COMPOSITION FOR CARE IN WASHING CLOTHING UNDERSTANDING BIS-AZO DYES FOR USE AS BLUEBERING AGENTS

专利摘要:
bis-azo dyes for use as bleaching agents the present invention relates to bis-azo dyes for use as bleaching agents, laundry care compositions comprising bis-azo dyes that can serve as bleaching agents, processes to produce bleaching agents as compositions for washing clothes and methods for using them. bleaching agents are generally composed of at least two components: at least one chromophore component and at least one polymeric component. these bleaching agents are advantageous for providing a tissue whitening effect, while they do not accumulate over time, causing undesirable blue discoloration in the treated tissues.
公开号:BR112013009791B1
申请号:R112013009791-4
申请日:2011-10-21
公开日:2020-09-29
发明作者:Gregory Scot Miracle；Robert Linn Mchaffey；Xiaoyong Michael Hong；Eduardo Torres；Dominick Joseph Valent
申请人:The Procter & Gamble Company；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] This invention relates to bis-azo dyes for use as bleaching agents, compositions for washing clothes that comprise bis-azo dyes that can serve as bleaching agents, processes for producing bleaching agents as compositions for care in washing clothes and methods for using them. Bluing agents are generally composed of at least two components: at least one chromophore component and at least one polymeric component. These bleaching agents are advantageous for providing a tissue whitening effect, while they do not accumulate over time, causing undesirable blue discoloration in the treated tissues. BACKGROUND OF THE INVENTION
[002] As textile substrates age, their color tends to fade or yellow due to exposure to light, air, soil and the natural degradation of the fibers that make up the substrates. Thus, the purpose of bleaching agents is generally to visually shine these textile substrates and counteract the fading and yellowing of the substrates. Typically, bleaching agents can be found in laundry detergents, fabric softeners or rinsing aids and are therefore applied to textile substrates during the laundry process. However, it is important that the bleaching agents are able to target the treated textile substrates without causing undesirable staining to the textile substrates. Cellulosic substrates, in particular, tend to exhibit a yellowish matrix after exposure to light, air and / or dirt. It is often difficult to reverse this yellowing with normal laundry procedures. As a result, there is a need for improved bleaching agents that are able to eliminate the yellowing exhibited by aging cellulosic substrates. The use of such improved bleaching agents can extend the life of textile substrates, such as garments, table linen, etc. Unfortunately, current bleaching agents either do not provide a benefit after a single treatment cycle and / or they accumulate at an undesirable level, thereby over-toning the treated situs over multiple treatment cycles.
[003] The present invention offers advantages over previous efforts in this area, as the present invention takes advantage of compounds having a non-sulfonic acid substituent on the phenyl terminal ring of the bis-azo structure. Sulfonic acid groups are known to promote the deposition and staining of acid dyes in cellulosic tissues. These groups are also essential for the solubility and compatibility of dyes in laundry formulations. Although it is necessary for the bleaching agents to be deposited in the washing water, it is undesirable to stain the fabric by inadvertent contact, or through accumulation over time, that is, excessive toning. Applicants have recognized that modifying or replacing the sulfonic acid group at the phenyl terminal end of bis-azo with a non-ionic solubilizing group allows good bis-azo deposition, but mitigates its staining and excess toning trends and still allows that the bleaching agent is compatible in laundry formulations. In summary, applicants have recognized the source of current toning deficiencies and provide the solution to that problem in the present invention. The toning compounds disclosed in the present invention also absorb light at a wavelength suitable for neutralizing the yellowing of cellulosic substrates. These compounds ideally function as bleaching agents for cellulosic substrates and can be incorporated into compositions for washing clothes for use by consumers. SUMMARY OF THE INVENTION
[004] This invention relates to laundry care compositions comprising bis-azo dyes that can be used as bleaching agents, processes for producing such laundry care compositions and methods of using the same. Bluing agents are generally composed of at least two components: at least one chromophore component and at least one polymeric component. These bleaching agents are advantageous for providing a tissue whitening effect, while they do not accumulate over time, causing undesirable blue discoloration in the treated tissues. DETAILED DESCRIPTION
[005] For use in the present invention, the term "alkoxy" is intended to include C1-C6 alkoxy and alkoxy polyol derivatives having repeating units such as butylene oxide, glycidol oxide, ethylene oxide or propylene oxide.
[006] For use in the present invention, the terms "alkyl" and "finished alkyl" are intended to include C1-C6 alkyl groups.
[007] The terms "ethylene oxide", "propylene oxide" and "butylene oxide" shown in the present invention by the common designation "EO", "PO" and "BO", respectively.
[008] For use in the present invention, the term "composition for treatment in laundry washing" includes, except where otherwise indicated, unit dose of washing agents and / or compositions for treating fabrics of the granular, powder, liquid type , gel, paste, bar and / or flakes.
[009] For use in the present invention, the term "fabric treatment composition" includes, except where otherwise indicated, fabric softening compositions, fabric enhancing compositions, fabric cooling compositions and combinations of these substances. These compositions can, but need not be, compositions added during rinsing.
[0010] For use in the present invention, "cellulosic substrates" are intended to include any substrate that comprises at least a majority, by weight, of cellulose. Cellulose can be found in wood, cotton, linen, jute and hemp. Cellulosic substrates can be in the form of powders, fibers, pulp and articles formed 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 the pulp include paper.
[0011] For use in the present invention, the articles "o", "a", "one" and "one", when used in a claim, mean one or more of what is being claimed or described.
[0012] For use in the present invention, the terms "include", "includes" and "including" are intended to be non-limiting.
[0013] The test methods presented in the Test Methods section of this application need to be used to determine the respective values of the inventors' parameters of the applicants.
[0014] Unless otherwise specified, all component or composition levels refer to the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
[0015] All percentages and ratios are calculated by weight, except where indicated otherwise. All percentages and ratios are calculated based on the total composition, except where indicated otherwise.
[0016] It should be understood that each maximum numerical limit mentioned in this specification includes each of the lower numerical limits, as if such lower numerical limits were expressly registered in this document. Each minimum numerical limit mentioned in this specification includes each of the upper numerical limits, as if such upper numerical limits were expressly registered in this document. Each number range mentioned in this specification includes each more restricted number range that is within that broader number range, as if such more restricted number ranges were expressly recorded in this document.
[0017] All the documents cited are, in their relevant part, incorporated herein, by way of reference; the citation of any document should not be interpreted as admitting that it represents prior art with respect to the present invention. Suitable bleaching agents
[0018] The bleaching agents used in the present laundry washing compositions can be dyes, pigments, or polymeric dyes, preferably dyes that comprise a chromophore component and a polymeric component. The chromophore constituent is characterized by the fact that it absorbs light at the wavelength in the range of blue, red, violet, purple or combinations thereof when exposed to light. In one aspect, the chromophore component has a maximum absorbance spectrum from about 520 nanometers to about 640 nanometers of water and / or methanol, and in another aspect, from about 560 nanometers to about 610 nanometers of water and / or methanol.
[0019] Examples of suitable polymeric constituents include alkylene polyoxy chains that have multiple repeating units. In one aspect, polymeric constituents include alkylene polyoxy chains that have from 2 to about 30 repeat units, from 2 to about 20 repeat units, from 2 to about 10 repeat units, or even from about from 3 or 4 to about 6 repetition units. Some non-limiting examples of polyoxy alkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.
[0020] In one aspect, the bleaching agent used in the present laundry washing compositions may have the following general structure (I):

[0021] where:
[0022] R1 and R2 are independently H, alkyl, alkoxy, alkylene-oxy, alkylene-finished alkyl, polyalkylene-oxy, finished alkyl, polyalkylene-oxy, urea, starch or acetamido;
[0023] R3 is a substitute for the aryl group, which may be a substituted phenyl group or a naphthyl moiety;
[0024] X is a group of oxygen, nitrogen or sulfonamide additionally substituted with a substituted or unsubstituted amino, or a substituted or unsubstituted sulfonamide group, in which the substituents are selected from the group consisting of alkyl, alkylene-oxide, polyalkylene- oxy, or phenyl moieties where the phenyl group can be further substituted with alkyl, alkylene-oxy or polyalkylene-oxy moieties.
[0025] Preferably R1 and R2 are independently selected from the group formed by H, alkyl, alkoxy, alkylene-oxy, finished alkyl, alkylene-oxy and starch. Or, R1 and R2 are independently alkyl, alkoxy, alkylene-oxy, polyalkylene-oxy, or acetamido H. In a preferred aspect, R1 is an alkoxy group and R2 is an alkyl or alkoxy group. In a preferred aspect, X is an oxygen atom, nitrogen or a sulfonamido group additionally substituted with alkyl, alkylene-oxy, polyalkylene-oxy, or phenyl moieties where the phenyl group can be further substituted with alkyl, radicals or alkylene- polyalkylene oxide. In a preferred aspect, X is a substituted group comprising a sulfonamide moiety and optionally an alkyl and / or aryl moiety, and wherein the substituting group comprises at least one alkylene-oxy chain comprising at least 4 alkylene-oxy moieties.
[0026] In another aspect, suitable bleaching agents can have the following general structure (II):

[0027] where:
[0028] R1 and R2 are independently alkyl, alkoxy or acetamido H;
[0029] W is a substituted amino moiety;
[0030] X is a hydrogen atom, an amino group or an amino group substituted with an acyl group;
[0031] Y is a portion of hydrogen or sulfonic acid; and
[0032] Z is a portion of sulfonic acid or an amino group substituted with a phenyl group.
[0033] In additional aspects, suitable bleaching agents may have the following general structure (III):

[0034] where:
[0035] R1 is alkoxy;
[0036] R2 is alkyl;
[0037] W is a substituted amino moiety;
[0038] X is a hydrogen atom, an amino group or an amino group substituted with an acyl group;
[0039] Y is a portion of hydrogen or sulfonic acid; and
[0040] Z is a portion of sulfonic acid or an amino group substituted with a phenyl group.
[0041] In one aspect, said bleaching agent may comprise: (a) at least one chromophore component comprising a bis-azo dye, and (b) at least one polymeric component or substituted sulfonamide component;
[0042] in which the bleaching agent has the following structure:

[0043] where:
[0044] R1 and R2 are independently alkyl, alkoxy, alkylene-oxy, alkyl-alkylene-oxy, polyalkylene-oxy, polyalkylene-oxy-terminated alkyl, urea, or H-starch;
[0045] R3 is a substituent for the aryl group, which may be a substituted phenyl group or a naphthyl moiety;
[0046] X is a substituted oxygen, a substituted or unsubstituted amino, or a substituted or unsubstituted sulfonamide group in which the substituents are selected from the group consisting of alkyl, alkylene-oxy, polyalkylene-oxy, or portions of phenyl in which the phenyl group can be further substituted with alkyl, alkylene-oxy or polyalkylene-oxy moieties.
[0047] In one aspect, said bleaching agent may comprise an alkylene polyoxy chain containing from 2 to about 30 repeating units.
[0048] In one aspect, said bleaching agent may comprise an alkylene polyoxy chain containing from 2 to about 20 repeating units.
[0049] In one aspect, said bleaching agent may comprise an alkylene polyoxy chain containing from 2 to about 10 repeating units.
[0050] In one aspect, said bleaching agent may comprise a polyoxy alkylene chain containing from about 4 to about 6 repeat units.
[0051] In one aspect, said bleaching agent may comprise an alkoxylated bis-azo polymeric dye.
[0052] In one aspect, the chromophore of said bleaching agent can have a maximum absorbance spectrum in water from about 520 nanometers to about 640 nanometers.
[0053] In one aspect, the chromophore of said bleaching agent can have a maximum absorbance spectrum in water from about 560 nanometers to about 610 nanometers.
[0054] In one aspect, said bleaching agent can have an absolute shade angle in the range of 265 ° to 310 °.
[0055] In one aspect, said bleaching agent can have an angle of absolute shade in the range of 273 ° to 287 °.
[0056] In one aspect, said bleaching agent can have the following general structure:

[0057] where:
[0058] R1 and R2 are independently alkyl, alkoxy, alkylene-oxy, alkyl-alkoxy-terminated, polyalkylene-oxy, polyalkylene-terminated alkyl or H-starch;
[0059] W is a substituted amino moiety;
[0060] U is a hydrogen, an amino group or an amino group substituted with an acyl group;
[0061] Y is a portion of hydrogen or sulfonic acid; and
[0062] Z is a portion of sulfonic acid or an amino group substituted with a phenyl group.
[0063] In one aspect, of said bleaching agent, R1 is alkoxy and R2 is alkyl.
[0064] In one aspect of the invention, suitable bluing agents include, but are not limited to, the following structures:















