WO2011011799A2 - Thiophene azo dyes and laundry care compositions containing the same - Google Patents

Thiophene azo dyes and laundry care compositions containing the same Download PDF

Info

Publication number
WO2011011799A2
WO2011011799A2 PCT/US2010/056508 US2010056508W WO2011011799A2 WO 2011011799 A2 WO2011011799 A2 WO 2011011799A2 US 2010056508 W US2010056508 W US 2010056508W WO 2011011799 A2 WO2011011799 A2 WO 2011011799A2
Authority
WO
WIPO (PCT)
Prior art keywords
moiety
selected
alkyl
laundry care
ch
Prior art date
Application number
PCT/US2010/056508
Other languages
French (fr)
Other versions
WO2011011799A3 (en
Inventor
Gregory Scot Miracle
Robert Linn Mahaffey, Jr.
Xiaoyong Michael Hong
Eduardo Torres
Dominick Joseph Valenti
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US2010/056508 priority Critical patent/WO2011011799A2/en
Publication of WO2011011799A2 publication Critical patent/WO2011011799A2/en
Publication of WO2011011799A3 publication Critical patent/WO2011011799A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00Monoazo dyes prepared by diazotising and coupling
    • C09B29/06Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08Amino benzenes
    • C09B29/0801Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls
    • C09B29/0802Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls containing COOH
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00Monoazo dyes prepared by diazotising and coupling
    • C09B29/06Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08Amino benzenes
    • C09B29/0801Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls
    • C09B29/0803Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls containing SO3H, OSO3H
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Abstract

This application relates to thiophene azo dyes for use as hueing agents, laundry care compositions comprising such thiophene azo dyes, processes for making such thiophene azo dyes, and laundry care compositions and methods of using the same. The thiophene azo dyes contain a formally charged moiety and are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. These thiophene azo dyes are advantageous in providing a hueing effect, for example, a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics. The thiophene azo dyes are also generally stable to bleaching agents used in laundry care compositions.

Description

THIOPHENE AZO DYES AND LAUNDRY CARE COMPOSITIONS

CONTAINING THE SAME

TECHNICAL FIELD

This application relates to thiophene azo dyes for use as hueing agents, laundry care compositions comprising such thiophene azo dyes, processes for making such thiophene azo dyes and laundry care compositions and methods of using the same. The aforementioned thiophene azo dyes contain a formally charged moiety and are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. These thiophene azo dyes are advantageous in providing a hueing effect, for example, a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics. The thiophene azo dyes are also generally stable to bleaching agents used in laundry care compositions.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due to exposure to light, air, soil, and natural degradation of the fibers that comprise the substrates. Thus, the purpose of hueing agents is generally to visually brighten these textile substrates and counteract the fading and yellowing of the substrates. Typically, hueing agents may be found in laundry detergents, fabric softeners, or rinse aids and are therefore applied to textile substrates during the laundering process. However, it is important that hueing agents function to visually brighten treated textile substrates without causing undesirable staining of the textile substrates. Cellulosic substrates, in particular, tend to exhibit a yellow hue after exposure to light, air, and/or soiling. This yellowness is often difficult to reverse by normal laundering procedures. As a result, there exists a need for improved hueing agents which are capable of eliminating the yellowness exhibited by ageing cellulosic substrates. By utilizing such improved hueing agents, the life of the textile substrates, such as clothing articles, table linens, etc., may be extended. Unfortunately, current hueing agents either do not provide a hueing benefit after a single treatment cycle and/or they build up to an undesirable level, thus overhueing the treated situs over multiple treatment cycles.

The hueing agents disclosed herein and the laundry care compositions comprising same offer advantages over previous efforts in this area, as, unlike previous thiophene azo hueing agents, the present hueing agents comprise a formally charged moiety that allows such hueing agents to provide enhanced deposition, removal and hue angle when used in compositions such as laundry care compositions. In addition to the enhanced deposition, removal and hue angle, the present hueing agents offer improved stability in wash environments that contain bleaching agents, for example bleach boosters. While not being bound by theory, Applicants believe that such enhanced stability is, at least in part, due to the improved partitioning behavior of such hueing agents. The aforementioned benefits are offered over a range of fabric types. In short, Applicants recognized the source of the current hueing deficiencies and herein provide the solution to such problem. The hueing compounds disclosed herein also absorb light at a wavelength appropriate to visually neutralize the yellowness of substrates, including textile substrates. These compounds function ideally as hueing agents for substrates, including textile substrates, and may be incorporated into laundry care compositions for use by consumers.

SUMMARY OF INVENTION

This application relates to thiophene azo dyes for use as hueing agents, laundry care compositions comprising such thiophene azo dyes that may serve as hueing agents, processes for making such thiophene azo dyes and laundry care compositions and methods of using the same. The aforementioned thiophene azo dyes contain a formally charged moiety and are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. These thiophene azo dyes are advantageous in providing a hueing effect, for example, a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics. The thiophene azo dyes are also generally stable to bleaching agents used in laundry care compositions.

DETAILED DESCRIPTION

As used herein, the term "alkoxy" is intended to include C1-C8 alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the terms "alkyl" and "alkyl capped" are intended to include C1-C18 alkyl groups, and in one aspect, C1-C6 alkyl groups.

As used herein, the term "aryl" is intended to include C3-C12 aryl groups.

As used herein, the term "arylalkyl" is intended to include C1-C18 alkyl groups and, in one aspect, C1-C6 alkyl groups.

As used herein, the term "formally charged moiety" means a moiety having at least one formal positive charge or at least one formal negative charge in aqueous solution at a pH in the range from 7 to 11.

The terms "ethylene oxide," "propylene oxide" and "butylene oxide" may be shown herein by their typical designation of "EO," "PO" and "BO," respectively.

As used herein, the term "laundry care composition" includes, unless otherwise indicated, granular, powder, liquid, gel, paste, unit dose bar form and/or flake type washing agents and/or fabric treatment compositions.

As used herein, the term "fabric treatment composition" includes, unless otherwise indicated, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions and combinations there of. Such compositions may be, but need not be rinse added compositions.

As used herein, "cellulosic substrates" are intended to include any substrate which comprises at least a majority by weight of cellulose. Cellulose may be found in wood, cotton, linen, jute, and hemp. Cellulosic substrates may be in the form of powders, fibers, pulp and articles formed from powders, fibers and pulp. Cellulosic fibers, include, without limitation, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate), and mixtures thereof. Articles formed from cellulosic fibers include textile articles such as fabrics. Articles formed from pulp include paper.

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

As used herein, the terms "include", "includes" and "including" are meant to be non-limiting.

As used herein, the term "maximum extinction coefficient" is intended to describe the molar extinction coefficient at the maximum wavelength in the range of 400 nanometers to 750 nanometers.

As a consequence of their manufacturing process, the thiophene azo dyes disclosed herein may contain a distribution of repeating units in their polymeric moiety. Accordingly, in one aspect, the molecular weight of the thiophene azo dyes disclosed herein may be reported as an average molecular weight, as determined by its molecular weight distribution.

The test methods disclosed in the Test Methods Section of the present application should be used to determine the respective values of the parameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

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

It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

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

Laundry Care Composition Comprising Suitable Hueing Agents

In one aspect, a laundry care composition comprising a hueing agent and one or more laundry care ingredients is disclosed. Suitable hueing agents include all the hueing agents listed below.

The hueing agents of the present invention include thiophene azo dyes which contain a formally charged moiety. However, these thiophene azo dyes do not comprise a meta-bis(2- hydroxy-3-trimethylammonium propyl) amino tolyl group. In one aspect, the aforementioned thiophene azo dyes comprise a thiophene moiety, an azo moiety and a coupler moiety, said thiophene moiety being covalently bound to said azo moiety and said coupler being covalently bound to said azo moiety, at least one of said thiophene and/or azo moieties comprising a formally charged moiety.

The hueing agents of the present invention may be dyes, pigments, or polymeric colorants generally comprising a chromophore constituent and a polymeric constituent. The chromophore constituent is characterized in that it emits or absorbs wavelength in the range of blue, red, violet, purple, or combinations thereof upon exposure to light. In one aspect, the chromophore constituent exhibits an absorbance spectrum maximum in the wavelength range of about 400 nanometers to about 750 nanometers, in another aspect of about 520 nanometers to about 650 nanometers, in yet another aspect of about 540 nanometers to about 630 nanometers, in another aspect of about 560 nanometers to about 610 nanometers, in another aspect of about 565 nanometers to about 580 nanometers in methanol solution.

Examples of suitable polymeric constituents include polyoxyalkylene chains having multiple repeating units. In one aspect, the polymeric constituents include polyoxyalkylene chains having from 2 to about 30 repeating units, from 2 to about 20 repeating units, from 2 to about 10 repeating units or even from about 3 or 4 to about 6 repeating units. Non-limiting examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

In one aspect of the invention, the thiophene azo dye contains a formally charged moiety, with the proviso that the dye does not comprise a meta-bis(2-hydroxy-3- trimethylammoniumpropyl) amino tolyl group. The thiophene azo dye exhibits, in the wavelength range of about 400 nm to about 750 nm in methanol solution, or of about 520 nm to about 650 nm in methanol solution, or of about 540 nm to about 630 nm in methanol solution, or of about 560 nm to about 610 nm in methanol solution, or of about 565 nm to about 580 nm in methanol solution, a maximum extinction coefficient from about 1000 to about 1,000,000 liter/mol/cm, or from about 5,000 to about 750,000 liter/mol/cm, or from about 10,000 to about 500,000 liter/mol/cm, or from about 20,000 to about 250,000 liter/mol/cm. The thiophene azo dye exhibits a molecular weight from greater than 300 daltons, or from about 300 daltons to about 5000 daltons, or from about 350 daltons to about 3000 daltons, or from about 400 daltons to about 1500 daltons. The thiophene azo dye exhibits an aqueous partition value from about 10% to 100% or from about 20% to 100% or from about 30% to 100% or from about 40% to 100%, said dye comprising a non-covalently bound charge balancing counterion. The thiophene azo dye further exhibits an aqueous partition value from 0% to about 40%, from 0% to about 30%, from 0% to about 20%, or from about 1% to about 10%, said dye comprising a covalently bound charge balancing counterion.

The thiophene azo dye of the present invention may be represented by general Formula (I):

Figure imgf000008_0001

wherein:

a.) R1, R2 and R3 are each independently selected from hydrogen, electron- withdrawing moieties, and electron-donating moieties, provided that at least one of R1, R2 and R3 is an electron- withdrawing moiety; in another aspect, Ri is an electron-withdrawing moiety; in yet another aspect, Ri and R3 are electron- withdrawing moieties; and b.) wherein X is an organic moiety having a molecular weight from about 65 daltons to about 4855 daltons, or from about 150 daltons to about 2855 daltons, or from about 193 daltons to about 1355 daltons, or from about 300 daltons to about 855 daltons, or from about 400 daltons to about 600 daltons, or from about 420 daltons to about 575 daltons.

In yet another aspect of the thiophene azo dye, each R1, R2 and R3 may be independently selected from hydrogen, (C1-CzO-alkyl, (C3-C1o)-aryl, carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro, (C1-CzO-alkyl ester, halogen or amino moiety, or each R1, R2 and R3 may be independently selected from hydrogen, nitro, cyano, (C1-CzO-alkyl ester or (C1-C4)-alkyl.

In a further aspect of the thiophene azo dye, the X may be a moiety having Formula (II) below:

Figure imgf000009_0001
wherein:

i.) R4 is selected from a moiety having Formula (III) below

Figure imgf000009_0002

wherein: i.) Each R8 is independently selected from hydrogen, C1- Cs alkyl optionally substituted with a hydroxy, or acetyl;

ii.) m is an integer from 0 to 10;

iii.) Y is selected from a sulfonate, carboxylate, a phosphonate or quaternary ammonium species selected from an imidazolium, pyridinium, morpholinium, piperidinium, or a moiety having Formula (IV) below:

Figure imgf000010_0001

wherein:

i.) R9 is a C1-Cg alkyl moiety optionally substituted with -OH,

ii.) Rio is selected from C1-C18 alkyl moiety optionally substituted with -OH, or C2-Cg alkyl substituted with sulfonate, or C1-C8 alkyl substituted with carboxylate,

iii.) Z is a charge balancing counterion of unit charge c; the index b is 1 when Ri0 is a C1-C18 alkyl moiety optionally substituted with -OH, otherwise the index b = 0;

Or, R4 is selected from a moiety having Formula (V) below:

Figure imgf000010_0002
wherein

i.) Each Rn and Ri2 is independently selected from hydrogen, C1-Cs alkyl, aryl, acetyl or hydroxyl moiety; m and n are independent and are integers from 0 to 10, ii.) Y is as described above;

Or, R4 is selected from a moiety having Formula (VI) below:

Figure imgf000011_0001

wherein

i.) Rn is selected from an aryl moiety, arylalkyl moiety such as a benzyl moiety, C1-C18 alkyl moiety, or a siloxane moiety;

ii.) Each Ri4 is independently selected from hydrogen, C1-

C4 alkyl; m is an integer from 0 to 10; and iii.) Y is as described above; ii.) R5 can be the same as R4 or selected from C1-C12 alkyl moiety, aryl moiety or arylalkyl moiety such as a benzyl moiety; wherein the index a is an integer from 0 to 4, or from 0 to 3, or from 0 to 2, and each R6 may be independently selected from a C1-C6 alkyl, a C1-C4 alkoxy, a nitro, a hydroxyl, a halogen, or -NHC(O)R22 wherein R22 is selected from H, -NH2, C1-C6 alkyl, phenyl, -(CH2)SOR23 where the index s is 1 or 2 and R23 is selected from Me, phenyl, and - CO2CH2CN; - NHSO2R24 wherein R24 is C1-C4 alkyl or phenyl; said alkyl, alkoxy and acetamido moieties may be optionally substituted with a formally charged moiety;

