JP6141369B2 - Thiopheneazo dye and laundry care composition containing the same - Google Patents

Description

TECHNICAL FIELD This application relates to thiophenazo dyes for use as hueing agents, laundry care compositions comprising such thiophenazo dyes, methods for making such thiophenazo dyes and laundry care compositions, and It relates to how to use these. The thiophenazo dyes described above contain a formal charge moiety and are generally composed of at least two components, at least one chromophore component and at least one polymer component. Appropriate chromophore components generally emit blue, red, violet, or purple fluorescence when exposed to ultraviolet light, or they absorb light and reflect these same shades Can do. These thiophenazo dyes do not accumulate over time and do not result in an undesirable blue discoloration for the treated fabric while providing a hue effect, for example a whitening effect, on the fabric. It is advantageous. Also, thiophenazo dyes are generally stable to bleach used in laundry care compositions.

Background As textile substrates age, these colors tend to fade or yellow due to light, air, exposure to soil, and natural degradation of the fibers that make up the substrate. Thus, the purpose of the hueing agent is generally to visually brighten these textile substrates and prevent fading and yellowing of the substrates. Typically, the hueing agent can be found in laundry detergents, fabric softeners, or rinse aids and is therefore applied to the textile substrate during the washing process. However, it is important that the hueing agent serves to lighten the treated textile substrate visually without causing undesired coloration of the textile substrate. Cellulose substrates tend to exhibit a yellow hue, especially after exposure to light, air, and / or soil. This yellowness is often difficult to reverse by normal washing procedures. As a result, there is a need for an improved hueing agent that can eliminate the yellowness exhibited by aging cellulose substrates. By utilizing such improved hueing agents, the lifetime of textile substrates such as clothing articles, table linens, etc. can be extended. Unfortunately, current hue agents do not realize the benefits of hue after a single processing cycle and / or they accumulate to an undesirable level, thereby causing the treated site to be excessively disposed of by multiple processing cycles. Either to tint.

  The hueing agents disclosed herein and the laundry care compositions containing them have been used in compositions, such as laundry care compositions, unlike previous thiopheneazo hueing agents. Sometimes, such a hueing agent includes a formal charge portion that allows enhanced deposition, removal and hue angle to be achieved, thus providing an advantage over previous efforts in this area. In addition to enhanced deposition, removal and hue angle, the hueing agent provides improved stability in a cleaning environment containing a bleaching agent, such as a bleaching effect accelerator. Without being bound by theory, Applicants believe that such enhanced stability is due, at least in part, to the improved distribution behavior of such hueing agents. The above advantages are realized across a variety of fabric types. In short, applicants are aware of the current cause of hueing defects and provide a solution to such a problem herein. The hueing compounds disclosed herein also absorb light at a wavelength that is appropriate to visually neutralize the yellowness of a substrate such as a textile substrate. These compounds ideally serve as hueing agents for substrates such as textile substrates and may be incorporated into laundry care compositions for use by consumers.

SUMMARY OF THE INVENTION This application relates to thiophenazo dyes for use as hueing agents, laundry care compositions comprising such thiophenazo dyes that can serve as hueing agents, such thiophenazo dyes and laundry care compositions And a method of using them. The thiophenazo dyes described above contain a formal charge moiety and are generally composed of at least two components, at least one chromophore component and at least one polymer component. Appropriate chromophore components generally emit blue, red, blue-violet, or violet fluorescence when exposed to ultraviolet light, or they absorb light and reflect these same shades be able to. These thiophenazo dyes do not accumulate over time and do not provide an undesirable blue discoloration to the treated fabric while providing a hueing effect, for example, a whitening effect, on the fabric. It is advantageous. Also, thiophenazo dyes are generally stable to bleach used in laundry care compositions.

DETAILED DESCRIPTION As used herein, the term “alkoxy” includes C ₁ -C ₈ alkoxy and alkoxy derivatives of polyols having repeat units such as butylene oxide, glycidol oxide, ethylene oxide or propylene oxide. Intended.

As used herein, the terms “alkyl” and “alkyl capped” are intended to include C ₁ -C ₁₈ alkyl groups and, in one aspect, C ₁ -C ₆ alkyl groups.

As used herein, the term “aryl” is intended to include C ₃ -C ₁₂ aryl groups.

As used herein, the term “arylalkyl” is intended to include C ₁ -C ₁₈ alkyl groups and, in one aspect, C ₁ -C ₆ alkyl groups.

  As used herein, the term “formal charge moiety” means a moiety having at least one positive or at least one negative formal charge in aqueous solution at a pH in the range of 7-11. To do.

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

  As used herein, the term “laundry care composition”, unless otherwise indicated, refers to granules, powders, liquids, gels, pastes, unit dose bar forms and / or flake type detergents and / or Or a fabric treatment composition.

  As used herein, the term “fabric treatment composition” includes fabric softening compositions, fabric enhancing compositions, fabric recovery compositions and combinations thereof, unless otherwise indicated. Such a composition may be a composition with rinsing, but it need not be.

  As used herein, “cellulose substrate” is intended to include any substrate in which at least a majority of the weight comprises cellulose. Cellulose can be found in wood, cotton, flax, jute and hemp. Cellulose substrates can be in the form of powders, fibers, pulp, and articles formed from powders, fibers and pulp. Cellulosic fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate), and mixtures thereof. Articles formed from cellulosic fibers include textile articles such as fabrics. Articles formed from pulp include paper.

  As used herein, articles such as “the”, “a”, and “an”, when used in the claims, refer to one or more of those recited or described in the claims. Is understood to mean.

  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 ranging from 400 nanometers to 750 nanometers.

  The thiophenazo dyes disclosed herein may contain a distribution of repeat units in these polymer moieties as a result of these manufacturing steps. Thus, in one aspect, the molecular weight of a thiophenazo dye disclosed herein can be reported as an average molecular weight as determined by its molecular weight distribution.

  The test methods disclosed in the Test Methods section of this application should be used to determine the respective values of the parameters of Applicants' invention.

  Unless otherwise stated, all component or composition levels are with respect to the active portion of that component or composition and can be present in commercial sources of such components or compositions. Remove impurities such as residual solvent or by-products.

  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.

  All maximum numerical limits presented throughout this specification should be understood to include such lower numerical limits as if all lower numerical limits were expressly set forth herein. All minimum numerical limits presented throughout this specification include such higher numerical limits as if all higher numerical limits were expressly set forth herein. All numerical ranges presented throughout this specification are all narrower numerical ranges that fall within such wider numerical ranges as if such narrower numerical ranges were all expressly set forth herein. including.

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

Suitable Hue Agents Hue agents of the present invention include thiophenazo dyes that contain a formal charge moiety. However, these thiophenazo dyes do not contain a meta-bis (2-hydroxy-3-trimethylammoniumpropyl) aminotolyl group.

  In one aspect, the thiophene azo dye includes a thiophene moiety, an azo moiety, and a coupler moiety, the thiophene moiety is covalently bonded to the azo moiety, and the coupler is covalently bonded to the azo moiety. Wherein at least one of the thiophene and / or azo moieties comprises a formal charge moiety.

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

  Examples of suitable polymer constructs include polyoxyalkylene chains having a plurality of repeating units. In one aspect, the polymer component has 2 to about 30 repeat units, 2 to about 20 repeat units, 2 to about 10 repeat units, or about 3 or 4 to about 6 repeat units. Contains polyoxyalkylene chains. 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 thiophenazo dye contains a formal charge moiety, provided that the dye does not contain a meta-bis (2-hydroxy-3-trimethylammoniumpropyl) aminotolyl group. Thiopheneazo dyes are about 400 nm to about 750 nm in methanol solution, or about 520 nm to about 650 nm in methanol solution, or about 540 nm to about 630 nm in methanol solution, or about 560 nm to about 610 nm in methanol solution. Of about 1000 to about 1,000,000 liters / mol / cm, or about 5,000 to about 750,000 liters / mol / cm, or about It exhibits a maximum extinction coefficient of 10,000 to about 500,000 liters / mol / cm, or about 20,000 to about 250,000 liters / mol / cm. Thiopheneazo dyes exhibit molecular weights 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. Thiopheneazo dyes exhibit an aqueous partition value of from about 10% to 100%, or from about 20% to 100%, or from about 30% to 100%, or from about 40% to 100%, and the dye is non-covalently bonded to charge balance. Including counter ions. The thiophenazo dye further exhibits an aqueous partition value of 0% to about 40%, 0% to about 30%, 0% to about 20%, or about 1% to about 10%, wherein the dye is covalently charged. Counter ions to balance

The thiophenazo dyes of the present invention may be represented by the general formula (I):

Where
a) R ₁ , R ₂ and R ₃ are each independently selected from hydrogen, electron withdrawing moiety, and electron donating moiety, provided that at least one of R ₁ , R ₂ and R ₃ is electron withdrawing In another aspect, R ₁ is an electron withdrawing moiety, and in yet another aspect, R ₁ and R ₃ are electron withdrawing moieties, and b) X is from about 65 Daltons to Molecular weight of about 4855 Daltons, or about 150 Daltons to about 2855 Daltons, or about 193 Daltons to about 1355 Daltons, or about 300 Daltons to about 855 Daltons, or about 400 Daltons to about 600 Daltons, or about 420 Daltons to about 575 Daltons Is an organic moiety having

In yet another aspect of the thiophenazo dye, each R ₁ , R _2, and R ₃ is hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₁₀ ) -aryl, carboxylate, cyano, sulfonate, May be independently selected from phosphonates, sulfates, acetates, nitros, (C ₁ -C ₄ ) -alkyl esters, halogen or amino moieties, or each R ₁ , R ₂ and R ₃ is hydrogen, nitro, cyano, (C ₁ ~C ₄₎ - alkyl esters or (C ₁ ~C ₄₎ - may be selected from alkyl.