[0065] Preferred dyes are selected from the group consisting of BA1, BA2, BA3, BA6, BA10, BA11, BA12, BA15, BA19, BA20, BA21, BA24, BA28, BA29, BA30, BA33, BA37, BA38, BA39 , BA42, BA46, BA47, BA48, BA51, BA55, BA56, BA57, BA60, BA64, BA65, BA66, BA69, BA73, BA74, BA75 and BA78. BA10, BA20, BA51, BA55, BA56, BA57, BA60, BA66, BA69 and BA78 are particularly preferred.
[0066] The bleaching agent, also defined herein as the dye, is typically formulated to be deposited on fabrics from the washing liquid to provide a relative shade angle of 220-320 ° on a corresponding consumer garment, from in order to optimize the perception of whiteness of the fabric. This shade angle can be generated by the essential shade agent specified for the present invention alone, or by a combination of the essential shade agent, in combination with an additional shade agent that together generate the desired shade angle. The tinting agent is typically described as blue or violet. It may be appropriate for the toning agent (s) to have a peak absorption wavelength of 550 nm to 650 nm, or from 570 nm to 630 nm. The toning agent can be a combination of dyes which together have the visual effect on the human eye as that of a single dye having a peak absorption for wavelength, on polyester, from 550 nm to 650 nm, or from 570 nm to 630 nm. This can be achieved, for example, by mixing red and blue-green dyes to produce a blue or violet hue.
[0067] Dyes are typically colored organic molecules that are soluble in aqueous media that contain surfactants. Dyes can be selected from the basic, acidic, hydrophobic, direct and polymeric dye classes, and dye conjugates. Suitable polymeric toner dyes are commercially available, for example, from Milliken, Spartanburg, South Carolina, USA.
[0068] Examples of suitable dyes are Liquitint © violet DD, Violet Direct 7 Violet Direct 9, Violet Direct 11, Violet Direct 26, Violet Direct 31, Violet Direct 35, Violet Direct 40, Violet Direct 41, Violet Direct 51, Violet Direct 66, Direct Violet 99, Acid Violet 50, Acid Blue 9 Acid Violet 17, Acid Black 1, Acid Red 17, Acid Blue 29, Solvent Violet 13, Scattered Violet 27 Scattered Violet 26, Scattered Violet 28, Scattered Violet 63 and Scattered Violet 77, Basic Blue 16, Basic Blue 65, Basic Blue 66, Basic Blue 67, Basic Blue 71, Basic Blue 159, Basic Violet 19, Basic Violet 35, Basic Violet 38, Basic Violet 48; Basic Blue 3, Basic Blue 75, Basic Blue 95, Basic Blue 122, Basic Blue 124, Basic Blue 141, thiazolium dyes, reactive blue 19, reactive blue 163, reactive blue 182, reactive blue 96, Liquitint® Violet CT (Milliken , Spartanburg, USA) and Azo-CM-Cellulose (Megazyme, Bray, Republic of Ireland). Other suitable toning agents are photo-bleaching dye conjugates such as the sulfonated zinc phthalocyanine conjugate with Direct Violet 99. A particularly suitable toning agent is a combination of Acid Red 52 and Acid Blue 80, or a combination of Direct Violet 9 and Solvent Violet 13.
[0069] A suitable synthesis route for certain biszo dyes described here is shown below:

[0070] where:
[0071] R is selected from the group consisting of alkyl, polyalkylene-oxy, phenyl and substituted phenyl, and
[0072] R 'is selected from the group consisting of hydrogen, alkyl, or alkoxy.
[0073] Other certain bis-azo dyes described in the present invention can be prepared in a similar way, by substituting 2- [2- [2- (2-methoxy ethoxy) ethoxy] ethoxy] -5-methyl benzenamine or by 2-methoxy-5-methyl benzenamine or 2,5-dimethoxy benzenamine in the above synthetic scheme.
[0074] The base used in the first stage of the reaction can be selected from sodium carbonate, sodium acetate, sodium hydroxide, or other cationic salts of these respective bases, and tertiary amines.
[0075] Acid hydrolysis can be performed using a strong acid such as hydrochloric acid or sulfuric acid.
Alternatively, the bis-azo dyes described herein can be made according to various procedures known in the art and / or according to the examples of the present invention. For example, coupling can be performed using polyalkylene-oxide substituted aniline compounds obtained by known procedures from starting materials such as 4-methoxy-2-nitrophenol and 4-methyl-2-nitrophenol, both of which are available from VWR International, LLC (West Chester, PA, USA). Compositions for laundry treatment
[0077] Any of the bleaching agents described in this specification can be incorporated into compositions for laundry care, including, but not limited to laundry detergents and fabric treatment compositions. Compositions for treatment in laundry washing including laundry detergents can be in solid or liquid form, including in the form of a gel. Such compositions may comprise one or more of said bleaching agents and an ingredient for laundry treatment. Bleaching agents can be added to the substrate, using a variety of application techniques. For example, for application on textile substrates containing cellulose, the bleaching agent can be included as a component of a laundry detergent. Thus, application to the textile substrate containing cellulose occurs, in fact, when a consumer adds laundry detergent to a washing machine. The bleaching agent can be present in the laundry detergent composition, in an amount of about 0.0001% to about 10% by weight of the composition, from about 0.0001% to about 5% by weight of the composition. composition, and from about 0.0001% to about 1% by weight of the composition.
The laundry detergent composition typically comprises a surfactant component in an amount sufficient to provide the desired cleaning properties. In one aspect, the laundry detergent composition may include, based on the total weight of the laundry detergent composition, from about 5% to about 90% of the surfactant, between about 5% to about 70% % of the surfactant, or even from about 5% to about 40% of the surfactant. The surfactant may comprise anionic, non-ionic, cationic, zwitterionic and / or amphoteric surfactants. In one aspect, the detergent composition comprises an anionic surfactant, a non-ionic surfactant, or mixtures thereof.
[0079] Compositions for treating fabrics are typically added to the rinse cycle, which is after the detergent solution has been used and replaced with the rinse solution in typical laundry processes. The tissue treatment compositions disclosed in the present invention may comprise active added fabric softeners and a suitable bleaching agent as described in the present specification.
[0080] The fabric treatment composition may comprise, based on the total weight of the fabric treatment composition, from about 1% to about 90%, or from about 5% to about 50% active fabric softeners . The bleaching agent can be present in the tissue treatment composition in an amount of about 0.5 ppm and about 50 ppm, or from about 0.5 ppm to about 30 ppm.
[0081] In one aspect, a laundry washing composition comprising a laundry washing ingredient and a bleaching agent comprising: (a) at least one chromophore component comprising a bis-azo dye, and (b) at least one polymeric component or substituted sulfonamide component;
[0082] in which the bleaching agent has the following structure:

[0083] where:
[0084] R1 and R2 are independently alkyl, alkoxy, alkylene-oxy, alkyl-alkylene-oxy, polyalkylene-oxy, polyalkylene-oxy-terminated, urea or H-starch;
[0085] R3 is a substituent for the aryl group, which may be a substituted phenyl group or naphthyl moiety;
[0086] X is a substituted oxygen, a substituted or unsubstituted amino, or a substituted or unsubstituted sulfonamide group in which the substituents are selected from the group consisting of alkyl, alkylene-oxy, polyalkylene-oxy, or portions of phenyl in which the phenyl group can be further substituted with alkyl, alkylene-oxy or polyalkylene-oxy moieties.
[0087] In one aspect, said bleaching agent comprises a polyoxy alkylene chain containing from 2 to about 30 repeating units.
[0088] In one aspect, said bleaching agent comprises a polyoxy alkylene chain containing from 2 to about 20 repeating units.
[0089] In one aspect, said bleaching agent comprises a polyoxy alkylene chain containing from 2 to about 10 repeating units.
[0090] In one aspect, said bleaching agent comprises a polyoxy alkylene chain containing from 4 to about 6 repeating units.
[0091] In one aspect, said bleaching agent comprises an alkoxylated polymeric bis-azo dye.
[0092] In one aspect, the chromophore of the said bleaching agent has a maximum absorbance spectrum in water from about 520 nanometers to about 640 nanometers.
[0093] In one aspect, the chromophore of the said bleaching agent has a maximum absorbance spectrum in water of about 560 nanometers to about 610 nanometers.
[0094] In one aspect, said bleaching agent has an absolute hue angle in the range of 265 ° to 310 °.
[0095] In one aspect, said bleaching agent has an absolute hue angle in the range of 273 ° to 287 °.
[0096] In one aspect, said bleaching agent has the following structure:

