Laundry washing and care compositions, methods and test kits for determining authenticity

Abstract

The present disclosure provides a laundry care composition having at least one laundry care ingredient and at least one leuco composition conforming to formula (I): Ar 1 Ar 2 Ar 3 CH(I) wherein Ar 2 and Ar 3 are independently a carbocyclic aryl or a heteroaryl, and Ar 1 is selected from: unsubstituted phenyl, electron-deficient carbocyclic aryl and heteroaryl. The present disclosure also provides a method for determining a true laundry care composition and a test kit for detecting a true laundry care composition.

Description

Technical Field

[0001] This patent application describes laundry care compositions comprising at least one leuco composition and the use of these compositions in differentiating genuine products from counterfeit products. The leuco composition is provided in a stable, colorless or substantially colorless state and is incorporated into the laundry care composition. This patent application also relates to a method for determining a genuine laundry care composition comprising at least one leuco composition. This patent application also relates to a test kit for detecting a genuine laundry care composition comprising at least one leuco composition. Background Art

[0002] In the consumer packaged goods industry, the manufacture and sale of counterfeit products is an increasingly serious problem. Counterfeit products generally have lower quality compared to the branded products they imitate. Counterfeit products can have an adverse impact on the brand by diverting profits and associating a lower quality and less effective product with the brand name. Counterfeit products can also be dangerous to consumers. The use of low-quality and ineffective ingredients may harm consumers' health.

[0003] Currently, packaging solutions have been developed to reduce the risk of counterfeit products being sold as genuine. Such solutions include tamper-evident seals, the introduction of holograms and color-shifting inks in label graphics, and unique packaging designs. However, these solutions themselves can be counterfeited and are ineffective when filling counterfeit products into the original containers. Therefore, there remains a continuing need for a quick and easy method for detecting the authenticity of products that does not affect the quality or functionality of the products.

[0004] Therefore, it would be beneficial to provide compositions, rapid methods, and test kits for detecting the authenticity of products without affecting the quality or functionality of the products. Summary of the Invention

[0005] The present disclosure relates to a laundry care composition comprising at least one leuco composition, wherein the laundry care composition is a first color at any given time during manufacture, shipping, shelving, and normal product use. The leuco composition is capable of changing from a colorless or substantially colorless state to a colored state in the presence of a sufficient trigger, thereby causing the laundry care composition to change from the first color to a second color.

[0006] The present disclosure provides a laundry care composition comprising at least one laundry care ingredient and at least one leuco composition conforming to formula (I):

[0007] Ar 1 Ar 2 Ar 3 CH (I)

[0008] wherein Ar 2 and Ar 3 are independently a carbocyclic aryl or a heteroaryl, and Ar 1 is selected from: unsubstituted phenyl, electron-deficient carbocyclic aryl, and heteroaryl.

[0009] The present disclosure also provides a method for determining a genuine laundry and fabric care composition, the method comprising the steps of: a) providing a laundry and fabric care composition having a first color and comprising at least one laundry and fabric care ingredient and at least one leuco composition; b) adding a trigger to the laundry and fabric care composition, wherein the trigger is sufficient to effect a change of the at least one leuco composition from a colorless state to a colored state; and c) detecting a change of the laundry and fabric care composition from the first color to a second color, wherein the change from the first color to the second color is visually perceptible.

[0010] The present disclosure also provides a test kit for detecting a genuine laundry and fabric care composition, the test kit comprising: a) a container for containing a quantity of a laundry and fabric care product; b) a trigger, wherein the trigger converts a leuco composition; and c) instructions for mixing the laundry and fabric care product and the trigger to detect a genuine laundry and fabric care composition. Detailed Description

[0011] Definition

[0012] As used herein, the term "alkoxy" is intended to include C 1 -C 8 alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide, or propylene oxide.