In a further aspect of the thiophenazo dye, X is a moiety having the following formula (II):

Where
i) R ₄ is selected from moieties having the following formula (III):

Where
i) each R ₈ is independently selected from hydrogen, C ₁ -C ₈ alkyl optionally substituted by hydroxy, or acetyl;
ii) m is an integer from 0 to 10,
iii) Y is selected from sulfonates, carboxylates, phosphonates or quaternary ammonium species selected from imidazolium, pyridinium, morpholinium, piperidinium, or a moiety having the following formula (IV):

Where
i) R ₉ is a C ₁ -C ₈ alkyl moiety optionally substituted with —OH;
ii) R ₁₀ is a C ₁ -C ₁₈ alkyl moiety optionally substituted by —OH, or a C ₂ -C ₈ alkyl substituted by a sulfonate, or a C ₁ -substituted by carboxylate. Selected from C ₈ alkyl;
iii) Z is a counter ion that balances the charge of the unit charge c, and the subscript b is when the R ₁₀ is a C ₁ -C ₁₈ alkyl moiety optionally substituted by —OH; 1; otherwise, subscript b = 0;
Alternatively, R ₄ is selected from a moiety having the following formula (V):

Where
i) each R ₁₁ and R ₁₂ is independently selected from hydrogen, C ₁ -C ₈ alkyl, aryl, acetyl or hydroxyl moieties, m and n are independently an integer from 0 to 10;
ii) Y is as described above;
Or, R ₄ is selected from a moiety having the following formula (VI):

Where
i) R ₁₃ is selected from an aryl moiety, an arylalkyl moiety, such as a benzyl moiety, a C ₁ -C ₁₈ alkyl moiety, or a siloxane moiety;
ii) each R ₁₄ is independently selected from hydrogen, C ₁ -C ₄ alkyl, m is an integer from 0 to 10;
iii) Y is as described above;
ii) R ₅ may be the same as R ₄ or may be selected from a C ₁ -C ₁₂ alkyl moiety, an aryl moiety or an arylalkyl moiety, such as a benzyl moiety, where the subscript a is 0-4, or 0 to 3, or 0 to 2, each R ₆ is C ₁ -C ₆ alkyl, C ₁ -C ₄ alkoxy, nitro, hydroxyl, halogen, or —NHC (O) R ₂₂ (R ₂₂ is , H, —NH ₂ , C ₁ -C ₆ alkyl, selected from phenyl), — (CH ₂ ) _s OR ₂₃ (subscript s is 1 or 2, R ₂₃ is Me, phenyl, and — Selected from CO ₂ CH ₂ CN); —NHSO ₂ R ₂₄ (wherein R ₂₄ is C ₁ -C ₄ alkyl or phenyl), wherein the alkyl, alkoxy and acetamide moieties are , Due to formal charge part Optionally may be substituted, an either,
Or, X is a moiety having the following formula VII:

Wherein each R ₄ and R ₅ can be independently selected from:
a) [(CH ₂ CR′HO) _x (CH ₂ CR ″ HO) _y R ₁₅ ];
b) alkyl, aryl or arylalkyl;
_{c) [CH 2 CH (OR} 16) CH 2 OR 17];
d) Amino addition of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl hexadecyl ether followed by 1-10 alkylene oxide units. Product upon addition (at least one such alkylene oxide unit is substituted by R ₁₅ which is not —H);
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z R ₁₅ , and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O) _z R ₁₅ , and mixtures thereof, x + y ≦ 20, y ≧ 1, z = 0-10, and each R ₁₅ is —H and —CH ₂ CHR ₁₈ N ⁺ R ₁₉ R ₂₀ R ₂₁ (R ₁₈ is selected from —H and —CH ₃ , and each R ₁₉ and R ₂₀ is C ₁ -C ₄ alkyl optionally substituted by —OH. R ₂₁ is independently selected from C _{1 to} C ₁₂ optionally -OH substituted alkyl or (CH ₂ ) _r O _p Q, and the subscript r is from 1 to 8 An integer, the subscript p is 0 or 1, and Q is an anionic group selected from —CO ₂ ⁻ and —SO ₃ ^— ) R ₁₆ is selected from the group consisting of H, (CH ₂ CH ₂ O) _z R ₁₅ (where z = 0 to 10), and mixtures thereof, and R ₁₇ is selected from C ₁ to Selected from the group consisting of C ₁₆ alkyl, C ₆ -C ₁₀ aryl groups, and mixtures thereof, subscript m is an integer from 0 to 4, each R ₆ is as defined above, and Z is a unit A counter-ion that balances the charge of charge c, the subscript b being equal to the number of non-H R ₁₅ groups that do not include a counter-ion that balances the charge by covalent bonds, provided that the molecule is at least Contains one R ₁₅ group that is not —H.

In a further aspect of the thiophenazo dye, X can be a moiety having the following formula (II):

Where
i) R ₄ is selected from moieties having the following formula (III):

Where
i) R ₈ is hydrogen, a C ₁ -C ₄ alkyl moiety or an aryl moiety;
ii) Y is a quaternary ammonium species selected from the group consisting of imidazoliums, or a moiety having the following formula (IV):

Where
i) R ₉ is a C ₁ -C ₂ alkyl moiety;
ii) R ₁₀ is a C ₁ -C ₈ alkyl moiety optionally substituted by —OH, or a C ₂ -C ₄ alkyl substituted by a sulfonate, or a C ₁ -substituted by carboxylate Selected from C ₄ alkyl;
iii) Z is a counter ion that balances the charge of the unit charge c, and the subscript b is when the R ₁₀ is a C ₁ -C ₈ alkyl moiety optionally substituted by —OH. 1, otherwise the subscript b = 0;
Alternatively, R ₄ is selected from a moiety having the following formula (V):

Where
i) each R ₁₁ and R ₁₂ is independently selected from hydrogen, C ₁ -C ₄ alkyl or aryl moieties, m and n are independently an integer from 0 to 5;
ii) Y is as described above or R ₄ is selected from moieties having the following formula (VI):

Where
i) R ₁₃ is selected from an aryl moiety, a benzyl moiety, or a C ₁ -C ₁₈ alkyl moiety;
ii) Each R ₁₄ is independently selected from hydrogen or —CH ₃ and m is an integer from 0 to 10 ii) R ₅ can be the same as R ₄ , or C ₁ -C ₆ Can be selected from alkyl or benzyl moieties,
iii) The subscript a is an integer from 0 to 2, and each R ₆ may be independently selected from a methyl, methoxy, or acetamide moiety.

In one aspect of the thiophenazo dye of the present invention, each R ₁ , R ₂ and R ₃ is hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₁₀ ) -aryl, carboxylate, cyano, sulfonate , Phosphonates, sulfates, acetates, nitros, (C ₁ -C ₄ ) -alkyl esters, halogen or amino moieties may be independently selected, or each R ₁ , R ₂ and R ₃ may be hydrogen, nitro, It may be independently selected from cyano, (C ₁ -C ₄ ) -alkyl ester or (C ₁ -C ₄ ) -alkyl.

In yet a further aspect, the thiophenazo dyes of the present invention may be represented by formula (VIII):

  In the formula, the A part is the number 1 to 118 of the A part of Table 1, or the numbers 6 to 11, 15, 21 to 23, 30 to 31, 33 to 39, 41, 43, 46 to 46 of the A part of Table 1. 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 Part number 9 to 11, 15, 23, 34 to 35, 37 to 39, 41, 43, 47, 50 to 51, 57 to 58, 77, 83, 89, 95, 106, and 110 to 118 The X portion is selected from the group consisting of numbers X1 to 31 of the X portion in Table 4.

In yet another aspect, the thiophenazo dyes of the present invention may be represented by the following formula:

In the formula, the part A is the number 1 to 118 of the A part in Table 1 or the number 6 to 11, 15, 21 to 23, 30 to 31, 33 to 39, 41, 43, 46 to the A part of Table 1. 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 Part number 9 to 11, 15, 23, 34 to 35, 37 to 39, 41, 43, 47, 50 to 51, 57 to 58, 77, 83, 89, 95, 106, and 110 to 118 If selected and a = 0-2 and a = 1 or 2, then R ₆ is R ₆ substituent identification and position number 1-40 in Table 2, or R ₆ substitution in Table 2. Group identification and position numbers 1, 3, 5, 7-9, 11-14, 21, 23-24 31,33～34,36 and 40, or is selected from the number 1,3,5,7,12,13,14,31,36 and 40 of the identification and location of the R ₆ substituent of Table 2, R ₄ and atomic group R ₅ is, Table 3 R ₄ and R ₅ atomic group numbers 1-69 or numbers in Table 3 of R ₄ and R ₅ atomic group, 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 the groups of R ₄ and R _{5 in} Table 3 Numbers 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 is selected.

Part A may be selected from the parts shown in Table 1:

R ₆ may be selected from the substituents shown in Table 2.

The atomic groups of R ₄ and R ₅ may be selected from the atomic groups shown in Table 3.

The X portion may be selected from the portions shown in Table 4.

A thiopheneazo dye having a formal charge moiety can be any one of the A moieties selected from Table 1, any one of the R ₆ substituents selected from Table 2, and the atoms of R ₄ and R ₅ selected from Table 3. It is intended within the scope of the present invention to include any one of the groups, as well as any one of the X moieties selected from Table 4.

In yet another aspect of the invention, suitable thiophenazo dyes include, but are not limited to, the structures shown in Table 5.

Laundry Care Compositions The hueing agents described herein may be incorporated into laundry care compositions including, but not limited to, laundry detergents and fabric care compositions. Laundry care compositions, including laundry detergents, may be in solid or liquid form, including gel form and / or unit dosage forms (including multi-compartment unit dosage forms). Such compositions may include one or more of the hueing agents and laundry care ingredients.

  In one aspect, the laundry care composition may comprise less than 15% builder, less than 10% builder, or even less than 5% builder, based on the weight of the total laundry care composition. In one aspect, the laundry care composition comprises a total of no more than 20% water, no more than 15% water, no more than 10% water, or even all, based on the weight of the total laundry care composition. It may contain up to 5% water. In one aspect, the laundry care composition may include a water miscible organic solvent having a molecular weight greater than about 70% to about 70 daltons, based on the weight of the total laundry care composition.

  In one aspect, the laundry care composition may include a fragrance microcapsule comprising a core and a shell encapsulating the core based on the weight of the total laundry care composition, the fragrance microcapsule comprising: Having a D [4,3] average particle of from about 0.01 microns to about 200 microns, supplied by adding microcapsules (contained in a fragrance microcapsule slurry added to laundry care ingredients), and An optional formaldehyde scavenger may be added directly to the laundry care composition. In one aspect, the fragrance microcapsule shell is made from polyethylene, polyamide, polystyrene, polyisoprene, polycarbonate, polyester, polyacrylate, polyurea, polyurethane, polyolefin, polysaccharide, epoxy resin, vinyl polymer, and mixtures thereof. It may be made of any material including a material selected from the group consisting of: In one aspect, useful shell materials include materials that are sufficiently impervious to the core material, and materials in environments where fragrance microcapsules that enable delivery of the resulting fragrance are used. Suitable impermeable shell materials are reaction products of one or more amines with one or more aldehydes, such as urea cross-linked with formaldehyde or glutaraldehyde; melamine cross-linked with formaldehyde; glutaraldehyde and Included is a material selected from the group consisting of gelatin-polyphosphate coacervate, optionally cross-linked; gelatin-gum arabic coacervate; cross-linked silicone fluid; polyamine reacted with polyisocyanate, and mixtures thereof. In one aspect, the shell material comprises melamine crosslinked with formaldehyde and / or polyacrylate. Suitable fragrance microcapsules may be obtained from Appleton Papers, Appleton Wisconsin, USA.

  In one aspect, suitable formaldehyde scavengers are 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, triethanolamine, succinamide, thiabendazole, benzotriazole, triazole, indoline, sulfanilic acid, oxamide Sorbitol, glucose, cellulose, poly (vinyl alcohol), partially hydrolyzed poly (vinylformamide), poly (vinylamine), poly (ethyleneimine), poly (oxyalkyleneamine), poly (vinyl alcohol) -co-poly (Vinylamine), poly (4-aminostyrene), poly (1-lysine), chitosan, hexanediol, ethylenediamine-N, N′-bisacetoacetamide, N- (2-ethylhexyl) acetoacetamide, 2-benzoylacetoacetamide N- (3-phenylpropyl) acetoacetamide, lyial, helional, melonal, tripral, 5,5-dimethyl-1,3-cyclohexanedione, 2,4-dimethyl-3-cyclohexenecarboxaldehyde, 2,2- The Til-1,3-dioxane-4,6-dione, 2-pentanone, dibutylamine, triethylenetetramine, ammonium hydroxide, benzylamine, hydroxycitronellol, cyclohexanone, 2-butanone, pentanedione, dehydroacetic acid, or these Including a material selected from the group consisting of a mixture. These formaldehyde scavengers are available from Sigma / Aldrich / Fluka, St. Louis, MO. U. S. A. Or PolySciences, Inc. , Warrington, PA, U.S.A. S. It may be obtained from A. Such formaldehyde scavengers are typically from about 2% to about 18%, from about 3.5% to about 14% or even from about 5% to about 13% by weight based on the weight of the total slurry. Combine with the slurry containing the fragrance microcapsules at the level of%.

