St Louis, Missouri, USA Bagsvaerd, Denmark.
[00266] Savinase®, Natalase®, Stainzyme®, Lipex®, CellucleanTM, Mannaway® and Whitezyme® are all products from Novozymes, Bags-vaerd, Denmark.
[00267] Proteases can be provided by Genencor International, Palo Alto, California, USA (for example, Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (for example, Liquanase®, Coronase®).
[00268] Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 is Tinopal® CBS-X, phthalocyanineC: sulfonated zinc phthalocyanine and Direct Violet 9 is Pergasol® Violet BN-Z all supplied by Ciba Specialty Chemicals, Basel, Switzerland.
[00269] Sodium percarbonate supplied by Solvay, Houston, Texas, USA.
[00270] Sodium perborate is supplied by Degussa, Hanau, Germany.
[00271] NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels, Batesville, USA.
[00272] TAED is tetracetylethylenediamine, supplied under the trade name of Peractive ® by Clariant GmbH, Sulzbach, Germany.
[00273] S-ACMC is carboxymethylcellulose conjugated to C.I.Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the trade name AZO-CM-CELLULOSE, product code S-ACMC.
[00274] Dirt release agent is Repel-o-tex®PF, supplied by Rhodia, Paris, France.
[00275] Acrylic Acid / Maleic Acid copolymer has a molecular weight of 70,000 and an acrylate: maleate ratio of 70:30, supplied by BASF, Ludwigshafen, Germany.
[00276] Sodium salt of ethylenediamino-N, N'-disuccinic acid, isomer (S, S) (EDDS) is supplied by Octel, Ellesmere Port, UK.
[00277] Hydroxyethane diphosphonate (HEDP) is available from Dow Chemical, Midland, Michigan, USA.
[00278] Foam suppressant is provided by Dow Corning, Midland, Michigan, USA.
[00279] HSAS is a medium chain alkyl sulfate as described in US 6,020,303 and US 6,060,443.
[00280] C12-14 dimethyl amine oxide is available from Procter & Gamble Chemicals, Cincinnati, USA.
[00281] Random copolymer graft is a copolymer of polyvinyl acetate grafted with polyethylene oxide that has a polyethylene oxide framework and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide framework is about 6000 and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40:60 and no more than one graft point per 50 units of ethylene oxide .
[00282] Polyethyleneimine ethoxylate is polyethyleneimine (MW = 600) with 20 ethoxide groups per -NH.
[00283] Cationic cellulose polymer is LK400, LR400 and / or JR30M from Amerchol Corporation, Edgewater NJ.
[00284] Note: all levels of enzyme are expressed as% of crude enzyme material.
[00285] The dimensions and values described here should not be understood as being strictly limited to the exact number of values cited. On the contrary, unless otherwise specified, each of these dimensions is intended to signify the quoted value and a functionally equivalent range that surrounds the value. For example, a dimension described as "40 mm" is intended to mean "about 40 mm".

权利要求:
Claims (10)
[0001]
1. Carboxylate dye, characterized by the fact that it is selected from compounds with the structure of Formula (5):
[0002]
2. Carboxylate dye according to claim 1, characterized by the compost
[0003]
Carboxylate dye according to claim 1 or 2, characterized in that L is an organic bonding group with a molecular weight of 14-1000 g / mol (Da), preferably 14600 g / mol (Da) and more preferably 28-300 g / mol (Da).
[0004]
Carboxylate dye according to any one of claims 1 to 3, characterized in that L essentially consists of C, H and, optionally O and / or N, and in the sequence of L-bonds that link the group With the carboxylate dye, any -C (= O) -O- group, if present, has the orientation of -C (R10) (R11) ...- C (= O) -O- ... CO2M.
[0005]
Carboxylate dye according to any one of claims 1 to 3, characterized in that L is a C120 alkylene chain optionally having ether (-O-) and / or ester and / or amide bonds present therein, and the chain optionally being replaced with Cl, Br, OH, CN, NO2, or SO2CH3.
[0006]
6. Carboxylate dye according to any one of claims 1 to 5, characterized by the fact that M is an H, Na or K.
[0007]
7. Carboxylate dye according to claim 1, characterized by the fact that at least R10 and R 11 is H.
[0008]
Carboxylate dye according to claim 1 or 7, characterized in that L has a molecular weight of 141000 g / mol (Da), preferably 14-600 g / mol (Da), and more preferably 14 -300 g / mol (Da).
[0009]
Carboxylate dye according to any one of claims 1, 7 and 8, characterized in that L consists essentially of C, H and optionally O and / or N.
[0010]
10. Carboxylate dye according to any one of claims 1 and 7-9, characterized by the fact that R1 and R 2 are selected independently from polyalkylene oxides and their copolymers.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2826551A|1954-01-04|1958-03-11|Simoniz Co|Nontangling shampoo|