[0097] where:
[0098] R1 and R2 are independently alkyl, alkoxy, alkylene-oxy, alkylene-oxy finished alkyl, polyalkylene-oxy, polyalkylene-oxy finished alkyl or H starch;
[0099] W is a substituted amino moiety;
[00100] U is a hydrogen, an amino group or an amino group substituted with an acyl group;
[00101] Y is a portion of hydrogen or sulfonic acid; and
[00102] Z is a portion of sulfonic acid or an amino group substituted with a phenyl group.
[00103] In one aspect, of said bleaching agent, Ri is alkoxy and R2 is alkyl. Suitable ingredients for laundry treatment
[00104] While not essential for the purposes of the present invention, the non-limiting list of laundry treatment ingredients illustrated hereafter in this document are suitable for use in laundry care compositions and can be desirably incorporated into certain aspects of the invention, for example, to aid or improve performance, for the treatment of the substrate to be cleaned, or to modify the aesthetics of the composition, as is the case with perfumes, dyes, or the like. It is understood that these ingredients are in addition to the components that were previously mentioned, for any particular aspect. The total amount of such auxiliary compounds can, once the amount of dye is taken into account, be in the range of about 90% to about 99.99999995% by weight of the laundry care composition.
[00105] The exact nature of these additional components, as well as their levels of incorporation, will depend on the physical form of the composition and the nature of the cleaning operation in which it will be used. Suitable laundry care ingredients include, but are not limited to, fabric softeners, polymers, for example, cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes and stabilizers. enzyme, catalytic materials, bleach activators, polymeric dispersing agents, dirt and clay removal agents / anti-reposition agents, bleaches, foam suppressants, dyes, perfume and additional scent release systems, structure elasticizing agents, fabric softeners , carriers, hydrotropes, processing auxiliary elements and / or pigments. In addition to the description below, suitable examples of these other auxiliary compounds, as well as their levels of use, are found in US patents No. 5,576,282, No. 6,306,812 B1 and No. 6,326,348 B1, which are incorporated herein by reference .
[00106] As reported, the ingredients for laundry treatment are not essential to the Applicants' laundry detergent compositions. Therefore, certain aspects of the Applicants' compositions do not contain one or more of the following auxiliary composite materials: active fabric softeners, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers , metal catalytic complexes, polymeric dispersing agents, dirt and clay removal agents / anti-reposition agents, bleaches, foam suppressants, dyes, perfume and additional perfume release systems, structural elastifying agents, fabric softeners, carriers, hydrotropes, processing auxiliary elements and / or pigments. However, when one or more auxiliary compounds are present, they can be present as detailed below: Surfactants
[00107] Suitable anionic surfactants useful in the present invention can comprise any of the conventional types of anionic surfactants 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.
[00108] Exemplary anionic surfactants are the alkali metal salts of C10-C16 alkyl benzene sulfonic acids, or C11-C14 sulfonic alkyl benzene acids. In one aspect, the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. These surfactants and their preparation are described, for example, in US patents No. 2,220,099 and 2,477,383. Sodium and potassium straight chain alkylbenzene sulfonates are especially useful, with the average number of carbon atoms in the alkyl group being about 11 to 14. C11-C14 sodium, for example, C12, LAS is a specific example of these surfactants.
[00109] Another exemplary type of anionic surfactant comprises surfactants based on ethoxylated alkyl sulfate. Such materials, also known as alkyl sulfates or alkyl sulfates, etromher polyethoxylate, are those that correspond to the formula: R '- O - (C2H4O) n-SO3M where R' is a C8-C20 alkyl group, n is about 0.5 to 20, or 1 to 20, and M is a salt-forming cation. In one aspect, R 'is C10-C18 alkyl, n is about 1 to 15, and M is sodium, potassium, ammonium, alkyl ammonium or ammonium alkanol. In one aspect, R 'is a C12-C16, n is about 0.5 to 6, or from 1 to 6 and M is sodium.
[00110] The alkyl ether sulfates will generally be used in the form of mixtures comprising different lengths of the R 'chain and varying degrees of ethoxylation. Often, these mixtures will inevitably contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula, where n = 0. Non-ethoxylated alkyl sulfates can also be added separately to the compositions of this invention, and used as, or in, any anionic surfactant component that may be present. Specific examples of non-ethoxylated surfactants, for example, alkyl ether sulfate surfactants, are those produced by the sulfation of higher C8-C20 fatty alcohols. Conventional primary alkyl sulfate surfactants have the following general formula: ROSO3-M +, where R is typically a linear C8-C20 hydrocarbyl group, which can be straight or branched, and M is a solubilization cation in Water. In one aspect, R is a C10-C15 alkyl, and M is alkali metal, more specifically R is C12-C14 and M is sodium.
[00111] Some specific non-limiting examples of anionic surfactants useful in the present invention include: a) C11-C18 alkyl benzene (LAS) sulfonates; b) primary (AS) C10-C20 alkyl sulfates, branched and random chain, predominantly including C12 alkyl sulfates; c) secondary C10-C18 alkyl sulfates (2,3) having formulas (I) and (II): where M in formula (I) and (II) is hydrogen or a cation that provides charge neutrality, and all the units of M, if associated with a surfactant or an auxiliary compound ingredient, can also be a hydrogen atom or a cation depending on the form isolated by the technically skilled element or the relative pH of the system in which the compound is used, with some non-limiting examples of suitable cations including sodium, potassium, ammonium and mixtures thereof, eg is an integer equal to at least 7 or at least about 9, and y is an integer equal to at least 8 or at least 9 ; d) C10-C18 alkylalkoxy sulfates (AExS) where x is 1-30; e) C10-C18 alkylalkoxy carboxylates in one aspect, which comprises 1-5 ethoxy units; f) branched medium chain alkyl sulfates as discussed in US Patent No. 6,020,303 and US Patent No. 6,060,443; g) branched middle chain alkoxy alkyl sulfates, as discussed in US patent no. 6,008,181 and US patent No. 6,020,303; h) modified alkyl benzene sulfonate (MLAS), as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549 and WO 00/23548; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).
[00112] A suitable anionic detersive surfactant is predominantly C16 alkyl branched medium chain alkyl sulfate. A predominantly suitable raw material for C16 alkyl branched medium chain alkyl sulfate is beta-farnesene, such as BioFene ™ supplied by Amyris, Emeryville, California.
[00113] Suitable nonionic surfactants useful in the present invention can comprise any of the conventional types of nonionic surfactants typically used in liquid detergent products. These include primary or secondary alkoxylated fatty amine oxide surfactants based on alcohol or based on alcohol and amine oxide surfactants In one aspect, for use in liquid detergent products in the present invention are the nonionic surfactants that they are usually liquid.
[00114] Nonionic surfactants suitable for use in the present invention include those based on alcohol alkoxylate. Alcohol alkoxylates are materials that correspond to the following general formula: R1 (CmH2mO) nOH, where R1 is a C8 to C16 alkyl group, m is 2 to 4, and is in the range of about 2 to 12. In one aspect, R1 is an alkyl group, which can be primary or secondary, comprising from about 9 to 15 carbon atoms, or from about 10 to 14 carbon atoms. In one aspect, the alkoxylated fatty alcohols will also be ethoxylated materials that contain about 2 to 12 portions of ethylene oxide per molecule, or about 3 to 10 portions of ethylene oxide per molecule.
[00115] The alkoxylated fatty alcohol materials useful in liquid detergent compositions in the present invention will often have a hydrophilic-lipophilic (HLB) balance that ranges from about 3 to 17 to about 6 to 15, or about 8 to 15. Non-ionic surfactants based on alkoxylated fatty alcohol are commercially available under the names Neodol and Dobanol, from the Shell Chemical Company.
[00116] Another suitable type of non-ionic surfactant useful in the present invention comprises amine oxide surfactants. Amine oxides consist of materials that are generally referred to in the art as non-ionic "semipolar" materials. Amine oxides have the following formula: R (EO) x (PO) y (BO) zN (O) (CH2R ') 2.qH2O. In this formula, R is a relatively long chain hydrocarbyl moiety that can be saturated or unsaturated, linear or branched, and can contain 8 to 20, 10 to 16 carbon atoms, or is a primary C12-C16 alkyl. R 'is a short chain portion, in an aspect R' can be selected from hydrogen, methyl and --CH2OH. When x + y + z is different from 0, EO is oxyethylene, PO is oxypropylene and BO is oxybutylene. Amine oxide surfactants are exemplified by C12-14 alkyl dimethyl amine oxide.
[00117] Some non-limiting examples of non-ionic surfactants include: a) C12-C18 alkyl ethoxylates, such as NEODOL® non-ionic surfactants, available from Shell; b) C6 to C12 alkyl phenol alkoxylates, where the alkoxylated units are a mixture of oxyethylene and oxypropylene units; c) condensates of C12-C18 alcohol and C6-C12 alkyl phenol with ethylene oxide / propylene oxide block polymers, such as Pluronic®, available from BASF; d) C14-C22 medium branched chain alcohols, AB, as discussed in US Patent No. 6,150,322; e) C14-C22 alkyl alkoxylates with medium branched chain, BAEx, where x is 1-30, as discussed in US patent No. 6,153,577, US patent No. 6,020,303, and US patent No. 6,093. 856; f) alkyl polysaccharides as discussed in US Patent No. 4,565,647 to Llenado, issued January 26, 1986; specifically poly glycoside alkyl as discussed in US Patent No. 4,483,780 and US Patent No. 4,483,779; g) Polyhydroxy fatty acid amides as discussed in US Patent No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) finished ether poly (oxyalkylated) alcohol surfactant as discussed in US Patent No. 6,482,994 and WO 01/42408.
[00118] In the laundry detergent compositions of the present invention, the detersive surfactant component may comprise combinations of anionic and non-ionic surfactant materials. When this is the case, the weight ratio between anionic and nonionic material is typically in the range of 10:90 to 90:10, more typically from 30:70 to 70:30.
[00119] Cationic surfactants are well known in the art, and some non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms. Additional examples include a) quaternary ammonium alkoxylate (AQA) surfactants as discussed in US Patent No. 6,136,769; b) dimethyl hydroxy ethyl quaternary ammonium as discussed in US Patent 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 US patents No. 4,228,042, 4,239,660 4,260,529 and US patents No. 6,022,844; and e) amino surfactants as discussed in US Patent No. 6,221,825 and WO 00/47708, specifically dimethyl starch propylamine (APA).
[00120] Non-limiting examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of secondary and tertiary heterocyclic amines or quaternary ammonium derivatives, quaternary phosphonium compounds or tertiary sulfonium. See US patent No. 3,929,678 issued to Laughlin et al., On December 30, 1975, from column 19, line 38 to column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl starch propyl betaine, C8 to C18 (in a C12 to C18 aspect) oxides of amine and sulfo and hydroxy betaines such as N-alkyl-N, N-dimethylamino-1-propanesulfonate where the alkyl group can be C8 to C18, or C10 to C14.
[00121] Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of secondary or tertiary heterocyclic amines in which the aliphatic radical can be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, for example carboxy, sulfonate or sulfate. See US patent No. 3,929,678, issued to Laughlin et al., On December 30, 1975, in column 19, lines 18 to 35, for examples of ampholytic surfactants. Non-active aqueous liquid surface vehicle
[00122] As noted, compositions for laundry care may be in the form of a solid, either in the form of a tablet or particulate, including, but not limited to, particles, flakes, plates, or the like, or the compositions may be in the form of a liquid. The liquid detergent compositions may comprise a non-active aqueous liquid surface vehicle. Generally, the amount of the aqueous, non-active liquid surface vehicle employed in the compositions of the present invention will be effective in solubilizing, suspending or dispersing the components of the composition. For example, liquid detergent compositions can comprise, based on the total weight of the liquid detergent composition, from about 5% to about 90%, from about 10% to about 70%, or about 20% about 70% non-active aqueous liquid surface vehicle.
[00123] The type of aqueous liquid vehicle with the best cost-benefit ratio is typically water. Consequently, the water-based non-active liquid vehicle component will generally comprise most, if not all, water. Although other types of water-miscible liquids, such as alkanols, diols, other polyols, ethers, amines and the like, have conventionally been added to liquid detergent compositions as cosolvents or stabilizers, for the purposes of the present invention the use of such miscible liquids in water is typically minimized to keep the cost of the composition low. Accordingly, the aqueous liquid carrier component of liquid detergent products of the present invention will generally comprise water present in concentrations ranging from about 5% to about 90%, or from about 5% to about 70% by weight , of the liquid detergent composition.
[00124] Liquid compositions can be structured as described in EP-A-1328616 or EP-A-1396536. Bleaching Agents
[00125] Bleaching agents - The cleaning compositions of the present invention can comprise one or more bleaching agents. Suitable bleaching agents, other than bleaching catalysts, include photoactivated bleaches, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids and combinations thereof. In general, when a bleaching agent is used, the compositions of the present invention can comprise from about 0.1% to about 50%, or even from about 0.1% to about 25% of bleaching agent, by weight of the present cleaning composition. Examples of suitable bleaching agents include: (1) photoactivated bleaches, for example sulfonated zinc phthalocyanine; (2) preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example Oxzone®, and combinations thereof. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids that have the formula R- (C = O) OOM, where R is an optionally branched alkyl group that has, when the peracid is hydrophobic, 6 to 14 carbon atoms, or 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and M is a counterion, for example, sodium, potassium or hydrogen; (3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium perborate salts (usually mono or tetrahydrate), percarbonate, persulfate, phosphate and persilicate salts, and combinations thereof . In one aspect of the invention, inorganic perhydrate salts are selected from the group consisting of perborate, percarbonate sodium salts, and combinations thereof. When used, inorganic perhydrate salts are typically present in amounts of 0.05% to 40%, or 1% to 30%, by weight of the total composition, and are typically incorporated into these compositions in the form of of a crystalline solid that can be coated. Suitable coatings include inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and (4) targeting activators that have R- (C = O) -L where R is an alkyl group, optionally branched, which has, when the targeting activator is hydrophobic, 6 to 14 carbon atoms, or 8 to 12 carbon atoms and, when the bleaching activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group. Examples of suitable leaving groups are benzoic acid and derivatives thereof, especially benzene sulfonate. Suitable bleach activators include dodecanoyl oxybenzene sulfonate, decanoyl oxybenzene sulfonate, decanoyl oxybenzoic acid or its salts, 3,5,5-trimethylhexanoyloxybenzene sulfonate, tetraacetyl ethylene diamine (TAED) and nonanoyl oxybenzene sulfonate (NOBS). Suitable bleach activators are also disclosed in WO 98/17767. Although any suitable bleach activator can be used, in one aspect of the invention the present cleaning composition can comprise NOBS, TAED or mixtures thereof.
[00126] When present, the peracid and / or bleach activator is generally present in the composition in an amount of about 0.1% to about 60%, from about 0.5% to about 40%, or even from about 0.6% to about 10% by weight, based on the composition. One or more hydrophobic peracids or precursors thereof can be used in combination with one or more hydrophilic peracids or precursors thereof.
[00127] The amounts of the hydrogen peroxide source and peracid or bleach activator can be selected so that the molar ratio between the available oxygen (from the peroxide source) and the peracid is from 1: 1 to 35: 1 or even 2: 1 to 10: 1.
[00128] Bleach reinforcement compounds - The compositions of the present invention can comprise one or more bleach reinforcement compounds. Bleach reinforcement compounds provide increased bleaching efficiency in lower temperature applications. Bleach boosters act in conjunction with conventional sources of peroxygen bleaching to provide increased bleaching efficiency. This is usually accomplished through the local formation of an active oxygen transfer agent such as dioxirane, oxaziridine or oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines and oxaziridines can be used.
[00129] Among the bleach reinforcing compounds suitable for use according to the present invention are cationic imines, zwitterionic imines, anionic imines and / or polyionic imines that have a net charge of about +3 to about -3, and mixtures thereof. Those imine-based bleach booster compounds of the present invention include those having the general structure:

[00130] wherein R1 - R4 can be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.
[00131] Suitable targeting reinforcement compounds include zwitterionic targeting reinforcements, which are described in US Patent Nos. 5,576,282 and 5,718,614. Other targeting reinforcement compounds include cationic targeting enhancers described in US Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.
[00132] The composition may comprise metal bleach catalyst which typically comprises copper, iron, titanium, ruthenium, tungsten, molybdenum, and / or manganese cations. Suitable transition metal bleaching catalysts include iron-based or manganese-based transition metal bleaching catalysts, preferably manganese-based transition metal bleaching catalysts.
[00133] Sources of peroxygen are well known in the art and the source of peroxygen employed in the present invention can comprise any of these well-known sources, including peroxygen compounds as well as compounds that, under the conditions of consumer use, provide an effective amount of peroxygen locally. The source of peroxygen may include a source of hydrogen peroxide, the local formation of a peracid by reacting a source of hydrogen peroxide and a bleach activator, preformed peracid compounds or mixtures of suitable sources of peroxygen. Obviously, one skilled in the art will recognize that other sources of peroxygen can be employed without departing from the scope of the invention. Bleach reinforcing compounds, when present, are typically employed in conjunction with a source of peroxygen in the bleaching systems of the present invention.
[00134] An adequate source of available oxygen (AvOx) is a source of hydrogen peroxide, such as percarbonate salts and / or perborate salts, such as sodium percarbonate. The source of peroxygen can be at least partially coated, or even completely coated, by a coating ingredient such as a carbonate salt, a sulfate salt, a silicate salt, borosilicate or any mixture of these materials, including mixed salts thereof. Suitable percarbonate salts can be prepared by a fluidized bed process or by a crystallization process. Suitable perborate salts include sodium perborate monohydrate (PB1), sodium perborate tetrahydrate (PB4), and anhydrous sodium perborate which is also known as effervescent sodium perborate. Other suitable sources of AvOx include percarbonate, such as oxone. Another suitable source of AvOx is hydrogen peroxide.
[00135] The composition may comprise a reducing bleach. However, the composition can be substantially free of reducing bleach; substantially exempt means "nothing deliberately added". Suitable reducing bleach includes sodium sulfite and / or thiourea dioxide (TDO).
[00136] The composition may comprise a co-bleaching particle. Typically, the coalescing particle comprises a bleach activator and a source of peroxide. It may be highly appropriate that a large amount of bleaching activator in relation to the source of hydrogen peroxide is present in the coalvious particle. The weight ratio of bleach activator to hydrogen peroxide source present in the coalescing particle can be at least 0.3: 1, or at least 0.6: 1, or at least 0.7: 1, or at least 0 , 8: 1, or at least 0.9: 1, or at least 1.0: 1.0, or even at least 1.2: 1 or more. The coalescing particle may comprise: (i) a bleaching activator, such as TAED, and (ii) a source of hydrogen peroxide, such as sodium percarbonate. The bleach activator can at least partially, or completely, involve the source of hydrogen peroxide. The coalescing particle can comprise a binder. Suitable binders are carboxylate polymers such as polyacrylate polymers and / or surfactants that include non-ionic detersive surfactants and / or anionic detersive surfactants such as C11-C13 linear benzene sulfonate. The coalescing particle can comprise bleaching catalyst, such as an oxaziride-based bleaching catalyst.
[00137] Suitable glossing agents are stilbens, as a glossing agent 15. Other suitable glossing agents are hydrophobic glossing agents and glossing agent 49. The glossing agent can be in the form of micronized particulate, with a medium size weighted particle in the range of 3 to 30 micrometers, or from 3 micrometers to 20 micrometers, or from 3 to 10 micrometers. The brightening agent can be alpha or beta crystalline form.
[00138] The composition preferably comprises whitener, preferably Cl fluorescent whitener 260. The whitener preferably has the following structure:

[00139] The fluorescent lightener C.l. 260 is preferably predominantly in alpha-crystalline form. The term "predominantly in alpha-crystalline form" means that preferably at least 50% by weight, or at least 75% by weight, or even at least 90% by weight, or at least 99% by weight, or even substantially all of the fluorescent whitening Cl 260 is in alpha-crystalline form.
[00140] The fluorescent lightener C.l. 260 may be in the form of micronized particulate, typically having an average primary particle size weight of 3-30 micrometers, preferably 3 micrometers to 20 micrometers, and more preferably 3 to 10 micrometers; this is particularly preferable when the C.l. 260 is predominantly in beta-crystalline form. Predominantly in beta-crystalline form means that preferably at least 50% by weight, or at least 75% by weight, or even at least 90% by weight, or at least 99% by weight, or even substantially all the fluorescent whitener Cl 260 is in beta-crystalline form.
[00141] Enzymatic targeting - Enzymatic systems can be used as targeting agents. Hydrogen peroxide can also be present by adding an enzyme system (ie, an enzyme and a substrate, therefore) that is capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing process. These enzyme systems are presented in patent application EP 91202655.6 filed on October 9, 1991.
[00142] The compositions and methods of the present invention can use alternative bleaching systems such as ozone, chlorine dioxide and the like. Bleaching with ozone can be accomplished by introducing ozone-containing gas that has an ozone content of about 20 to about 300 g / m3 in the solution that should come into contact with the tissues. The ratio of gas to liquid in the solution should be maintained from about 1: 2.5 to about 1: 6. US patent No. 5,346,588 describes a process for using ozone as an alternative to conventional bleaching systems and is incorporated herein by reference.
[00143] In one aspect, the active fabric softener (FSA) is a quaternary ammonium compound suitable for fabric softening in the rinse step. In one aspect, FSA is formed from a reaction product of a fatty acid and an amino alcohol obtaining mixtures of mono-, di-, and, in one aspect, triester compounds. In another aspect, the FSA comprises one or more quaternary ammonium softening compounds such as, but not limited to, a quaternary monoalkyl ammonium compound, a quaternary diamine compound and a diester quaternary ammonium compound, or a combination thereof.
[00144] In one aspect of the invention, the FSA comprises a composition of quaternary ammonium diester compound (hereafter "WFD", quaternary ammonium diester). In certain aspects of the present invention, the compositions of WFD compounds also encompass a description of diamide FSAs and FSAs with mixed starch and ester bonds, as well as the aforementioned diester bonds, all mentioned in the present invention as WFD.
[00145] A first type of WFD ("WFD (1)") suitable as an FSA in the present CFSC includes a compound comprising the formula: {R4-m-N + - [(CH2) n-Y-R1] m} X-
[00146] wherein each substituent R is either hydrogen, C1-C6 medium chain, for example C1-C3 an alkyl or hydroxy alkyl group, for example, methyl, ethyl, propyl, ethyl hydroxyl and the like, poly (C2-3 alkoxy), for example, polyethoxy, group, benzyl, or mixtures thereof; each m is 2 or 3; each n is 1 to about 4, or 2; each Y is -O- (O) C-, -C (O) -O-, -NR-C (O) -, or -C (O) -NR- and it is acceptable for each Y to be the same or different; the sum of the carbons in each R1, plus one, when Y is -O- (O) C- or -NR-C (O) -, is C12-C22, or C14-C20, with each R1 being a hydrocarbyl group or substituted hydrocarbyl; it is acceptable for R1 to be unsaturated or saturated and branched or linear and in one respect it is linear; it is acceptable for each R1 to be the same or different and, typically, they are the same; and X- can be any anion compatible with the softener, suitable anions include, chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate, and nitrate, in one aspect, the anions are methyl chloride or sulfate. Suitable WFD compounds are typically constituted by the reaction of alkanolamines, such as MDEA (methyl diethanol amine) and TEA (triethanol amine) with fatty acids. Some materials that typically result from these reactions include N, N-di (acyl-oxyethyl) -N, N-dimethyl ammonium chloride or N, N-di (acyl-oxyethyl) -N, methyl hydroxyl ethyl N-methyl sulfate ammonium, the acyl group being derived from animal fats, unsaturated and polyunsaturated fatty acids, for example tallow, hardened tallow, oleic acid, and / or partially hydrogenated fatty acids, derived from vegetable oils and / or partially vegetable oils hydrogenated, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, talanol oil, rice bran oil, babassu oil, etc.
[00147] Some non-limiting examples of suitable fatty acids are mentioned in US patent 5,759,990 in column 4, lines 45 to 66. In one aspect, the FSA comprises other assets in addition to the WFD (1) or WFD. In yet another aspect, the FSA comprises only WFD (1) or WFD and is free, or essentially free, of any other quaternary ammonium compound or other actives. In yet another aspect, the FSA comprises the precursor amine that is used to produce the WFD.
[00148] In another aspect of the invention, the FSA comprises a compound, identified as DTTMAC which comprises the formula: [R4-m - - R1m] A-
[00149] where each m is 2 or 3, each R1 is a C6-C22, or C14-C20, but no more than one being less than about C12, and then the other is at least about 16, hydrocarbyl, substituted hydrocarbyl substituent, for example, C10-C20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, sometimes also called "alkylene"), in a C12-C18 alkyl or alkenyl aspect, and branched or unbranched. In one aspect, the iodine (IV) value of the FSA is about 1 to 70; each R is H or a C1-C6 short chain, or C1-C3 an alkyl or hydroxy alkyl group, for example, methyl, ethyl, propyl, ethyl hydroxy, and the like benzyl or (R2 O) 2-4H where each R2 is a C 1-6 alkylene group; and A- is an anion compatible with the softener, suitable anions include chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate or nitrate; in one respect, anions are methyl chloride or sulfate.
[00150] Examples of such FSAs include dialkyl dimethyl ammonium salts and dialkylene dimethylammonium salts, such as dimethyl ammonium syrup and dimethyl ammonium methyl sulfate. Examples of commercially available dialkylene-dimethyl ammonium salts useful in the present invention are dimethyl ammonium tallow chloride dihydrogen and di-tallow dimethyl ammonium chloride available from Degussa under the trade names Adogen® 442 and Adogen® 470, respectively. In one respect, the FSA comprises other active ingredients in addition to DTTMAC. In yet another aspect, the FSA comprises only DTTMAC compounds and is free, or essentially free, of any other quaternary ammonium compound or other actives.
[00151] In one aspect, the FSA comprises an FSA described in US Patent Publication No. 2004/0204337 A1, published on October 14, 2004 to Corona et al, paragraphs 30 - 79. In another aspect, the FSA is described in US Patent Publication No. 2004/0229769 A1, published on November 18, 2005, to Smith et al, in paragraphs 26-31; or US patent No. 6,494,920, in column 1, line 51 et seq. describing an esterquats or a quaternized fatty acid triethanolamine ester salt.
[00152] In one respect, the FSA is chosen from at least one of the following: di-hydrogenated tallow chloride oxyethyl dimethyl ammonium chloride, dimethyl ammonium tallow chloride dimethyl ammonium chloride, dimethyl ammonium chloride dimethyl ammonium chloride tallow oxyethyl dimethyl ammonium dihydrogen, tallow oxyethyl dimethyl ammonium dihydrogen, or combinations thereof.
[00153] In one aspect, the FSA may also include compositions of compounds containing amide. Examples of compounds comprising diamide may include, but are not limited to, methyl bis sulphate (tallow ethyl starch) -2-hydroxy ethylammonium (available from Degussa under the trade names Varisoft 110 and Varisoft 222). An example of an amide ester-containing compound is N- [3- (stearoyl amino) propyl] -N- [2- (stearoyloxy) ethoxy) ethyl)] - N-methylamine.
[00154] Another aspect of the present invention provides a fabric softening composition added during rinsing, further comprising a cationic starch. Cationic starches are disclosed in US 2004/0204337 A1. In one aspect, the fabric softener composition added during the rinse comprises from about 0.1% to about 7% cationic starch by weight of the fabric softener composition. In one respect, cationic starch is HCP401 available from National Starch.
[00155] In another aspect, the active fabric softener is a particle that comprises silicone and clay, such as polydimethylsiloxane and bentonite clay. The particle may also comprise anionic detersive surfactant, such as linear alkyl benzene sulfonate.
[00156] Builders - The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30%, by weight, of said builder. Builders include, but are not limited to, alkali metal, ammonium and ammonium alkali polyphosphate salts, alkali metal silicates, alkaline earth metal and alkali metal carbonates, polycarboxylate compounds from aluminum silicate builders, polycarboxylate hydroxy ether, copolymers of maleic anhydride with ethylene or methyl vinyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid and carboxy methyl-succinic oxide, the various salts of alkali metal, ammonium and ammonium polyacetic acids such as ethylenediamine tetra-acetic acid and nitrile triacetic acid, as well as polycarboxylates such as melitic acid, succinic acid, oxidisuccinic acid, polymalleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methyl succinic acid and soluble salts thereof.
[00157] In one aspect of the present invention, the laundry care composition is a particulate detergent composition for free flowing solid laundry, and may comprise builders selected from the group consisting of: zeolites; phosphates; citrates; and combinations of these items. The composition typically comprises from 0% by weight to 10% by weight of zeolite-based builder, or above 0% by weight, and 8% by weight, or 6% by weight, or 4 % by weight, or 3% by weight or 2% by weight, or even 1% by weight of a zeolite builder. The composition may even be substantially free of a zeolite-based builder; substantially exempt means "not deliberately added". Typical zeolite builders include zeolite A, Zeolite P, Zeolite MAP, zeolite X and zeolite Y. The composition typically comprises from 0% by weight to 10% by weight of phosphate-based builder, or above 0% by weight, and 8% by weight, or 6% by weight, or 4% by weight, or 3% by weight, or 2% by weight, or even 1% by weight of a base builder phosphate. The composition can even be substantially free of phosphate builder; substantially exempt means "not deliberately added". A typical phosphate-based builder is sodium tri-polyphosphate (STPP). A suitable citrate is sodium citrate. However, citric acid can also be incorporated into the composition, which can form citrate in the washing liquid.
[00158] Buffer and alkalinity source: Suitable buffers and alkalinity sources include carbonate salts and / or silicate salts and / or double salts such as burqueite.
[00159] Carbonate salt: A suitable carbonate salt is sodium carbonate and / or sodium bicarbonate. The composition can comprise bicarbonate salt. It may be suitable for the composition to comprise low levels of carbonate salt, for example, it may be suitable for the composition to comprise from 0% by weight to 10% by weight of carbonate salt, or up to 8% by weight, or up to 6% by weight, or up to 4% by weight, or up to 3% by weight, or up to 2% by weight, or even up to 1% by weight of carbonate salt. The composition may even be substantially free of the carbonate salt; substantially exempt means "not deliberately added".
[00160] The carbonate salt can have a weight average particle size of 100 to 500 micrometers. Alternatively, the carbonate salt can have a weight average particle size of 10 to 25 micrometers.
[00161] The composition may comprise from 0% by weight to 20% by weight of silicate salt, or up to 15% by weight, or up to 10% by weight, or up to 5% by weight, or up to 4% by weight, or even up to 2% by weight, and can comprise from above 0% by weight, or from 0.5% by weight, or even from 1% by weight of silicate salt. The silicate can be crystalline or amorphous. Suitable crystalline silicates include crystalline layered silicate, such as SKS-6. Other suitable silicates include 1.6R silicate and / or 2, OR silicate. A suitable silicate salt is sodium silicate. Another suitable silicate salt is sodium metasilicate.
[00162] The composition can comprise from 0% to 70%, by weight, of charge. Suitable fillers include sulfate salts and / or biocharge materials. A suitable biocharge material consists of agricultural waste treated with alkali and / or bleach. A suitable sulfate salt is sodium sulfate. The sulfate salt can have a weight average particle size of 100 to 500 micrometers, alternatively, the sulfate salt can have a weight average particle size of 10 to 45 micrometers.
[00163] Chelating agents - The compositions of the present invention may also optionally contain one or more copper, iron and / or manganese chelating agents. If used, chelating agents will generally comprise from about 0.1% by weight of the composition of the present invention to about 15%, or even from about 3.0% to about 15% by weight of the compositions of the present invention. Suitable chelators can be selected from: penta diethylene triamine acetate, diethylene triamine penta (methyl phosphonic acid), ethylenediamine-N'N'-disuccinic acid, ethylenediamine tetraacetate, ethylenediamine tetra (methylene phosphonic acid), hydroxyethane di phosphonic methylene), and any combination thereof. A suitable chelator is ethylenediamine-N'N'-disuccinic acid (EDDS) and / or diphosphonic hydroxyethane (HEDP). The laundry detergent composition may comprise ethylene diamine-N'N'-disuccinic acid or salt thereof. Ethylene diamine-N'N'-disuccinic acid can be in the form of S, S enantiomeric. The composition may comprise 4,5-dihydroxy-m-disodium salt of benzene disulfonic acid, N-glutamic acid, N-diacetic acid (GLDA) and / or its salts, 2-hydroxypyridine-1-oxide, Trilon P ™ available from BASF, Ludwigshafen, Germany. Suitable chelators can also be inhibitors of carbonate crystal formation. Suitable calcium carbonate crystal inhibitors can be selected from the group consisting of: 1-hydroxy ethane diphosphonic acid (HEDP) and its salts, N, N-dicarboxy methyl-2-aminopentane-1,5-dioic acid and its salts, 2-phosphonobutane-1,2,4-tricarboxylic acid and its salts, and any combination thereof.
[00164] The composition may comprise a growth inhibitor of calcium carbonate crystals, as one selected from the group consisting of: 1-hydroxy ethane diphosphonic acid (HEDP) and its salts, N, N-dicarboxy methyl-2-aminopentane acid -1,5-dioic and its salts, 2-phosphonobutane-1,2,4-tricarboxylic acid and its salts, and any combination thereof.
[00165] Photo-bleaches - Suitable are phthalocyanines sulfonated with zinc and / or ammonium.
[00166] Pigment transfer inhibiting agents - The compositions of the present invention may also contain one or more pigment transfer inhibiting agents. Suitable dye transfer inhibiting polymeric agents include, but are not limited to, polyvinyl pyrrolidone polymers, N-oxide polyamine polymers, N-vinyl pyrrolidone and N-vinyl imidazole copolymers, polyvinyl oxazolidones and polyvinyl imidazoles, or mixtures thereof. . When present in the compositions of the present invention, dye transfer inhibiting agents are in the range of about 0.0001%, about 0.01%, about 0.05% by weight of the composition for cleaning at about 10%, about 2%, or even about 1% by weight of the cleaning composition.
[00167] Dispersants - The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials are homo or copolymeric acids, or their salts, in which the polycarboxylic acid contains at least two carboxyl radicals separated from each other by no more than two carbon atoms.
[00168] Polymers - Suitable polymers include carboxylate polymers, polyethylene glycol polymers, polymers for releasing polyester dirt such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibiting polymers, polymers for dye lock as a condensation oligomer produced by condensation of imidazole and epichlorohydrin, optionally, in 1: 4: 1 ratio, polymers derived from hexamethylene diamine, and any combination thereof.
[00169] Suitable carboxylate polymers include random maleate / acrylate copolymer or polyacrylate homopolymer. The carboxylate polymer can be a polyacrylate homopolymer with a molecular weight of 4,000 Da to 9,000 Da, or 6,000 Da to 9,000 Da. Other suitable carboxylate polymers are copolymers of maleic acid and acrylic acid, and can have a molecular weight in 4,000 Da to 90,000 Da.
[00170] Suitable polyethylene glycol polymers include random graft copolymers comprising: (i) hydrophilic backbone comprising polyethylene glycol, and (ii) hydrophobic side chains selected from the group consisting of: C4- C25 group alkyl, polypropylene, polybutylene, C1-C6 saturated monocarboxylic acid vinyl ester, C1-C6 alkyl ester of acrylic or methacrylic acid and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol main chain can be in the range of 2,000 Da to 20,000 Da, or 4,000 Da to 8,000 Da. The molecular weight ratio of the polyethylene glycol main chain to the polyvinyl acetate side chains can be in the range of 1: 1 to 1: 5, or 1: 1.2 to 1: 2. The average number of graft sites per ethylene oxide units can be less than 1, or less than 0.8, the average number of graft sites per ethylene oxide units can be in the range of 0.5 to 0, 9, or the average number of graft sites per ethylene oxide units can be in the range of 0.1 to 0.5, or 0.2 to 0.4. A suitable polyethylene glycol polymer is Sokalan HP22.
[00171] Polyester polymers for dirt release have a structure as defined by one of the following structures (I), (II) or (III): (l) - [(OCHR1-CHR2) aO-OC-Ar-CO -] d (II) - [(OCHR3-CHR4) bO-OC-sAr-CO-] e (III) - [(OCHR5-CHR6) c-OR7] f
[00172] where: a, b and c are from 1 to 200; d, e and f are from 1 to 50; Ar is a 1,4-substituted phenylene; sAr is 1,3-substituted phenylene at position 5 with SOaMe; Me is H, Na, Li, K, Mg / 2, Ca / 2, AI / 3, ammonium, mono-, di-, tri-, or tetraalkyl ammonium with alkyl groups being C1-C18 alkyl or C2 -C10 hydroxy alkyl, or any mixture thereof;
[00173] R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C18 n or iso-alkyl; and
[00174] R7 is a straight or branched C1-C18 alkyl or a straight or branched C2-C30 alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group . Suitable polymers for releasing polyester dirt are terephthalate polymers having the structure of formula (I) or (II) above.
[00175] Polymers for releasing polyester dirt include the Repel-o-tex series of polymers such as Repel-o-tex SF2 (Rhodia) and / or the Texcare series of polymers such as Texcare SRA300 (Clariant).
[00176] Suitable amine polymers include polyethylene polymers, such as alkoxylated polyalkyleneimines, which optionally comprise a polyethylene block and / or polypropylene oxide.
[00177] The composition may comprise cellulosic polymers, such as polymers selected from alkyl cellulose, alkyl alkoxy alkyl cellulose, carboxy alkyl cellulose, alkyl carboxy alkyl, and any combination thereof. Suitable cellulosic polymers are selected from carboxy methyl cellulose, methyl cellulose, methyl hydroxy ethyl cellulose, methyl carboxy methyl cellulose, and mixtures thereof. Carbo methyl methyl cellulose can have a degree of substitution of methyl carboxy from 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da. Another suitable cellulosic polymer is hydrophobically modified carboxy methyl cellulose such as Finnfix SH- 1 (CP Kelco).
[00178] Other suitable cellulosic polymers can have a degree of substitution (DS) from 0.01 to 0.99 and a block degree (DB) such that DS + DB is at least 1.00 or DB + 2DS- DS2 is at least 1.20. The substituted cellulosic polymer can have a degree of substitution (DS) of at least 0.55. The substituted cellulosic polymer can have a block grade (DB) of at least 0.35. The cellulosic polymer substituted can have a DS + DB of 1.05 to 2.00. A suitable substituted cellulosic polymer is carboxy methyl cellulose.
[00179] Another suitable cellulosic polymer is cationically modified hydroxy ethyl cellulose. Suitable polymers include polymers derived from hexamethylene diamine, typically with the following formula: R2 (CH3) N + (CH2) 6N + (CH3) R2. 2X-
[00180] where X- is a suitable counterion, for example, chloride and R is a poly (ethylene glycol) chain with an average degree of ethoxylation from 20 to 30. Optionally, the poly (ethylene glycol) chains can be independently terminated with sulfate and / or sulfonate groups, typically with the charge being balanced by reducing the number of X- or counterions (in cases where the average degree of sulfation per molecule is greater than two), introduction of Y + counterions, for example, sodium cations.
[00181] Carboxylate modified polymers - suitable polymers are copolymers comprising (i) 50 to less than 98% by weight of structural units derived from one or more monomers containing carboxyl groups, (ii) 1 to less than 49% by weight of structural units derived from one or more monomers comprising sulfonate moieties and (iii) 1-49% by weight of structural units derived from one or more types of monomers selected from monomers containing an ether bond represented by the formulas (I) and (II): Formula (I):