  In one aspect, such a formaldehyde scavenger may be combined with a product containing fragrance microcapsules, and the scavenger is about about 1% of the product formulation based on the weight of the product and the total product. Combine at a level of 0.005% to about 0.8%, alternatively about 0.03% to about 0.5%, alternatively about 0.065% to about 0.25%.

  In another aspect, such a formaldehyde scavenger is about 2 wt% to about 14 wt%, about 3.5 wt% to about 14 wt%, or even about 5 wt% to about 14 wt%, based on the total slurry weight %, May be combined with the slurry containing the fragrance microcapsules, and the slurry may be added to the product matrix, with the same or different scavengers being added based on the total product weight. At a level of about 0.005% to about 0.5% of the product formulation, alternatively about 0.01% to about 0.25%, alternatively about 0.05% to about 0.15% May be added.

  In one aspect, one or more of the above formaldehyde scavengers is added from 0.005% to about 0.8% of the product formulation, instead of about 0.03%, based on the weight of the total liquid fabric augmentation product. May be combined with a liquid fabric enhancement product containing fragrance microcapsules at a level of about 0.4%, alternatively about 0.06% to about 0.25%.

  In one aspect, such a formaldehyde scavenger may be combined with a liquid laundry detergent product containing fragrance microcapsules, said scavenger being 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, pyroglutamate, pyrogallol, methyl gallate, ethyl gallate, propyl gallate, triethanolamine, succina , Thiabendazole, benzotriazole, triazole, indoline, sulfanilic acid, oxamide, sorbitol, glucose, cellulose, poly (vinyl alcohol), partially hydrolyzed poly (vinylformamide), poly (vinylamine), poly (ethyleneimine), Poly (oxyalkyleneamine), poly (vinyl alcohol) -co-poly (vinylamine), poly (4-aminostyrene), poly (1-lysine), chitosan, hexanediol, ethylenediamine-N, N′-bisacetoacetamide , N- (2-ethylhexyl) acetoacetamide, 2-benzoylacetoacetamide, N- (3-phenylpropyl) acetoacetamide, lyial, helional, melonal, tripral, 5,5-dimethyl- , 3-cyclohexanedione, 2,4-dimethyl-3-cyclohexenecarboxaldehyde, 2,2-dimethyl-1,3-dioxane-4,6-dione, 2-pentanone, dibutylamine, triethylenetetramine, hydroxylation Selected from the group consisting of ammonium, benzylamine, hydroxycitronellol, cyclohexanone, 2-butanone, pentanedione, dehydroacetic acid, and mixtures thereof, the weight of the liquid laundry detergent product and the total liquid laundry detergent product weight Based on a level of about 0.003% to about 0.20%, about 0.03% to about 0.20%, or even about 0.06% to about 0.14% by weight.

  Hue agents may be added to the substrate using various application techniques. For example, a hueing agent may be included as a component of a laundry detergent for application to a cellulose-containing textile substrate. Thus, application to a cellulose-containing textile substrate actually occurs when the consumer adds laundry detergent to the washing machine. The hueing agent is about 0.000001% to about 10% by weight of the composition, about 0.00001% to about 10% by weight of the composition, about 0.0001% to about 5% by weight of the composition, and Rather, it may be present in the laundry detergent composition in an amount from about 0.0001% to about 1% by weight of the composition.

  Laundry detergent compositions typically include a surfactant in an amount sufficient to provide the desired cleansing properties. In one aspect, the laundry detergent composition comprises from about 0.5% to about 99% surfactant, from about 1% to about 95% surfactant, based on the weight of the total laundry detergent composition. It may comprise from 5% to about 90% surfactant, from about 5% to about 70% surfactant, or even from about 5% to about 40% surfactant. Surfactants may include anionic, nonionic, cationic, zwitterionic and / or amphoteric surfactants. In one aspect, the detergent composition comprises an anionic surfactant, a nonionic surfactant, or a mixture thereof.

  Fabric care compositions are typically added to a rinse cycle after using a detergent solution and replacing it with a rinse solution in a typical laundry process. The fabric care compositions disclosed herein may comprise a rinsed fabric softening active and a suitable hueing agent as disclosed herein. The fabric care composition may comprise from about 1% to about 90%, or from about 5% to about 50%, fabric softening active, based on the weight of the total fabric care composition. 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 exemplified herein below is suitable for use in laundry care compositions, for example, It may be desirably incorporated in certain aspects of the invention to aid or enhance performance for the treatment of the substrate to be cleaned, or to modify the aesthetic appearance of the composition as well as fragrances, colorants, pigments, and the like. . It is understood that such components are other than the components previously listed for any particular aspect. The total amount of such adjuvants may range from about 90% to about 99.99999995% by weight of the laundry care composition, taking into account the amount of pigment.

  The exact nature of these additional components and the level of their incorporation will depend on the physical form of the composition and the nature of the work in which the composition is used. Suitable laundry care ingredients include, but are not limited to, fabric softening actives, polymers such as cationic polymers, surfactants, builders, chelators, dye transfer inhibitors, dispersants, enzymes, and enzyme stable Agents, catalyst materials, bleach activators, polymer dispersants, clay soil removal / redeposition agents, brighteners, foam suppressants, pigments, fragrance (s) (including quadrant fragrance), and Additional fragrance delivery systems (including fragrance filled zeolite, starch encapsulated accord, and Schiff base pro fragrance), structural elasticizers, fabric softeners, carriers, hydrotropes, processing aids, and / or pigments included. In addition to the disclosure below, suitable examples and levels of use of such other adjuvants are described in US Pat. Nos. 5,576,282, 6,306,812 B1, and Found in 6,326,348B1.

  As noted, the laundry care ingredients are not essential to applicants' laundry care compositions. Accordingly, certain aspects of Applicants' compositions include the following adjunct materials: fabric softening activators, bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes And enzyme stabilizers, catalytic metal complexes, polymer dispersants, clay and soil removal / anti-deposition agents, brighteners, foam suppressors, dyes, additional fragrances and fragrance delivery systems, structural elasticizers, fabric flexibility Contains no one or more of agents, carriers, hydrotropes, processing aids, and / or pigments. However, when one or more adjuvants are present, such one or more adjuvants may be present as detailed below.

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

Exemplary anionic surfactants are C ₁₀ -C ₁₆ alkyl benzene sulfonic acids, or alkali metal salts of C ₁₁ -C ₁₄ 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, particularly LAS, are well known in the art. Such surfactants and their preparation are described, for example, in US Pat. Nos. 2,220,099 and 2,477,383. Particularly useful are sodium and potassium linear linear alkyl benzene sulfonates, where the average number of carbon atoms in the alkyl group is about 11-14. Sodium C ₁₁ -C _14, for example, C _12, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant includes ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, have the formula R′—O— (C ₂ H ₄ O) _n —SO ₃ M (R ′ is C ₈ to a C ₂₀ alkyl group, n is about 1 to 20, M is equivalent to a is) salt formation cations. In one aspect, R ′ is C ₁₀ -C ₁₈ alkyl, n is about 1-15, and M is sodium, potassium, ammonium, alkyl ammonium, or alkanol ammonium. In one aspect, R ′ is C ₁₂ -C ₁₆ , n is about 1-6, and M is sodium.

Alkyl ether sulfates are generally used in the form of a mixture containing varying R ′ chain lengths and varying degrees of ethoxylation. Such mixtures often also contain some non-ethoxylated alkyl sulfate materials, ie surfactants of the above ethoxylated alkyl sulfate formulation (where n = 0). Non-ethoxylated alkyl sulfates may also be added separately to the compositions of the present invention and used as such or in any anionic surfactant component that may be present. Specific examples of non-alkoxylated, for example, non-ethoxylated alkyl ether sulfate surfactants, are those produced by sulfation of higher C ₈ -C ₂₀ fatty alcohols. Conventional primary alkyl sulfate surfactants are of the general formula: ROSO ₃ -M ⁺ (R is a linear C ₈ -C ₂₀ hydrocarbyl group, which may typically be linear or branched, M is a water-soluble cation). In one aspect, R is C ₁₀ -C ₁₅ alkyl, M is an alkali metal, and more specifically, R is C ₁₂ -C ₁₄ and M is sodium.

Specific non-limiting examples of anionic surfactants useful herein include: a) C ₁₁ -C ₁₈ alkyl benzene sulfonate (LAS); b) C ₁₀ -C ₂₀ primary, branched and random Alkyl sulfate (AS); c) Formulas (I) and (II) (M in Formulas (I) and (II) is hydrogen or a cation providing charge neutrality, and all M units are Regardless of whether it is associated with a surfactant or adjuvant component, it may be either a hydrogen atom or a cation, depending on the form isolated by those skilled in the art, or the relative pH of the system in which the compound is used, as appropriate Non-limiting examples of cations include sodium, potassium, ammonium, and mixtures thereof, x is at least about 7, or an integer of at least about 9, and y is at least , Or at least C ₁₀ -C ₁₈ secondary having about 9 is an integer) (2,3) alkyl sulfates; d) C ₁₀ ~C ₁₈ alkyl alkoxy sulfates (AE _x S) (x is 1 E) In one aspect, C ₁₀ -C ₁₈ alkyl alkoxycarboxylates containing 1 to 5 ethoxy units; f) US Pat. No. 6,020,303 and US Pat. No. 6,060, Medium chain branched alkyl sulfates as discussed in 443; g) medium chain branches as discussed in US Pat. No. 6,008,181 and US Pat. No. 6,020,303 H) WO99 / 05243, WO99 / 05242, WO99 / 05244, WO99 / 05082, WO99 / 05084, WO99 / 0 5241, WO 99/07656, WO 00/23549, and WO 00/23548, modified alkylbenzene sulfonates (MLAS); i) methyl ester sulfonates (MES); and j) α-olefin sulfonates (AOS). .

  Suitable nonionic surfactants useful herein can include any of the common nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. In one aspect, there are these nonionic surfactants that are usually liquid for use in the liquid detergent products herein.

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

  Alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein may have a hydrophilic-lipophilic balance (HLB) that is in the range of about 3-17, about 6-15, or about 8-15. Many. Alkoxylated fatty alcohol non-ionic surfactants have been marketed by the Shell Chemical Company under the trade names Neodol and Dobanol.