---

BE551361A|1955-10-27|

---

GB849433A|1957-08-22|1960-09-28|Raymond Woolston|Hair washing preparations|

---

BE680847A|1963-05-27|1966-11-14|

---

NL136759C|1966-02-16|

---

US3943120A|1967-09-19|1976-03-09|Ciba-Geigy Ag|Succinimido azo dyestuffs|

---

US3646015A|1969-07-31|1972-02-29|Procter & Gamble|Optical brightener compounds and detergent and bleach compositions containing same|

---

LU60943A1|1970-05-20|1972-02-23|

---

US3793305A|1970-09-14|1974-02-19|Du Pont|One-step process of preparing azo dyes by simultaneous diazotization|

---

US3958581A|1972-05-17|1976-05-25|L'oreal|Cosmetic composition containing a cationic polymer and divalent metal salt for strengthening the hair|

---

GB1407997A|1972-08-01|1975-10-01|Procter & Gamble|Controlled sudsing detergent compositions|

---

GB1428395A|1972-09-08|1976-03-17|Ici Ltd|Disperse monoazo dyestuffs|

---

CA1018893A|1972-12-11|1977-10-11|Roger C. Birkofer|Mild thickened shampoo compositions with conditioning properties|

---

IT985593B|1973-04-20|1974-12-10|Montedison Spa|AZO DYES INSOLUBLE IN WATER|

---

US3964500A|1973-12-26|1976-06-22|Lever Brothers Company|Lusterizing shampoo containing a polysiloxane and a hair-bodying agent|

---

US4217914A|1974-05-16|1980-08-19|L'oreal|Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin|

---

US4422853A|1974-05-16|1983-12-27|L'oreal|Hair dyeing compositions containing quaternized polymer|

---

US4197865A|1975-07-04|1980-04-15|L'oreal|Treating hair with quaternized polymers|

---

AT365448B|1975-07-04|1982-01-11|Oreal|COSMETIC PREPARATION|

---

US4075118A|1975-10-14|1978-02-21|The Procter & Gamble Company|Liquid detergent compositions containing a self-emulsified silicone suds controlling agent|

---

US4152416A|1976-09-17|1979-05-01|Marra Dorothea C|Aerosol antiperspirant compositions delivering astringent salt with low mistiness and dustiness|

---

EP0008830A1|1978-09-09|1980-03-19|THE PROCTER &amp; GAMBLE COMPANY|Suds-suppressing compositions and detergents containing them|

---

US4663158A|1979-07-02|1987-05-05|Clairol Incorporated|Hair conditioning composition containing cationic polymer and amphoteric surfactant and method for use|

---

US4507280A|1979-07-02|1985-03-26|Clairol Incorporated|Hair conditioning composition and method for use|

---

US4529586A|1980-07-11|1985-07-16|Clairol Incorporated|Hair conditioning composition and process|

---

GR76237B|1981-08-08|1984-08-04|Procter & Gamble|

---

US4364837A|1981-09-08|1982-12-21|Lever Brothers Company|Shampoo compositions comprising saccharides|

---

US4489574A|1981-11-10|1984-12-25|The Procter & Gamble Company|Apparatus for highly efficient laundering of textiles|

---

US4489455A|1982-10-28|1984-12-25|The Procter & Gamble Company|Method for highly efficient laundering of textiles|

---

GB8401875D0|1984-01-25|1984-02-29|Procter & Gamble|Liquid detergent compositions|

---

US4760025A|1984-05-29|1988-07-26|Genencor, Inc.|Modified enzymes and methods for making same|

---

JPH0314481B2|1984-05-30|1991-02-26|Dow Corning Kk|

---

US4790856A|1984-10-17|1988-12-13|Colgate-Palmolive Company|Softening and anti-static nonionic detergent composition with sulfosuccinamate detergent|

---

USRE34584E|1984-11-09|1994-04-12|The Procter & Gamble Company|Shampoo compositions|

---

US4652392A|1985-07-30|1987-03-24|The Procter & Gamble Company|Controlled sudsing detergent compositions|

---

US4762636A|1986-02-28|1988-08-09|Ciba-Geigy Corporation|Process for the preparation of granules containing an active substance and to the use thereof as speckles for treating substrates|

---

US4798679A|1987-05-11|1989-01-17|The Procter & Gamble Co.|Controlled sudsing stable isotropic liquid detergent compositions|