Or, X is a moiety having Formula VII below:

Figure imgf000012_0001

wherein each R4 and R5 can independently be selected from:

a) [(CH2CRHO)X(CH2CR11HO)XR15] ;

b) alkyl, aryl or aryl alkyl;

c) [CH2CH(ORI6)CH2ORI7] ;

d) the amino addition product of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether, 2- ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by the addition of from 1 to 10 alkylene oxide units wherein at least one such alkyleneoxide unit is substituted with R15 that is not -H;

wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)zRi5, and mixtures thereof; R" is selected from the group consisting of H, CH2O(CH2CH2O)Z Ri5, and mixtures thereof; x + y < 20; y > 1; z = 0 to 10; each Ri5 is independently selected from -H and -CH2CHRi8N+Ri9R2oR2i wherein Ri8 is selected from -H and -CH3; each Ri9 and R20 is independently selected from C1-C4 alkyl optionally substituted with -OH; R2i is independently selected from C1-C12 optionally -OH substituted alkyl or (CH2)rOpQ; the index r is an integer from 1 to 8; the index p is 0 or 1; and wherein Q is an anionic group selected from -CO2-, and - SO3-; R16 is selected from the group consisting of H, (CH2CH2O)zRi5 wherein z = 0 to 10, and mixtures thereof; R17 is selected from the group consisting of C1-C16 alkyl, C6-C1O aryl groups, and mixtures thereof; the index m is an integer from 0 to 4 and each R6 is as defined above; Z is a charge balancing counterion of unit charge c; the index b is equal to the number of non-H R45 groups that do not comprise a covalently bound charge balancing counterion; further provided the molecule contains at least one non-H R15 group. ther aspect of the thiophene azo dye, X may be a moiety having Formula (II) below:

Figure imgf000013_0001
wherein:

i.) R4 is selected from a moiety having Formula (III) below

Figure imgf000013_0002

wherein:

i.) Rg is a hydrogen, C1-C4 alkyl moiety or aryl moiety; ii.) Y is a quaternary ammonium species selected from a group consisting of an imidazolium, or a moiety having

Formula (IV) below:

Figure imgf000013_0003

wherein: i.) R9 is a C1-C2 alkyl moiety,

ii.) Rio is selected from C1-C8 alkyl moiety optionally substituted with -OH, or C2-C4 alkyl substituted with sulfonate, or C1-C4 alkyl substituted with carboxylate,

iii.) Z is a charge balancing counterion of unit charge c; the index b is 1 when Rio is a C1-Cs alkyl moiety optionally substituted with -OH, otherwise the index b = 0;

Or, R4 is selected from a moiety having Formula (V) below:

Figure imgf000014_0001

wherein

i.) Each Rn and Ri2 is independently selected from hydrogen, C1-C4 alkyl or aryl moiety; m and n are independent and are integers from 0 to 5,

ii.) Y is as described above,

Or, R4 is selected from a moiety having Formula (VI) below:

Figure imgf000014_0002

wherein i.) Rn is selected from an aryl moiety, benzyl moiety, or a

C1-C18 alkyl moiety;

ii.) Each R14 is independently selected from hydrogen or -

CH3; m is an integer from 0 to 10,

ii.) R5 can be the same as R4 or selected from C1-C6 alkyl moiety or benzyl moiety;

iii.)Wherein the index a is an integer from 0 to 2, and each R6 may be independently selected from methyl, methoxy, or acetamido moiety.

In one aspect of the thiophene azo dye of the present invention, each R1, R2 and R3 may be independently selected from hydrogen, (C1-C4)-alkyl, (C3-C1o)-aryl, carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro, (C1-C4)-alkyl ester, halogen or amino moiety, or each R1, R2 and R3 may be independently selected from hydrogen, nitro, cyano, (C1-C4)- alkyl ester or (C1-C4)-alkyl.

In yet a further aspect, the thiophene azo dye of the present invention may be represented by Formula (VIII):

A-N=N-X

Formula VIII wherein the A moiety is selected from the group consisting of Table 1 A Moieties Nos. 1 - 118, or Table 1 A Moieties Nos. 6 - 11, 15, 21 - 23, 30 - 31, 33 - 39, 41, 43, 46 - 48, 50 - 55, 57 - 58, 64 - 65, 70 - 73, 77 - 78, 82 - 86, 88 - 90, 93 - 95, 99 - 100, 104 - 106, and 110 - 118, or Table 1 A Moieties Nos. 9 - 11, 15, 23, 34 - 35, 37 - 39, 41, 43, 47, 50 - 51, 57 - 58, 77, 83, 89, 95, 106, and 110 - 118; and wherein the X moiety is selected from the group consisting of Table 4 X Moieties Nos. 1 - 31. In yet another aspect, the thiophene azo dye of the present invention may be represented by t tVhife f fnoililnowwiinngcr f foorrmmuullaa *:

Figure imgf000016_0001
wherein the moiety A is selected from Table 1 A Moieties Nos. 1 - 118, or from Table 1 A Moieties Nos. 6 - 11, 15, 21 - 23, 30 - 31, 33 - 39, 41, 43, 46 - 48, 50 - 55, 57 - 58, 64 - 65, 70 - 73, 77 - 78, 82 - 86, 88 - 90, 93 - 95, 99 - 100, 104 - 106, and 110 - 118, or from Table 1 A Moieties Nos. 9 - 11, 15, 23, 34 - 35, 37 - 39, 41, 43, 47, 50 - 51, 57 - 58, 77, 83, 89, 95, 106, and 110 - 118; a = 0 to 2; when a = 1 or 2, R6 is selected from Table 2 R6 Substituent Identity and Position Nos. 1 - 40, or from Table 2 R6 Substituent Identity and Position Nos. 1, 3, 5, 7 - 9, 11 - 14, 21, 23 - 24, 31, 33 - 34, 36 and 40, or from Table 2 R6 Substituent Identity and Position Nos. 1, 3, 5, 7, 12, 13, 14, 31, 36 and 40; and R4 and R5 grouping is selected from Table 3 R4 and R5 Groupings Nos. 1 - 69, or from Table 3 R4 and R5 Groupings Nos. 3 - 6, 10, 13 - 14, 17 - 21, 23 - 24, 27 - 28, 31 - 35, 37 - 38, 41, 44 - 49, 51 - 52, 54 - 56, 58, 60 - 69, or from Table 3 R4 and R5 Groupings Nos. 3, 5 - 6, 10, 13 - 14, 17, 19 - 21, 24, 27 - 28, 31 - 34, 38, 41, 44 - 48, 52, 54 - 55, 58, 60 - 64 and 69.

A moieties may be selected from the moieties shown in Table 1 :

Table 1 : A Moieties

Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001

Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001

Figure imgf000023_0002

Re may be selected from the substituents shown in Table 2:

Table 2: R6 Substituent - Identity and Position

Figure imgf000023_0001
Figure imgf000023_0003
Figure imgf000024_0001
Figure imgf000025_0001

R4 and R5 groupings may be selected from the groupings shown in Table 3:

Table 3: R4 and R5 Groupings

Figure imgf000025_0002

Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001

Figure imgf000036_0001

The "*" denotes point of attachment to additional moieties. "Z" denotes the appropriate charge balancing counterion. X moieties may be selected from the moieties shown in Table 4:

Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001

Figure imgf000041_0001
Figure imgf000042_0001

Figure imgf000043_0001
Figure imgf000044_0001

Figure imgf000045_0001

Figure imgf000046_0001

It is contemplated to be within the scope of this invention that the thiophene azo dye having a formally charged moiety may comprise any one of the A moieties selected from Table 1, any one of the R6 substituents selected from Table 2, any one of the R4 and R5 groupings selected from Table 3, and any one of the X moieties selected from Table 4. In yet another aspect of the invention, suitable thiophene azo dyes include, but are not limited to, the structures shown in Table 5:

Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001

Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001

Figure imgf000057_0001

As indicated previously, the hueing agents described in the present specification may be incorporated into laundry care compositions including but not limited to laundry detergents and fabric care compositions. The laundry care compositions including laundry detergents may be in solid or liquid form, including a gel form, and/or unit does forms, including multicompartment unit dose forms. Such compositions may comprise one or more of said hueing agents and a laundry care ingredient.

In one aspect, said laundry care composition may comprise, based on total laundry care composition weight, less than 15% builder, less than 10% builder, or even less than 5% builder.

In one aspect, said laundry care composition may comprise, based on total laundry care composition weight, a total of no more than 20% water; a total of no more than 15% water; a total of no more than 10% water; or even a total of no more than 5% water.

In one aspect, said laundry care composition may comprise, rising, based on total laundry care composition weight, from about 10% to about 70% of a water-miscible organic solvent having a molecular weight of greater than 70 Daltons.

In one aspect, said laundry care composition may comprise, based on total laundry care composition weight, a perfume microcapsule comprising a core and a shell that encapsulates said core, said perfume microcapsule having a D[4,3] average particle of from about 0.01 microns to about 200 microns and optionally a formaldehyde scavenger that is supplied via the addition of the microcapsules (contained in a perfume microcapsule slurry that is added to the laundry care ingredient) and/or added directly to the laundry care composition. In one aspect, the shell of said perfume microcapsules may be made of any material, including materials selected from the group consisting of polyethylenes, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyacrylates, polyureas, polyurethanes, polyolefins, polysaccharides, epoxy resins, vinyl polymers, and mixtures thereof. In one aspect, useful shell materials include materials that are sufficiently impervious to the core material and the materials in the environment in which the perfume microcapsule will be employed, to permit the delivery perfume to be obtained. Suitable impervious shell materials include materials selected from the group consisting of reaction products of one or more amines with one or more aldehydes, such as urea cross-linked with formaldehyde or gluteraldehyde, melamine cross-linked with formaldehyde; gelatin-polyphosphate coacervates optionally cross-linked with gluteraldehyde; gelatin-gum Arabic coacervates; cross-linked silicone fluids; polyamine reacted with polyisocyanates and mixtures thereof. In one aspect, the shell material comprises melamine cross-linked with formaldehyde and/or a polyacrylate. Suitable perfume microcapsules may be obtained from Appleton Papers of Appleton Wisconsin, USA.

In one aspect, suitable formaldehyde scavengers include materials selected from the group consisting of sodium bisulfite, urea, ethylene urea, cysteine, cysteamine, lysine, glycine, serine, carnosine, histidine, glutathione, 3,4-diaminobenzoic acid, allantoin, glycouril, anthranilic acid, methyl anthranilate, methyl 4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide, ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide, benzoguanamine, pyroglutamic acid, pyrogallol, methyl gallate, ethyl gallate, propyl gallate, Methanol amine, succinamide, thiabendazole, benzotriazol, triazole, indoline, sulfanilic acid, oxamide, sorbitol, glucose, cellulose, poly(vinyl alcohol), partially hydrolyzed poly(vinylformamide), poly( vinyl amine), poly(ethylene imine), poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine), poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol, ethylenediamine-N,N'-bisacetoacetamide, N-(2-ethylhexyl)acetoacetamide, 2- benzoylacetoacetamide, N-(3-phenylpropyl)acetoacetamide, lilial, helional, melonal, triplal, 5,5-dimethyl-1,3-cyclohexanedione, 2,4-dimethyl-3-cyclohexenecarboxaldehyde, 2,2- dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine, triethylenetetramine, ammonium hydroxide, benzylamine, hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione, dehydroacetic acid, or a mixture thereof. These formaldehyde scavengers may be obtained from Sigma/ Aldrich/Fluka of St. Louis, MO. U.S.A. or PolySciences, Inc. of Warrington, PA U.S.A.

Such formaldehyde scavengers are typically combined with a slurry containing said perfume microcapsules, at a level, based on total slurry weight, of from about 2 wt.% to about 18 wt.%, from about 3.5 wt.% to about 14 wt.% or even from about 5 wt.% to about 13 wt.%.

In one aspect, such formaldehyde scavengers may be combined with a product containing a perfume microcapsule, said scavengers being combined with said product at a level, based on total product weight, of from about 0.005% to about 0.8%, alternatively from about 0.03% to about 0.5%, alternatively from about 0.065% to about 0.25% of the product formulation,.

In another aspect, such formaldehyde scavengers may be combined with a slurry containing said perfume microcapsules, at a level, based on total slurry weight, of from about 2 wt.% to about 14 wt.%, from about 3.5 wt.% to about 14 wt.% or even from about 5 wt.% to about 14 wt.% and said slurry may be added to a product matrix to which addition an identical or different scavenger may be added at a level, based on total product weight, of from about 0.005% to about 0.5%, alternatively from about 0.01% to about 0.25%, alternatively from about 0.05% to about 0.15% of the product formulation,

In one aspect, one or more of the aforementioned formaldehyde scavengers may be combined with a liquid fabric enhancing product containing perfume microcapsules at a level, based on total liquid fabric enhancing product weight, of from 0.005% to about 0.8%, alternatively from about 0.03% to about 0.4%, alternatively from about 0.06% to about 0.25% of the product formulation In one aspect, such formaldehyde scavengers may be combined with a liquid laundry detergent product containingperfume microcapsules, said scavengers being selected from the group consisting of sodium bisulfite, urea, ethylene urea, cysteine, cysteamine, lysine, glycine, serine, carnosine, histidine, glutathione, 3,4-diaminobenzoic acid, allantoin, glycouril, anthranilic acid, methyl anthranilate, methyl 4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide, ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide, benzoguanamine, pyroglutamic acid, pyrogallol, methyl gallate, ethyl gallate, propyl gallate, triethanol amine, succinamide, thiabendazole, benzotriazol, triazole, indoline, sulfanilic acid, oxamide, sorbitol, glucose, cellulose, poly( vinyl alcohol), partially hydrolyzed poly(vinylformamide), poly(vinyl amine), poly(ethylene imine), poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine), poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol, ethylenediamine-N,N'-bisacetoacetamide, N-(2-ethylhexyl)acetoacetamide, 2- benzoylacetoacetamide, N-(3-phenylpropyl)acetoacetamide, lilial, helional, melonal, triplal, 5,5-dimethyl- 1 ,3-cyclohexanedione, 2,4-dimethyl-3-cyclohexenecarboxaldehyde, 2,2- dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine, triethylenetetramine, ammonium hydroxide, benzylamine, hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione, dehydroacetic acid and mixtures thereof, and combined with said liquid laundry detergent product at a level, based on total liquid laundry detergent product weight, of from about 0.003 wt.% to about 0.20 wt.%, from about 0.03 wt.% to about 0.20 wt.% or even from about 0.06 wt.% to about 0.14 wt.%.