[00182] in Formula (I), Ro represents a hydrogen atom or a CH3 group, R represents a CH2 group, CH2CH2 group or single bond, X represents a number 0-5 (since X represents a number 1-5 when R is single bond), and Ri is a hydrogen atom or Ci to C20 organic group, Formula (II)

[00183] In Formula (II), Ro represents a hydrogen atom or a CH3 group, R represents a CH2 group, a CH2CH2 group or a single bond, X represents a number 0-5, and Ri is a hydrogen atom or Ci to C20 organic group.
[00184] Enzymes - The compositions can comprise one or more detergent enzymes, which provide benefits of cleaning performance and / or tissue treatment. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pululanases, tannases, tannases , malanases, β-glycanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases or mixtures thereof. A typical combination is a cocktail of conventionally applicable enzymes, such as protease, lipase, cutinase and / or cellulase, together with amylase.
[00185] The composition can comprise a protease. Suitable proteases include metalloproteases and / or serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such a suitable protease may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease can be a serine protease, such as an alkaline microbial protease and / or a trypsin-like protease. Examples of suitable neutral or alkaline proteases include: (a) subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO), Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BAC), SUBT_B Bacillus pumilus (P07518) and Bacillus gibsonii (DSM14391). (b) trypsin-like or chymotrypsin-like proteases, such as trypsin (e.g., of porcine or bovine origin), including Fusarium protease and Cellumonas-derived chymotrypsin proteases (A2RQE2). (c) metalloproteases, including those derived from Bacillus amyloliquefaciens (P06832, NPRE_BACAM).
Suitable proteases include those derived from Bacillus gibsonii or Bacillus Lentus such as subtilisin 309 (P29600) and / or DSM 5483 (P29599).
[00187] Suitable commercially available protease enzymes include: those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase® , Everlase® and Esperase® from Novozymes A / S (Denmark); those sold under the trade name Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® from Genencor International; those sold under the trade name Opticlean® and Optimase® from Solvay Enzymes; those available from Henkel / Kemira, namely BLAP (P29599 with the following mutations S99D + S101 R + S103A + V104I + G159S), and variants thereof including BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D) , BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) all from Henkel / Kemira; and KAP (Bacillus alkalophilus subtilisin with A230V + S256G + S259N mutations) from Kao.
[00188] Suitable amylases are alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A suitable alkaline alpha amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., Like Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM 9375, DSM 12368, DSMZ No. 12649, KSM AP1378, KSM K36 or KSM K38. Suitable amylases include: (a) alpha-amylase derived from Bacillus licheniformis (P06278, AMY_BACLI), and variants thereof, specifically variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128 , 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391,408 and 444. (b) amylase AA560 (CBU30457, HD066534) and variants thereof, especially variants with one or more substitutions in the following positions: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471,482, 484, which optionally also contain the D183 * and G184 * deletions. (c) variants that show at least 90% identity with the naturally occurring enzyme of Bacillus SP722 (CBU30453, HD066526), specifically variants with deletions at positions 183 and 184.
[00189] Suitable commercially available alpha-amylases are Duramyl®, Liquezyme® Termamyl®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme®, Stainzyme Plus®, Fungamyl® and BAN® (Novozymes A / S), Bioamylase® and variants thereof (Biocon India Ltd.), Kemzym® AT 9000 (Biozym Ges. mbH, Austria), Rapidase®, Purastar®, Optisize HT Plus®, Enzysize®, Powerase® and Purastar Oxam®, Maxamyl® (Genencor International Inc.) and KAM® (KAO, Japan). Suitable amylases are Natalase®, Stainzyme® and Stainzyme Plus®.
[00190] The composition can comprise a cellulase. Suitable cellulases include those of bacterial or fungal origin. Included are mutants chemically modified or obtained by protein engineering. Suitable cellulases include cellulases of the genus Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example, fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum.
[00191] Commercially available cellulases include Celluzyme® and Carezyme® (Novozymes A / S), Clazinase® and Puradax HA® (Genencor International Inc.), and KAC-500 (B) ® (Kao Corporation).
[00192] Cellulase may include microbial-derived endoglucanases that exhibit endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), including an endogenous bacterial polypeptide to a member of the genus bacillus sp. AA349 and mixtures thereof. Suitable endoglucanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bagsvaerd, Denmark).
[00193] The composition may comprise a cleaning cellulase belonging to the family of glycosyl hydrolase 45 with a molecular weight of 17 kDa to 30 kDa, for example, endoglucanases sold under the trade name Biotouch® NCD, DCC and DCL (AB Enzymes , Darmstadt, Germany).
[00194] Suitable cellulases can also exhibit xyloglucanase activity, such as Whitezyme®.
[00195] The composition can comprise a lipase. Suitable lipases include those of bacterial or fungal origin. Included are mutants chemically modified or obtained by protein engineering. Examples of useful lipases include Humicola lipases (synonymous with Thermomyces), for example, H. lanuginosa (T. lanuginosus), or H. insolens, a pseudomonas lipase, for example, P. alcaligenes or P. pseudoalcaligenes, P cepacia, P. stutzeri, P. fluorescens, Pseudomonas sp. strain SD 705, P. wisconsinensis, Bacillus lipase, for example, from B. subtilis, B. stearothermophilus or B. pumilus.
[00196] The lipase can be a "first-cycle lipase", optionally a variant of the naturally occurring lipase from Thermomyces lanuginosus which comprises T231R and N233R mutations. The naturally occurring sequence is the 269 amino acids (amino acids 23 to 291) of the Swissprot accession number Swiss-Prot 059952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)). Suitable lipases would include those sold under the trade names Lipex®, Lipolex® and Lipoclean® from Novozymes, Bagsvaerd, Denmark.
[00197] The composition may comprise a lipase variant of Thermomyces lanuginosa (059952) having> 90% identity with the naturally occurring amino acid and comprising substitution (s) in T231 and / or N233, optionally, T231R and / or N233R.
[00198] Suitable xyloglucanase enzymes can have enzymatic activity for both xyloglucan and amorphous cellulose substrates. The enzyme can be a glycosyl hydrolase (GH) selected from the GH 5, 12, 44 or 74 families. The glycosyl hydrolase selected from the GH 44 family is particularly suitable. Suitable glycosyl hydrolases of the GH 44 family are the XYG1006 glycosyl hydrolase from Paenibacillus polyxyma (ATCC 832) and variants thereof.
[00199] Suitable pectate lyases are of naturally occurring types or variants of bacillus-derived pectate lyases (CAF05441, AAU25568) sold under the trade names Pectawash®, Pectaway® and X-Pect® (from Novozymes A / S, Bagsvaerd, Denmark).
[00200] Suitable mannanases are sold under the trade names Mannaway® (from Novozymes A / S, Bagsvaerd, Denmark), and Purabrite® (Genencor International Inc., Paio Alto, California).
[00201] Suitable targeting enzymes include oxidoreductases, for example, oxidases such as glucose, choline or carbohydrate oxidases, oxygenases, catalases, peroxidases, such as halo, chlorine, bromine, lignin, glucose or manganese peroxidases, dioxigenases or laccases (phenoloxidases, polyphenoloxidases ). Suitable commercial products are sold under Novozymes' Guardzyme® and Denilite® bands. It may be advantageous for additional organic compounds, specifically aromatics, to be incorporated with the targeting enzyme; These compounds interact with the targeting enzyme to enhance the oxidoreductase activity (intensifier) or to facilitate the electron flow (mediator) between the oxidizing enzyme and the stain, typically over strongly different redox potentials.
[00202] Other suitable targeting enzymes include peridrolases, which catalyze the formation of peracids from an ester substrate and source of peroxygen. Suitable peridrolases include Mycobacterium smegmatis peridrolase variants, variants called CE-7 peridrolases, and naturally occurring Carlsberg subtilisin variants that have peridrolase activity.
[00203] Suitable cutinases are defined by EC class 3.1.1.73, which optionally have at least 90% or 95%, or more optionally at least 98% identity with that of naturally occurring derived from a Fusarium solani, pseudomonas Mendocina or Humicola Insolens.
[00204] The relationship between the two amino acid sequences is described by the parameter "identity". For the purposes of the present invention, the alignment of two amino acid sequences is determined using the Needle program from EMBOSS package (http://emboss.org) version 2.8.0. The Needle program implements the global alignment algorithm described in Needleman, S. B. and Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453. The substitution matrix used is BLOSUM62, the penalty for opening a hole is 10, and the penalty for enlarging a hole is 0.5.
[00205] Enzyme Stabilizers - Enzymes for use in compositions, for example, detergents can be stabilized by various techniques. The enzymes used in this case can be stabilized by the presence of water-soluble sources of calcium and / or magnesium ions in the final compositions that supply these ions to the enzymes.
[00206] Perfumes - suitable perfumes include perfume microcapsules, polymer-assisted perfume delivery systems including Schiff / polymer based perfume complexes, perfume chords encapsulated in starch, zeolites loaded with perfume, volatile perfume chords and any combination thereof. A suitable perfume microcapsule is based on melamine formaldehyde, which comprises perfume which is encapsulated by a housing comprising melamine formaldehyde. It may be highly suitable for such perfume microcapsules to comprise cationic precursor material and / or cationic precursor material in the carcass, such as polyvinyl formamide (PVF) and / or cationically modified hydroxyethyl cellulose (catHEC).
Suitable fabric softening agents include clay, silicone and / or quaternary ammonium compounds. Suitable clays include montmorillonite clay, hectorite clay and / or laponite clay. A suitable clay is montmorillonite clay. Suitable silicones include aminosilicones and / or polydimethylsiloxane (PDMS). A suitable fabric softener is a particle comprising clay and silicone, such as a particle comprising montmorillonite clay and PDMS.
[00208] Suitable flocculants include polyethylene oxide; for example having an average molecular weight of 300,000 Da to 900,000 Da.
[00209] Suitable foam suppressants include silicone and / or fatty acid, such as stearic acid.
[00210] Suitable aesthetic particles include soap rings, lamellar aesthetic particles, gelatin microspheres, splashes of carbonate and / or sulfate salt, colored clay particles and any combination thereof.
[00211] pH profile - Typically, the composition has a pH profile such that when dissolved in deionized water at 20 ° C and a concentration of 2 g / L, the composition provides a washing solution having a balance pH 9.5-11, preferably 10-11. Alternatively, the composition can provide a pH profile such that: (i) 3 minutes after contact with water, the pH of the washing liquid is greater than 10; (ii) 10 minutes after contact with water, the pH of the washing liquid is greater than 9.5; (iii) 20 minutes after contact with water, the pH of the washing liquid is greater than 9.0; and (iv) optionally, the equilibrium pH of the washing liquid being in the range of above 7.0 to 8.5. This dynamic pH profile can be influenced by the reduction of the reserve alkalinity of the composition, for example, such that the composition has a reserve alkalinity to a pH of 7.5 or less than 15, and, delaying the release of acid to the washing solution, for example, by coating the acid source, such as citric acid coated with wax, or citric acid coated with palmitic acid. Alternatively, the composition may have a more neutral pH profile, for example, such that after dilution in deionized water to a concentration of 2 g / L at 20 ° C, the composition has a pH balance of 7.6 to 8.8. Production process
[00212] Liquid detergent compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, bleaching agent and certain other optional ingredients, some of which may normally be in solid form, having been combined with the normally liquid components of the composition, such as liquid nonionic ethoxylated alcohol, the aqueous liquid carrier and any other optional ingredients normally liquid. Such a solution, dispersion or suspension will have acceptable phase stability and, typically, a viscosity that is in the range of about 100 to 600 cps, or about 150 to 400 cps. For the purposes of this invention, viscosity is measured using a Brookfield LVDV-II + viscometer, using a No. 21 spindle.
[00213] The liquid detergent compositions of the present invention can be prepared by combining their components in any order that is convenient, and by mixing, for example by stirring, the resulting combination of components to form a stable phase liquid detergent composition . In a process for preparing these compositions, a liquid matrix is formed containing at least a large proportion or even substantially all of the liquid components, for example, non-ionic surfactant, non-active liquid surface vehicles and other optional liquid components, said liquid components carefully mixed by applying shear stirring to that combination of liquids. Rapid agitation with a mechanical stirrer, for example, can be useful. While shear agitation is maintained, substantially all of the anionic surfactants and solid ingredients can be added. Stirring of the mixture continues and, if necessary, can be increased to form a solution or a uniform dispersion of insoluble solid phase particles within the liquid phase. After some or all of the materials in solid form have been added to the mixture with stirring, particles of any enzyme material to be included, such as enzyme nuggets, are incorporated. As a variation of the composition preparation procedure described above, one or more of the solid components can be added to the mixture in the form of a solution or a paste of premixed particles with a minimum portion of one or more liquid components. After adding all the components of the composition, the mixing of the mixture continues for a period of time sufficient to form compositions having the indispensable characteristics of viscosity and stability of the phases. This often involves stirring for a period of about 30 to 60 minutes.
[00214] In an aspect of forming liquid detergent compositions, the bleaching agent is first combined with one or more liquid components, to form a blending agent premix, and this blending agent premix is added to a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, greater than 70% by weight, and even more specifically, greater than 90%, by weight, of the balance of components detergent composition for washing clothes. For example, in the methodology described above, both the bluing agent premix and the enzyme component are added in a final stage of component addition. In another aspect, the bleaching agent is encapsulated prior to addition to the detergent composition, the encapsulated blending agent is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the rest of the composition components. laundry detergent.
[00215] In a preferred embodiment of the invention, the composition is supplied in the form of a unitized dose, either in tablet form or preferably a composition comprising any form, such as liquid / gel / granules kept within a water-soluble film , in what is known as a containment bag or sachet. The product can be a bag with one or multiple compartments. Small multi-compartment shells are described in more detail in EP-A-2133410. Water soluble film
[00216] Film suitable for forming the small wrappers is soluble or dispersible in water, preferably has a solubility in water of at least 50%, preferably at least 75% or even at least 95%, as measured by the method described here after using a glass filter with a maximum pore size of 20 microns:
[00217] 50 grams ± 0.1 gram of material for containment bag is added in a pre-weighed 400 ml beaker and 245 ml ± 1 ml of distilled water is added. This is shaken vigorously on a magnetic stirrer set at 600 rpm for 30 minutes. The mixture is then filtered through a qualitative folded sintered glass filter, with pore size as defined above (max. 20 microns). The water is dried from the filtrate collected by any conventional method, and the weight of the remaining material (which is the dissolved or dispersed fraction) is determined. The percentage of solubility or dispersibility can then be calculated. Preferred film materials are preferably polymeric materials. The skin material, for example, can be obtained by casting, blow molding, extrusion or blow extrusion of the polymeric material, as known in the art.
[00218] The preferred polymers, copolymers or derivatives of these substances suitable for use as material for bags are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, amides of cellulose, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic / acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan and carrageenan. More preferably, the polymers are selected from water soluble polyacrylates and acrylate copolymers, methyl cellulose, sodium methyl cellulose carboxy, dextrin, ethyl cellulose, hydroxy ethyl cellulose, propyl methyl cellulose hydroxyl, maltodextrin, polymethacrylates and, most preferably, selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxy propyl methyl cellulose (HPMC), as well as from combinations of these substances. Preferably, the level of polymer in the bag material, for example a PVA polymer, is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000, most preferably from about 20,000 to 150,000.
[00219] Polymer mixtures can also be used as the pouch material. This can be advantageous for controlling the mechanical and / or dissolving properties of the compartments or bag, depending on their application and the needs to be met. Suitable mixtures include, for example, mixtures in which one polymer has a higher water solubility than that of the other polymer, and / or one polymer has a higher mechanical strength than that of another polymer. Mixtures of polymers having different weight average molecular weights are also suitable, for example, a mixture of PVA or a copolymer thereof with a weight average molecular weight of about 10,000 to 40,000, preferably approximately 20,000, and PVA or of a copolymer thereof having a weight average molecular weight of about 100,000 to 300,000, preferably approximately 150,000. Also suitable for use in the present invention are polymeric blend compositions, for example, which comprise hydrolytically degradable and water-soluble polymeric blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising approximately 1 to 35 % by weight of polylactide and about 65% to 99% by weight of polyvinyl alcohol. Preferred, for use in the present invention, are polymers that are from about 60% to about 98% hydrolyzed, preferably about 80% to about 90% hydrolyzed, to optimize the dissolution characteristics of the material.
[00220] Naturally, different film materials and / or films of different thicknesses can be used to make the compartments. A benefit of selecting different films is such that the resulting compartments can exhibit different characteristics of solubility or release.
[00221] Most preferred film materials are PVA films known under the reference trade name MonoSol M8630, M8900, H8779 (as described in applicant's co-pending application ref 44528 and 11599) and those described in US 6,166,117 and US 6,787,512 and PVA films corresponding solubility and deformability characteristics.
[00222] The film material of the present invention can also comprise one or more additive ingredients. For example, it may be beneficial to add plasticizers, for example, glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol and mixtures of these substances. Other additives include functional detergent additives to be applied to the wash water, for example, organic polymeric dispersants, etc. Process for the production of the water-soluble pouch