---

AT129523T|1988-01-07|1995-11-15|Novo Nordisk As|SPECIFIC PROTEASE.|

---

GB8806016D0|1988-03-14|1988-04-13|Danochemo As|Encapsulated photoactivator dyes for detergent use|

---

US4983316A|1988-08-04|1991-01-08|Dow Corning Corporation|Dispersible silicone antifoam formulations|

---

US4978471A|1988-08-04|1990-12-18|Dow Corning Corporation|Dispersible silicone wash and rinse cycle antifoam formulations|

---

DE3826670C2|1988-08-05|1994-11-17|Framatome Connectors Int|Flat contact socket|

---

US5104646A|1989-08-07|1992-04-14|The Procter & Gamble Company|Vehicle systems for use in cosmetic compositions|

---

ES2144990T3|1989-08-25|2000-07-01|Henkel Of America Inc|ALKALINE PROTEOLYTIC ENZYME AND PRODUCTION METHOD.|

---

US5135972A|1989-09-18|1992-08-04|Milliken Research Corporation|Poly modified phthalocyanine colorants|

---

GB8927361D0|1989-12-04|1990-01-31|Unilever Plc|Liquid detergents|

---

US5106609A|1990-05-01|1992-04-21|The Procter & Gamble Company|Vehicle systems for use in cosmetic compositions|

---

AU4398793A|1992-06-15|1994-01-04|Procter & Gamble Company, The|Liquid laundry detergent compositions with silicone antifoam agent|

---

EP0651794B1|1992-07-23|2009-09-30|Novozymes A/S|MUTANT $g-AMYLASE, DETERGENT AND DISH WASHING AGENT|

---

DE69415659T3|1993-02-11|2010-05-12|Genencor International, Inc., Palo Alto|OXIDATIVE STABLE ALPHA AMYLASE|

---

US5486303A|1993-08-27|1996-01-23|The Procter & Gamble Company|Process for making high density detergent agglomerates using an anhydrous powder additive|

---

WO1995010591A1|1993-10-14|1995-04-20|The Procter & Gamble Company|Protease-containing cleaning compositions|

---

MX196038B|1994-03-29|2000-04-14|Novo Nordisk As|Alkaline bacillus amylase.|

---

PT101492A|1994-04-15|1995-10-20|Jaime Isidoro Naylor Da Rocha|COLORS WITH REACTIVE GROUP OF CARBOXYLIC ANCERID TYPE, FOR LA, POLYAMIDE AND CURTUMES|

---

US5879584A|1994-09-10|1999-03-09|The Procter & Gamble Company|Process for manufacturing aqueous compositions comprising peracids|

---

US5691297A|1994-09-20|1997-11-25|The Procter & Gamble Company|Process for making a high density detergent composition by controlling agglomeration within a dispersion index|

---

US5489392A|1994-09-20|1996-02-06|The Procter & Gamble Company|Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties|

---

US5516448A|1994-09-20|1996-05-14|The Procter & Gamble Company|Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate|

---

US6093562A|1996-02-05|2000-07-25|Novo Nordisk A/S|Amylase variants|

---

US5534179A|1995-02-03|1996-07-09|Procter & Gamble|Detergent compositions comprising multiperacid-forming bleach activators|

---

ES2390901T3|1995-02-03|2012-11-19|Novozymes A/S|Method for designing alpha-amylase mutants with predetermined properties|

---

AR000862A1|1995-02-03|1997-08-06|Novozymes As|VARIANTS OF A MOTHER-AMYLASE, A METHOD TO PRODUCE THE SAME, A DNA STRUCTURE AND A VECTOR OF EXPRESSION, A CELL TRANSFORMED BY SUCH A DNA STRUCTURE AND VECTOR, A DETERGENT ADDITIVE, DETERGENT COMPOSITION, A COMPOSITION FOR AND A COMPOSITION FOR THE ELIMINATION OF|

---

US5574005A|1995-03-07|1996-11-12|The Procter & Gamble Company|Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties|

---

US5569645A|1995-04-24|1996-10-29|The Procter & Gamble Company|Low dosage detergent composition containing optimum proportions of agglomerates and spray dried granules for improved flow properties|

---

JP3025627B2|1995-06-14|2000-03-27|花王株式会社|Liquefied alkaline α-amylase gene|

---

US5597936A|1995-06-16|1997-01-28|The Procter & Gamble Company|Method for manufacturing cobalt catalysts|

---

US5565422A|1995-06-23|1996-10-15|The Procter & Gamble Company|Process for preparing a free-flowing particulate detergent composition having improved solubility|