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

Non-limiting examples of non-ionic surfactants include: a) C ₁₂ -C ₁₈ alkyl ethoxylates such as NEODOL® non-ionic surfactants from Shell; b) C ₆ -C ₁₂ alkyl phenols Alkoxylates (alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units); c) C ₁₂ -C ₁₈ alcohol and C ₆ -C ₁₂ alkylphenol condensates with ethylene oxide / propylene oxide block polymers, eg from BASF of Pluronic (R); d) U.S. Pat. C ₁₄ -C ₂₂ chain branched alcohols, such as discussed in No. 6,150,322, BA; e) U.S. Patent No. 6,153,577 In US Pat. No. 6,020,303 and US Pat. No. 6,093,856. Consideration is C _14, such as -C ₂₂ chain branched alkyl alkoxylates, BAE _x (x is a 1 to 30); f) U.S. Patent to Llenado, issued Jan. 26, 1986 Alkyl polysaccharides as discussed in US Pat. No. 4,565,647; in particular, alkyl polyglycosides as discussed in US Pat. No. 4,483,780 and US Pat. No. 4,483,779; g) polyhydroxy fatty acid amides as discussed in US Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) US Pat. No. 6,482. 994 and WO01 / 42408 as ether-capped poly (oxy) Alkylation) include alcohol surfactants.

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

  Cationic surfactants are well known in the art, and non-limiting examples of these include quaternary ammonium surfactants that can have up to 26 carbon atoms. Further examples include: a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in US Pat. No. 6,136,769; b) discussed in US Pat. No. 6,004,922. 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) US Pat. No. 6,221,825 and WO 00/47708. Amino surfactants as are Oite discussed, in particular, include dimethylamine (APA) is.

Non-limiting examples of zwitterionic surfactants include secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or quaternary ammonium, quaternary phosphonium Alternatively, a derivative of a tertiary sulfonium compound is included. Zwitterionic surfactants; betaine (including alkyl dimethyl betaine and coco amidopropyl betaine), (in one _{aspect, C 12 ~C 18) C 8} ~C 18 amine oxides, and sulfo and hydroxy betaines, such as , N-alkyl-N, N-dimethylamino-1-propanesulfonate (the alkyl group can be C ₈ -C ₁₈ , or C ₁₀ -C ₁₄ ), published December 30, 1975 U.S. Pat. No. 3,929,678 to Laughlin et al., Column 19, lines 38 through 22, line 48.

  Non-limiting examples of ampholyte surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where aliphatic radicals are May be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one of the anionic water-soluble groups such as carboxy, sulfonate, Contains sulfate. For examples of ampholyte surfactants, see U.S. Pat. No. 3,929,678, column 19, lines 18-35 to Laughlin et al., Issued Dec. 30, 1975.

Liquid Carriers Not Aqueous Surface Active As noted above, laundry care compositions may be in solid form, either in tablet or particulate form, including but not limited to particles, flakes, sheets, etc. The object may be in liquid form. The liquid detergent composition may comprise a liquid carrier that is not aqueous surface active. In general, the amount of non-aqueous surface active liquid carrier used in the compositions herein is effective to solubilize, suspend or disperse the composition components. For example, the liquid detergent composition is not about 5% to about 90%, about 10% to about 70%, or about 20% to about 70% aqueous surface activity based on the weight of the total liquid detergent composition. A liquid carrier may be included.

  The most cost effective type of non-aqueous surface active liquid carrier is typically water. Thus, liquid carrier components that are not aqueous surface active are generally mostly, if not completely, water. While other types of water miscible liquids (alkanols, diols, other polyols, ethers, amines, etc.) have been conventionally added to liquid detergent compositions as cosolvents or stabilizers for the purposes of the present invention The use of such water miscible liquids is typically minimized to reduce the cost of the composition. Accordingly, the aqueous liquid carrier component of the liquid detergent product herein is generally present at a concentration ranging from about 5% to about 90%, or from about 5% to about 70%, by weight of the liquid detergent composition. Contains water.

Bleaching Agents-The cleaning composition of the present invention may comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photobleaching agents, bleach activators, hydrogen peroxide, a source of hydrogen peroxide, preformed peracids and mixtures thereof. Generally, when bleaching agents are used, the compositions of the present invention 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. But you can. Examples of suitable bleaching agents include:
(1) a photobleaching agent such as sulfonated zinc phthalocyanine;
(2) Pre-formed peracid: Suitable pre-formed peracids include, but are not limited to, percarboxylic acids and salts, percarbonate and salts, perimidic acid and salts, peroxymonosulfuric acid and salts, such as , Oxzone <(R)>, and compounds selected from the group consisting of mixtures thereof. Suitable percarboxylic acids are of the formula R— (C═O) O—O—M, wherein R is 6-14 carbon atoms, or 8-12 carbon atoms when the peracid is hydrophobic. When the peracid is hydrophilic, when the peracid is hydrophilic, it is an alkyl group which may be optionally branched with less than 6 carbon atoms, or even less than 4 carbon atoms, and M is a counter ion, For example, hydrophobic and hydrophilic peracids with sodium, potassium or hydrogen.

  (3) Sources of hydrogen peroxide, such as alkali metal salts, such as sodium perborate (usually monohydrate or tetrahydrate), percarbonate, persulfate, perphosphate, Inorganic perhydrate salts including persilicates and mixtures thereof. In one aspect of the invention, the inorganic hydrate salt is selected from the group consisting of sodium perborate, percarbonate, and mixtures thereof. When used, inorganic hydrate salts are typically present in amounts of 0.05 to 40%, or 1 to 30% by weight of the total composition, and are coated in such compositions. Typically incorporated as an optional crystalline solid. Suitable coatings include inorganic salts such as silicic acid, carbonic acid or alkali metal borate salts or mixtures thereof, or organic materials such as water soluble or dispersible polymers, waxes, oils or fatty soaps.

  (4) R— (C═O) —L (R has 6-14 carbon atoms, or 8-12 carbon atoms, when the bleach activator is hydrophobic, bleach activation When the agent is hydrophilic, bleaching activity having less than 6 carbon atoms, or even an optionally branched alkyl group having less than 4 carbon atoms, and L is a leaving group) Agent. Examples of suitable leaving groups are benzoic acid and its derivatives, in particular benzenesulfonate. Suitable bleach activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED) and Nonanoyloxybenzene sulfonate (NOBS) is included. Suitable bleach activators are also disclosed in WO 98/17767. While any suitable bleach activator may be used, 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 about 0.1 to about 60%, about 0.5 to about 40%, or even about 0, in the composition, based on the composition. Present in an amount of from 6 to about 10% by weight. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracids or precursors thereof.

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

  Bleaching effect promoting compound-The compositions herein may comprise one or more bleaching effect promoting compounds. Bleaching effect promoting compounds provide increased bleach effectiveness in lower temperature applications. Bleaching effect accelerators work in conjunction with normal peroxygen bleaching sources to achieve increased bleaching effectiveness. This is usually accomplished by in situ formation of an active oxygen transfer agent such as dioxirane, oxaziridine, or oxaziridinium. Alternatively, preformed dioxirane, oxaziridine and oxaziridinium may be used.

Among the suitable bleaching effect promoting compounds for use according to the present invention are cationic imines, zwitterionic imines, anionic imines and / or polyionic imines having an effective charge of about +3 to about -3, and There are mixtures of these. These imine bleaching effect promoting compounds of the present invention include those having the following general structure:

In the formula, R ^{1 to} R ⁴ may be hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocycle, alkyl and cycloalkyl radicals.

  Suitable bleaching effect promoting compounds include zwitterionic bleaching effect promoters described in US Pat. Nos. 5,576,282 and 5,718,614. Other bleaching effect promoting compounds include U.S. Pat. Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 482,515; 5,550,256; and WO95 / 13351, WO95 / 13352, and WO95 / 13353.

  Peroxygen sources are well known in the art, and peroxygen sources used in the present invention include peroxygen compounds and compounds that provide an effective amount of peroxygen in situ under consumer use conditions. Any of these known sources may be included. Peroxygen sources include hydrogen peroxide sources, in situ formation of peracid anions by reaction of hydrogen peroxide sources with bleach activators, preformed peracid compounds or a mixture of suitable peroxygen sources. Also good. Of course, those skilled in the art will recognize that other sources of peroxygen may be used without departing from the scope of the present invention. Bleaching effect promoting compounds, when present, are typically used in conjunction with a peroxygen source in the bleaching system of the present invention.

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

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

  In one aspect, fabric softening actives (“FSA”) are quaternary ammonium compounds that are suitable for softening fabrics in a rinsing step. In one aspect, FSA is formed from the reaction product of a fatty acid and an amino alcohol, and in one aspect, a mixture of triester compounds is obtained. In another aspect, the FSA includes one or more softener quaternary ammonium compounds, such as, but not limited to, monoalkyl quaternary ammonium compounds, diamide quaternary compounds and diester quaternary ammonium compounds, 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 invention, the DQA compound composition also includes a description of diamide FSA, and mixed amide and ester linkages, and FSAs having the above diester linkages (all referred to herein as DQA). .

The first type of DQA (“DQA (1)”) suitable as FSA in the present CFSC includes compounds comprising the following formula:

Wherein each R substituent is hydrogen, short chain C ₁ -C ₆ , eg, C ₁ -C ₃ alkyl or hydroxyalkyl group, eg, methyl, ethyl, propyl, hydroxyethyl, poly (C _2-3 Alkoxy), for example, any of a polyethoxy group, benzyl, or mixtures thereof, each m is 2 or 3, each n is 1 to about 4, or 2, and each Y is —O -(O) C-, -C (O) -O-, -NR-C (O)-, or -C (O) -NR-, where each Y is allowed to be the same or different; The sum of carbons in R ¹ (plus one when Y is —O— (O) C— or —NR—C (O) —) is C ₁₂ -C ₂₂ , or C ₁₄ -C ₂₀ , each R ¹ is hydrocarbyl or substituted hydrocarbyl group,, R ¹ is unsaturated or saturated Is allowed to be called branched or linear, in one aspect, R ¹ is a linear, each R ^1, is allowed the same or different, typically they are the same, X ⁻ may be any softener compatible anion, suitable anions include chloride anion, bromide anion, methyl sulfate anion, ethyl sulfate anion, sulfate anion, phosphate anion, and nitrate anion; In one aspect, the anion is a chloride anion or a methylsulfate anion. Suitable DQA compounds are typically made by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials typically resulting from such reactions include N, N-di (acyl-oxyethyl) -N, N-dimethylammonium chloride or N, N-di (acyl-oxyethyl) -N, A moiety derived from animal fats, unsaturated and polyunsaturated fatty acids such as tallow, hardened tallow, oleic acid, and / or vegetable oils, including N-methylhydroxyethylammonium methylsulfate Derived from hydrogenated fatty acids 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 and the like.