The hueing agents may be added to substrates using a variety of application techniques. For instance, for application to cellulose-containing textile substrates, the hueing agent may be included as a component of a laundry detergent. Thus, application to a cellulose-containing textile substrate actually occurs when a consumer adds laundry detergent to a washing machine. The hueing agent may be present in the laundry detergent composition in an amount from about 0.000001% to about 10% by weight of the composition, from about 0.00001% to about 10% by weight of the composition, from about 0.0001% to about 5% by weight of the composition, and even from about 0.0001% to about 1% by weight of the composition. The laundry detergent composition typically comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one aspect, the laundry detergent composition may comprise, based on total laundry detergent composition weight, from about 0.5% to about 99% of the surfactant; from about 1% to about 95% of the surfactant; from about 5% to about 90% of the surfactant, from about 5% to about 70% of the surfactant, or even from about 5% to about 40% of the surfactant. The surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants. In one aspect, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.

Fabric care compositions are typically added in the rinse cycle, which is after the detergent solution has been used and replaced with the rinsing solution in typical laundering processes. The fabric care compositions disclosed herein may be comprise a rinse added fabric softening active and a suitable hueing agent as disclosed in the present specification. The fabric care composition may comprise, based on total fabric care composition weight, from about 1% to about 90%, or from about 5% to about 50% fabric softening active. The hueing agent may be present in the fabric care composition in an amount from about 0.5 ppb to about 50 ppm, or from about 0.5 ppm to about 30 ppm.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, the non-limiting list of laundry care ingredients illustrated hereinafter are suitable for use in the laundry care compositions and may be desirably incorporated in certain aspects of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. It is understood that such ingredients are in addition to the components that were previously listed for any particular aspect. The total amount of such adjuncts may range, once the amount of dye is taken into consideration from about 90% to about 99.99999995% by weight of the laundry care composition. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable laundry care ingredients include, but are not limited to, fabric softening actives, polymers, for example cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfume(s) including quadrant perfumes and additional perfume delivery systems including perfume loaded zeolites, starch encapsuled accords, and Schiff base pro-perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 Bl and 6,326,348 Bl that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants' laundry care compositions. Thus, certain aspects of Applicants' compositions do not contain one or more of the following adjuncts materials: fabric softening actives, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:

Surfactants

Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials. Exemplary anionic surfactants are the alkali metal salts of C1O-C16 alkyl benzene sulfonic acids, or C11-C14 alkyl benzene sulfonic acids. In one aspect, the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in U.S. Pat. Nos. 2,220,099 and 2,477,383. Especially useful are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium Cn-C14, e.g., C12, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'—O— (C2H4O)n-SO3M wherein R' is a Cg-C2O alkyl group, n is from about 1 to 20, and M is a salt-forming cation. In one aspect, R' is C1O-C18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In one aspect, R' is a C12-C16, n is from about 1 to 6 and M is sodium.

The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present. Specific examples of non-alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C2o fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROSO3-M+ wherein R is typically a linear Cg-C2O hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In one aspect, R is a C1O-C15 alkyl, and M is alkali metal, more specifically R is C12-C14 and M is sodium.

Specific, non-limiting examples of anionic surfactants useful herein include: a) C11-C18 alkyl benzene sulfonates (LAS); b) C10-C20 primary, branched-chain and random alkyl sulfates (AS); c) C1O-C18 secondary (2,3) alkyl sulfates having formulae (I) and (II): wherein M in formulae (I) and (II) is hydrogen or a cation which provides charge neutrality, and all M units, whether associated with a surfactant or adjunct ingredient, can either be a hydrogen atom or a cation depending upon the form isolated by the artisan or the relative pH of the system wherein the compound is used, with non-limiting examples of suitable cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, or at least about 9, and y is an integer of at least 8, or at least about 9; d) C1O-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1-30; e) C1O-C18 alkyl alkoxy carboxylates in one aspect, comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. In one aspect, for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.

Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula: RZ(CmH21nO)nOH wherein R1 is a Cs-C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. In one aspect, R1 is an alkyl group, which may be primary or secondary, that comprises from about 9 to 15 carbon atoms, or from about 10 to 14 carbon atoms. In one aspect, the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, or from about 3 to 10 ethylene oxide moieties per molecule. The alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17 from about 6 to 15, or from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.

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

Non-limiting examples of nonionic surfactants include: a) C12-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-C1S alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed in U.S. Pat. No. 6,150,322; e) C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x if from 1-30, as discussed in U.S. Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,093,856; f) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 26, 1986; specifically alkylpolyglycosides as discussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; g) Polyhydroxy fatty acid amides as discussed in U.S. Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat. No. 6,482,994 and WO 01/42408. In the laundry detergent compositions herein, the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is the case, the weight ratio of anionic to nonionic will typically range from 10:90 to 90:10, more typically from 30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms. Additional examples include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d) cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042, 4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) amino surfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708, specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, Cg to C18 (in one aspect C12 to C18) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1- propane sulfonate where the alkyl group can be C8 to C18, or C1O to C14.

Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents comprises at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one comprises an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.

Aqueous, non-surface active liquid carrier

As noted, the laundry care compositions may be in the form of a solid, either in tablet or particulate form, including, but not limited to particles, flakes, sheets, or the like, or the compositions may be in the form of a liquid. The liquid detergent compositions may comprise an aqueous, non-surface active liquid carrier. Generally, the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the composition components. For example, the liquid detergent compositions may comprise, based on total liquid detergent composition weight, from about 5% to about 90%, from about 10% to about 70%, or from about 20% to about 70% of the aqueous, non-surface active liquid carrier.

The most cost effective type of aqueous, non-surface active liquid carrier is typically water. Accordingly, the aqueous, non- surface active liquid carrier component will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, for purposes of the present invention, the utilization of such water-miscible liquids typically is minimized to hold down composition cost. Accordingly, the aqueous liquid carrier component of the liquid detergent products herein will generally comprise water present in concentrations ranging from about 5% to about 90%, or from about 5% to about 70%, by weight of the liquid detergent composition.

Bleaching Agents

Bleaching Agents - The cleaning compositions of the present invention may comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids and mixtures thereof. In general, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent by weight of the subject cleaning

composition. Examples of suitable bleaching agents include:

(1) photobleaches for example sulfonated zinc phthalocyanine;

(2) preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxzone ®, and mixtures thereof. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R-(C=O)O-O-M wherein R is an alkyl group, optionally branched, having, when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and M is a counterion, for example, sodium, potassium or hydrogen;

(3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof. In one aspect of the invention the inorganic perhydrate salts are selected from the group consisting of sodium salts of perborate, percarbonate and mixtures thereof. When employed, inorganic perhydrate salts are typically present in amounts of from 0.05 to 40 wt%, or 1 to 30 wt% of the overall composition and are typically incorporated into such compositions as a crystalline solid that may be coated. Suitable coatings include, inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water- soluble or dispersible polymers, waxes, oils or fatty soaps; and

(4) bleach activators having R-(C=O)-L wherein R is an alkyl group, optionally branched, having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 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 leaving group. Examples of suitable leaving groups are benzoic acid and derivatives thereof - especially benzene sulphonate. Suitable bleach activators include dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS). Suitable bleach activators are also disclosed in WO 98/17767. While any suitable bleach activator may be employed, in one aspect of the invention the subject cleaning composition may comprise NOBS, TAED or mixtures thereof.

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

The amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.

Bleach Boosting Compounds - The compositions herein may comprise one or more bleach boosting compounds. Bleach boosting compounds provide increased bleaching effectiveness in lower temperature applications. The bleach boosters act in conjunction with conventional peroxygen bleaching sources to provide increased bleaching effectiveness. This is normally accomplished through in situ formation of an active oxygen transfer agent such as a dioxirane, an oxaziridine, or an oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums may be used.

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

Figure imgf000070_0001
where RI - R^ may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.

Suitable bleach boosting compounds include zwitterionic bleach boosters zwitterionic bleach boosters, which are described in U.S. Patent Nos. 5,576,282 and 5,718,614. Other bleach boosting compounds include cationic bleach boosters described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen source employed in the present invention may comprise any of these well known sources, including peroxygen compounds as well as compounds, which under consumer use conditions, provide an effective amount of peroxygen in situ. The peroxygen source may include a hydrogen peroxide source, the in situ formation of a peracid anion through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources. Of course, one of ordinary skill in the art will recognize that other sources of peroxygen may be employed without departing from the scope of the invention. The bleach boosting compounds, when present, are typically employed in conjunction with a peroxygen source in the bleaching systems of the present invention.

Enzyme Bleaching - Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991. The present invention compositions and methods may utilize alternative bleach systems such as ozone, chlorine dioxide and the like. Bleaching with ozone may be accomplished by introducing ozone-containing gas having ozone content from about 20 to about 300 g/m3 into the solution that is to contact the fabrics. The gas:liquid ratio in the solution should be maintained from about 1:2.5 to about 1:6. U.S. Patent No. 5,346, 588 describes a process for the utilization of ozone as an alternative to conventional bleach systems and is herein incorporated by reference.

In one aspect, the fabric softening active ("FSA") is a quaternary ammonium compound suitable for softening fabric in a rinse step. In one aspect, the FSA is formed from a reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and, in one aspect, triester compounds. In another aspect, the FSA comprises one or more softener quaternary ammonium compounds such, but not limited to, as a monoalkyquaternary ammonium compound, a diamido quaternary compound and a diester quaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternary ammonium (hereinafter "DQA") compound composition. In certain aspects of the present invention, the DQA compounds compositions also encompasses a description of diamido FSAs and FSAs with mixed amido and ester linkages as well as the aforementioned diester linkages, all herein referred to as DQA.

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

{R4.m - N+ - [(CH2)n - Y - R1W X"

wherein each R substituent is either hydrogen, a short chain C^-Cg, for example C\- C3 alkyl or hydroxyalkyl group, e.g., methyl, ethyl, propyl, hydroxyethyl, and the like, poly (C2-3 alkoxy), for example, polyethoxy, group, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4, or 2; each Y is -0-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)-NR- and it is acceptable for each Y to be the same or different; the sum of carbons in each R.1, plus one when Y is -0-(O)C- or -NR-C(O) -, is Qγ∑-^-22, or C14-C20 with each RI being a hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R^ to be unsaturated or saturated and branched or linear and in one aspect it is linear; it is acceptable for each R^ to be the same or different and typically these are the same; and X" can be any softener- compatible anion, suitable anions include, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and nitrate, in one aspect the anions are chloride or methyl sulfate. Suitable DQA compounds are typically made by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that typically result from such reactions include N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium methylsulfate wherein the acyl group is derived from animal fats, unsaturated, and polyunsaturated, fatty acids, e.g., tallow, hardended tallow, oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in US Patent No. 5,759,990 at column 4, lines 45-66. In one aspect, the FSA comprises other actives in addition to DQA (1) or DQA. In yet another aspect, the FSA comprises only DQA (1) or DQA and is free or essentially free of any other quaternary ammonium compounds or other actives. In yet another aspect, the FSA comprises the precursor amine that is used to produce the DQA.

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

[R4.m - N(+) - Rlm] A- wherein each m is 2 or 3, each RI is a Cg-C22> or C14-C20 but no more than one being less than about C^2 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, for example, C10-C20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene"), in one aspect C]^Ci 8 alkyl or alkenyl, and branch or unbranched. In one aspect, the Iodine Value (IV) of the FSA is from about 1 to 70; each R is H or a short chain C^-Cg, or C1-C3 alkyl or hydroxyalkyl group, e.g., methyl, ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R.2 O)2-4.H where each R2 is a C^.g alkylene group; and A" is a softener compatible anion, suitable anions include chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; in one aspect the anions are chloride or methyl sulfate.

Examples of these FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate. Examples of commercially available dialkylenedimethylammonium salts usable in the present invention are di-hydrogenated tallow dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available from Degussa under the trade names Adogen® 442 and Adogen® 470 respectively. In one aspect, the FSA comprises other actives in addition to DTTMAC. In yet another aspect, the FSA comprises only compounds of the DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other actives.

In one aspect, the FSA comprises an FSA described in U.S. Pat. Pub. No. 2004/0204337 Al, published Oct. 14, 2004 to Corona et al., from paragraphs 30 - 79. In another aspect, the FSA is one described in U.S. Pat. Pub. No. 2004/0229769 Al, published Nov. 18, 2005, to Smith et al., on paragraphs 26 - 31; or U.S. Pat. No. 6,494,920, at column 1, line 51 et seq. detailing an "esterquat" or a quaternized fatty acid triethanolamine ester salt.

In one aspect, the FSA is chosen from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.

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

Another aspect of the invention provides for a rinse added fabric softening composition further comprising a cationic starch. Cationic starches are disclosed in US 2004/0204337 Al. In one aspect, the rinse added fabric softening composition comprises from about 0.1% to about 7% of cationic starch by weight of the fabric softening composition. In one aspect, the cationic starch is HCP401 from National Starch.

Builders - The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, of said builder. Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders polycarboxylate compounds. ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Chelating Agents - The compositions herein may also optionally contain one or more copper, iron and/or manganese chelating agents. If utilized, chelating agents will generally comprise from about 0.1% by weight of the compositions herein to about 15%, or even from about 3.0% to about 15% by weight of the compositions herein.