[00223] The process of the present invention can be carried out using any suitable equipment and method. However, multi-compartment bags are preferably produced using the horizontal filling process. The film is preferably moistened, more preferably, heated to increase its malleability. Most preferably, the method also involves using a vacuum to place the film in a suitable mold. The vacuum placement of the film in the mold can be for 0.2 to 5 seconds, preferably 0.3 to 3 or even more preferably, 0.5 to 1.5 seconds, once the film is on horizontal portion of the surface. This vacuum can preferably be such that it provides a pressure between -10 kPa (-100 mbar) to -100 kPa (-1000 mbar), or up to -20 kPa (-200 mbar) to -60 kPa (-600 mbar).
[00224] The molds in which the bags are produced can have any shape, length, width and depth, depending on the necessary dimensions of the bags. The molds can also vary in size and shape from one to the other, if desired. For example, it may be preferable that the volume of the small final wrappers is between 5 and 300 ml, or even 10 and 150 ml, or even 20 and 100 ml, and that the mold sizes are adjusted accordingly.
[00225] Heat can be applied to the film, in a process commonly called thermoforming, by any means. For example, the film can be heated directly by passing it under a heating element or through hot air, before feeding it on the surface or, when it is on the surface. Alternatively, it can be heated indirectly, for example, by heating the surface, or by applying a hot item on the film. With the utmost preference, the film is heated using an infrared light. The film is preferably heated to a temperature of 50 to 120 ° C, or even 60 to 90 ° C. Alternatively, the film can be moistened by any means, for example directly by spraying a wetting agent (including water, solutions of the film material or plasticizers for the film material) on the film, before feeding on the surface, or once on the surface, or indirectly, by moistening the surface or by applying a wet item on the film.
[00226] In the case of bags comprising powders, it is advantageous to pin the film for a number of reasons: first, to reduce the possibility of defects in the film during the formation of the bag. For example, defects in the film that cause the film to break can be generated if the film stretches too quickly. Second, to allow the release of any gases derived from the product contained in the bag, such as, for example, the formation of oxygen in the case of bleaching powders. Third, to allow the continued release of perfume. In addition, when heat and / or moistening is used, the pin can be used before, during or after using the vacuum, preferably during or before applying the vacuum. It is preferred, therefore, that each mold comprises one or more orifices that are connected to a system that can provide vacuum through these orifices, on the film above the orifices, as described in the present invention in more detail.
[00227] Once the film has been heated / moistened, it is placed in a suitable mold, preferably using a vacuum. The filling of the molded film can be carried out using any known method for filling (in motion) items. The method of maximum preference will depend on the shape of the product and the required filling speed. Preferably, the molded film is filled using in-line filling techniques. The filled open pouches are then closed, using a second film, using any suitable method. Preferably, this is also done while in a horizontal position and in constant, continuous movement. Preferably, the closure is carried out by continuously feeding a second material or film, preferably water-soluble film, on top and over the blanket of open bags and then, preferably, sealing the first film and the second film together, typically in the area between the molds and thus between the bags.
[00228] Preferred sealing methods include heat sealing, solvent welding, and solvent or wet sealing. It is preferred that only the area that is to form the seal is treated with heat or solvent. The heat or solvent can be applied by any method, preferably on the closing material, preferably only on the areas that are for forming the seal. If a weld, or wet seal, or a solvent is used, it may be preferable that heat is also applied. Preferred solvent or wet sealing / welding methods include selectively applying a solvent over the area between the molds, or on the closing material, for example, by spraying or stamping it on those areas, and then applying pressure on these areas to form the fence. Sealing mats and cylinders as described above (optionally also providing heat) can be used, for example.
[00229] The formed bags can then be cut with a cutting device. Cutting can be done using any known method. It may be preferable that the cut is also made in a continuous manner and, preferably, with a constant speed and, preferably, while in a horizontal position. The cutting device, for example, can be a sharp item or a hot item, so that in the second case, the hot item 'burns' through the film / sealing area.
[00230] The different compartments of a multi-compartment bag can be made together in a side-by-side style and consecutive bags are not cut. Alternatively, the compartments can be made separately. According to this process and preferential arrangement, the bags are produced according to the process comprising the steps of: a) forming a first compartment (as described above); b) forming a recess within part or all of the closed compartment formed in step (a), to generate a second molded compartment superimposed on the first compartment; c) fill and close the second compartments with a third film; d) prohibit said first, second and third films; and e) cutting the films to produce a bag with multiple compartments.
[00231] Said recess formed in step b is preferably achieved by applying vacuum to the compartment prepared in step a).
[00232] Alternatively, the second and, optionally, the third compartment (s) can be produced in a separate step and then combined with the first compartment as described in our copending order EP 08101442.5 which is incorporated herein by reference. A particularly preferred process comprises the steps of: a) forming a first compartment, optionally using heat and / or vacuum, using a first film in a first forming machine; b) filling said first compartment with a first composition; c) in a second forming machine, deform a second film, optionally with the use of heat and vacuum, to produce a second and, optionally, a third molded compartment; d) fill the second and, optionally, the third compartments; e) seal the second and, optionally, the third compartment with the use of a third film; f) place the second and, optionally, the sealed third compartments on the first compartment; g) seal the first, second and, optionally, the third compartments; and h) cutting the films to produce a multi-compartment pouch.
[00233] The first and second forming machines are selected based on their suitability to perform the above process. The first forming machine is preferably a horizontal forming machine. The second forming machine is preferably a rotating drum forming machine, preferably located above the first forming machine.
[00234] Additionally, it will be understood that, through the use of suitable feeding stations, it is possible to manufacture multiple compartment bags incorporating numerous different or different compositions and / or different or distinct liquid, paste or gel compositions.
[00235] As noted earlier, detergent compositions can be in solid form. Suitable solid forms include tablets and particulates, such as granular particles, flakes and sheet material. Various techniques for forming detergent compositions in these solid forms are well known in the art, and can be used in the present invention. In one aspect, for example, when the composition is in the form of a granular particle, the bleaching agent is provided in the form of a particulate, optionally including additional components, but not all components of the laundry detergent composition. The bleaching agent particulate is combined with one or more additional particulates containing the remainder of the laundry detergent composition components. In addition, the bleaching agent, which optionally includes, but not all, additional components of the laundry detergent composition, can be supplied in an encapsulated form, and the encapsulated bleaching agent is combined with the particles containing an equilibrium substantial amount of components of the laundry detergent composition.
[00236] The compositions of this invention, prepared as described earlier in this document, can be used to form aqueous washing solutions for use in washing fabrics. In general, an effective amount of these compositions is added to the water, for example in a conventional automatic washing machine, to form these aqueous laundry solutions. The aqueous washing solution thus formed is then brought into contact, typically under agitation, with the fabrics to be washed. An effective amount of the liquid detergent compositions added in the present invention to water to form aqueous washing solutions can comprise amounts sufficient to form between about 500 to 7,000 ppm of the composition in aqueous washing solution, or from about 1,000 to 3,000 ppm of the detergent compositions of the present invention will be provided in the aqueous wash solution.
[00237] Typically, the washing liquid is formed by contacting the laundry detergent with water in such an amount that the concentration of laundry detergent composition in the washing liquid is above 0 g / l to 5 g / l, or 1 g / l, and 4.5 g / l, or up to 4.0 g / l, or up to 3.5 g / l, or up to 3.0 g / l, or up to 2.5 g / l, or even up to 2.0 g / l, or even up to 1.5 g / l. The fabric washing method can be performed in a top-loading or front-loading automatic washing machine or it can be used in a hand-washing laundry application. In these applications, the washing liquid formed and the concentration of laundry detergent composition in the washing liquid are those of the main washing cycle. Any water intake during any optional rinsing step is not included when determining the volume of the washing liquid.
[00238] The washing liquid can comprise 40 liters or less water, 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less of water. The washing liquid can comprise from 0 to 15 liters, or from 2 liters to 12 liters, or even up to 8 liters of water. Typically, from 0.01 kg to 2 kg of fabric per liter of washing liquid is dosed in said washing liquid. Typically, 0.01 kg, or 0.05 kg, or 0.07 kg, or 0.10 kg, or 0.15 kg, or 0.20 kg, or 0.25 kg fabric per liter of washing liquid is dosed in said washing liquid. Optionally, 50 g or less, 45 g or less, 40 g or less, 35 g or less, 30 g or less, 25 g or less, 20 g or less, or even 15 g or less, or even 10 g or less of the composition are placed in contact with water to form the washing liquid. Method of use
[00239] Some of the products intended for the consumer presented in the present invention can be used to clean or treat a situs among others a surface or fabric. Typically, at least a portion of the situs is placed in contact with a modality of the Claimants' product intended for the consumer, in its pure form or diluted in an aqueous solution, for example an aqueous washing solution, and then the situs can be optionally washed and / or rinsed. In one aspect, a situs is optionally washed and / or rinsed, brought into contact with an aspect of the product intended for the consumer and then optionally washed and / or rinsed. For the purposes of the present invention, washing includes, but is not limited to, rubbing and mechanical agitation. The fabric can be the majority of fabrics capable of treating laundry or treating under normal consumer conditions. Liquids that can comprise the compositions shown can have a pH of about 3 to about 11.5. Such compositions are typically used in concentrations of about 500 ppm to about 15,000 ppm, in solution. When the wash solvent is water, the water temperature is typically in the range of about 5 ° C to about 90 ° C and, when the site comprises a fabric, the mass ratio between water and fabric is typically in the range of about 1: 1 to about 30: 1. Using one or more of the aforementioned methods results in a treated site. Examples
[00240] The following examples are provided to further illustrate the bleaching agents of the present invention; however, they are not to be construed as limiting the invention as defined in the claims attached to this document. In fact, it should be obvious to those skilled in the art that various changes and modifications can be made to this invention without departing from the scope and spirit of the invention. All parts and percentages given in these examples are expressed in weight except where indicated otherwise. Sample preparation and testing methods A. Sample Preparation
[00241] The following bis-azo dyes are prepared as described in the present invention. The UV-visible spectrum of each dye is determined by dissolving in a suitable solvent, typically water or methanol, at a concentration that gives an absorbance at lambda max of less than 1.0 at a path length of 1.0 cm. A Beckman Coulter DU 800 spectrophotometer was used to measure the UV-visible spectrum and determine the max lambda ("Àmax") of each sample. Example 1
[00242] To an aqueous suspension of 11.68 grams of p-acetamido benzene sulfonyl chloride cooled to 15-20 ° C is added 8.15 grams of 3- (2- (2-hydroxy ethoxy) ethoxy) -propylamine, at a rate sufficient to keep the temperature below 20 ° C. Aqueous sodium hydroxide solution is added as needed to maintain the pH at> 7. After 2 hours of stirring, the reaction is complete and 50 ml of concentrated hydrochloric acid is added, and the mixture was refluxed until the infrared spectrum indicated that the acetyl group was cleaved. The mixture is cooled to 0-5 ° C and 3.58 g of sodium nitrite is added to the mixture and is stirred for 2 hours. The resulting diazonium salt is added to a chilled solution of 6.85 g of 2-methoxy-5-methyl aniline in dilute aqueous hydrochloric acid, resulting in a dark reddish orange product. This product is further diazotized at 0-5 ° C by the addition of 3.58 g of sodium nitrite with additional hydrochloric acid as necessary to maintain the pH at <2. The mixture is stirred for 2 hours. The resulting diazonium salt is added to a cooled solution (0-5 ° C) an aqueous solution of H-acid in water containing sufficient sodium hydroxide to dissolve the H- acid. The pH of the reaction mixture is maintained at 10-12 during the addition of the diazonium salt, by adding a sodium hydroxide solution as necessary. This resulted in a solution of the dark violet colored product represented by Formula BA4 in the present invention. The product has a Àmax of 569 nm in water. Example 2
[00243] The product represented by Formula BA13 of the present invention is prepared in a similar manner to example 1, except 7.65 grams of 2,5-di-methoxy aniline are replaced by 2-methoxy-5-methyl aniline. The product has an Àmax of 583 nm in water. Example 3
[00244] The product represented by the formula BA31 of the present invention is prepared in a similar manner to Example 1, except 9.75 grams of N-acetyl H are replaced by acid H. The product has an Àmax of 560 nm in water. Example 4
[00245] The product represented by the formula BA58 of the present invention is prepared in a similar manner to Example 1, except 15.75 grams of N-phenyl J are replaced by acid H. The product has an Àmax of 545 nm in water. Example 5
[00246] The product represented by the BA formula of the present invention is prepared in a similar manner to Example 2, except 15.75 grams of N-phenyl J are replaced by acid H. The product has an Àmax of 558 nm in water. Example 6
[00247] The product represented by the BA5 formula of the present invention is prepared in a similar manner to Example 1, except 8.85 grams of 3- (2- (2-methoxy ethoxy) ethoxy) -propylamine is replaced by 3- ( 2- (2-hydroxy ethoxy) ethoxy) -propylamine. The product has an Àmax of 577 nm in water. Example 7
[00248] The product represented by Formula BA14 of the present invention is prepared in a similar manner to example 6, except 7.65 grams of 2,5-di-methoxy aniline are replaced by 2-methoxy-5-methyl aniline. The product has a Àmax of 608 nm in methanol. Example 8
[00249] The product represented by the BA12 formula of the present invention is prepared in a similar manner to that of Example 7, except 30.70 grams of Surfonamine® B60 are replaced by 3- (2- (2-methoxy ethoxy) ethoxy) -propylamine . The product has an Àmax of 590 nm in water. Example 9
[00250] The product represented by the BA2 formula of the present invention is prepared in a similar manner to Example 6, except 52.90 grams of Surfonamine® L100 are replaced by 3- (2- (2-methoxy ethoxy) ethoxy) -propylamine. The product has an Àmax of 581 nm in water. Example 10
[00251] The product represented by the BA11 formula of the present invention is prepared in a similar manner to Example 8, except 52.90 grams of Surfonamine® L100 are replaced by 3- (2- (2-methoxy ethoxy) ethoxy) -propylamine. The product has an Àmax of 578 nm in water. Example 11
[00252] To a cold solution (0-5 ° C) of p-poly alkylene oxide phenylamine (27.45 g in 100 ml of water), containing sufficient hydrochloric acid to obtain a pH of 1, 3.58 are added g of sodium nitrite. The mixture is stirred for 2 hours. The mixture is then added to a cold solution of 7.65 g of 2,5-di methoxy aniline in dilute hydrochloric acid to give an orange product. This product is also diazotized by the addition of sufficient hydrochloric acid to maintain the pH at 1, followed by 3.58 g of sodium nitrite. After stirring for 2 hours at 0-5 ° C, the mixture is added to an aqueous solution of 15.85 grams of acid H, together with sufficient sodium hydroxide to dissolve the acid H. During the addition of the diazonium salt, the pH is maintained at 10-12 by the addition of aqueous sodium hydroxide solution. This resulted in a solution of the dark violet colored product represented by Formula BA18 in the present invention. The product has a Àmax of 574 nm in methanol. Example 12
[00253] The product represented by the BA15 formula of the present invention is prepared in a similar manner to Example 2, except 27.45 grams of p-poly alkylene oxide phenylamine are replaced by 3- (2- (2-hydroxy ethoxy) ethoxy) propylamine. The product has a Àmax of 574 nm in methanol. Example 13
[00254] The product represented by the BA17 formula of the present invention is prepared in a similar manner to Example 2, except 5.25 grams of diethanol amine are replaced with 3- (2- (2-hydroxy ethoxy) ethoxy) propylamine. The product has an Àmax of 581 nm in water. Example 14
[00255] The product represented by the BA1 formula of the present invention is prepared in a similar manner to Example 1, except 35.75 grams of Jeffamine® M715 are replaced with 3- (2- (2-hydroxy ethoxy) ethoxy) propylamine. The product has an Àmax of 578 nm in water. Example 15
[00256] The product represented by the BA28 formula of the present invention is prepared in a similar manner to Example 3, except 35.75 grams of Jeffamine® M715 are replaced with 3- (2- (2-hydroxy ethoxy) ethoxy) propylamine. The product has a Àmax of 563 nm in water. Example 16
[00257] The product represented by the BA55 formula of the present invention is prepared in a similar manner to Example 4, except 35.75 grams of Jeffamine® M715 are replaced with 3- (2- (2-hydroxy ethoxy) ethoxy) propylamine. The product has a Àmax of 545 nm in methanol. Example 17
[00258] The product represented by the BA34 formula of the present invention is prepared in a similar manner to Example 3, except 3.65 grams of diethylamine are replaced by 3- (2- (2-hydroxy ethoxy) ethoxy) propylamine. The product has an À max of 560 nm in water. Example 18
[00259] The product represented by the BA61 formula of the present invention is prepared in a similar manner to Example 17, except 15.75 grams of N-phenyl J are replaced by H N-acetyl acid. The product has a Àmax of 551 nm in methanol. Example 19
[00260] The product represented by Formula BA7 of the present invention is prepared in a similar manner to Example 17, except 15.90 grams of H acid are replaced by N-acetyl H acid. The product has a Àmax of 599 nm in methanol.
[00261] The bis-azo dyes shown in Table A generally conform to structure (II) and are prepared according to the methods described here. Table A: Bis-Azo dyes