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

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

Wherein each m is 2 or 3, and each R ¹ is C ₆ -C ₂₂ , or C ₁₄ -C ₂₀ , but one or less is less than about C ₁₂ and then the others are at least About 16, hydrocarbyl, or substituted hydrocarbyl substituents, for example, C ₁₀ -C ₂₀ alkyl or alkenyl (also unsaturated alkyl, including polyunsaturated alkyl, which may also be referred to as “alkylene”), in one aspect , C ₁₂ -C ₁₈ alkyl or alkenyl, and branched or unbranched. In one aspect, FSA iodine value (IV) is about 1 to 70, each R is H or a short chain C ₁ -C ₆ or C ₁ -C ₃ alkyl or hydroxyalkyl group, e.g., methyl, Ethyl, propyl, hydroxyethyl, etc., benzyl, or (R ² O) _2-4 H (where each R ² is a C _1-6 alkylene group), A ⁻ is a softener compatible anion, Suitable anions include chloride anions, bromide anions, methyl sulfate anions, ethyl sulfate anions, sulfate anions, phosphate anions, or nitrate anions. In one aspect, the anions are chloride anions or methyl sulfates. is there.

  Examples of these FSA include dialkyl dimethyl ammonium salts and dialkylene dimethyl ammonium salts, such as dimethyl ditallow ammonium and dimethyl ditallow ammonium methyl sulfate. Examples of commercially available dialkylenedimethylammonium salts that can be used in the present invention are dihydrogenated dimethyl ditallow ammonium chloride and dimethyl dichloride available from Degussa under the trade names Adogen® 442 and Adogen® 470, respectively. Tallow ammonium chloride. In one aspect, the FSA includes other active agents in addition to DTTMAC. In yet another aspect, the FSA includes only DTTMAC compounds and is free or essentially free of any other quaternary ammonium compounds or other active agents.

  In one aspect, the FSA includes the FSA described in US Patent Application Publication No. 2004 / 0204337A1, published October 14, 2004 to Corona et al., Paragraphs 30-79. In another aspect, FSA is disclosed in US Patent Application Publication No. 2004 / 0229769A1, paragraphs 26-31 to Smith et al., Published November 18, 2005; or US Pat. No. 6,494,920, Column 1, line 51 et seq. (“Esterquat” or quaternized fatty acid triethanolamine ester salts are detailed).

  In one aspect, the FSA is selected from at least one of the following: oil oxyethyl dimethyl ditallow ammonium chloride, dihydrogenated-oil oxyethyl dimethyl ditallow ammonium chloride, dimethyl ditallow ammonium chloride, oil oxyethyl dimethyl di Tallow ammonium methyl sulfate, dihydrogenated-oiloxyethyldimethyl ditallow ammonium chloride, dihydrogenated-oiloxyethyldimethyl ditallow ammonium chloride, or combinations thereof.

  In one aspect, the FSA may also include an amide-containing compound composition. Examples of compounds containing diamides may include, but are 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 a fabric softening composition with a rinse further comprising cationic starch. Cationic starch is disclosed in US 2004/0204337 A1. In one aspect, the rinsed fabric softening composition comprises about 0.1% to about 7% 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 include one or more detergent builders or builder systems. When present, the composition typically comprises at least about 1% builder, or about 5%, or 10% to about 80%, 50%, or even 30% by weight of the builder. Builders include, but are not limited to, alkali metals, ammonium and alkanol ammonium salts of polyphosphates, alkali metal silicates, alkaline earth carbonates and alkali metal salts, aluminosilicate builders polycarboxylate compounds, ether hydroxy polycarboxylates , Copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyl-oxysuccinic acid, various alkali metals, ammonium polyacetate And substituted ammonium salts such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as melittic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,3 - tricarboxylic acid, carboxymethyloxysuccinic acid, as well as soluble salts thereof.

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

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

  Dispersants-The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials are homo- or co-polymeric acids or their salts, and the polycarboxylic acid may contain at least two carboxyl radicals separated from each other by no more than two carbon atoms.

  The enzyme-composition can include one or more detergent enzymes that provide cleansing performance and / or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, Tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof are included. A typical combination is a cocktail of commonly applicable enzymes (eg, protease, lipase, cutinase and / or cellulase combined with amylase).

  Enzyme stabilizers—compositions such as enzymes for use in detergents can be stabilized by a variety of techniques. The enzyme used herein can be stabilized by the presence of a water soluble source of calcium and / or magnesium ions (providing such ions to the enzyme) in the final composition.

Methods for Making Laundry Care Compositions The laundry care compositions of the present invention can be formulated into any suitable form by the formulator and can be prepared by any selected method, non-limiting examples of which are In our example, and in US 5,879,584; US 5,691,297; US 5,574,005; US 5,569,645; US 5,565,422; US 5,516,448; US 5,489, 392; US 5,486,303, all of which are incorporated herein by reference.

  The liquid detergent composition may be in the form of an aqueous solution or a uniform dispersion or suspension of surfactants, hueing agents, and certain optional other ingredients, some of which are compositions It may be in a generally solid form combined with optional components of a conventional liquid component such as a nonionic liquid alcohol ethoxylate, an aqueous liquid carrier, and any other normal liquid. Such solutions, dispersions or suspensions are phase stable as acceptable and typically have a viscosity in the range of about 100-600 cps, or about 150-400 cps. For the purposes of the present invention, viscosity is measured with a Brookfield LVDV-II + viscometer instrument using a # 21 spindle.

  The liquid detergent composition herein is a phase-stable liquid detergent by combining its components in any convenient order and mixing, eg, stirring, the combination of components thus obtained. It can be prepared by forming a composition. In methods for preparing such compositions, liquid components such as non-ionic surfactants, non-surface active liquid carriers and at least a major proportion of other optional liquid components, or even substantial An all-containing liquid matrix is formed and the liquid components are thoroughly mixed by applying shear agitation to the liquid combination. For example, high-speed stirring by a mechanical stirrer may be usefully used. While maintaining shear agitation, substantially all of the optional anionic surfactant and solid form components can be added. Stirring of the mixture can be continued and increased at this point as needed to form a solution or uniform dispersion of insoluble solid phase particulates in the liquid phase. After some or all of the solid form material is added to the stirred mixture, any enzyme material particles to be included, such as the enzyme prill, are incorporated. As a variation of the procedure for preparing the compositions described herein above, one or more of the solid components were agitated as a solution or slurry of particles premixed with one or more minor portions of the liquid component. It may be added to the mixture. After all of the composition components have been added, the mixture is continued to be stirred for a time sufficient to form a composition having the necessary viscosity and phase stability characteristics. This often involves stirring for a period of about 30-60 minutes.

  In one aspect of forming a liquid detergent composition, a hueing agent is first combined with one or more liquid components to form a hueing agent premix that is used as a component of the laundry detergent composition. It is added to the composition formulation containing the remaining substantial portion, for example, greater than 50 wt%, more specifically greater than 70 wt%, and even more specifically greater than 90 wt%. For example, in the methodology described above, both the hueing agent premix and the enzyme component are added at the final stage of component addition. In another aspect, the hueing agent is encapsulated prior to addition to the detergent composition, the encapsulated hueing agent is suspended in the structured liquid, and the suspension is left as a residual component of the laundry detergent composition. To a composition formulation containing a substantial portion of.

  As mentioned above, the detergent composition may be in solid form. Suitable solid forms include tablets and particulate forms such as granular particles, flakes or sheets. Various techniques for forming detergent compositions in such solid form are well known in the art and may be used herein. In one aspect, for example, when the composition is in the form of granular particles, the hueing agent is provided in a particulate form that may optionally include additional components, but not all of the laundry detergent composition. The hueing agent microparticles are combined with one or more additional microparticles that contain the remainder of the components of the laundry detergent composition. Furthermore, a hueing agent that may optionally include additional components, but not all of the laundry detergent composition, may be provided in an encapsulated form, and the hueing agent encapsulant may be provided in the laundry detergent composition. Combine with the microparticles containing a substantial remainder of the component.

  The compositions of the present invention prepared as described hereinabove can be used to form aqueous cleaning solutions for use in fabric laundering. In general, an effective amount of such a composition is added to water, for example, in a conventional fabric washing automatic washing machine, to form such an aqueous washing solution. The aqueous cleaning solution thus formed is then brought into contact with the fabric to be washed, typically with stirring. An effective amount of the liquid detergent composition herein added to water to form a wash aqueous solution can comprise an amount sufficient to form about 500-7,000 ppm of the composition in the wash aqueous solution, Or about 1,000-3,000 ppm of the detergent composition herein is provided in an aqueous wash solution.

Methods of Use Some of the consumer products disclosed herein can be used to clean or treat a site, especially a surface or fabric. Typically, at least one portion of the site is contacted with one aspect of Applicant's consumer product in undiluted form or diluted into a liquid, such as a cleaning solution, and then the site is optionally washed and It may also be rinsed. In one aspect, the site may optionally be washed and / or rinsed, contacted with one side 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. Fabrics may include most any fabric that can be washed or processed under normal consumer use conditions. Liquids that may include the disclosed compositions may have a pH of about 3 to about 11.5. Such compositions are typically used at a concentration of about 500 ppm to about 15,000 ppm in solution. When the wash solvent is water, the temperature of the water typically ranges from about 5 ° C. to about 90 ° C., and when the site is composed of fabric, the ratio of water to fabric is typically About 1: 1 to about 30: 1. By using one or more of the above methods, a treated site is produced.

  In one aspect, the surface or fabric is optionally washed and / or rinsed, the surface or fabric is contacted with any laundry care composition disclosed herein, and then the surface and / or fabric is optionally A method of treating and / or purifying a surface or fabric comprising: washing and / or rinsing, then optionally drying the surface or fabric and / or actively drying the surface or fabric.

Examples The following examples are presented to further illustrate the hueing agents of the present invention. They should not, however, 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 the present invention without departing from the scope or spirit of the invention. All parts and percentages presented in these examples are by weight unless otherwise indicated.

Sample Preparation and Test Methods A. Sample Preparation The thiophenazo dyes of the present invention were prepared using the following general procedure.

Preparation of glycidol material

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

Preparation of alkoxylation intermediates General procedure for alkoxylation-Method A:
Intermediate type 1, single site starting polymer

  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 holding the reaction at room temperature for 24 hours, the vessel was charged with 0.2 parts NaOH and heated to 125 ° C. Ethylene oxide was then added over about 1 hour. The reaction was continued at 125 ° C. for an additional 3 hours, after which residual EO was removed by vacuum. This was then cooled to room temperature and the resulting intermediate was an amber viscous liquid. A constant average number of EO could be achieved each time by controlling the amount of ethylene oxide in the synthesis.

Intermediate type 2, double chain starting polymer

  18 parts 2-methoxy-5-methylaniline, 14 parts acetic acid, and 20 parts water were charged into a 200 mL stainless steel autoclave at room temperature. 22 parts of ethylene oxide were added over several hours. After holding the reaction at room temperature for 24 hours, the vessel was charged with 0.2 parts NaOH and heated to 125 ° C. 40 parts of ethylene oxide were then added over about 1 hour. The reaction was continued at 125 ° C. for an additional 3 hours, after which residual EO was removed by vacuum. This was then cooled to room temperature and the resulting intermediate was an amber viscous liquid. A constant average number of EO could be achieved each time by controlling the amount of ethylene oxide in the synthesis.

General procedure for alkoxylation-Method B:

18 parts aniline, 60 parts mono-bromo-polyethylene glycol-200, 20 parts NaHCO ₃ 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 was removed from the filtrate by low pressure distillation. The crude product was used without further purification for the next step.

  It is also possible to use mono-bromo-mono-chloroglycol to make the halogenated product directly using this same procedure described above.