---

US5576282A|1995-09-11|1996-11-19|The Procter & Gamble Company|Color-safe bleach boosters, compositions and laundry methods employing same|

---

US5674478A|1996-01-12|1997-10-07|The Procter & Gamble Company|Hair conditioning compositions|

---

US5750122A|1996-01-16|1998-05-12|The Procter & Gamble Company|Compositions for treating hair or skin|

---

WO1997032917A1|1996-03-04|1997-09-12|Osi Specialities, Inc.|Silicone aminopolyalkyleneoxide block copolymers|

---

EG21623A|1996-04-16|2001-12-31|Procter & Gamble|Mid-chain branced surfactants|

---

PH11997056158B1|1996-04-16|2001-10-15|Procter & Gamble|Mid-chain branched primary alkyl sulphates as surfactants|

---

MA24137A1|1996-04-16|1997-12-31|Procter & Gamble|MANUFACTURE OF BRANCHED SURFACES.|

---

US5763385A|1996-05-14|1998-06-09|Genencor International, Inc.|Modified α-amylases having altered calcium binding properties|

---

BR9712360A|1996-10-18|2001-06-19|Procter & Gamble|Detergent compositions|

---

WO1998023690A1|1996-11-27|1998-06-04|Eastman Chemical Company|Method for preparing light-absorbing polymeric compositions|

---

BR9808657A|1997-03-07|2000-05-23|Procter & Gamble|Improved methods of producing cross-linked macropolicycles|

---

EP0973855B1|1997-03-07|2003-08-06|The Procter & Gamble Company|Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids|

---

EP0884352B1|1997-06-11|2001-09-05|Kuraray Co., Ltd.|Water-soluble film|

---

BR0009392B1|1999-03-31|2012-06-12|mutant of a polypeptide with alpha-amylase activity, and use of the polypeptide or variant.|

---

AR015977A1|1997-10-23|2001-05-30|Genencor Int|PROTEASA VARIANTS MULTIPLY SUBSTITUTED WITH ALTERED NET LOAD FOR USE IN DETERGENTS|

---

EP1027428B1|1997-10-30|2010-12-01|Novozymes A/S|Alpha-amylase mutants|

---

GB9807477D0|1998-04-07|1998-06-10|Unilever Plc|Coloured granular composition for use in particulate detergent compositions|

---

DE59910042D1|1998-05-18|2004-09-02|Ciba Sc Holding Ag|Water-soluble granules of phthalocyanine compounds|

---

US6207782B1|1998-05-28|2001-03-27|Cromption Corporation|Hydrophilic siloxane latex emulsions|

---

EP1135392A2|1998-11-30|2001-09-26|The Procter & Gamble Company|Process for preparing cross-bridged tetraaza macrocycles|

---

US6403355B1|1998-12-21|2002-06-11|Kao Corporation|Amylases|

---

US6939702B1|1999-03-31|2005-09-06|Novozymes A/S|Lipase variant|

---

PL353873A1|1999-09-10|2003-12-01|Ciba Specialty Chemicals Holding Inc.Ciba Specialty Chemicals Holding Inc.|Triazinylaminostilbene derivative as fluorescent whitening agents|

---

EP1230293A1|1999-09-23|2002-08-14|The Dow Chemical Company|Solvent composition|

---

JP2002020660A|2000-07-05|2002-01-23|Hiroshi Takimoto|Recording liquid|

---

US7041767B2|2000-07-27|2006-05-09|Ge Bayer Silicones Gmbh & Co. Kg|Polysiloxane polymers, method for their production and the use thereof|

---

DE10036533B4|2000-07-27|2005-02-03|Ge Bayer Silicones Gmbh & Co. Kg|Use of polyquaternary polysiloxanes as washable hydrophilic plasticizers|

---

AU9168701A|2000-07-27|2002-02-13|Ge Bayer Silicones Gmbh And Co|Polyammonium-polysiloxane compounds, methods for the production and use thereof|

---

US7153818B2|2000-07-28|2006-12-26|Henkel Kgaa|Amylolytic enzyme extracted from bacillus sp. A 7-7 and washing and cleaning agents containing this novel amylolytic enzyme|

---

CN100340648C|2000-10-27|2007-10-03|宝洁公司|Stabilized liquid compositions|

---

US7041488B2|2001-06-06|2006-05-09|Novozymes A/S|Endo-beta-1,4-glucanase from bacillus|

---

BRPI0211408B1|2001-08-20|2017-01-31|Unilever Nv|granular composition, particulate laundry detergent composition, and process for manufacturing a granular composition|

---

GB0120160D0|2001-08-20|2001-10-10|Unilever Plc|Photobleach speckle and laundry detergent compositions containing it|