[0013] As used herein, the interchangeable terms "alkyleneoxy" and "oxirane", and the interchangeable terms "polyalkyleneoxy" and "polyoxirane" generally refer to molecular structures comprising one or more than one of the following repeating units: -C 2 H 4 O-, -C 3 H 6 O-, -C 4 H 8 O- and any combination thereof. Non-limiting structures corresponding to these groups include, for example, -CH 2 CH 2 O-, -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 CH2 CH 2 O−, -CH 2 CH(CH 3 )O− and -CH 2 CH(CH 2 CH 3 )O−. In addition, the polyoxyalkylene component may be selected from one or more monomers selected from C 2-20 alkyleneoxy groups, glycidyl groups, or mixtures thereof.

[0014] The terms “ethylene oxide,” “propylene oxide,” and “butylene oxide” may be represented herein by their typical designations “EO,” “PO,” and “BO,” respectively.

[0015] As used herein, the terms “alkyl” and “alkyl - terminated” are intended to mean any monovalent group formed by removing a hydrogen atom from a substituted or unsubstituted hydrocarbon. Non - limiting examples include branched or unbranched, substituted or unsubstituted hydrocarbon moieties, which include C 1 -C 18 alkyl groups, and in one aspect, C 1 -C 6 alkyl groups.

[0016] As used herein, unless otherwise specified, the term “aryl” is intended to include C 3 -C 12 aryl groups. The term “aryl” refers to carbocyclic and heterocyclic aryl groups.

[0017] As used herein, the term “alkaryl” refers to any alkyl - substituted aryl substituent and aryl - substituted alkyl substituent. More specifically, the term is intended to refer to C 7-16 alkyl - substituted aryl substituents and C 7-16 aryl - substituted alkyl substituents, which may or may not contain additional substituents.

[0018] As used herein, the term “detergent composition” is part of a laundry care composition and includes cleaning compositions, including but not limited to products for washing fabrics. Such compositions may be pretreatment compositions used prior to the washing step, or may be rinse - added compositions, as well as cleaning aids such as bleach additives and “stain sticks” or pretreatment types.

[0019] As used herein, unless otherwise specified, the term "laundry care composition" includes detergents and / or fabric treatment compositions in the form of granules, powders, liquids, gels, pastes, unit dose bars, and / or sheet types, including but not limited to products for washing fabrics, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, and other products for fabric care and maintenance, and combinations thereof. Such compositions can be pretreatment compositions used prior to the washing step, or can be rinse - added compositions and cleaning aids such as bleach additives and / or "stain sticks" or pretreatment compositions, or substrate - loaded products such as dryer sheets.

[0020] As used herein, the term "leuco" (as used in connection with, for example, a compound, moiety, radical, dye, monomer, fragment, or polymer) refers to an entity (e.g., an organic compound or a moiety thereof) that undergoes one or more chemical and / or physical changes upon exposure to a particular chemical or physical trigger, where the chemical and / or physical changes result in a transition from a first color state (e.g., uncolored or substantially colorless) to a second, more highly colored state. Suitable chemical or physical triggers include, but are not limited to, changes in oxidation, pH, temperature, and exposure to electromagnetic radiation (e.g., light). Suitable chemical or physical changes occurring in the leuco entity include, but are not limited to, oxidation and non - oxidation changes such as intramolecular cyclization. Thus, in one aspect, a suitable leuco entity can be a reversibly reduced form of a chromophore. In one aspect, the leuco moiety preferably comprises at least first and second π - systems that are capable of converting, upon exposure to one or more of the above - mentioned chemical and / or physical triggers, into a third combined conjugated π - system that combines the first and second π - systems.

[0021] As used herein, the term "leuco composition" or "leuco colorant composition" refers to a composition comprising at least two leuco compounds having independently selected structures, as described in further detail herein.

[0022] As used herein, the "average molecular weight" of a leuco colorant is reported as the weight - average molecular weight as determined by its molecular weight distribution: due to its manufacturing process, the leuco colorants disclosed herein can contain a distribution of repeating units in their polymer moieties.

[0023] As used herein, the terms "maximum extinction coefficient" and "maximum molar extinction coefficient" are intended to describe the molar extinction coefficient at the maximum absorption wavelength (also referred to herein as the maximum wavelength) in the range of 400 nanometers to 750 nanometers.