[00262] Products * Surfonamine® and Jeffamine® are interrupted polyalkylene-oxy amino acid ethers available from Huntsman Corporation of The Woodlands, Texas, which have the general structure:

[00263] For Example 11, which generally conforms to Structure (I), R1 = OCH3, R2 = OCH3, R3 = 6-substituted acid, and X = p-poly alkylene oxide phenylazo.
[00264] The chemical names for the corresponding dyes in Table A are respectively provided in Table B below. Chemical names are determined using ChemDraw Ultra; Version 7.0.1, available from CambridgeSoft, Cambridge, Massachusetts, USA. Table B: Chemical names for bis-azo dyes


Structural representations of Examples 1-19 are provided here. B. Test Methods I. Method for assessing molar absorptivity (ε)
[00265] Molar absorptivity is determined by dissolving a known quantity of the compound in a suitable solvent and measuring the absorbance of the solution in an ultraviolet-visible spectrophotometer. Absorptivity is calculated by dividing the absorbance by the molar concentration in moles / liter and the trajectory length, which is typically one centimeter.
[00266] Fabric Wash: Each dye is passed in a simulated wash of CW120 (453.6 g (16 oz) of white cotton weave fabric with 270 g / square meter, cleared by the fluorescent whitening agent llvitex BNB, available with Test Fabrics. PO Box 26, Weston, PA, USA18643) using typical North American heavy duty detergent conditions ("NA HDL" or "HDL") (788 ppm, 20 ° C, 6 gpg 3: 1 Ca: Mg, ratio of 30: 1 liquid: fabric, 30 minutes) in six dilutions, with greater absorbance of washing water being set to a value close to 1.0 The fabrics are washed once for 5 minutes and air dried.
[00267] L *, a * and b * values are measured on each fabric (four internal replicates for each washing condition), using a Hunter LabScan XE reflectance spectrophotometer with D65 illumination, 10 ° viewer and UV filter excluded , and the difference values calculated against HDL reference null dye. II. Method for assessing specific deposition (AbsΔb ~ 2)
[00268] From the absorbance graph of the washing solution versus Δb *, the absorbance of the washing solution necessary to release the Δb * of -2.0 in the tissue is determined by linear interpolation of the two data points that group the target Δb *. III. Method for evaluating the relative pitch angle (0R) and Absolute pitch angle (0A)
[00269] From a lot of Δa * vs Δb * for each concentration point of a given compound, the value of Δa * Δb * = -2.0 is determined by interpolating the two data points that group Δb * = -2.0. The relative angle of the tint 0R is then calculated as 270 + arcotangent (| Δa * / Δb * |) for positive values of Δa * and 270 - arcotangent (| Δa * / Δb * |) where Δa * is negative.
[00270] The value of Δa * in Δb * = -2.0 is added to the value of a *, and -2.0 is added to the value of b * of a signal fabric washed in null-dye HDL (a * = 2.0; b * = -15.5; mean of 24 replicates). The absolute shade angle is determined in the concentration of dye that releases Δb * = -2.0, using the dye θ b COITIO dye defined below