---

US6482969B1|2001-10-24|2002-11-19|Dow Corning Corporation|Silicon based quaternary ammonium functional compositions and methods for making them|

---

US6607717B1|2001-10-24|2003-08-19|Dow Corning Corporation|Silicon based quaternary ammonium functional compositions and their applications|

---

DE10162728A1|2001-12-20|2003-07-10|Henkel Kgaa|New alkaline protease from Bacillus gibsonii and washing and cleaning agents containing this new alkaline protease|

---

KR101136843B1|2002-09-04|2012-05-25|시바 홀딩 인코포레이티드|Formulations comprising water-soluble granulates|

---

EP1396535B1|2002-09-05|2004-12-15|The Procter & Gamble Company|Structured liquid fabric treatment compositions|

---

EP1396536B1|2002-09-05|2005-10-19|The Procter & Gamble Company|Structuring systems for fabric treatment compostions|

---

KR100554479B1|2002-09-11|2006-03-03|씨제이라이온 주식회사|Complex salt for detergent to prevent spotting|

---

GB0300808D0|2003-01-14|2003-02-12|Unilever Plc|Home and personal care compositions with lubricants|

---

US9068234B2|2003-01-21|2015-06-30|Ptc Therapeutics, Inc.|Methods and agents for screening for compounds capable of modulating gene expression|

---

US7022656B2|2003-03-19|2006-04-04|Monosol, Llc.|Water-soluble copolymer film packet|

---

EP1502943A1|2003-08-01|2005-02-02|The Procter & Gamble Company|Aqueous liquid cleaning composition comprising visible beads|

---

GB0325432D0|2003-10-31|2003-12-03|Unilever Plc|Ligand and complex for catalytically bleaching a substrate|

---

JP5244317B2|2003-11-19|2013-07-24|ジェネンコー・インターナショナル・インク|Serine protease, nucleic acid encoding serine enzyme, vector and host cell incorporating the same|

---

US7208459B2|2004-06-29|2007-04-24|The Procter & Gamble Company|Laundry detergent compositions with efficient hueing dye|

---

WO2006002643A2|2004-07-05|2006-01-12|Novozymes A/S|Alpha-amylase variants with altered properties|

---

WO2006053598A1|2004-11-22|2006-05-26|Unilever Plc|Laundry treatment compositions|

---

US20070041929A1|2005-06-16|2007-02-22|Torgerson Peter M|Hair conditioning composition comprising silicone polymers containing quaternary groups|

---

GB0514146D0|2005-07-11|2005-08-17|Unilever Plc|Dye delivery granules|

---

GB0519347D0|2005-09-22|2005-11-02|Unilever Plc|Composition of enhanced stability and a process for making such a composition|

---

ES2529815T3|2005-10-12|2015-02-25|The Procter & Gamble Company|Use and production of stable neutral metalloprotease in storage|

---

AR059389A1|2005-10-28|2008-04-09|Procter & Gamble|COMPOSITION CONTAINING ANIONICALLY MODIFIED CATECOL AND SUSPENSION POLYMERS|

---

US7585376B2|2005-10-28|2009-09-08|The Procter & Gamble Company|Composition containing an esterified substituted benzene sulfonate|

---

US9427391B2|2006-01-09|2016-08-30|The Procter & Gamble Company|Personal care compositions containing cationic synthetic copolymer and a detersive surfactant|

---

EP1976968B1|2006-01-23|2017-08-09|The Procter and Gamble Company|Laundry care compositions with thiazolium dye|

---

JP2009523900A|2006-01-23|2009-06-25|ザプロクターアンドギャンブルカンパニー|Composition comprising lipase and bleach catalyst|

---

ZA200807030B|2006-02-25|2009-11-25|Unilever Plc|Shading dye granule its use in a detergent formulation and process to make it|

---

US20070286837A1|2006-05-17|2007-12-13|Torgerson Peter M|Hair care composition comprising an aminosilicone and a high viscosity silicone copolymer emulsion|

---

GB0615487D0|2006-08-04|2006-09-13|Reckitt Benckiser Nv|Detergent composition|

---

DE102006036889A1|2006-08-04|2008-02-07|Clariant International Limited|Use of aminoacetones and their salts as bleaching force enhancers for peroxygen compounds|

---

WO2008087497A1|2007-01-19|2008-07-24|The Procter & Gamble Company|Laundry care composition comprising a whitening agent for cellulosic substrates|

---

DE102007003372A1|2007-01-23|2008-07-24|Dystar Textilfarben Gmbh & Co. Deutschland Kg|Disperse dyes, their preparation and their use|