[0024] As used herein, the term "first color" is used to refer to the color of a laundry care composition prior to triggering, and is intended to include any color, including colorless and substantially colorless.

[0025] As used herein, the term "second color" is used to refer to the color of a fabric washing and care composition after triggering, and is intended to include any color that can be distinguished from the first color of the fabric washing and care composition by visual inspection or by using analytical techniques such as spectrophotometric analysis.

[0026] As used herein, the term "converting agent" refers to any oxidizing agent known in the art other than molecular oxygen in any of its known forms (singlet and triplet).

[0027] As used herein, the term "triggering agent" refers to a reactant suitable for converting a leuco composition from a colorless or substantially colorless state to a colored state.

[0028] As used herein, the term "whitening agent" refers to a dye or a leuco colorant that forms a dye upon triggering, which provides a hue on white cotton fabric with a relative hue angle of 210 to 345, or even 240 to 320, or even 250 to 300 (e.g., 250 to 290).

[0029] As used herein, "cellulosic substrate" is intended to include any substrate that is at least mostly composed of cellulose by weight. Cellulose can be present in wood, cotton, linen, jute, and hemp. The cellulosic substrate can be in the form of powder, fiber, pulp, and articles formed from powder, fiber, and pulp. Cellulosic fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetates (cellulose acetate), triacetates (cellulose triacetate), and mixtures thereof. Articles formed from cellulosic fibers include textile articles such as fabrics. Articles formed from pulp include paper.

[0030] As used herein, when used in claims, articles such as "a" and "an" are understood to mean one or more of the substances claimed or described.

[0031] As used herein, the terms "comprising" and "including" are intended to be non-limiting.

[0032] As used herein, the term "solid" includes particulate, powder, bar, and tablet product forms.

[0033] As used herein, the term "fluid" includes liquid, gel, paste, and gas product forms.

[0034] The test methods disclosed in the test method section of this application are applied to determine the corresponding parameter values of the applicant's invention.

[0035] Unless otherwise indicated, all component or composition contents are based on the active portion of the component or composition and do not include impurities that may be present in commercially available sources of such components or compositions, such as residual solvents or by-products.

[0036] Unless otherwise indicated, all percentages and ratios are by weight. Unless otherwise indicated, all percentages and ratios are based on the total composition.

[0037] As used herein, the term "electron-deficient carbocyclic aryl group" refers to a C 3 -C 12 carbocyclic aryl group having an electron-withdrawing substituent covalently bonded to the aryl group.

[0038] As used herein, unless otherwise indicated, the term "heteroaryl" refers to a C 3 -C 12 aryl group in which at least one ring carbon has been replaced by a heteroatom selected from -O-, -S-, -N=, -N(R)-, and mixtures thereof, where R is not hydrogen.

[0039] The term "substituted heteroaryl" refers to a C 3 -C 12 aryl group in which at least one ring carbon has been replaced by a heteroatom selected from -O-, -S-, -N=, -N(R)-, and mixtures thereof, and in which an atom or group other than hydrogen is covalently bonded to any ring atom of the heteroaryl.

[0040] As used herein, the term "electron-donating substituent" refers to an atom or functional group that contributes a portion of its electron density to a conjugated π-system via resonance or inductive effects, thereby making the π-system more nucleophilic. When attached to a benzene molecule, an electron-donating substituent makes it more likely to participate in an electrophilic substitution reaction. Benzene itself will typically undergo substitution by an electrophile, but additional substituents can alter the reaction rate or product by electronically or sterically influencing the interaction of the two reactants. Electron-donating substituents are often referred to as activating groups. Suitable electron-donating substituents include, but are not limited to, tertiary amines (-NR 2 ), secondary amines (-NHR), primary amines (-NH 2 ), ethers (-OR), thioethers (-SR), hydroxyl (-OH), thiol (-SH), amides (-NHC(O)R), esters (-OC(O)R), alkyl groups (-R), phenyl groups (-C 6 H 5 ), and vinyl groups (e.g., -CH=CH 2 , -CH=CHR, -CR=CH 2 , -CR=CHR), where R represents an organic group.