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

Dispersants - The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.

Enzymes - The compositions can comprise one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.

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

Processes of Making Laundry Care Compositions

The laundry care compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in Applicants' examples and in 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. 5,486,303 all of which are incorporated herein by reference.

The liquid detergent compositions may be in the form of an aqueous solution or uniform dispersion or suspension of surfactant, hueing agent, and certain optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and any other normally liquid optional ingredients. Such a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity which ranges from about 100 to 600 cps, or from about 150 to 400 cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition. In a process for preparing such compositions, a liquid matrix is formed containing at least a major proportion, or even substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination. For example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated. As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After addition of all of the composition components, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes.

In one aspect of forming the liquid detergent compositions, the hueing agent is first combined with one or more liquid components to form a hueing agent premix, and this hueing agent premix is added to a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition. For example, in the methodology described above, both the hueing agent premix and the enzyme component are added at a final stage of component additions. In another aspect, the hueing agent is encapsulated prior to addition to the detergent composition, the encapsulated hueing agent is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of components of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form. Suitable solid forms include tablets and particulate forms, for example, granular particles, flakes or sheets. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein. In one aspect, for example when the composition is in the form of a granular particle, the hueing agent is provided in particulate form, optionally including additional but not all components of the laundry detergent composition. The hueing agent particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition. Further, the hueing agent, optionally including additional but not all components of the laundry detergent composition, may be provided in an encapsulated form, and the hueing agent encapsulate is combined with particulates containing a substantial balance of components of the laundry detergent composition.

The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering of fabrics. Generally, an effective amount of such compositions is added to water, for example in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, typically under agitation, with the fabrics to be laundered therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution, or from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.

Method of Use

Certain of the consumer products disclosed herein can be used to clean or treat a situs inter alia a surface or fabric. Typically at least a portion of the situs is contacted with an embodiment of Applicants' consumer product, in neat form or diluted in a liquor, for example, a wash liquor and then the situs may be optionally washed and/or rinsed. In one aspect, a situs is optionally washed and/or rinsed, contacted with an aspect of the consumer product and then optionally washed and/or rinsed. For purposes of the present invention, washing includes but is not limited to, scrubbing, and mechanical agitation. The fabric may comprise most any fabric capable of being laundered or treated in normal consumer use conditions. Liquors that may comprise the disclosed compositions may have a pH of from about 3 to about 11.5. Such compositions are typically employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. When the wash solvent is water, the water temperature typically ranges from about 5 °C to about 90 °C and, when the situs comprises a fabric, the water to fabric ratio is typically from about 1:1 to about 30:1. Employing one or more of the aforementioned methods results in a treated situs.

In one aspect, method of treating and/or cleaning a surface or fabric comprising the steps of optionally washing and/or rinsing said surface or fabric, contacting said surface or fabric with any laundry care composition disclosed in this specification, then optionally washing and/or rinsing said surface and/or fabric then optionally letting said surface or fabric to dry and/or actively drying said surface or fabric, is disclosed.

Examples

The following examples are provided to further illustrate the hueing agents of the present invention; however, they are not to be construed as limiting the invention as defined in the claims appended hereto. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in this invention without departing from the scope or spirit of the invention. All parts and percents given in these examples are by weight unless otherwise indicated.

Sample Preparation and Test Methods

A. Sample Preparation

The following general procedures were used to prepare the thiophene azo dyes of the present invention.

Preparation ofGlycidol Materials

Figure imgf000080_0001

18 parts N-ethyl-m-toluidine, 52 parts isopropyl-glycidyl ether, and 50 parts toluene were charged into a 200 niL round bottom flask at room temperature. The mixture was refluxed overnight. The solvent was removed and the resulting material was used crude for the next step. These materials were then alkoxylated as described herein.

Preparation of Alkoxylated Intermediates General procedure for alkoxylation - Method A:

Intermediate Type 1, initial single site polymer

Figure imgf000080_0002

18 parts N-ethyl-m-toluidine, 14 parts acetic acid, and 20 parts water were charged into a 200 mL stainless steel autoclave at room temperature. 11 parts ethylene oxide was added over several hours. After the reaction was kept for 24 hours at room temperature, the vessel was charged with 0.2 parts NaOH and heated up to 125°C. Then, ethylene oxide was added over about 1 hour. After continuing the reaction for another 3 hours at 125°C, residual EO was removed by vacuum. Then it was cooled to room temperature and the intermediate obtained was an amber-colored viscous liquid. The constant average number of EO could be achieved every time by controlling the amount of ethylene oxide in the synthesis.

Intermediate Type 2, initial dual chain polymer

Figure imgf000081_0001

18 parts 2-Methoxy-5-methylaniline, 14 parts acetic acid, and 20 parts water were charged into a 200 niL stainless steel autoclave at room temperature. 22 parts ethylene oxide was added over several hours. After the reaction was kept for 24 hours at room temperature, the vessel was charged with 0.2 parts NaOH and heated up to 125°C. Then, 40 parts ethylene oxide was added over about 1 hour. After continuing the reaction for another 3 hours at 125°C, residual EO was removed by vacuum. Then it was cooled to room temperature and the intermediate obtained was an amber-colored viscous liquid. The constant average number of EO could be achieved every time by controlling the amount of ethylene oxide in the synthesis.

General procedure for alkoxylation - Method B:

Figure imgf000081_0002

18 parts aniline, 60 parts mono-bromo-polyethylene glycol-200, 20 parts NaHCO3 and 50 parts toluene were charged into a 200 mL round bottom flask at room temperature. The reaction mixture was heated to 80°C for 5 hours. The salt was filtered and the solvent removed from the filtrate via low pressure distillation. The crude product was used with no further purification for the next step.

Figure imgf000082_0001

It is also possible to use a mono-bromo-mono-chloro glycol in order to directly make the halogenated product using this same procedure above.

General Procedure for Tosylation of Intermediates Intermediate Type 1

Figure imgf000082_0002

To a mixture of 44 parts N-ethyl -N-alkylene oxide-m-toluidine and 41 parts tosyl chloride in 20 parts water was slowly added 20 parts 25% NaOH. The reaction mixture was then allowed to stir for 4 hours at room temperature. The mixture was diluted with 400 parts water and then neutralized by addition of 33% hydrochloric acid. 400 parts ethyl acetate was added and the mixture was phase separated. The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent evaporated. The crude product was immediately used for the next step.

Intermediate Type 2

Figure imgf000083_0001

To a mixture of 44 parts 2-methoxy-5-methyl-N-bis-alkyleneoxide-aniline and 82 parts tosyl chloride in 30 parts water was slowly added 30 parts 25% NaOH. The reaction mixture was then allowed to stir for 4 hours at room temperature. The mixture was diluted with 400 parts water and then neutralized by addition of 33% hydrochloric acid. 400 parts ethyl acetate was added and the mixture was phase separated. The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent evaporated. The crude product was immediately used for the next step.

General Procedure for Quaternization

Intermediate Type 1

Figure imgf000083_0002

40 parts of the tosylated intermediate, 20 parts dimethylaminopropyl sulfonate and 100 parts chloroform were mixed and refluxed for 6 hours. The material was then cooled down and 200 parts water was added. The material was phase separated and the aqueous phase was found to contain the desired product. The aqueous phase was dried down via low pressure distillation. The chloride material can be used in the same way to make the chloro salt version. Intermediate Type 2

Figure imgf000084_0001

40 parts of the tosylated intermediate, 30 parts triethylamine and 100 parts chloroform were mixed and refluxed for 6 hours. The material was then cooled down and 200 parts water was added. The material was phase separated and the aqueous phase was found to contain the desired product. The aqueous phase was dried down via low pressure distillation

General Procedures for Color Synthesis

All colors were prepared following the same general procedure.

Example 12

Figure imgf000084_0002

2 parts amino-thiophene, and 30 parts phosphoric acid, were charged into 200 mL glass flask and cooled to 0-5°C. 1 part NaNO2 was slowly added as a solid, maintaining the temperature below 10°C. When addition was completed for diazotization, the mixture was stirred for 30 minutes and excess sodium nitrite was consumed by adding 0.3 parts sulfamic acid. Enough sulfamic acid was added until starch iodide paper provided a negative result. To a separate flask was added the 6 parts of the quaternized material prepared following Intermediate Type 1 route, wherein quaternization was done using 1 molar equivalent of triethylamine and 12 parts water. The prepared diazonium salt solution was slowly added into the above solution for coupling reaction. Care was taken to not allow the temperature to rise above 10°C. After complete addition of diazonium salt solution, the reaction was allowed to slowly reach room temperature over an hour. The mixture was then neutralized with sodium hydroxide and phase separated. The product layer was then dissolved with methanol and filtered to remove any excess salts. The filtrate was evaporated and the product of this reaction can be used at this point or further diluted with water to a lower viscosity.

Example 1

Example 1 was prepared via the Intermediate Type 2 procedures, wherein only 2 moles of ethylene oxide were added to the initial material and the tosylated material was quaternized by using 2 molar equivalents N-methyl imidazole. Colorant synthesis was as described in Example 12.

Example 2

Example 2 was prepared as Example 1, except the initial alkoxylation was done using m- toluidine.

Example 7

Example 7 was prepared via the Intermediate Type 1 procedures, wherein only 1 mole of ethylene oxide was added to the N-ethyl- aniline and the tosylated material was quaternized by using 1 molar equivalent triethylamine. Colorant synthesis was as described in Example 12. Example 13

Example 13 was prepared as Example 12, except quaternization was done with N-methyl imidazole.

Example 14

Example 14 was prepared as Example 12, except quaternization was done with N5N- Dimethyl-glycine.

Example 15

Example 15 was prepared as Example 12, except quaternization was done with N5N- Dimethylpropyl sulfonate.

Example 18

Example 18 was prepared via the Intermediate Type 2 procedures and colorant synthesis was as described in Example 12.

Example 19

Example 19 was prepared via the Intermediate Type 2 procedures, wherein the initial alkoxylation was done using 2,5-dimethoxyaniline and colorant synthesis was as described in Example 12.

Example 21 Example 21 was prepared via the Intermediate Type 2 procedures, wherein quaternization was done using dimethylethanolamine and colorant synthesis was as described in Example 12.

Example 22

Example 22 was prepared via the Intermediate Type 2 procedures, wherein quaternization was done using triethanolamine and colorant synthesis was as described in Example 12.

Example 35

Example 35 was prepared via the Intermediate Type 2 procedures, wherein alkoxylation was done using m-toluidine and quaterinzation was done using triethylamine. Colorant synthesis was as described in Example 12.

Example 36

Example 36 was prepared as Example 1, except that the initial alkoxylation was done using m-toluidine and quaternization was done using triethylamine. Color synthesis was as described in Example 12.

B. Test Methods

I. Method for Determining the Aqueous Partition Value of a Dye

Dissolve in deionized water to a final volume of 10.0 mL an amount of dye sufficient to provide a solution absorbance value between 0.25 and 1.0, said absorbance being determined at the dye λmax between 400 nm and 750 nm, using a cuvette with 1.0 cm path length.

Measure the absorbance of the sample at the dye X1n^x in a UVNis spectrophotometer, then transfer the entire 10.0 mL solution to a 50.0 mL plastic centrifuge tube. Add 10.0 mL of 1- octanol, cap the tube, and mix vigorously for 30 seconds using a Vortex™ mixer. Leave the tube standing undisturbed until the layers cleanly phase separate. If the layers do not cleanly separate within several hours, centrifuge to obtain phase separation.

Using a transfer pipette, withdraw an aliquot of the aqueous (bottom) layer and transfer it to a cuvette with 1.0 cm path length for spectrophotometric analysis. Analyze the solution as before, and quantify the absorbance loss at λmax as "% of Dye Remaining in Aqueous Layer" as detailed below:

% of Dye Remaining in Aqueous Layer = Aqueous Partition Value (APV) = (AfZA1) x 100% wherein A1 is the initial solution absorbance at λmax and Af is the final solution absorbance at

II. Method for Determining Hueing Efficiency for Detergents

a.) Two 25 cm x 25 cm fabric swatches of 16 oz white cotton interlock knit fabric (270 g/square meter, brightened with Uvitex BNB fluorescent whitening agent, from Test Fabrics. P.O. Box 26, Weston, PA, 18643) are obtained. b.) Prepare two one liter aliquots of tap water containing 1.55 g of AATCC standard heavy duty liquid (HDL) test detergent.

c.) Add a sufficient amount the dye to be tested to one of the aliquots from Step b.) above to produce an aqueous solution absorbance of 1 AU. d.) Wash one swatch from a.) above in one of the aliquots of water containing 1.55 g of AATCC standard heavy duty liquid (HDL) test detergent and wash the other swatch in the other aliquot. Such washing step should be conducted for 30 minutes at room temperature with agitation. After such washing step separately rinse the swatches in tap water and air dry the swatches in the dark. e.) After rinsing and drying each swatch, the hueing efficiency, DE*eff, of the dye is assessed by determining the L*, a*, and b* value measurements of each swatch using a Hunter LabScan XE reflectance spectrophotometer with D65 illumination, 10° observer and UV filter excluded. The hueing efficiency of the dye is then calculated using the following equation:

DE*eff = ((L*c - IΛ)2 + (a*c - a*s)2 + (b*c - b*s)2)1/2 wherein the subscripts c and s respectively refer to the L*, a*, and b* values measured for the control, i.e., the fabric sample washed in detergent with no dye, and the fabric sample washed in detergent containing the dye to be screened.