---

WO2008153882A1|2007-06-11|2008-12-18|Appleton Papers Inc.|Benefit agent containing delivery particle|

---

DE102007038031A1|2007-08-10|2009-06-04|Henkel Ag & Co. Kgaa|Agents containing proteases|

---

GB0719161D0|2007-10-01|2007-11-07|Unilever Plc|Improvements relating to fabrick treatment compositions|

---

ES2401836T3|2007-11-26|2013-04-24|Basf Se|Enhanced Matting Process|

---

CA2709703A1|2008-01-07|2009-07-16|The Procter & Gamble Company|Detergents having acceptable color|

---

CN101910396B|2008-01-10|2012-10-17|荷兰联合利华有限公司|Granules|

---

EP2085434A1|2008-01-11|2009-08-05|Universita' Degli Studi di Firenze|Disperse dyes soluble in water|

---

MX2010009457A|2008-02-29|2010-09-24|Procter & Gamble|Detergent composition comprising lipase.|

---

CN101980772A|2008-03-26|2011-02-23|宝洁公司|Delivery particle|

---

MY153627A|2008-05-02|2015-02-27|Unilever Plc|Reduced spotting granules|

---

ES2527645T3|2008-06-06|2015-01-27|Danisco Us Inc.|Alpha-amylase variants of Geobacillus stearothermophilus with improved properties|

---

AT539141T|2008-06-13|2012-01-15|Procter & Gamble|BAG WITH MULTIPLE CHAMBERS|

---

WO2010022775A1|2008-08-27|2010-03-04|Symrise Gmbh & Co. Kg|Multi-coloured cleaning article|

---

CN102224233A|2008-09-25|2011-10-19|荷兰联合利华有限公司|Liquid detergents|

---

WO2010084039A1|2009-01-26|2010-07-29|Unilever Plc|Incorporation of dye into granular laundry composition|

---

US20100311184A1|2009-06-04|2010-12-09|Aat Bioquest, Inc.|Azo heterocyclic dyes and their biological conjugates|

---

GB0914437D0|2009-08-18|2009-09-30|Brunner Mond Uk Ltd|Granular hueing ingredient for fabric washing compositions|

---

CN102652175B|2009-12-09|2016-02-10|宝洁公司|Fabric and household care product|

---

WO2011163457A1|2010-06-23|2011-12-29|The Procter & Gamble Company|Product for pre-treatment and laundering of stained fabric|

---

CN102958909B|2010-06-28|2016-11-09|巴斯夫欧洲公司|Metal-free bleaching composition|

---

GB201011511D0|2010-07-08|2010-08-25|Unilever Plc|Composions comprising optical benefits agents|

---

US20120101018A1|2010-10-22|2012-04-26|Gregory Scot Miracle|Bis-azo colorants for use as bluing agents|

---

US8715368B2|2010-11-12|2014-05-06|The Procter & Gamble Company|Thiophene azo dyes and laundry care compositions containing the same|

---

MX2013005276A|2010-11-12|2013-06-03|Procter & Gamble|Thiophene azo dyes and laundry care compositions containing the same.|

---

BR112013011604B1|2010-11-12|2020-01-07|Milliken & Company|Azo thiophene dyes|

---

FR2967684B1|2010-11-18|2015-09-11|Oreal|ANIONIC DIRECT DYE AGAINST TETRA-ALKYLAMMONIUM ION, DYE COMPOSITION COMPRISING SAME, AND PROCESS FOR COLORING KERATINIC FIBERS FROM THESE DYES|

---

US9163146B2|2011-06-03|2015-10-20|Milliken & Company|Thiophene azo carboxylate dyes and laundry care compositions containing the same|

---

US8888865B2|2011-06-03|2014-11-18|The Procter & Gamble Company|Thiophene azo carboxylate dyes and laundry care compositions containing the same|

---

JP5883127B2|2011-06-03|2016-03-09|ザ プロクター アンド ギャンブルカンパニー|Laundry care compositions containing dyes|

---

US20140371435A9|2011-06-03|2014-12-18|Eduardo Torres|Laundry Care Compositions Containing Thiophene Azo Dyes|EP2078732B1|2006-07-10|2015-09-16|Fujita Health University|Method of identifying a candidate diagnostic or therapeutic antibody using flow cytometry|

---

US8715368B2|2010-11-12|2014-05-06|The Procter & Gamble Company|Thiophene azo dyes and laundry care compositions containing the same|

---

EP2929005A1|2012-12-06|2015-10-14|The Procter and Gamble Company|Soluble pouch comprising hueing dye|