General procedure for tosylation of intermediates Intermediate type 1

  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 stirred at room temperature for 4 hours. The mixture was diluted with 400 parts water and then neutralized by adding 33% hydrochloric acid. 400 parts of ethyl acetate were added and the mixture was phase separated. The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent was evaporated. The crude product was used immediately for the next step.

Intermediate type 2

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

General procedure for quaternization Intermediate type 1

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

Intermediate type 2

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

General procedure for color synthesis All colors were prepared by the same general procedure:

Two parts amino-thiophene and 30 parts phosphoric acid were charged into a 200 mL glass flask and cooled to 0-5 ° C. While maintaining the temperature below 10 ° C., 1 part of NaNO ₂ was slowly added as a solid. When the addition was complete due to diazotization, the mixture was stirred for 30 minutes and excess sodium nitrite was consumed by adding 0.3 part sulfamic acid. Sufficient sulfamic acid was added until iodine starch paper produced negative results. To a separate flask was added 6 parts quaternized material prepared according to the Intermediate Type 1 route and quaternization was performed using 1 molar equivalent of triethylamine and 12 parts water. The prepared diazonium salt solution was slowly added into the above solution for the coupling reaction. Care was taken not to raise the temperature above 10 ° C. After complete addition of the diazonium salt solution, the reaction was allowed to slowly reach room temperature over 1 hour. The mixture was then neutralized with sodium hydroxide and the phases were separated. The product layer was then dissolved in methanol and filtered to remove any excess salt. The filtrate was evaporated, but 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 by an intermediate type 2 procedure where only 2 moles of ethylene oxide were added to the initial material and the tosylated material was quaternized by using 2 mole equivalents of N-methylimidazole. Colorant synthesis was as described in Example 12.

Example 2
Example 2 was prepared as in Example 1 except that the initial alkoxylation was performed using m-toluidine.

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

Example 13
Example 13 was prepared as in Example 12, except that quaternization was performed with N-methylimidazole.

Example 14
Example 14 was prepared as in Example 12, except that quaternization was performed with N, N-dimethyl-glycine.

Example 15
Example 15 was prepared as in Example 12, except that quaternization was performed with N, N-dimethylpropyl sulfonate.

  Example 18 Example 18 was prepared by the procedure of Intermediate Type 2, and the colorant synthesis was as described in Example 12.

Example 19
Example 19 was prepared by the procedure of Intermediate Type 2, the initial alkoxylation was performed using 2,5-dimethoxyaniline and the colorant synthesis was as described in Example 12.

Example 21
Example 21 was prepared by Intermediate Type 2 procedure, quaternization was performed using dimethylethanolamine and colorant synthesis was as described in Example 12.

Example 22
Example 22 was prepared by Intermediate Type 2 procedure, quaternization was performed using triethanolamine and colorant synthesis was as described in Example 12.

Example 35
Example 35 was prepared by the Intermediate Type 2 procedure, alkoxylation was performed using m-toluidine and quaternization was performed using triethylamine. Colorant synthesis was as described in Example 12.

Example 36
Example 36 was prepared as in Example 1 except that initial alkoxylation was performed using m-toluidine and quaternization was performed using triethylamine. The color synthesis was as described in Example 12.

B. Test Method I. Method for Measuring Aqueous Partition Value of Dye A sufficient amount of dye to achieve a solution absorbance value of 0.25 to 1.0 is dissolved in deionized water to a final volume of 10.0 mL and the absorbance is 1 Determine with dye λ _{max from} 400 nm to 750 nm using a cuvette with a path length of 0.0 cm. The absorbance of the sample is measured with a dye λ _max in a UV / visible spectrophotometer, and then 10.0 mL of the entire solution is transferred to a 50.0 mL plastic centrifuge tube. Add 10.0 mL of 1-octanol, cap the tube and mix vigorously using a Vortex ™ mixer for 30 seconds. The tube is allowed to stand until the layers are well phase separated. If the layers do not separate well within a few hours, centrifuge and phase separate.

Using a whole pipette, remove an aliquot of the aqueous (bottom) layer and transfer it to a cuvette with a 1.0 cm path length for spectrophotometric analysis. The solution is analyzed as before and the decrease in absorbance at λ _max is quantified as “% dye remaining in the aqueous layer” as described below.

% Dye remaining in aqueous layer = aqueous partition value (APV) = (A _f / A _i ) × 100% where A _i is the absorbance of the first solution at λ _max and A _f is The absorbance of the final solution at λ _max .

II. Method for Measuring the Hue Efficiency of Detergents a) 16 oz. White cotton interlock knit fabric (270 g / m 2, brightened with Uvitex BNB optical brightener from Test Fabrics, PO Box 26, Weston, PA, 18643 Get two 25cm x 25cm fabric swatches.

  b) Prepare two 1 liter portions of tap water containing 1.55 g of AATCC standard heavy duty liquid (HDL) test detergent.

  c) A sufficient amount of dye to be tested is added to one of the aliquots from step b) above to give an aqueous solution absorbance of 1 AU.

  d) Wash one swatch from a) above with one aliquot of water containing 1.55 g of AATCC standard heavy duty liquid (HDL) test detergent, and the other swatch with another aliquot. Wash with. Such a washing step should be performed at room temperature for 30 minutes with stirring. After such a washing step, the swatch is rinsed separately with tap water and the swatch is allowed to air dry in the dark.

e) After rinsing and drying each swatch, the hue efficiency of the dye, DE ^* _eff , is calculated using the Hunter LabScan XE reflectance spectrophotometer for each swatch's L ^* , a ^* , and b ^* values. Evaluate by determining the measurements (D65 illumination, 10 ° observer and UV filter (excluded)). The hue efficiency of the dye is then calculated using the following equation:

Where the subscripts c and s are the L ^* , a ^* , and measured for the control, that is, the fabric sample washed with the dye-free detergent and the fabric sample washed with the detergent containing the dye to be screened, respectively. It means b ^* value.

III. Method for Determining Detergency a) Prepare two separate 150 ml HDL detergent solutions containing 1.55 g / liter AATCC HDL formulation in distilled water according to AATCC Test Method 61-2003, Test 2A .

  b) A 15 cm × 5 cm sample of each fabric swatch from the method for determining the hue efficiency of the detergent described above was obtained at 45 ° C. at 49 ° C. in a 150 ml HDL detergent solution prepared by Step II, a) above. Wash for minutes.

c) Samples are rinsed with separate aliquots of rinse water, air dried in the dark, and then the L ^* , a ^* , and b ^* values of each swatch are measured using a Hunter LabScan XE reflectance spectrophotometer (D65 illumination, 10 ° observer and UV filter (excluded)). The amount of coloration remaining is assessed by measuring DE ^* _res calculated using the following equation:

Where the subscripts c and s are the L ^* measured for the control, that is, the fabric sample that was first washed with the detergent without dye and the fabric sample that was first washed with the detergent containing the dye to be screened, Mean a ^* and b ^* values. The wash removal value for the dye is then calculated by the formula:% removal = 100 × (1−DE ^* _res / DE ^* _eff ).

C. Test Results The aqueous partition values for some examples are shown in Table 6.

Exemplary Detergent Formulations Formulations 1a-11: Liquid Detergent Formulations Tables 7A and 7B show examples of liquid detergent formulations that include at least one thiophenazo dye of the present invention as a hueing agent. Formulations are shown as Formulations 1a-1f in Table 7A and as Formulations 1g-1l in Table 7B.

Formulations 2a-2e: Granular detergent formulations Table 8 shows examples of granular detergent formulations containing at least one thiophenazo dye of the present invention as a hueing agent. The formulations are shown in Table 8 as formulations 2a-2e.

Exemplary Fabric Care Composition Formulations 3a-3d: Liquid Fabric Care Composition Table 9 shows examples of liquid fabric care compositions that include at least one thiophenazo dye of the present invention as a hueing agent. The compositions are shown in Table 9 as formulations 3a-3d.

  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 a 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 hereby incorporated by reference in the relevant part. Citation of any document should not be construed as an admission that the citation is prior art with respect to the present invention. In this document, to the extent that any meaning or definition of a term 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 takes precedence. It shall be.

式中、
ａ）Ｒ ₁ 、Ｒ ₂ およびＲ ₃ は、それぞれ独立に、水素、電子吸引性部分、および電子供与性部分から選択され、ただし、Ｒ ₁ 、Ｒ ₂ およびＲ ₃ の少なくとも１つは、電子吸引性部分であり、
ｂ）Ｘは、約６５ダルトン〜約４８５５ダルトンの分子量を有する有機部分である。
［８］
各Ｒ ₁ 、Ｒ ₂ およびＲ ₃ が、水素、（Ｃ ₁ 〜Ｃ ₄ ）−アルキル、（Ｃ ₃ 〜Ｃ ₁₀ ）−アリール、カルボキシレート、シアノ、スルホネート、ホスホネート、スルフェート、アセテート、ニトロ、（Ｃ ₁ 〜Ｃ ₄ ）−アルキルエステル、ハロゲンまたはアミノ部分から独立に選択される、［７］に記載のチオフェンアゾ色素。
［９］
Ｘが、下記の式（ＩＩ）を有する部分：

式中、
ｉ）Ｒ ₄ は、下記の式（ＩＩＩ）を有する部分から選択される：

式中、
ｉ）各Ｒ ₈ は、水素、ヒドロキシにより任意に置換されていてもよいＣ ₁ 〜Ｃ ₈ アルキル、またはアセチルから独立に選択される、
ｉｉ）ｍは０〜１０の整数であり、
ｉｉｉ）Ｙは、スルホネート、カルボキシレート、ホスホネート、またはイミダゾリウム、ピリジニウム、モルホリニウム、ピペリジニウムから選択される第四級アンモニウム種、または下記の式（ＩＶ）を有する部分から選択される：

式中、
ｉ）Ｒ ₉ は、−ＯＨにより任意に置換されていてもよいＣ ₁ 〜Ｃ ₈ アルキル部分であり、
ｉｉ）Ｒ ₁₀ は、−ＯＨにより任意に置換されていてもよいＣ ₁ 〜Ｃ ₁₈ アルキル部分、またはスルホネートにより置換されているＣ ₂ 〜Ｃ ₈ アルキル、またはカルボキシレートにより置換されているＣ ₁ 〜Ｃ ₈ アルキルから選択され、
ｉｉｉ）Ｚは、単位電荷ｃの電荷のバランスをとる対イオンであり、添字ｂは、Ｒ ₁₀ が−ＯＨにより任意に置換されていてもよいＣ ₁ 〜Ｃ ₁₈ アルキル部分である場合には１であり、そうでなければ添字ｂ＝０である；
または、Ｒ ₄ は、下記の式（Ｖ）を有する部分から選択される：

式中、
ｉ）各Ｒ ₁₁ およびＲ ₁₂ は、水素、Ｃ ₁ 〜Ｃ ₈ アルキル、アリール、アセチルまたはヒドロキシル部分から独立に選択され、ｍおよびｎは、独立しており、０から１０までの整数であり、
ｉｉ）Ｙは、上記の通りである；
または、Ｒ ₄ は、下記の式（ＶＩ）を有する部分から選択される：