III. Method for Determining Wash Removability

a.) Prepare two separate 150 ml aliquots of HDL detergent solution, according to AATCC Test Method 61-2003, Test 2A and containing 1.55 g/ liter of the AATCC HDL formula in distilled water.

b.) A 15 cm x 5 cm sample of each fabric swatch from the Method for Determining of Hueing Efficiency For Detergents described above is washed in a Launderometer for 45 minutes at 49°C in 150 ml of a the HDL detergent solution prepared according to Step II. a.) above.

c.) The samples are rinsed with separate aliquots of rinse water and air dried in the dark, and then L*, a*, and b* value measurements of each swatch are taken using a Hunter LabScan XE reflectance spectrophotometer with D65 illumination, 10° observer and UV filter excluded. The amount of residual coloration is assessed by measuring the DE*res, calculated using the following equation:

DE*res = ((IΛ - L*s)2 + (a*c - a*s)2 + (b*c - b*s)2)1/2 wherein the subscripts c and s respectively refer to the L*, a*, and b* values measured for the control, i.e., the fabric sample initially washed in detergent with no dye, and the fabric sample initially washed in detergent containing the dye to be screened. The wash removal value for the dye is then calculated according to the formula: % removal = 100 x (1 - DE*res/DE*eff). C. Test Results

The aqueous partitioning values of several examples are provided in Table 6.

Table 6: Aqueous Partitioning Values of Thiophene Azo Dyes

Figure imgf000090_0001

Exemplary Detergent Formulations

Formulations Ia - 11: Liquid Detergent Formulations Tables 7A and 7B provide examples of liquid detergent formulations which include at least one thiophene azo dye of the present invention as a hueing agent. The formulations are shown in Table 7 A as Formulations Ia through If and in Table 7B as Formulations Ig through 11.

Table 7A - Liquid Detergent Formulations Comprising the

Inventive Hueing Agent

Figure imgf000091_0001

Figure imgf000092_0001

Table 7B - Liquid Detergent Formulations Comprising the

Inventive Hueing Agent

Figure imgf000093_0001

Footnotes for Formulations Ia-I:

1 diethylenetriaminepentaacetic acid, sodium salt

diethylenetriaminepentakismethylenephosphonic acid, sodium salt

3 ethylenediaminetetraacetic acid, sodium salt

4 a non-tinting dyes used to adjust formula color 5 compact formula, packaged as a unitized dose in polyvinyl alcohol film

6 thiophene azo hueing agent from Table 5, Examples 1-21, preferably with hueing efficiency >10 and wash removability 30-85%

7 thiophene azo hueing agent from Table 5, Examples 22-42, preferably with hueing efficiency >10 and wash removability 30-85%

8 Acusol OP301

Formulations 2a - 2e: Granular Detergent Formulations

Table 8 provides examples of granular detergent formulations which include at least one thiophene azo dye of the present invention as a hueing agent. The formulations are shown in Table 8 as Formulations 2a through 2e.

Table 8 - Granular Detergent Formulations Comprising the

Inventive Hueing Agent

Figure imgf000094_0001

Figure imgf000095_0001

Footnotes for Formulations 2a-e:

Hhiophene azo hueing agent from Table 5, Examples 1-21, preferably with hueing efficiency

>10 and wash removability 30-85%

2thiophene azo hueing agent from Table 5, Examples 22-42, preferably with hueing efficiency >10 and wash removability 30-85%

Exemplary Fabric Care Compositions

Formulations 3a - 3d: Liquid Fabric Care Compositions

Table 9 provides examples of liquid fabric care compositions which include at least one thiophene azo dye of the present invention as a hueing agent. The compositions are shown in Table 9 as Formulations 3a through 3d.

Table 9 - Liquid Fabric Care Compositions

Comprising the Inventive Hueing Agent

Figure imgf000095_0002
Figure imgf000096_0001

Footnotes for Formulations 3a-d:

a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.

b Cationic starch based on common maize starch or potato starch, containing 25% to 95% amylose and a degree of substitution of from 0.02 to 0.09, and having a viscosity measured as Water Fluidity having a value from 50 to 84.

c Copolymer of ethylene oxide and terephthalate having the formula described in US

5,574,179 at col.15, lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R1 is essentially 1,4-phenylene moieties, each R2 is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.

d Diethylenetriaminepentaacetic acid.

e KATHON® CG available from Rohm and Haas Co.

f Silicone antifoam agent available from Dow Corning Corp. under the trade name DC2310. g thiophene azo hueing agent from Table 5, Examples 1-21, preferably with hueing efficiency >10 and wash removability 30-85%

h thiophene azo hueing agent from Table 5, Examples 22-42, preferably with hueing efficiency >10 and wash removability 30-85%

1 thiophene azo hueing agent from Table 5, Examples 1-42, preferably with hueing efficiency >10 and wash removability 30-85%

J Disodium 4,4'-bis-(2-sulfostyryl) biphenyl, available from Ciba Specialty Chemicals.

k Cocomethyl ethoxylated [15] ammonium chloride, available from Akzo Nobel.

* * *

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

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

Claims

What we claim is:
1. A laundry care composition comprising:
a) a thiophene azo dye containing a formally charged moiety, with the proviso that the dye does not comprise a meta-bis(2-hydroxy-3- trimethylammoniumpropyl) amino tolyl group; and
b) a laundry care ingredient, preferably said laundry care composition comprises, based on total laundry care composition weight, a perfume microcapsule comprising a core and a shell that encapsulates said core, said perfume microcapsule having a D[4,3] average particle of from 0.01 microns to 200 microns.
2. The laundry care composition of Claim 1, wherein said thiophene azo dye has, in the wavelength range of 400 nm to 750 nm in methanol solution, a maximum extinction coefficient from 1000 to 1,000,000 liter/mol/cm.
3. The laundry care composition according to any preceding claim, wherein said thiophene azo dye has, in the wavelength range of 560 nm to 610 nm, a maximum extinction coefficient from 20,000 to 250,000 liter/mol/cm.
4. The laundry care composition according to any preceding claim, wherein said thiophene azo dye has an aqueous partition value from 10% to 100%, said dye comprising a non- covalently bound charge balancing counterion.
5. The laundry care composition according to any of Claims 1 to 3, wherein said thiophene azo dye has an aqueous partition value from 0% to 40%, said dye comprising a covalently bound charge balancing counterion.
6. The laundry care composition according to any preceding claim, wherein said thiophene azo dye is represented by general Formula (I):
Figure imgf000099_0001
wherein:
a.) R1, R2 and R3 are each independently selected from hydrogen, electron- withdrawing moieties, and electron-donating moieties, provided that at least one of R1, R2 and R3 is an electron- withdrawing moiety, preferably each R1, R2 and R3 is independently selected from hydrogen, (C1-C4)- alkyl, (C3-C1o)-aryl, carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro, (C1-C4)-alkyl ester, halogen or amino moiety; and b.) wherein X is an organic moiety having a molecular weight from 65 daltons to 4855 daltons.
7. The laundry care composition according to any preceding claim, wherein for said thiophene azo dye X is a moiety having Formula (II) below:
Figure imgf000099_0002
wherein:
i.) R4 is selected from a moiety having Formula (III) below
Figure imgf000100_0001
wherein:
i.) Each R8 is independently selected from hydrogen, C1- Cs alkyl optionally substituted with a hydroxy, or acetyl;
ii.) m is an integer from 0 to 10;
iii.) Y is selected from a sulfonate, carboxylate, a phosphonate or quaternary ammonium species selected from an imidazolium, pyridinium, morpholinium, piperidinium, or a moiety having Formula (IV) below:
Figure imgf000100_0002
wherein:
i.) R9 is a C1-Cg alkyl moiety optionally substituted with -OH,
ii.) Rio is selected from C1-C18 alkyl moiety optionally substituted with -OH, or C2-Cg alkyl substituted with sulfonate, or C1-C8 alkyl substituted with carboxylate,
iii.) Z is a charge balancing counterion of unit charge c; the index b is 1 when Rio is a C1-C18 alkyl moiety optionally substituted with -OH, otherwise the index b = 0; Or, R4 is selected from a moiety having Formula (V) below:
Figure imgf000101_0001
wherein
i.) Each Rn and R12 is independently selected from hydrogen, C1-C8 alkyl, aryl, acetyl or hydroxyl moiety; m and n are independent and are integers from 0 to 10, ii.) Y is as described above;
Or, R4 is selected from a moiety having Formula (VI) below:
Figure imgf000101_0002
Formula VI
wherein
i.) R13 is selected from an aryl moiety, arylalkyl moiety,
C1-C18 alkyl moiety, or a siloxane moiety; ii.) Each R14 is independently selected from hydrogen, C1-
C4 alkyl; m is an integer from 0 to 10;
iii.) Y is as described above; ii.) R5 can be the same as R4 or selected from C1-C12 alkyl moiety, aryl moiety or arylalkyl moiety; wherein the index (a) is an integer from 0 to 4, and each R6 may be independently selected from a C1-C6 alkyl, a C1-C4 alkoxy, a nitro, a hydroxyl, a halogen, or -NHC(O)R22 wherein R22 is selected from H, -NH2, C1-C6 alkyl, phenyl, -(CH2)SOR23 where the index s is 1 or 2 and R23 is selected from Me, phenyl, and - CO2CH2CN; -NHSO2R24 wherein R24 is C1-C4 alkyl or phenyl; said alkyl, alkoxy and acetamido moieties may be optionally substituted with a formally charged moiety; or X a moiety having Formula VII below:
Figure imgf000102_0001
wherein each R4 and R5 can independently be selected from:
a) [(CH2CR1HO)X(CH2CR-HO)XR15];
b) alkyl, aryl or aryl alkyl;
c) [CH2CH(ORI6)CH2ORI7];
d) the amino addition product of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether, 2- ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by the addition of from 1 to 10 alkylene oxide units wherein at least one such alkyleneoxide unit is substituted with R15 that is not -H;
wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)zRi5, and mixtures thereof; R" is selected from the group consisting of H, CH2O(CH2CH2O)Z Ri5, and mixtures thereof; x + y < 20; y > 1; z = 0 to 10; each Ri5 is independently selected from -H and -CH2CHRi8N+Ri9R2oR2i wherein Ri8 is selected from -H and -CH3; each Ri9 and R20 is independently selected from C1-C4 alkyl optionally substituted with -OH; R2i is independently selected from C1-C12 optionally -OH substituted alkyl or (CH2)rOpQ; the index r is an integer from 1 to 8; the index p is 0 or 1; and wherein Q is an anionic group selected from -CO2-, and - SO3-; Ri6 is selected from the group consisting of H, (CH2CH2O)zRi5 wherein z = 0 to 10, and mixtures thereof; Ri7 is selected from the group consisting of C1-C16 alkyl, C6-C1O aryl groups, and mixtures thereof; the index m is an integer from 0 to 4 and each R6 is as defined above; Z is a charge balancing counterion of unit charge c; the index b is equal to the number of non-H R15 groups that do not comprise a covalently bound charge balancing counterion; further provided the molecule contains at least one non-H R15 group.
8. The laundry care composition according to any preceding claim, wherein for said thiophene azo dye X is a moiety having Formula (II) below:
Figure imgf000103_0001
wherein:
i.) R4 is selected from a moiety having Formula (III) below
Figure imgf000103_0002
wherein:
i.) Rg is a hydrogen, C1-C4 alkyl moiety or aryl moiety; ii.) Y is a quaternary ammonium species selected from a group consisting of an imidazolium, or a moiety having
Formula (IV) below:
Figure imgf000104_0001
wherein:
i.) R9 is a C1-C2 alkyl moiety,
ii.) Rio is selected from C1-Cs alkyl moiety optionally substituted with -OH, or C2-C4 alkyl substituted with sulfonate, or C1-C4 alkyl substituted with carboxylate,
iii.) Z is a charge balancing counterion of unit charge c; the index b is 1 when Rio is a C1-Cs alkyl moiety optionally substituted with -OH, otherwise the index b = 0; or, R4 is selected from a moiety having Formula (V) below:
Figure imgf000104_0002
wherein
i.) Each Rn and R12 is independently selected from hydrogen, C1-C4 alkyl or aryl moiety; m and n are independent and are integers from 0 to 5,
ii.) Y is as described above;
Or, R4 is selected from a moiety having Formula (VI) below:
Figure imgf000105_0001
wherein
i.) Rn is selected from an aryl moiety, benzyl moiety, or a
C1-C18 alkyl moiety;
ii.) Each Ri4 is independently selected from hydrogen or -
CH3; m is an integer from 0 to 10,
ii.) R5 can be the same as R4 or selected from C1-C6 alkyl moiety or benzyl moiety;
iii.)Wherein the index a is an integer from 0 to 2, and each R6 may be independently selected from methyl, methoxy, or acetamido moiety.
9. The laundry care composition according to any preceding claim, wherein said thiophene azo dye has Formula (VIII):
Figure imgf000105_0002
wherein the A moiety is selected from the group consisting of Table 1 A Moieties Nos. 1 - 118, preferably Table 1 A Moieties Nos. 9 - 11, 15, 23, 34 - 35, 37 - 39, 41, 43, 47, 50 - 51, 57 - 58, 77, 83, 89, 95, 106, and 110 - 118; and wherein X is selected from the group consisting of Table 4 X Moieties Nos. 1 - 31, preferably X is selected from the group consisting of Table 4 X Moieties Nos. 1 - 31.
10. The laundry care composition according to any of Claim 1 to 8, wherein said thiophene azo dye has the following formula:
Figure imgf000106_0001
wherein the moiety A is selected from Table 1 A Moieties Nos. 1 - 118, preferably A is selected from Table 1 A Moieties Nos. 9 - 11, 15, 23, 34 - 35, 37 - 39, 41, 43, 47, 50 - 51, 57 - 58, 77, 83, 89, 95, 106, and 110 - 118; a = 0 to 2; when a = 1 or 2, R6 is selected from Table 2 R6 Substituent Identity and Position Nos. 1 - 40, preferably R6 is selected from Table 2 R6 Substituent Identity and Position Nos. 1, 3, 5, 7, 12, 13, 14, 31, 36 and 40; and the R4 and R5 grouping is selected from Table 3 R4 and R5 Groupings Nos. 1 - 69, preferably the R4 and R5 grouping is selected from Table 3 R4 and R5 Groupings Nos. 3, 5 - 6, 10, 13 - 14, 17, 19 - 21, 24, 27 - 28, 31 - 34, 38, 41, 44 - 48, 52, 54 - 55, 58, 60 - 64 and 69.
11. The laundry care composition of Claim 1, wherein said thiophene azo dye has a formula selected from Table 5 Formula Nos. 1 - 42.
12. The laundry care composition according to any preceding claim, said laundry care composition comprising, based on total laundry care composition weight, less than 15% builder, less than 10% builder, or even less than 5% builder.
13. The laundry care composition according to any preceding claim, said laundry care composition comprising, based on total laundry care composition weight, a total of no more than 20% water; a total of no more than 15% water; a total of no more than 10% water; or even a total of no more than 5% water.
14. The laundry care composition according to any preceding claim, said laundry care composition comprising, based on total laundry care composition weight, from 10% to 70% of a water-miscible organic solvent having a molecular weight of greater than 70 Daltons.
15. A method of treating and/or cleaning a surface or fabric comprising the steps of optionally washing and/or rinsing said surface or fabric, contacting said surface or fabric with a laundry care composition of any of Claims 1-14, then optionally washing and/or rinsing said surface and/or fabric then optionally letting said surface or fabric to dry and/or actively drying said surface or fabric.
PCT/US2010/056508 2010-11-12 2010-11-12 Thiophene azo dyes and laundry care compositions containing the same WO2011011799A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2010/056508 WO2011011799A2 (en) 2010-11-12 2010-11-12 Thiophene azo dyes and laundry care compositions containing the same