---

WO2014190130A1|2013-05-24|2014-11-27|The Procter & Gamble Company|Concentrated surfactant composition|

---

EP3004310B1|2013-05-24|2021-07-14|The Procter & Gamble Company|Low ph detergent composition|

---

CA2910953C|2013-05-24|2018-06-26|The Procter & Gamble Company|Low ph detergent composition comprising nonionic surfactants|

---

US9834682B2|2013-09-18|2017-12-05|Milliken & Company|Laundry care composition comprising carboxylate dye|

---

US9267096B2|2013-10-29|2016-02-23|Ecolab USA, Inc.|Use of amino carboxylate for enhancing metal protection in alkaline detergents|

---

EP2899260A1|2014-01-22|2015-07-29|Unilever PLC|Process to manufacture a liquid detergent formulation|

---

JP6445128B2|2014-07-23|2018-12-26|ザ プロクター アンド ギャンブル カンパニー|Treatment composition|

---

EP3172303B1|2014-07-23|2019-01-02|The Procter and Gamble Company|Fabric and home care treatment compositions|

---

EP3172300B1|2014-07-23|2018-12-26|The Procter and Gamble Company|Fabric and home care treatment composition|

---

WO2016014732A1|2014-07-23|2016-01-28|The Procter & Gamble Company|Fabric and home care treatment compositions|

---

EP3172299B1|2014-07-23|2019-09-25|The Procter and Gamble Company|Fabric and home care treatment compositions|

---

WO2016014802A1|2014-07-23|2016-01-28|The Procter & Gamble Company|Fabric and home care treatment compositions|

---

EP3172298B1|2014-07-23|2019-01-02|The Procter and Gamble Company|Fabric and home care treatment compositions|

---

CN107072849B|2014-11-06|2020-10-30|宝洁公司|Moire effect laminate and method for producing same|

---

CN109072130B|2015-05-27|2020-10-27|荷兰联合利华有限公司|Laundry detergent compositions|

---

EP3098295A1|2015-05-29|2016-11-30|The Procter and Gamble Company|Process for making a single or multi-compartment pouch|

---

WO2016192905A1|2015-06-02|2016-12-08|Unilever Plc|Laundry detergent composition|

---

US10208422B2|2015-06-15|2019-02-19|Monosol, Llc|Laundry stain removal device|

---

EP3118292B1|2015-07-16|2018-02-14|The Procter and Gamble Company|Method of manual dishwashing|

---

BR112018006212A2|2015-10-01|2018-10-09|Unilever N.V.|phosphate-free carbonate powder detergent composition and method of domestic treatment of a fabric|

---

US9902923B2|2015-10-13|2018-02-27|The Procter & Gamble Company|Polyglycerol dye whitening agents for cellulosic substrates|

---

US9745544B2|2015-10-13|2017-08-29|The Procter & Gamble Company|Whitening agents for cellulosic substrates|

---

US10597614B2|2015-10-13|2020-03-24|The Procter & Gamble Company|Whitening agents for cellulosic substrates|

---

JP6738900B2|2016-01-25|2020-08-12|ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ|Treatment composition|

---

CA3010919A1|2016-01-25|2017-08-03|The Procter & Gamble Company|Treatment compositions|

---

US20170218202A1|2016-01-29|2017-08-03|Milliken & Company|Bis-Azo Colorants For Use As Bluing Agents|

---

WO2017140391A1|2016-02-17|2017-08-24|Unilever Plc|Whitening composition|

---

BR112018016674A2|2016-02-17|2018-12-26|Unilever Nv|laundry detergent composition and household method of treating a fabric|

---

WO2017162378A1|2016-03-21|2017-09-28|Unilever Plc|Laundry detergent composition|

---

EP3440172B1|2016-04-08|2019-08-21|Unilever PLC|Laundry detergent composition|

---

AU2017267127B2|2016-05-17|2020-04-02|Unilever Global Ip Limited|Liquid laundry detergent compositions|

---

EP3458561B1|2016-05-17|2020-10-14|Unilever PLC|Liquid laundry detergent compositions|

---

CN109790491B|2016-09-27|2021-02-23|荷兰联合利华有限公司|Household washing method|

---

WO2018072979A1|2016-10-18|2018-04-26|Unilever Plc|Whitening composition|

---

CN110023469A|2016-12-15|2019-07-16|荷兰联合利华有限公司|Laundry detergent composition|

---

WO2018152272A1|2017-02-16|2018-08-23|The Procter & Gamble Company|Absorbent articles with substrates having repeating patterns of apertures comprising a plurality of repeat units|

---

US10920177B2|2017-03-16|2021-02-16|Encapsys, Llc|Benefit agent containing delivery particle composition|