式中、
ｉ）Ｒ ₁₃ は、アリール部分、アリールアルキル部分、Ｃ ₁ 〜Ｃ ₁₈ アルキル部分、またはシロキサン部分から選択され、
ｉｉ）各Ｒ ₁₄ は、水素、Ｃ ₁ 〜Ｃ ₄ アルキルから独立に選択され、ｍは、０〜１０の整数であり、
ｉｉｉ）Ｙは、上記の通りである；
ｉｉ）Ｒ ₅ は、Ｒ ₄ と同じでもよいし、またはＣ ₁ 〜Ｃ ₁₂ アルキル部分、アリール部分またはアリールアルキル部分から選択することができ、添字（ａ）は０〜４の整数であり、各Ｒ ₆ は、Ｃ ₁ 〜Ｃ ₆ アルキル、Ｃ ₁ 〜Ｃ ₄ アルコキシ、ニトロ、ヒドロキシル、ハロゲン、または−ＮＨＣ（Ｏ）Ｒ ₂₂ （Ｒ ₂₂ は、Ｈ、−ＮＨ ₂ 、Ｃ ₁ 〜Ｃ ₆ アルキル、フェニルから選択される）、−（ＣＨ ₂ ） _s ＯＲ ₂₃ （添字ｓは、１または２であり、Ｒ ₂₃ は、Ｍｅ、フェニル、および−ＣＯ ₂ ＣＨ ₂ ＣＮから選択される）；−ＮＨＳＯ ₂ Ｒ ₂₄ （Ｒ ₂₄ は、Ｃ ₁ 〜Ｃ ₄ アルキルまたはフェニルである）から独立に選択されていてもよく、前記アルキル、アルコキシおよびアセトアミド部分は、形式電荷部分により任意に置換されていてもよい
であるか、
または、Ｘが、下記の式ＶＩＩを有する部分：

式中、各Ｒ ₄ およびＲ ₅ は、下記から独立に選択することができる：
ａ）［（ＣＨ ₂ ＣＲ’ＨＯ） _x （ＣＨ ₂ ＣＲ’’ＨＯ） _y Ｒ ₁₅ ］；
ｂ）アルキル、アリールまたはアリールアルキル；
ｃ）［ＣＨ ₂ ＣＨ（ＯＲ ₁₆ ）ＣＨ ₂ ＯＲ ₁₇ ］；
ｄ）スチレンオキシド、グリシジルメチルエーテル、イソブチルグリシジルエーテル、イソプロピルグリシジルエーテル、ｔ−ブチルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、およびグリシジルヘキサデシルエーテルのアミノ添加、およびその後の、１〜１０個のアルキレンオキシド単位の添加（少なくとも１個のこのようなアルキレンオキシド単位は、−ＨではないＲ ₁₅ により置換されている）による生成物；
ここで、Ｒ’は、Ｈ、ＣＨ ₃ 、ＣＨ ₂ Ｏ（ＣＨ ₂ ＣＨ ₂ Ｏ） _z Ｒ ₁₅ 、およびこれらの混合物からなる群から選択され、Ｒ’’は、Ｈ、ＣＨ ₂ Ｏ（ＣＨ ₂ ＣＨ ₂ Ｏ） _z Ｒ ₁₅ 、およびこれらの混合物からなる群から選択され、ｘ＋ｙ≦２０であり、ｙ≧１であり、ｚ＝０〜１０であり、各Ｒ ₁₅ は、−Ｈおよび−ＣＨ ₂ ＣＨＲ ₁₈ Ｎ ⁺ Ｒ ₁₉ Ｒ ₂₀ Ｒ ₂₁ （Ｒ ₁₈ は、−Ｈおよび−ＣＨ ₃ から選択され、各Ｒ ₁₉ およびＲ ₂₀ は、−ＯＨにより任意に置換されていてもよいＣ ₁ 〜Ｃ ₄ アルキルから独立に選択され、Ｒ ₂₁ は、Ｃ ₁ 〜Ｃ ₁₂ の任意に−ＯＨ置換されていてもよいアルキルまたは（ＣＨ ₂ ） _r Ｏ _p Ｑから独立に選択され、添字ｒは、１〜８の整数であり、添字ｐは、０または１であり、Ｑは、−ＣＯ ₂ ^- 、および−ＳＯ ₃ ^- から選択されるアニオン基である）から独立に選択され、Ｒ ₁₆ は、Ｈ、（ＣＨ ₂ ＣＨ ₂ Ｏ） _z Ｒ ₁₅ （ｚ＝０〜１０である）、およびこれらの混合物からなる群から選択され、Ｒ ₁₇ は、Ｃ ₁ 〜Ｃ ₁₆ アルキル、Ｃ ₆ 〜Ｃ ₁₀ アリール基、およびこれらの混合物からなる群から選択され、添字ｍは、０〜４の整数であり、各Ｒ ₆ は上記定義の通りであり、Ｚは、単位電荷ｃの電荷のバランスをとる対イオンであり、添字ｂは、共有結合により電荷のバランスをとる対イオンを含まない−ＨではないＲ ₁₅ 基の数と等しく、さらに、ただし、分子は、少なくとも１個の−ＨではないＲ ₁₅ 基を含有する
である、［７］に記載のチオフェンアゾ色素。
［１０］
Ｘが、下記の式（ＩＩ）を有する部分である［９］に記載のチオフェンアゾ色素：

式中、
ｉ）Ｒ ₄ は、下記の式（ＩＩＩ）を有する部分から選択される：

式中、
ｉ）Ｒ ₈ は、水素、Ｃ ₁ 〜Ｃ ₄ アルキル部分またはアリール部分であり、
ｉｉ）Ｙは、イミダゾリウムからなる群から選択される第四級アンモニウム種、または下記の式（ＩＶ）を有する部分である：

式中、
ｉ）Ｒ ₉ は、Ｃ ₁ 〜Ｃ ₂ アルキル部分であり、
ｉｉ）Ｒ ₁₀ は、−ＯＨにより任意に置換されていてもよいＣ ₁ 〜Ｃ ₈ アルキル部分、またはスルホネートにより置換されているＣ ₂ 〜Ｃ ₄ アルキル、またはカルボキシレートにより置換されているＣ ₁ 〜Ｃ ₄ アルキルから選択され、
ｉｉｉ）Ｚは、単位電荷ｃの電荷のバランスをとる対イオンであり、添字ｂは、Ｒ ₁₀ が、−ＯＨにより任意に置換されていてもよいＣ ₁ 〜Ｃ ₈ アルキル部分である場合には１であり、そうでなければ添字ｂ＝０である；
または、Ｒ ₄ は、下記の式（Ｖ）を有する部分から選択される：

式中、
ｉ）各Ｒ ₁₁ およびＲ ₁₂ は、水素、Ｃ ₁ 〜Ｃ ₄ アルキルまたはアリール部分から独立に選択され、ｍおよびｎは、独立しており、０から５までの整数であり、
ｉｉ）Ｙは、上記の通りである
または、Ｒ ₄ は、下記の式（ＶＩ）を有する部分から選択される：

式中、
ｉ）Ｒ ₁₃ は、アリール部分、ベンジル部分、またはＣ ₁ 〜Ｃ ₁₈ アルキル部分から選択され、
ｉｉ）各Ｒ ₁₄ は、水素または−ＣＨ ₃ から独立に選択され、ｍは、０〜１０の整数である
ｉｉ）Ｒ ₅ は、Ｒ ₄ と同じであることができ、またはＣ ₁ 〜Ｃ ₆ アルキル部分またはベンジル部分から選択することができ、
ｉｉｉ）添字ａは、０〜２の整数であり、各Ｒ ₆ は、メチル、メトキシ、またはアセトアミド部分から独立に選択されていてもよい。
［１１］
各Ｒ ₁ 、Ｒ ₂ およびＲ ₃ が、水素、（Ｃ ₁ 〜Ｃ ₄ ）−アルキル、（Ｃ ₃ 〜Ｃ ₁₀ ）−アリール、カルボキシレート、シアノ、スルホネート、ホスホネート、スルフェート、アセテート、ニトロ、（Ｃ ₁ 〜Ｃ ₄ ）−アルキルエステル、ハロゲンまたはアミノ部分から独立に選択される、［１０］に記載のチオフェンアゾ色素。
［１２］
式（ＶＩＩＩ）を有する、［１］に記載のチオフェンアゾ色素：

式中、Ａ部分は、表１のＡ部分の番号１〜１１８からなる群から選択され、Ｘは、表４のＸ部分の番号１〜３１からなる群から選択される。
［１３］
式（ＶＩＩＩ）を有する、［１］に記載のチオフェンアゾ色素：

式中、Ａ部分は、表１のＡ部分の番号９〜１１、１５、２３、３４〜３５、３７〜３９、４１、４３、４７、５０〜５１、５７〜５８、７７、８３、８９、９５、１０６、および１１０〜１１８からなる群から選択され、Ｘ部分は、表４のＸ部分の番号１〜３１からなる群から選択される。
［１４］
下記の式を有する、［１］に記載のチオフェンアゾ色素：

式中、部分Ａは、表１のＡ部分の番号１〜１１８から選択され、ａ＝０〜２であり、ａ＝１または２である場合には、Ｒ ₆ は、表２のＲ ₆ 置換基の同定および位置の番号１〜４０から選択され、Ｒ ₄ およびＲ ₅ の原子団は、表３のＲ ₄ およびＲ ₅ の原子団の番号１〜６９から選択される。
［１５］
下記の式を有する、［１］に記載のチオフェンアゾ色素：

式中、部分Ａは、表１のＡ部分の番号９〜１１、１５、２３、３４〜３５、３７〜３９、４１、４３、４７、５０〜５１、５７〜５８、７７、８３、８９、９５、１０６、および１１０〜１１８から選択され、ａ＝０〜２であり、ａ＝１または２である場合には、Ｒ ₆ は、表２のＲ ₆ 置換基の同定および位置の番号１、３、５、７、１２、１３、１４、３１、３６および４０から選択され、Ｒ ₄ およびＲ ₅ の原子団は、表３のＲ ₄ およびＲ ₅ の原子団の番号３、５〜６、１０、１３〜１４、１７、１９〜２１、２４、２７〜２８、３１〜３４、３８、４１、４４〜４８、５２、５４〜５５、５８、６０〜６４および６９から選択される。
［１６］
表５の式番号１〜４２から選択される式を有する、［１］に記載のチオフェンアゾ色素。 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. Accordingly, it is intended in the appended claims to cover all such changes and modifications that are within the scope of this invention.
The invention described in the original claims is appended below.
[1]
Thiopheneazo dyes containing a formal charge moiety, except that they do not contain a meta-bis (2-hydroxy-3-trimethylammoniumpropyl) aminotolyl group.
[2]
The thiophenazo dye according to [1], which has a maximum extinction coefficient of about 1000 to about 1,000,000 liters / mol / cm in a wavelength band of about 400 nm to about 750 nm in a methanol solution.
[3]
The thiophenazo dye according to [2], which has a maximum extinction coefficient of about 20,000 to about 250,000 liters / mol / cm in a wavelength band of about 560 nm to about 610 nm.
[4]
The thiophenazo dye according to [1], which has a molecular weight of more than 300 daltons.
[5]
The thiopheneazo dye according to [1], comprising a counter ion having an aqueous partition value of about 10% to 100% and balancing the charge by non-covalent bonding.
[6]
The thiopheneazo dye according to [1], comprising a counter ion having an aqueous partition value of 0% to about 40% and balancing the charge by covalent bond.
[7]
The thiophenazo dye represented by the general formula (I) according to [1]:

Where
a) R ₁ , R ₂ and R ₃ are each independently selected from hydrogen, electron withdrawing moiety, and electron donating moiety, provided that at least one of R ₁ , R ₂ and R ₃ is electron withdrawing Sex part,
b) X is an organic moiety having a molecular weight of about 65 daltons to about 4855 daltons.
[8]
Each R _1, R ₂ and R ₃ is hydrogen, (C ₁ ~C ₄₎ - alkyl, (C ₃ ~C ₁₀₎ - aryl, carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro, (C ₁ -C ₄₎ - alkyl esters, are independently selected from halogen or amino moieties, thiophene azo dyes described in [7].
[9]
A moiety where X has the following formula (II):

Where
i) R ₄ is selected from moieties having the following formula (III):

Where
i) each R ₈ is independently selected from hydrogen, C ₁ -C ₈ alkyl optionally substituted with hydroxy , or acetyl;
ii) m is an integer from 0 to 10,
iii) Y is selected from sulfonates, carboxylates, phosphonates or quaternary ammonium species selected from imidazolium, pyridinium, morpholinium, piperidinium, or a moiety having the following formula (IV):

Where
i) R ₉ is a C ₁ -C ₈ alkyl moiety optionally substituted with —OH ;
ii) R ₁₀ is an optionally substituted C ₁ optionally -C ₁₈ alkyl moiety by -OH or C ₂ -C ₈ alkyl which is substituted by sulphonate or carboxylate C ₁ is replaced by ~,, Selected from C ₈ alkyl;
iii) Z is a counter ion that balances the charge of the unit charge c, and the subscript b is 1 when R ₁₀ is a C ₁ -C ₁₈ alkyl moiety optionally substituted by —OH. Otherwise subscript b = 0;
Alternatively, R ₄ is selected from a moiety having the following formula (V):

Where
i) each R ₁₁ and R ₁₂ is independently selected from hydrogen, C ₁ -C ₈ alkyl, aryl, acetyl or hydroxyl moieties, m and n are independently an integer from 0 to 10;
ii) Y is as described above;
Or, R ₄ is selected from a moiety having the following formula (VI):

Where
i) R ₁₃ is selected from an aryl moiety, an arylalkyl moiety, a C ₁ -C ₁₈ alkyl moiety, or a siloxane moiety;
ii) each R ₁₄ is independently selected from hydrogen, C ₁ -C ₄ alkyl, m is an integer from 0 to 10;
iii) Y is as described above;
ii) R ₅ may be the same as R ₄ or may be selected from a C ₁ -C ₁₂ alkyl moiety, an aryl moiety or an arylalkyl moiety, wherein the subscript (a) is an integer from 0 to 4; R ₆ is C ₁ -C ₆ alkyl, C ₁ -C ₄ alkoxy, nitro, hydroxyl, halogen, or —NHC (O) R ₂₂ (R ₂₂ is H, —NH ₂ , C ₁ -C ₆ alkyl, -(CH ₂ ) _s OR ₂₃ (subscript s is 1 or 2, R ₂₃ is selected from Me, phenyl, and -CO ₂ CH ₂ CN); -NHSO ₂ R ₂₄ (R ₂₄ is C ₁ -C ₄ alkyl or phenyl) may be independently selected and the alkyl, alkoxy and acetamide moieties may be optionally substituted with formal charge moieties.
Or
Or a moiety wherein X has the following formula VII:

Wherein each R ₄ and R ₅ can be independently selected from:
a) [(CH ₂ CR′HO) _x (CH ₂ CR ″ HO) _y R ₁₅ ];
b) alkyl, aryl or arylalkyl;
_{c) [CH 2 CH (OR} 16) CH 2 OR 17];
d) Amino addition of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl hexadecyl ether, followed by 1-10 alkylene oxide units Product of at least one such alkylene oxide unit is replaced by R ₁₅ which is not —H ;
Wherein R ′ is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z R ₁₅ , and mixtures thereof, and R ″ is H, CH ₂ O (CH ₂ CH ₂ O) _z R ₁₅ , and mixtures thereof, x + y ≦ 20, y ≧ 1, z = 0-10, and each R ₁₅ is —H and —CH ₂ CHR ₁₈ N ⁺ R ₁₉ R ₂₀ R ₂₁ (R ₁₈ is selected from —H and —CH ₃ , and each R ₁₉ and R ₂₀ is C ₁ -C ₄ alkyl optionally substituted by —OH. R ₂₁ is independently selected from C _{1 to} C ₁₂ optionally -OH substituted alkyl or (CH ₂ ) _r O _p Q, and the subscript r is from 1 to 8 An integer, the subscript p is 0 or 1, and Q is an anionic group selected from —CO ₂ ⁻ and —SO ₃ ^— ) R ₁₆ is selected from the group consisting of H, (CH ₂ CH ₂ O) _z R ₁₅ (where z = 0 to 10), and mixtures thereof, and R ₁₇ is selected from C ₁ to Selected from the group consisting of C ₁₆ alkyl, C ₆ -C ₁₀ aryl groups, and mixtures thereof, subscript m is an integer from 0 to 4, each R ₆ is as defined above, and Z is a unit A counter-ion that balances the charge of charge c, the subscript b being equal to the number of non-H R ₁₅ groups that do not include a counter-ion that balances the charge by covalent bonds , provided that the molecule is at least Contains one R ₁₅ group that is not —H
The thiopheneazo dye according to [7].
[10]
The thiophenazo dye according to [9], wherein X is a moiety having the following formula (II):

Where
i) R ₄ is selected from moieties having the following formula (III):

Where
i) R ₈ is hydrogen, a C ₁ -C ₄ alkyl moiety or an aryl moiety;
ii) Y is a quaternary ammonium species selected from the group consisting of imidazoliums, or a moiety having the following formula (IV):

Where
i) R ₉ is a C ₁ -C ₂ alkyl moiety;
ii) R ₁₀ is optionally substituted C ₁ optionally -C ₈ alkyl moiety by -OH or C ₂ -C ₄ alkyl which is substituted by sulphonate or carboxylate C ₁ is replaced by ~,, Selected from C ₄ alkyl;
iii) Z is a counter ion that balances the charge of the unit charge c, and the subscript b is when the R ₁₀ is a C ₁ -C ₈ alkyl moiety optionally substituted by —OH. 1; otherwise, subscript b = 0;
Alternatively, R ₄ is selected from a moiety having the following formula (V):

Where
i) each R ₁₁ and R ₁₂ is independently selected from hydrogen, C ₁ -C ₄ alkyl or aryl moieties, m and n are independently an integer from 0 to 5;
ii) Y is as described above.
Or, R ₄ is selected from a moiety having the following formula (VI):

Where
i) R ₁₃ is selected from an aryl moiety, a benzyl moiety, or a C ₁ -C ₁₈ alkyl moiety;
ii) Each R ₁₄ is independently selected from hydrogen or —CH ₃ , and m is an integer from 0 to 10.
ii) R ₅ can be the same as R ₄ or can be selected from a C ₁ -C ₆ alkyl moiety or a benzyl moiety;
iii) The subscript a is an integer from 0 to 2, and each R ₆ may be independently selected from a methyl, methoxy, or acetamide moiety.
[11]
Each R _1, R ₂ and R ₃ is hydrogen, (C ₁ ~C ₄₎ - alkyl, (C ₃ ~C ₁₀₎ - aryl, carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro, (C ₁ -C ₄₎ - alkyl esters, are independently selected from halogen or amino moieties, thiophene azo dyes described in [10].
[12]
The thiophenazo dye according to [1], which has the formula (VIII):

In the formula, the A part is selected from the group consisting of the numbers 1 to 118 of the A part of Table 1, and X is selected from the group consisting of the numbers 1 to 31 of the X part of Table 4.
[13]
The thiophenazo dye according to [1], which has the formula (VIII):

In the formula, the A part is the number 9 to 11, 15, 23, 34 to 35, 37 to 39, 41, 43, 47, 50 to 51, 57 to 58, 77, 83, 89 of the A part in Table 1. 95, 106, and 110-118, and the X moiety is selected from the group consisting of numbers X1-31 in the X part of Table 4.
[14]
The thiophenazo dye according to [1], which has the following formula:

Wherein moiety A is selected from numbers 1 to 118 of the A moiety in Table 1 and when a = 0-2 and a = 1 or 2, R ₆ is the R ₆ substitution of Table 2. is selected from the numbers 1 to 40 of the identification and location of a group, atomic of R ₄ and R ₅ is selected from the numbers 1 to 69 of R ₄ and atomic group R ₅ in Table 3.
[15]
The thiophenazo dye according to [1], which has the following formula:

In the formula, the part A is the number 9 to 11, 15, 23, 34 to 35, 37 to 39, 41, 43, 47, 50 to 51, 57 to 58, 77, 83, 89 of the A part in Table 1. 95, 106, and 110-118, where a = 0-2 and a = 1 or 2, R ₆ is the R ₆ substituent identification and position number 1 in Table 2 , is selected from 3,5,7,12,13,14,31,36 and 40, atomic group R ₄ and R _5, Table 3 of R ₄ and R ₅ atomic group number 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.
[16]
The thiophenazo dye according to [1], which has a formula selected from the formula numbers 1 to 42 in Table 5.

Claims (5)

A composition comprising a thiophorene azo dye containing a formal charge moiety, wherein the dye does not contain a meta-bis (2-hydroxy-3-trimethylammoniumpropyl) aminotolyl group:
The thiophenazo dye has the following formula:

In the formula, the moiety A is represented by the following chemical formula:

a is 1 and R ₆ is entry no. 5,

The atomic groups of R ₄ and R ₅ are entry no. 13 ,

Composition . The composition of claim 1, comprising:
The thiophenazo dye is entry no. Having 14 equations ,

Composition . A composition comprising a thiophorene azo dye containing a formal charge moiety, wherein the dye does not contain a meta-bis (2-hydroxy-3-trimethylammoniumpropyl) aminotolyl group:
The thiophenazo dye has the formula (VIII)

In the formula, the moiety A is represented by the following chemical formula:

In the formula, X is a partial number . 9 ,

Composition . A composition comprising a thiophorene azo dye containing a formal charge moiety, wherein the dye does not contain a meta-bis (2-hydroxy-3-trimethylammoniumpropyl) aminotolyl group:
The thiopheneazo dye has the following formula:

In the formula, part A is part no. Selected from the group consisting of 52 to 59, and 111 to 118;

R ₆ is entry no. 7, a is 2,

The atomic groups of R ₄ and R ₅ are entry no. 55 ,

Composition . A composition comprising a thiophorene azo dye containing a formal charge moiety, wherein the dye does not contain a meta-bis (2-hydroxy-3-trimethylammoniumpropyl) aminotolyl group:
The thiophenazo dye has formula no. 18 has a,

Composition .