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2013538698A JP5833133B2 (en) 2010-11-12 2010-11-12 Thiophene azo dyes and laundry care compositions containing the same
BR112013011851A BR112013011851A2 (en) 2010-11-12 2010-11-12 "Care composition for the laundering clothes comprising azo dyes thiophene and method for treating and / or cleaning a surface or fabric"
MX2013005276A MX2013005276A (en) 2010-11-12 2010-11-12 Thiophene azo dyes and laundry care compositions containing the same.
EP10781555.7A EP2638142B1 (en) 2010-11-12 2010-11-12 Thiophene azo dyes and laundry care compositions containing the same
CN201080070050.7A CN103210073B (en) 2010-11-12 2010-11-12 Thiophene-azo dyes containing them and laundry care compositions
CA2817718A CA2817718C (en) 2010-11-12 2010-11-12 Laundry care compositions comprising charged thiophene azo dyes
PCT/US2010/056508 WO2011011799A2 (en) 2010-11-12 2010-11-12 Thiophene azo dyes and laundry care compositions containing the same

Publications (2)

Publication Number Publication Date
WO2011011799A2 true WO2011011799A2 (en) 2011-01-27
WO2011011799A3 WO2011011799A3 (en) 2011-10-06

Family

ID=43499689

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/056508 WO2011011799A2 (en) 2010-11-12 2010-11-12 Thiophene azo dyes and laundry care compositions containing the same

Country Status (7)

Country Link
EP (1) EP2638142B1 (en)
JP (1) JP5833133B2 (en)
CN (1) CN103210073B (en)
BR (1) BR112013011851A2 (en)
CA (1) CA2817718C (en)
MX (1) MX2013005276A (en)
WO (1) WO2011011799A2 (en)

Cited By (92)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05260462A (en) * 1991-08-21 1993-10-08 Sgs Thomson Microelectron Sa Predictor
WO2012159778A1 (en) 2011-05-26 2012-11-29 Unilever Plc Liquid laundry composition
WO2012166699A1 (en) * 2011-06-03 2012-12-06 The Procter & Gamble Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
WO2012166768A1 (en) * 2011-06-03 2012-12-06 The Procter & Gamble Company Laundry care compositions containing dyes
WO2012163871A1 (en) * 2011-06-01 2012-12-06 Unilever Plc Liquid detergent composition containing dye polymer
EP2540825A2 (en) 2011-06-30 2013-01-02 The Procter and Gamble Company Cleaning compositions comprising amylase variants reference to a sequence listing
WO2013011071A1 (en) 2011-07-21 2013-01-24 Unilever Plc Liquid laundry composition
EP2551336A1 (en) 2011-07-25 2013-01-30 The Procter and Gamble Company Detergent compositions
WO2013025742A1 (en) 2011-08-15 2013-02-21 The Procter & Gamble Company Detergent compositions containing pyridinol-n-oxide compounds
WO2013006871A3 (en) * 2012-02-13 2013-03-14 Milliken & Company Laundry care compositions containing dyes
CN102972395A (en) * 2012-12-06 2013-03-20 扬州大学 2, 5-bithiophene-2-ethinyl thiophene nano microcapsule preparation for preventing lygocoris lucorum and method for preparing 2, 5-bithiophene-2-ethinyl thiophene nano microcapsule preparation for preventing and treating lygocoris lucorum
WO2013043855A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company High suds detergent compositions comprising isoprenoid-based surfactants
WO2013043805A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid - based surfactants
WO2013043852A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Easy-rinse detergent compositions comprising isoprenoid-based surfactants
WO2013043803A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants
WO2013043857A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants
CN103230766A (en) * 2013-05-08 2013-08-07 天津城市建设学院 Preparation and application of self-adhesive double-wall essence microcapsule
WO2013189615A1 (en) 2012-06-21 2013-12-27 Unilever Plc Liquid laundry detergent
WO2014012921A1 (en) 2012-07-17 2014-01-23 Unilever Plc Bright detergent composition
WO2014012923A1 (en) 2012-07-17 2014-01-23 Unilever Plc Bright detergent composition
WO2014018309A1 (en) 2012-07-26 2014-01-30 The Procter & Gamble Company Low ph liquid cleaning compositions with enzymes
EP2712915A1 (en) 2012-10-01 2014-04-02 The Procter and Gamble Company Methods of treating a surface and compositions for use therein
WO2014066308A1 (en) 2012-10-24 2014-05-01 The Procter & Gamble Company Anti foam compositions comprising aryl bearing polyorganosilicons
WO2014066309A1 (en) 2012-10-24 2014-05-01 The Procter & Gamble Company Anti foam compositions comprising partly phenyl bearing polyorganosilicons
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
EP2740785A1 (en) 2012-12-06 2014-06-11 The Procter and Gamble Company Use of composition to reduce weeping and migration through a water soluble film
WO2014089386A1 (en) 2012-12-06 2014-06-12 The Procter & Gamble Company Soluble pouch comprising hueing dye
EP2767581A1 (en) 2013-02-19 2014-08-20 The Procter & Gamble Company Method of laundering a fabric
EP2767579A1 (en) 2013-02-19 2014-08-20 The Procter and Gamble Company Method of laundering a fabric
EP2767582A1 (en) 2013-02-19 2014-08-20 The Procter and Gamble Company Method of laundering a fabric
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
WO2014168942A1 (en) 2013-04-12 2014-10-16 The Procter & Gamble Company Fibrous structures comprising polysaccharide filaments
WO2014168776A1 (en) 2013-04-12 2014-10-16 The Procter & Gamble Company Hydroxyl polymer fiber structures comprising ammonium alkylsulfonate salts and methods for making same
WO2014168775A1 (en) 2013-04-12 2014-10-16 The Procter & Gamble Company Fibrous structures exhibiting improved whiteness index values
EP2808372A1 (en) 2013-05-28 2014-12-03 The Procter and Gamble Company Surface treatment compositions comprising photochromic dyes
JP2015500888A (en) * 2011-06-03 2015-01-08 ミリケン・アンド・カンパニーMilliken & Company Thiophene azo carboxylate dyes, and laundry care compositions containing them
EP2832843A1 (en) 2013-07-30 2015-02-04 The Procter and Gamble Company Method of making granular detergent compositions comprising polymers
EP2832842A1 (en) 2013-07-30 2015-02-04 The Procter and Gamble Company Method of making granular detergent compositions comprising surfactants
WO2015041887A3 (en) * 2013-09-18 2015-05-14 Milliken & Company Laundry care composition comprising carboxylate dye
JP2015514141A (en) * 2012-03-19 2015-05-18 ザ プロクター アンド ギャンブルカンパニー Laundry care compositions containing a dye
EP2899260A1 (en) 2014-01-22 2015-07-29 Unilever PLC Process to manufacture a liquid detergent formulation
WO2015112340A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Method of treating textile fabrics
WO2015112339A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Fabric treatment composition
WO2015112341A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Fabric treatment composition
WO2015112338A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Method of treating textile fabrics
WO2015126547A1 (en) 2014-02-19 2015-08-27 Milliken & Company Composition comprising benefit agent and aprotic solvent
WO2015127004A1 (en) 2014-02-19 2015-08-27 The Procter & Gamble Company Composition comprising benefit agent and aprotic solvent
WO2015130653A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
WO2015130669A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
WO2015148360A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015148361A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015168194A1 (en) 2014-04-29 2015-11-05 The Procter & Gamble Company Fabric care compositions comprising polyurethane, polyurea and/or polyurethaneurea polymers
WO2015187757A1 (en) 2014-06-06 2015-12-10 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
EP2987849A1 (en) 2014-08-19 2016-02-24 The Procter and Gamble Company Method of Laundering a Fabric
EP2987848A1 (en) 2014-08-19 2016-02-24 The Procter & Gamble Company Method of laundering a fabric
WO2016032991A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032993A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016044200A1 (en) 2014-09-15 2016-03-24 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
WO2016048969A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Detergent compositions containing a polyetheramine and an anionic soil release polymer
WO2016049388A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
WO2016049387A1 (en) 2014-09-26 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016048674A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016081437A1 (en) 2014-11-17 2016-05-26 The Procter & Gamble Company Benefit agent delivery compositions
JP2016530392A (en) * 2013-09-18 2016-09-29 ザ プロクター アンド ギャンブル カンパニー Laundry care compositions containing thiophene azo carboxylate dyes
EP3088502A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
EP3088503A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
EP3088505A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
EP3088506A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Detergent composition
EP3088504A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
JP2016536433A (en) * 2013-09-18 2016-11-24 ザ プロクター アンド ギャンブル カンパニー Laundry care compositions comprising a carboxylate dyes
WO2016188693A1 (en) 2015-05-27 2016-12-01 Unilever Plc Laundry detergent composition
WO2016192905A1 (en) 2015-06-02 2016-12-08 Unilever Plc Laundry detergent composition
JP2016538350A (en) * 2013-09-23 2016-12-08 ザ プロクター アンド ギャンブル カンパニー particle
WO2016200440A1 (en) 2015-06-11 2016-12-15 The Procter & Gamble Company Device and methods for applying compositions to surfaces
EP2992054B1 (en) 2013-05-03 2017-01-04 Unilever Plc. Alkoxylated bis azo dyes
WO2017055205A1 (en) 2015-10-01 2017-04-06 Unilever Plc Powder laundry detergent composition
EP3173467A1 (en) 2015-11-26 2017-05-31 The Procter & Gamble Company Cleaning compositions comprising enzymes
WO2017140391A1 (en) 2016-02-17 2017-08-24 Unilever Plc Whitening composition
WO2017140392A1 (en) 2016-02-17 2017-08-24 Unilever Plc Whitening composition
WO2017198438A1 (en) 2016-05-17 2017-11-23 Unilever Plc Liquid laundry detergent compositions
WO2017198574A1 (en) 2016-05-17 2017-11-23 Unilever Plc Liquid laundry detergent compositions
EP3301162A1 (en) * 2016-10-03 2018-04-04 The Procter & Gamble Company Low ph laundry detergent composition
EP3301164A1 (en) * 2016-10-03 2018-04-04 The Procter & Gamble Company Low ph laundry detergent composition
EP3301163A1 (en) * 2016-10-03 2018-04-04 The Procter & Gamble Company Low ph laundry detergent composition
WO2018060139A1 (en) 2016-09-27 2018-04-05 Unilever Plc Domestic laundering method
WO2018072979A1 (en) 2016-10-18 2018-04-26 Unilever Plc Whitening composition
EP3357994A1 (en) 2017-02-01 2018-08-08 The Procter & Gamble Company Cleaning compositions comprising amylase variants
WO2019008036A1 (en) 2017-07-07 2019-01-10 Unilever Plc Whitening composition
WO2019008035A1 (en) 2017-07-07 2019-01-10 Unilever Plc Laundry cleaning composition
WO2019105675A1 (en) 2017-11-30 2019-06-06 Unilever Plc Detergent composition comprising protease

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2920497A1 (en) * 2013-09-18 2015-03-26 The Procter & Gamble Company Laundry care composition comprising carboxylate dye