---

CN110892053A|2017-07-07|2020-03-17|荷兰联合利华有限公司|Laundry cleaning compositions|

---

WO2019008036A1|2017-07-07|2019-01-10|Unilever Plc|Whitening composition|

---

CA3074938A1|2017-10-12|2019-04-18|The Procter & Gamble Company|Leuco colorants as bluing agents in laundry care composition|

---

WO2019105675A1|2017-11-30|2019-06-06|Unilever Plc|Detergent composition comprising protease|

---

WO2019192813A1|2018-04-03|2019-10-10|Unilever N.V.|Dye granule|

---

WO2019219302A1|2018-05-17|2019-11-21|Unilever Plc|Cleaning composition comprising rhamnolipid and alkyl ether carboxylate surfactants|

---

WO2019219531A1|2018-05-17|2019-11-21|Unilever Plc|Cleaning composition|

---

EP3578629A1|2018-06-07|2019-12-11|Henkel AG & Co. KGaA|Method for the preparation of a liquid detergent composition comprising a preservative-free dye solution|

---

CN112513236A|2018-07-17|2021-03-16|联合利华知识产权控股有限公司|Use of rhamnolipids in surfactant systems|

---

CN112703246A|2018-09-17|2021-04-23|联合利华知识产权控股有限公司|Detergent composition|

---

US11155771B2|2018-11-09|2021-10-26|Henkel Ag & Co. Kgaa|Method for preparing a liquid washing or cleaning agent using a preservative-free dye solution|

---

BR112021009789A2|2018-11-20|2021-08-17|Unilever Ip Holdings B.V.|detergent composition, method of treating a fabric substrate and use of an esterase enzyme|

---

BR112021009807A2|2018-11-20|2021-08-17|Unilever Ip Holdings B.V.|detergent composition, method of treating a fabric substrate and use of an isomerase enzyme|

---

EP3884026A1|2018-11-20|2021-09-29|Unilever Global Ip Limited|Detergent composition|

---

CN113056550A|2018-11-20|2021-06-29|联合利华知识产权控股有限公司|Detergent composition|

---

BR112021009837A2|2018-11-20|2021-08-17|Unilever Ip Holdings B.V.|detergent composition, method of treating a fabric substrate and use of a fatty acid amide hydrolase|

---

EP3750979A1|2019-06-12|2020-12-16|Unilever N.V.|Use of laundry detergent composition|

---

EP3750978A1|2019-06-12|2020-12-16|Unilever N.V.|Laundry detergent composition|

---

WO2020260006A1|2019-06-28|2020-12-30|Unilever Plc|Detergent compositions|

---

CN114008183A|2019-06-28|2022-02-01|联合利华知识产权控股有限公司|Detergent composition|

---

CN114008184A|2019-06-28|2022-02-01|联合利华知识产权控股有限公司|Detergent composition|

---

CN113993981A|2019-06-28|2022-01-28|联合利华知识产权控股有限公司|Detergent composition|

---

WO2020259948A1|2019-06-28|2020-12-30|Unilever Plc|Detergent composition|

---

BR112021023398A2|2019-06-28|2022-01-04|Unilever Ip Holdings B V|Detergent composition, home method of treating a textile and use of an ether sulfate alcohol|

---

WO2021043764A1|2019-09-02|2021-03-11|Unilever Global Ip Limited|Detergent composition|

---

WO2021069516A1|2019-10-07|2021-04-15|Unilever Ip Holdings B.V.|Detergent composition|

---

WO2021185956A1|2020-03-19|2021-09-23|Unilever Ip Holdings B.V.|Detergent composition|

---

WO2021185870A1|2020-03-19|2021-09-23|Unilever Ip Holdings B.V.|Detergent composition|

---

WO2021249927A1|2020-06-08|2021-12-16|Unilever Ip Holdings B.V.|Method of improving protease activity|

---

WO2022023250A1|2020-07-27|2022-02-03|Unilever Ip Holdings B.V.|Use of an enzyme and surfactant for inhibiting microorganisms|

---

WO2022042989A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Surfactant and detergent composition|

---

WO2022043138A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Surfactant and detergent composition|

---

WO2022042977A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Detergent composition|

---

WO2022043042A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Detergent composition|

---

WO2022043045A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Detergent composition|

法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2021-01-05| B09A| Decision: intention to grant|

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2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261612539P| true| 2012-03-19|2012-03-19|

---

US61/612,539|2012-03-19|

---

PCT/US2013/032967|WO2013142495A1|2012-03-19|2013-03-19|Carboxylate dyes|

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