[00271] The absolute tint angle 0A is calculated as 270 + arcotangent (| a * dye / b * dye |) for positive values of the dye θ 270 - arcotangent (| a dye / b dye |) where the dye is negative . IV. Method for assessing surface color
[00272] The surface color of an article can be quantified using a series of measurements - L *, a * and b * - generated by measuring the samples with a spectrophotometer. The equipment used for this test is a Gretag Macbeth Color Eye 7000A spectrophotometer. The software program used is "Color imatch." "L" is a measure of the amount of white or black in a sample; higher "L" values indicate a lighter color sample. A measure of the amount of red or green in a sample is determined by the "a *" values. A measure of the amount of blue or yellow in a sample is determined by the values of "b *". Lower (more negative) values of b * indicate more blue in a sample. V. Method for assessing tinting efficiency for detergents a.) Two 25 cm x 25 cm fabric samples of white cotton interlaced mesh with 453.6 grams (16 ounces) (270 g / square meter cleared by the agent fluorescent brightener Uvitex BNB, available from Test Fabrics (PO Box 26, Weston, PA, USA18643), are obtained. b.) Prepare two one-liter aliquots of tap water containing 1.55 g of AATCC standard heavy duty detergent (HDL) as shown in Table 3. c.) Add a sufficient amount of dye to be tested in one of the aliquots of step b.) above to produce an absorbance of aqueous solution of 1 AU. d.) Wash a sample from step a.) above in one of the water aliquots containing 1.55 g of AATCC standard heavy duty detergent (HDL) and wash the other sample in the other aliquot. This washing step must be carried out for 30 minutes at room temperature with agitation. After the washing step, rinse the samples separately in tap water and air dry the samples in the dark. e.) After rinsing and drying each sample, the tinting efficiency, DE * eff, of the dye is evaluated by determining the measurements of the L *, a * and b * values of each sample using a Hunter reflectance spectrophotometer LabScan XE with D65 illumination, 10 ° observer and excluded UV filter. The tinting efficiency of the dye is then calculated using the following equation: DE * eff = ((L * c - L * s) 2 + (a * c - a * s) 2 + (b * c - b * s) 2) 1/2
[00273] where subscribed "c" and "s" refer, respectively, to the L *, a * and b * values measured for the control, that is, for the fabric sample washed in dye-free detergent, and for the tissue sample washed in the detergent containing the dye to be tested. SAW. Wash removability assessment method a.) Prepare two 150 ml aliquots of the heavy duty liquid detergent solution presented in Table 1, according to the AATCC 61-2003 test method, test 2A and containing 1.55 g / liter of AATCC standard heavy duty liquid detergent formula in distilled water. b.) A 15 cm x 5 cm sample of each tissue sample of the Detergent Toning Efficiency Assessment Method described above is washed in a launderometer for 45 minutes at 49 ° C in 150 ml of a liquid detergent solution for heavy tasks prepared according to step II. a.) above. c.) The samples are washed with separate aliquots of washing water and air dried in the dark, then L *, a *, and b * measurements of the value of each sample are taken using a reflectance spectrophotometer Hunter LabScan XE with D65 illumination, 10 ° observer and UV filter excluded. The amount of residual staining is assessed by measuring the DE * res, calculated using the following equation: DE * res = ((L * c - L * s) 2 + (a * c - a * s) 2 + (b * c - b * s) 2) 1/2
[00274] where subscribed "c" and "s" refer, respectively, to the L *, a * and b * values measured for the control, that is, for the fabric sample initially washed in dye-free detergent, and for the tissue sample initially washed in the detergent containing the dye to be tested. The wash removal value for the dye is then calculated according to the formula:% removal = 100 x (1 - DE * res / DE * eff). VII. Method for assessing staining
[00275] This procedure uses three types of fabric to determine the propensity of a dye dissolved in a detergent matrix to dye fabric in a similar way to a domestic laundry pre-treatment scenario. The three primary fibers examined are cotton, nylon and spandex (a synthetic polymer having urethane blocks), which comprise the following fabrics: 16 oz. 453.6 grams (270 g / sq. llvitex BNB fluorescent whitening agent, obtained from Test Fabrics PO Box 26, Weston, PA, USA 18643), 178.6 grams (6.3 oz) 90% cotton / 10% Lycra®, stock # CLF, obtained from Dharma Trading Co., 1604 Fourth St. San Rafael, CA 94901, 80% Nylon I 20% Spandex, Item # 983684GN, obtained from Hancock Fabrics, One Fashion Way, Baldwyn, Mississippi 38824.
[00276] A 2.54 cm (one inch) diameter circle for each of the dyed detergent samples was extracted using a template and identified with the dye identification on the test fabrics with a non-staining textile marker acrylic paint (TEXPEN textile marker made by Mark-tex Corp, Englewood, NJ 07631).
[00277] The test fabrics were placed on top of a piece of backing paper with plastic backing, or alternatively, a single layer of paper towel on an aluminum sheet, and stained at intervals of 16 hours, 1 hour and 15 min. The staining was done by placing approximately 0.5 g of the dyed detergent on the fabric allowing it to be absorbed through the fabric with the excess being absorbed by the counter sheet, so that the circular test area was saturated with detergent without spreading to adjacent test circles. Due to the possible fading of the dyes by light, they were placed in a covered area to avoid direct exposure to light, while allowing air to pass through the fabrics. The 16 hour stains were applied at night, while the 1 hour and 15 minute samples were stained the next morning before washing. The approximate total amount of detergent applied is calculated by multiplying the total number of stained areas with the amount of detergent delivered to each stain. If this amount exceeds the recommended dose for the detergent then divide the total detergent by the recommended dosage to determine the number of washing loads for the distribution of the stained fabrics. If the stained fabrics do not provide the total recommended amount of detergent for the load, then the rest of the detergent is filled with Tide Free detergent (null dye).
[00278] The pre-treated fabrics are washed in a Kenmore full-scale washing machine with a top load with 2.5 kg (5.5 pounds) of cloths used as ballast under average US conditions of 64.4 liters ( 17 gallons) of 32.2 ° C (90 ° F) g / 0.1 per Liter (6 grains per gallon) of wash water hardness with a 15.6 ° C (60 ° F) / 0 rinse, 1 grams per liter (6 grains per gallon) of water hardness. After washing is complete, the test fabrics are ballasted dry in a forced air dryer heated to the highest temperature setting for 60 minutes, or until completely dry.
[00279] The areas of circled stains were analyzed using a Hunter Colorquest Labscan XE or with D65 illumination, not including UV filter and a 1.3 cm (0.5 ") door opening. A pretreatment of null dye stain control was used as a standard reference instrument for calculating ED * because the detergent contains bleach, visual assessment is done under fluorescent lights, with a white paper (92 gloss) as a background under the sample. Visual / DE * scale allows communication of stain intensity in a non-technical way Visual / DE * scale: <1 = 0 No visible coloring 1 - 2.5 = 1 slightly discolored area 2.5 - 5 = 2 light spot but visible 5-10 = 3 clearly visible stain> 10 = 4 a dark stain Test results Test 1: Determination of component parts of bis-azo dyes Table 1: Portions A, B and C used to build bleaching agents AN = NBN = NC.

Test 2: Determination of molar absorptivity of bis-azo dyes
[00280] The molar absorptivity (ε) of each example is given in Table 2. Table 2: Molar absorptivity of bis-azo dyes
Test 3: Determination of deposition and tint angle
[00281] Table 3 provides the hue angle and deposition for Examples 1 - 19. The data are classified by variation in components A, B and C, as previously determined.
[00282] Components A, B and C, as previously determined.



[00283] With regard to the data contained in Table 3, the angle of absolute hue describes the angle of actual shade of the fabric in the a *, b * plane. This is the angle that a consumer really sees when looking at the fabric. Relative shade angle is determined against a fabric marker washed in HDL null dye (ie, equal detergent, but without dye), and thus gives circulation within the a *, b * plane in relation to the control of null dye.
[00284] Thus, the bluing agent of the present invention can have an absolute tint angle in the range of 265 ° to 310 °, 265 ° to 300 °, 265 ° to 295 °, 270 ° to 295 °, 270 ° to 290 °, or even in the range of 273 ° to 287 °. Exemplary detergent formulations Formulations 1a - 11: Liquid detergent formulations
[00285] Tables 4A and 4B provide examples of liquid detergent formulations that include at least one bleaching agent of the present invention. The formulations are shown, in table 4A, as formulations 1a to 1f and in table 4B, as formulations 1g to 11. Table 4A - Liquid detergent formulations comprising Bluing Agent of the invention

Table 4B - Liquid detergent formulations comprising Bluing Agent of the invention


[00286] Footnotes of Formulations 1 al: 1 diethylene triamine penta-acetic acid, sodium salt 2 diethylene triamine acid pentaquis methylene phosphonic, sodium salt 3 ethylenediamine tetra-acetic acid, sodium salt 4 a non-toning dye or a mixture of dyes non-tinting used to adjust the color of formula 5 compact formula, packaged as a unit dose in polyvinyl alcohol film 6 bis-azos dye selected from Examples 1-19, preferably with tinting efficiency> 10 and wash removability of 30 -85% 7 Acusol OP301 Formulations 2a - 2e: Granular detergent formulations
[00287] Tables 5a and 5b provide examples of granular detergent formulations that include at least one bleaching agent of the present invention. The formulations are shown in table 5a as formulations 2a through 2e. Table 5a - Granular detergent formulations that comprise the Bluing Agent of the invention

1 Bis-azos dye selected from Examples 1 - 19, preferably with toning efficiency> 10 and Dirt removability of 30-85%. Table 5b - Granular detergent formulations comprising Bluing Agent of the invention



Exemplary compositions for tissue treatment Formulations 3a - 3d: Liquid compositions for tissue treatment
[00288] Table 6 provides examples of liquid compositions for treating fabrics, which include at least one bleaching agent of the present invention. The compositions are shown in Table 6 as Formulations 3a to 3d. Table 6 - Compositions of liquid for treatment of tissues comprising the bleaching agent of the invention

aN, N-di (tallow oxyethyl) -N, N-dimethyl ammonium chloride. b Cationic starch based on corn starch or common potato starch, containing 25% to 95% amylose and a substitution degree of 0.02 to 0.09, and with a viscosity measured as fluidity of water having a value of 50 to 84. c Ethylene oxide and terephthalate copolymer which has the following formula described in US patent 5,574,179 in column 15, lines 1 to 5, each X being methyl, each n is 40, u is 4, each R1 consists essentially of 1,4-phenylene moieties, each R2 essentially consists of ethylene, 1,2-prolylene moieties, or mixtures thereof. d Diethylene triamine pentaacetic acid. and KATHON® CG available from Rohm and Haas Co. f Silicone defoaming agent, available from Dow Corning Corp, under the trade name DC2310. 9 4,4'-bis- (2-sulfostyryl) disodium biphenyl, available from Ciba Specialty Chemicals. h Cocomethyl ethoxylated ammonium chloride [15], available from Akzo Nobel. 'bis-azo dyes selected from Examples 1 - 19, preferably with toning efficiency> 10 and wash removability of 30-85%. Exemplary dose unit compositions Table 7 - Liquid detergent compositions according to small wrappers


1 Mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (2-ethyl hexyl oxymethyl) -ethyl] sulfuric acid ester as described in US7169744 2PAP = Peroxicaproic phthaloylamino acid, as a wet compact at 70% 3 ethoxylated thiophene, EO (R1 + R2) = 5 4 RA = reverse alkalinity (g NaOH / dose)
[00289] Accordingly, the present invention provides a bleaching agent for textiles and / or paper substrates, which comprises at least one component comprising a biszo dye chromophore and at least one polymeric component. A laundry detergent composition and an added fabric treatment rinse containing such a bleaching agent is also contemplated in the present invention. * * *
[00290] Although particular aspects of the present invention have been illustrated and described, it should be apparent to those skilled in the art that various other changes and modifications can be made without departing from the character and scope of the invention. Therefore, it is intended to cover in the appended claims all such changes and modifications that fall within the scope of the present invention.
[00291] The dimensions and values presented in the present invention should not be understood as being strictly limited to the exact numerical values mentioned. Instead, unless otherwise specified, each of these dimensions is intended to mean both the mentioned value and a range of functionally equivalent values around that value. For example, a dimension displayed as "40 mm" is intended to mean "about 40 mm".
[00292] Each of the documents cited in the present invention, including any cross-reference, related patent or patent application, is hereby incorporated in its entirety, by way of reference, unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art in relation to any invention presented or claimed in this document, or that it, alone or in any combination with any other reference or references, teaches, suggest or present any invention like that. In addition, if there is a conflict between any meaning or definition of a term mentioned in this document and 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 will take precedence.

权利要求:
Claims (13)
[0001]
1. Laundry care composition characterized by comprising an ingredient for laundry treatment and a bleaching agent comprising: (a) at least one chromophore component comprising a bis-azo dye, and (b) at least one polymeric component or substituted sulfonamide component; where the bleaching agent has the following structure:
[0002]
2. Composition according to claim 1, characterized by the fact that the bluing agents Ri and R2 are independently selected from the group formed by H, alkyl, alkoxy, alkylene-oxy, alkyl terminated in alkylene-oxy and starch.
[0003]
Composition according to claim 1 or 2, characterized in that the bluing agent, Ri is an alkoxy group and R2 is an alkyl or alkoxy group.
[0004]
Composition according to any one of the preceding claims, characterized in that the bleaching agent comprises a polyoxyalkylene chain with 2 to 30, preferably with 2 to 10 repetition units.
[0005]
Composition according to any one of the preceding claims, characterized in that the bluing agent, X is a substituted group comprising a sulfonamide part and an optionally alkyl and / or aryl portion, and wherein the substituting group comprises at least an alkylene oxide chain comprising at least 4 portions of alkylene oxide.
[0006]
6. Laundry care composition according to any one of the preceding claims, characterized in that the bleaching agent comprises an alkoxylated bis-azo polymeric dye.
[0007]
7. Washing care composition according to any of the preceding claims, characterized by the fact that the chromophore of the bleaching agent has a maximum absorbance spectrum in water of 520 nanometers to 640 nanometers, preferably 560 nanometers to 610 nanometers.
[0008]
8. Washing care composition according to any of the preceding claims, characterized by the fact that the bleaching agent has an absolute shade angle in the range of 265 ° to 310 °, preferably from 273 ° to 287 °.
[0009]
9. Washing care composition according to any of the preceding claims, characterized by the fact that the bleaching agent has the following structure
[0010]
10. Laundry care composition according to claim 9, characterized in that Ri is alkoxy and R2 is alkyl.
[0011]
11. Washing care composition according to any one of the preceding claims, characterized by the fact that the composition comprises imine bleach reinforcing compounds having the general structure of:
[0012]
12. Washing care composition according to any one of the preceding claims, characterized in that the composition comprises dye transfer inhibiting agents.
[0013]
13. Laundry care composition according to any one of the preceding claims, characterized in that the composition is a free flowing solid particulate detergent composition, a liquid laundry detergent composition or a optimizing tissue composition optionally in the form of a unified dose.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-06-18| B06T| Formal requirements before examination|

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2020-04-07| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-07-07| B09A| Decision: intention to grant|

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2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/910,258|2010-10-22|

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