Citations (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4228042A (en) 1978-06-26 1980-10-14 The Procter & Gamble Company Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group
US4239660A (en) 1978-12-13 1980-12-16 The Procter & Gamble Company Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source
US4260529A (en) 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
WO1992006162A1 (en) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent containing alkyl sulfate and polyhydroxy fatty acid amide surfactants
WO1993019038A1 (en) 1992-03-26 1993-09-30 The Procter & Gamble Company Process for reducing the levels of fatty acid contaminants in polyhydroxy fatty acid amide surfactants
WO1993019146A1 (en) 1992-03-16 1993-09-30 The Procter & Gamble Company Fluid compositions containing polyhydroxy fatty acid amides
WO1994009099A1 (en) 1992-10-13 1994-04-28 The Procter & Gamble Company Fluid compositions containing polyhydroxy fatty acid amides
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5346588A (en) 1989-10-30 1994-09-13 Lenzing Aktiengesellschaft Process for the chlorine-free bleaching of cellulosic materials with ozone
US5360569A (en) 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
US5370826A (en) 1993-11-12 1994-12-06 Lever Brothers Company, Division Of Conopco, Inc. Quaternay oxaziridinium salts as bleaching compounds
WO1995013353A1 (en) 1993-11-12 1995-05-18 Unilever N.V. Activation of bleach precursors with imine quaternary salts
WO1995013352A1 (en) 1993-11-12 1995-05-18 Unilever N.V. Imine quaternary salts as bleach catalysts
US5482515A (en) 1993-11-12 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5486303A (en) 1993-08-27 1996-01-23 The Procter & Gamble Company Process for making high density detergent agglomerates using an anhydrous powder additive
US5489392A (en) 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 (en) 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
US5565422A (en) 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
US5569645A (en) 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
US5574005A (en) 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
US5576282A (en) 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
US5691297A (en) 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
US5718614A (en) 1995-08-28 1998-02-17 Electro-Matic Products Company Control apparatus for grinder
WO1998017767A1 (en) 1996-10-18 1998-04-30 The Procter & Gamble Company Detergent compositions
US5759990A (en) 1996-10-21 1998-06-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
WO1998035006A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Liquid cleaning composition
WO1998035004A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Solid detergent compositions
WO1998035003A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Detergent compound
WO1998035005A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company A cleaning composition
WO1998035002A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Cleaning compositions
WO1999005241A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof
WO1999005244A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkyl aryl sulfonate surfactants
WO1999005084A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Process for making alkylbenzenesulfonate surfactants from alcohols and products thereof
WO1999005242A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkylbenzenesulfonate surfactants
WO1999005082A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved processes for making alkylbenzenesulfonate surfactants and products thereof
WO1999005243A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Detergent compositions containing mixtures of crystallinity-disrupted surfactants
WO1999007656A2 (en) 1997-08-08 1999-02-18 The Procter & Gamble Company Improved processes for making surfactants via adsorptive separation and products thereof
US5879584A (en) 1994-09-10 1999-03-09 The Procter & Gamble Company Process for manufacturing aqueous compositions comprising peracids
US6004922A (en) 1996-05-03 1999-12-21 The Procter & Gamble Company Laundry detergent compositions comprising cationic surfactants and modified polyamine soil dispersents
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6022844A (en) 1996-03-05 2000-02-08 The Procter & Gamble Company Cationic detergent compounds
WO2000023549A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
WO2000023548A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
WO2000047708A1 (en) 1999-02-10 2000-08-17 The Procter & Gamble Company Low density particulate solids useful in laundry detergents
US6136769A (en) 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
US6221825B1 (en) 1996-12-31 2001-04-24 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
WO2001042408A2 (en) 1999-12-08 2001-06-14 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US6494920B1 (en) 1999-02-04 2002-12-17 Cognis Deutschland Gmbh & Co. Kg Detergent mixtures
US20040204337A1 (en) 2003-03-25 2004-10-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US20040229769A1 (en) 2000-12-27 2004-11-18 Colgate-Palmolive Company Thickened fabric conditioners

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1389266A (en) * 1972-05-18 1975-04-03 Ici Ltd Basic monoazo dyestuffs
US4459229A (en) * 1981-10-09 1984-07-10 Eastman Kodak Company Heterocyclic azo dyes with couplers having sulfoaralkyl groups
JPH0464340B2 (en) * 1983-03-18 1992-10-14 Mitsubishi Chem Ind
DE3528759A1 (en) * 1985-08-10 1987-02-19 Basf Ag heterocyclic azo dyes
DE3707715A1 (en) * 1987-03-11 1988-09-22 Basf Ag piperazine dyes with N- (2-aminoethyl)
DE4215495A1 (en) * 1992-05-12 1993-11-18 Basf Ag Azo dyes having a diazo component from the acetalized thiophene or thiazole
EP1976968B1 (en) * 2006-01-23 2017-08-09 The Procter and Gamble Company Laundry care compositions with thiazolium dye
EP2104729B1 (en) * 2007-01-19 2010-11-03 The Procter & Gamble Company Laundry care composition comprising a whitening agent for cellulosic substrates
CN101910394B (en) * 2008-01-10 2012-06-27 荷兰联合利华有限公司 Shading composition
EP2133410B1 (en) * 2008-06-13 2011-12-28 The Procter and Gamble Company Multi-compartment pouch
EP2163608A1 (en) * 2008-09-12 2010-03-17 The Procter & Gamble Company Laundry particle made by extrusion comprising a hueing dye and fatty acid soap
EP2169042B1 (en) * 2008-09-30 2012-04-18 The Procter and Gamble Company Composition comprising microcapsules
JP2010209294A (en) * 2009-03-12 2010-09-24 Lion Corp Detergent composition
WO2011017719A2 (en) * 2010-11-12 2011-02-10 Milliken & Company Thiophene azo dyes and laundry care compositions containing the same

Patent Citations (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4228042A (en) 1978-06-26 1980-10-14 The Procter & Gamble Company Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group
US4260529A (en) 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4239660A (en) 1978-12-13 1980-12-16 The Procter & Gamble Company Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US5346588A (en) 1989-10-30 1994-09-13 Lenzing Aktiengesellschaft Process for the chlorine-free bleaching of cellulosic materials with ozone
WO1992006162A1 (en) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent containing alkyl sulfate and polyhydroxy fatty acid amide surfactants
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
WO1993019146A1 (en) 1992-03-16 1993-09-30 The Procter & Gamble Company Fluid compositions containing polyhydroxy fatty acid amides
WO1993019038A1 (en) 1992-03-26 1993-09-30 The Procter & Gamble Company Process for reducing the levels of fatty acid contaminants in polyhydroxy fatty acid amide surfactants
WO1994009099A1 (en) 1992-10-13 1994-04-28 The Procter & Gamble Company Fluid compositions containing polyhydroxy fatty acid amides
US5486303A (en) 1993-08-27 1996-01-23 The Procter & Gamble Company Process for making high density detergent agglomerates using an anhydrous powder additive
US5370826A (en) 1993-11-12 1994-12-06 Lever Brothers Company, Division Of Conopco, Inc. Quaternay oxaziridinium salts as bleaching compounds
WO1995013353A1 (en) 1993-11-12 1995-05-18 Unilever N.V. Activation of bleach precursors with imine quaternary salts
WO1995013351A1 (en) 1993-11-12 1995-05-18 Unilever N.V. Quarternary oxaziridinium salts as bleaching compounds
WO1995013352A1 (en) 1993-11-12 1995-05-18 Unilever N.V. Imine quaternary salts as bleach catalysts
US5442066A (en) 1993-11-12 1995-08-15 Lever Brothers Company, Division Of Conopco, Inc. Quaternary oxaziridinium salts as bleaching compounds
US5478357A (en) 1993-11-12 1995-12-26 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with imine quaternary salts
US5482515A (en) 1993-11-12 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5360569A (en) 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
US5550256A (en) 1993-11-12 1996-08-27 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5879584A (en) 1994-09-10 1999-03-09 The Procter & Gamble Company Process for manufacturing aqueous compositions comprising peracids
US5516448A (en) 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
US5489392A (en) 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
US5691297A (en) 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
US5574005A (en) 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 (en) 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
US5565422A (en) 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
US5718614A (en) 1995-08-28 1998-02-17 Electro-Matic Products Company Control apparatus for grinder
US5576282A (en) 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
US6022844A (en) 1996-03-05 2000-02-08 The Procter & Gamble Company Cationic detergent compounds
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6004922A (en) 1996-05-03 1999-12-21 The Procter & Gamble Company Laundry detergent compositions comprising cationic surfactants and modified polyamine soil dispersents
US6136769A (en) 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
WO1998017767A1 (en) 1996-10-18 1998-04-30 The Procter & Gamble Company Detergent compositions
US5759990A (en) 1996-10-21 1998-06-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
US6153577A (en) 1996-11-26 2000-11-28 The Procter & Gamble Company Polyoxyalkylene surfactants
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
US6221825B1 (en) 1996-12-31 2001-04-24 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
WO1998035004A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Solid detergent compositions
WO1998035006A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Liquid cleaning composition
WO1998035003A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Detergent compound
WO1998035002A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company Cleaning compositions
WO1998035005A1 (en) 1997-02-11 1998-08-13 The Procter & Gamble Company A cleaning composition
WO1999005243A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Detergent compositions containing mixtures of crystallinity-disrupted surfactants
WO1999005082A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved processes for making alkylbenzenesulfonate surfactants and products thereof
WO1999005241A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof
WO1999005244A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkyl aryl sulfonate surfactants
WO1999005084A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Process for making alkylbenzenesulfonate surfactants from alcohols and products thereof
WO1999005242A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkylbenzenesulfonate surfactants
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
WO1999007656A2 (en) 1997-08-08 1999-02-18 The Procter & Gamble Company Improved processes for making surfactants via adsorptive separation and products thereof
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
WO2000023549A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
WO2000023548A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
US6494920B1 (en) 1999-02-04 2002-12-17 Cognis Deutschland Gmbh & Co. Kg Detergent mixtures
WO2000047708A1 (en) 1999-02-10 2000-08-17 The Procter & Gamble Company Low density particulate solids useful in laundry detergents
WO2001042408A2 (en) 1999-12-08 2001-06-14 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US20040229769A1 (en) 2000-12-27 2004-11-18 Colgate-Palmolive Company Thickened fabric conditioners
US20040204337A1 (en) 2003-03-25 2004-10-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch

Cited By (146)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05260462A (en) * 1991-08-21 1993-10-08 Sgs Thomson Microelectron Sa Predictor
US9487740B2 (en) 2010-11-12 2016-11-08 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US8979946B2 (en) 2010-11-12 2015-03-17 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US9856439B2 (en) 2010-11-12 2018-01-02 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
WO2012159778A1 (en) 2011-05-26 2012-11-29 Unilever Plc Liquid laundry composition
EP3354792A1 (en) * 2011-06-01 2018-08-01 Unilever PLC, a company registered in England and Wales under company no. 41424 of Liquid detergent composition containing dye polymer
WO2012163871A1 (en) * 2011-06-01 2012-12-06 Unilever Plc Liquid detergent composition containing dye polymer
US8888865B2 (en) 2011-06-03 2014-11-18 The Procter & Gamble Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
WO2012166699A1 (en) * 2011-06-03 2012-12-06 The Procter & Gamble Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
JP2015500888A (en) * 2011-06-03 2015-01-08 ミリケン・アンド・カンパニーMilliken & Company Thiophene azo carboxylate dyes, and laundry care compositions containing them
WO2012166768A1 (en) * 2011-06-03 2012-12-06 The Procter & Gamble Company Laundry care compositions containing dyes
JP2014520177A (en) * 2011-06-03 2014-08-21 ザ プロクター アンド ギャンブル カンパニー Thiophene azo carboxylate dyes and laundry care compositions containing the same
US9752104B2 (en) 2011-06-03 2017-09-05 The Procter & Gamble Company Thiophene AZO carboxylate dyes and laundry care compositions containing the same
CN103703117B (en) * 2011-06-03 2015-11-25 宝洁公司 Thiophene azo carboxylate dyes and laundry care compositions comprising thereof
CN103582696B (en) * 2011-06-03 2015-11-25 宝洁公司 Dye-containing washing laundry care composition
CN103703117A (en) * 2011-06-03 2014-04-02 宝洁公司 Thiophene azo carboxylate dyes and laundry care compositions containing the same
US8858651B2 (en) 2011-06-03 2014-10-14 The Procter & Gamble Company Laundry care compositions containing dyes
RU2598853C2 (en) * 2011-06-03 2016-09-27 Дзе Проктер Энд Гэмбл Компани Composition for washing clothes containing dyes
CN103582696A (en) * 2011-06-03 2014-02-12 宝洁公司 Laundry care compositions containing dyes
EP3121270A2 (en) 2011-06-30 2017-01-25 The Procter & Gamble Company Cleaning compositions comprising amylase variants reference to a sequence listing
EP2540825A2 (en) 2011-06-30 2013-01-02 The Procter and Gamble Company Cleaning compositions comprising amylase variants reference to a sequence listing
WO2013011071A1 (en) 2011-07-21 2013-01-24 Unilever Plc Liquid laundry composition
EP2551336A1 (en) 2011-07-25 2013-01-30 The Procter and Gamble Company Detergent compositions
EP2551335A1 (en) 2011-07-25 2013-01-30 The Procter and Gamble Company Enzyme stabilized liquid detergent composition
WO2013016368A1 (en) 2011-07-25 2013-01-31 The Procter & Gamble Company Detergent compositions
WO2013025742A1 (en) 2011-08-15 2013-02-21 The Procter & Gamble Company Detergent compositions containing pyridinol-n-oxide compounds
WO2013043855A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company High suds detergent compositions comprising isoprenoid-based surfactants
WO2013043803A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants
WO2013043852A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Easy-rinse detergent compositions comprising isoprenoid-based surfactants
WO2013043857A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants
WO2013043805A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid - based surfactants
WO2013006871A3 (en) * 2012-02-13 2013-03-14 Milliken & Company Laundry care compositions containing dyes
JP2015514141A (en) * 2012-03-19 2015-05-18 ザ プロクター アンド ギャンブルカンパニー Laundry care compositions containing a dye
CN104379718A (en) * 2012-06-21 2015-02-25 荷兰联合利华有限公司 Liquid laundry detergent
US20150159121A1 (en) * 2012-06-21 2015-06-11 Conopco, Inc., D/B/A Unilever Liquid laundry detergent
WO2013189615A1 (en) 2012-06-21 2013-12-27 Unilever Plc Liquid laundry detergent
US9249379B2 (en) 2012-06-21 2016-02-02 Conopco, Inc. Liquid laundry detergent
WO2013189640A1 (en) 2012-06-21 2013-12-27 Unilever Plc Liquid laundry detergent
CN104428405A (en) * 2012-07-17 2015-03-18 荷兰联合利华有限公司 Bright detergent composition
CN104471049B (en) * 2012-07-17 2017-07-21 荷兰联合利华有限公司 Bright detergent composition
US9200240B2 (en) 2012-07-17 2015-12-01 Conopco, Inc. Bright detergent composition
CN104428405B (en) * 2012-07-17 2018-03-27 荷兰联合利华有限公司 Bright detergent composition
CN104471049A (en) * 2012-07-17 2015-03-25 荷兰联合利华有限公司 Bright detergent composition
US9193941B2 (en) 2012-07-17 2015-11-24 Conopco, Inc. Bright detergent composition
EP2875112B1 (en) 2012-07-17 2017-02-08 Unilever Plc. Bright detergent composition
WO2014012923A1 (en) 2012-07-17 2014-01-23 Unilever Plc Bright detergent composition
WO2014012921A1 (en) 2012-07-17 2014-01-23 Unilever Plc Bright detergent composition
US20150141317A1 (en) * 2012-07-17 2015-05-21 Conopco, Inc., D/B/A Unilever Bright detergent composition
US20150175942A1 (en) * 2012-07-17 2015-06-25 Conopco, Inc., D/B/A Unilever Bright detergent composition
WO2014018309A1 (en) 2012-07-26 2014-01-30 The Procter & Gamble Company Low ph liquid cleaning compositions with enzymes
EP2712915A1 (en) 2012-10-01 2014-04-02 The Procter and Gamble Company Methods of treating a surface and compositions for use therein
WO2014055245A1 (en) 2012-10-01 2014-04-10 The Procter & Gamble Company Methods of treating a surface and compositions for use therein
US9095787B2 (en) 2012-10-24 2015-08-04 The Procter & Gamble Company Compositions comprising anti-foams
US9133421B2 (en) 2012-10-24 2015-09-15 The Procter & Gamble Company Compositions comprising anti-foams
WO2014066309A1 (en) 2012-10-24 2014-05-01 The Procter & Gamble Company Anti foam compositions comprising partly phenyl bearing polyorganosilicons
WO2014066308A1 (en) 2012-10-24 2014-05-01 The Procter & Gamble Company Anti foam compositions comprising aryl bearing polyorganosilicons
WO2014089270A1 (en) 2012-12-06 2014-06-12 The Procter & Gamble Company Use of composition to reduce weeping and migration through a water soluble film
JP2016504440A (en) * 2012-12-06 2016-02-12 ザ プロクター アンド ギャンブルカンパニー Use of a composition for reducing the migration and leaking through the water-soluble film
CN102972395B (en) 2012-12-06 2014-09-10 扬州大学 2, 5-bithiophene-2-ethinyl thiophene nano microcapsule preparation for preventing lygocoris lucorum and method for preparing 2, 5-bithiophene-2-ethinyl thiophene nano microcapsule preparation for preventing and treating lygocoris lucorum
EP2740785A1 (en) 2012-12-06 2014-06-11 The Procter and Gamble Company Use of composition to reduce weeping and migration through a water soluble film
CN102972395A (en) * 2012-12-06 2013-03-20 扬州大学 2, 5-bithiophene-2-ethinyl thiophene nano microcapsule preparation for preventing lygocoris lucorum and method for preparing 2, 5-bithiophene-2-ethinyl thiophene nano microcapsule preparation for preventing and treating lygocoris lucorum
WO2014089386A1 (en) 2012-12-06 2014-06-12 The Procter & Gamble Company Soluble pouch comprising hueing dye
EP2767581A1 (en) 2013-02-19 2014-08-20 The Procter & Gamble Company Method of laundering a fabric
EP2767579A1 (en) 2013-02-19 2014-08-20 The Procter and Gamble Company Method of laundering a fabric
WO2014130509A1 (en) 2013-02-19 2014-08-28 The Procter & Gamble Company Method of laundering a fabric
WO2014130508A1 (en) 2013-02-19 2014-08-28 The Procter & Gamble Company Method of laundering a fabric
WO2014130512A1 (en) 2013-02-19 2014-08-28 The Procter & Gamble Company Method of laundering a fabric
EP2767582A1 (en) 2013-02-19 2014-08-20 The Procter and Gamble Company Method of laundering a fabric
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
WO2014160820A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2014168942A1 (en) 2013-04-12 2014-10-16 The Procter & Gamble Company Fibrous structures comprising polysaccharide filaments
WO2014168776A1 (en) 2013-04-12 2014-10-16 The Procter & Gamble Company Hydroxyl polymer fiber structures comprising ammonium alkylsulfonate salts and methods for making same
WO2014168775A1 (en) 2013-04-12 2014-10-16 The Procter & Gamble Company Fibrous structures exhibiting improved whiteness index values
EP2992054B1 (en) 2013-05-03 2017-01-04 Unilever Plc. Alkoxylated bis azo dyes
CN103230766A (en) * 2013-05-08 2013-08-07 天津城市建设学院 Preparation and application of self-adhesive double-wall essence microcapsule
CN103230766B (en) * 2013-05-08 2014-12-10 天津城市建设学院 Preparation and application of self-adhesive double-wall essence microcapsule
EP2808372A1 (en) 2013-05-28 2014-12-03 The Procter and Gamble Company Surface treatment compositions comprising photochromic dyes
WO2014193859A1 (en) 2013-05-28 2014-12-04 The Procter & Gamble Company Surface treatment compositions comprising photochromic dyes
EP2832843A1 (en) 2013-07-30 2015-02-04 The Procter and Gamble Company Method of making granular detergent compositions comprising polymers
EP2832842A1 (en) 2013-07-30 2015-02-04 The Procter and Gamble Company Method of making granular detergent compositions comprising surfactants
WO2015041887A3 (en) * 2013-09-18 2015-05-14 Milliken & Company Laundry care composition comprising carboxylate dye
JP2016536433A (en) * 2013-09-18 2016-11-24 ザ プロクター アンド ギャンブル カンパニー Laundry care compositions comprising a carboxylate dyes
US9834682B2 (en) 2013-09-18 2017-12-05 Milliken & Company Laundry care composition comprising carboxylate dye
JP2016530392A (en) * 2013-09-18 2016-09-29 ザ プロクター アンド ギャンブル カンパニー Laundry care compositions containing thiophene azo carboxylate dyes
JP2016538350A (en) * 2013-09-23 2016-12-08 ザ プロクター アンド ギャンブル カンパニー particle
WO2015112340A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Method of treating textile fabrics
WO2015110444A1 (en) 2014-01-22 2015-07-30 Unilever Plc Process to manufacture a liquid detergent formulation
WO2015112339A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Fabric treatment composition
WO2015112341A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Fabric treatment composition
WO2015112338A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Method of treating textile fabrics
EP2899260A1 (en) 2014-01-22 2015-07-29 Unilever PLC Process to manufacture a liquid detergent formulation
WO2015126547A1 (en) 2014-02-19 2015-08-27 Milliken & Company Composition comprising benefit agent and aprotic solvent
WO2015127004A1 (en) 2014-02-19 2015-08-27 The Procter & Gamble Company Composition comprising benefit agent and aprotic solvent
WO2015130669A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
WO2015130653A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
WO2015148360A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015148361A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015168194A1 (en) 2014-04-29 2015-11-05 The Procter & Gamble Company Fabric care compositions comprising polyurethane, polyurea and/or polyurethaneurea polymers
US9574161B2 (en) 2014-04-29 2017-02-21 The Procter & Gamble Company Fabric care compositions comprising polyurethane, polyurea and/or polyurethaneurea polymers
WO2015187757A1 (en) 2014-06-06 2015-12-10 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
EP2987848A1 (en) 2014-08-19 2016-02-24 The Procter & Gamble Company Method of laundering a fabric
EP2987849A1 (en) 2014-08-19 2016-02-24 The Procter and Gamble Company Method of Laundering a Fabric
WO2016032991A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032993A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016044200A1 (en) 2014-09-15 2016-03-24 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
WO2016049388A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
WO2016048674A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016048969A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Detergent compositions containing a polyetheramine and an anionic soil release polymer
WO2016049387A1 (en) 2014-09-26 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016081437A1 (en) 2014-11-17 2016-05-26 The Procter & Gamble Company Benefit agent delivery compositions
EP3088503A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
WO2016176241A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Detergent composition
WO2016176296A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Method of laundering a fabric
WO2016176240A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Method of treating a fabric
WO2016176282A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Method of treating a fabric
WO2016176280A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Method of treating a fabric
EP3088502A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
EP3088504A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
EP3088505A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Method of treating a fabric
EP3088506A1 (en) 2015-04-29 2016-11-02 The Procter and Gamble Company Detergent composition
WO2016188693A1 (en) 2015-05-27 2016-12-01 Unilever Plc Laundry detergent composition
WO2016192905A1 (en) 2015-06-02 2016-12-08 Unilever Plc Laundry detergent composition
WO2016200440A1 (en) 2015-06-11 2016-12-15 The Procter & Gamble Company Device and methods for applying compositions to surfaces
WO2017055205A1 (en) 2015-10-01 2017-04-06 Unilever Plc Powder laundry detergent composition
EP3173467A1 (en) 2015-11-26 2017-05-31 The Procter & Gamble Company Cleaning compositions comprising enzymes
WO2017091674A1 (en) 2015-11-26 2017-06-01 The Procter & Gamble Company Liquid detergent compositions comprising protease and encapsulated lipase
WO2017140391A1 (en) 2016-02-17 2017-08-24 Unilever Plc Whitening composition
WO2017140392A1 (en) 2016-02-17 2017-08-24 Unilever Plc Whitening composition
WO2017198574A1 (en) 2016-05-17 2017-11-23 Unilever Plc Liquid laundry detergent compositions
WO2017198438A1 (en) 2016-05-17 2017-11-23 Unilever Plc Liquid laundry detergent compositions
WO2018060139A1 (en) 2016-09-27 2018-04-05 Unilever Plc Domestic laundering method
WO2018067488A1 (en) * 2016-10-03 2018-04-12 The Procter & Gamble Company Low ph laundry detergent composition
EP3301162A1 (en) * 2016-10-03 2018-04-04 The Procter & Gamble Company Low ph laundry detergent composition
EP3301163A1 (en) * 2016-10-03 2018-04-04 The Procter & Gamble Company Low ph laundry detergent composition
WO2018067487A1 (en) * 2016-10-03 2018-04-12 The Procter & Gamble Company Low ph laundry detergent composition
WO2018067486A1 (en) * 2016-10-03 2018-04-12 The Procter & Gamble Company Low ph laundry detergent composition
EP3301164A1 (en) * 2016-10-03 2018-04-04 The Procter & Gamble Company Low ph laundry detergent composition
WO2018072979A1 (en) 2016-10-18 2018-04-26 Unilever Plc Whitening composition
EP3357994A1 (en) 2017-02-01 2018-08-08 The Procter & Gamble Company Cleaning compositions comprising amylase variants
WO2018144399A1 (en) 2017-02-01 2018-08-09 The Procter & Gamble Company Cleaning compositions comprising amylase variants
WO2019008036A1 (en) 2017-07-07 2019-01-10 Unilever Plc Whitening composition
WO2019008035A1 (en) 2017-07-07 2019-01-10 Unilever Plc Laundry cleaning composition
WO2019105675A1 (en) 2017-11-30 2019-06-06 Unilever Plc Detergent composition comprising protease

Also Published As

Publication number Publication date
JP5833133B2 (en) 2015-12-16
CA2817718C (en) 2016-02-09
EP2638142A2 (en) 2013-09-18
BR112013011851A2 (en) 2016-08-16
JP2014501802A (en) 2014-01-23
EP2638142B1 (en) 2017-05-10
CA2817718A1 (en) 2011-01-27
MX2013005276A (en) 2013-06-03
CN103210073A (en) 2013-07-17
WO2011011799A3 (en) 2011-10-06
CN103210073B (en) 2016-06-08

Similar Documents

Publication Publication Date Title
EP2231845B1 (en) Detergents having acceptable color
EP2382299B1 (en) Incorporation of dye into granular laundry composition
CN102015989B (en) Reduced spotting granules
US7597723B2 (en) Unsubstituted and polymeric triphenymethane colorants for coloring consumer products
CN102149807B (en) Prepared by extrusion of the laundry particle comprising a hueing dye and a fatty acid soap
US7205269B2 (en) Laundry detergent compositions with hueing dye
EP2118256B1 (en) Shading composition
CN102741357B (en) Dye polymers
US20060183658A1 (en) Laundry detergent compositions with efficient hueing dye
US9487739B2 (en) Cleaning compositions containing a polyetheramine
US20050288206A1 (en) Laundry detergent compositions with efficient hueing dye
JP5683960B2 (en) Detergent composition
CN101023159B (en) Laundry treatment compositions
CN103582696B (en) Dye-containing washing laundry care composition
JP5236289B2 (en) Shading method
CN103180425B (en) Bluing agent comprising a low-built detergent compositions
KR20040023249A (en) Complex salt for detergent to prevent spotting
ES2355763T3 (en) Care composition on laundry comprising a whitening agent for cellulosic substrates.
JP2012502169A (en) Detergent particles produced by extrusion molding comprising a hueing dye
CN104220535B (en) Carboxylate dyes
US20180245025A1 (en) Leuco Triphenylmethane Colorants As Bluing Agents In Laundry Care Compositions
CN101600760B (en) Novel whitening agents for cellulosic substrates
CN101027383A (en) Laundry treatment compositions
JP6046167B2 (en) Laundry care compositions containing a dye
JP2016534205A (en) Cleaning compositions containing polyetheramine

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10781555

Country of ref document: EP

Kind code of ref document: A2

REEP

Ref document number: 2010781555

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2010781555

Country of ref document: EP

ENP Entry into the national phase in:

Ref document number: 2013538698

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: MX/A/2013/005276

Country of ref document: MX

ENP Entry into the national phase in:

Ref document number: 2817718

Country of ref document: CA

NENP Non-entry into the national phase in:

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013011851

Country of ref document: BR

ENP Entry into the national phase in:

Ref document number: 112013011851

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20130513