[0041] As used herein, the term "electron-withdrawing substituent" refers to an atom or functional group that removes electron density from a π-system, making the π-system more electrophilic. When attached to a benzene molecule, an electron-withdrawing substituent makes electrophilic aromatic substitution reactions slower and more complex. Electron-withdrawing substituents are often referred to as deactivating groups. Suitable electron-withdrawing substituents include, but are not limited to, trihalides (e.g., -CF 3 , -CCl 3 ), cyano (-CN), sulfonate (-SO 3 H), sulfonate ester (-SO 3 R), sulfone (-SO 2 R), sulfoxide (-S(O)R), ammonium (-NH 3 +), quaternary ammonium (-NR 3 +), nitro (-NO 2 ), aldehyde (-C(O)H), ketone (-C(O)R), carboxylic acid (-COOH), carboxylic acid ester (-C(O)OR), acyl chloride (-C(O)Cl), amide (-C(O)NH 2 , -C(O)NHR, -C(O)NR 2 ) and halides (e.g., F). In the case where there are multiple substituents on a carbocyclic aryl group and the substituents are a mixture of electron-withdrawing substituents and electron-donating substituents, or the structure of the substituents is unknown, it is possible to determine whether the carbocyclic aryl group is electron-deficient by following the method of "determination of electron-deficient carbocyclic aromatic rings" as described herein. This method is followed only in the case where there is a mixture of electron-withdrawing substituents and electron-donating substituents.

[0042] Laundry care composition

[0043] This disclosure relates to laundry care compositions comprising a leuco composition. Leuco dyes are known to exhibit a change from a colorless or light-colored state to a colored state upon exposure to specific chemical or physical triggers. The resulting color change is generally visually perceptible to the human eye. The color change upon triggering results from a change in the molar attenuation coefficient (in some literature, also referred to as the molar extinction coefficient, molar absorption coefficient, and / or molar absorptivity) of the leuco dye molecule in the range of 400 - 750 nm.

[0044] Leuco dyes are also known as bluing agents or toners capable of masking fabric yellowing. These leuco dyes are capable of changing from a first color to a second color during the laundry process. These leuco dyes are also capable of depositing onto the fabric to achieve a whitening effect.

[0045] While traditional leuco dyes can be effectively used for the above purposes, they are not suitable for use as anti-counterfeiting agents because they change the appearance and functionality of the product and deposit onto the fabric when used.

[0046] It has now surprisingly been found that the color change of the laundry care composition containing the leuco composition claimed in the present invention occurs only when it is contacted with a sufficient trigger. In this way, the leuco composition does not affect the quality or functionality of the laundry care composition during manufacturing, shipping, shelf storage or use; it is only affected when testing authenticity. Additionally, the leuco composition may not deposit onto the fabric, thus maintaining the suitability of the composition for use with any fabric type and color.

[0047] The present disclosure relates to a laundry care composition comprising at least one laundry care ingredient and at least one leuco composition conforming to formula (I):

[0048] Ar 1 Ar 2 Ar 3 CH (I)

[0049] wherein Ar 2 and Ar 3 are independently a carbocyclic aryl or a heteroaryl, and Ar 1 is selected from: unsubstituted phenyl, electron-deficient carbocyclic aryl and heteroaryl. Ar 1 is preferably selected from unsubstituted phenyl, nitro-substituted carbocyclic aryl, furan, thiophene, pyridine and indole. More preferably, Ar 1 is furan. The representation of formula (I) above does not infer or limit in any way the arrangement of the substituent Ar groups.

[0050] As described above, the laundry care composition may comprise at least one laundry care component and at least one leuco composition conforming to formula (I), wherein at least one of Ar 2 and Ar 3 is a benzene ring substituted with an electron-donating group. The electron-donating group is preferably a substituted amine covalently bonded to the benzene ring at the para position of the carbon atom connecting the three Ar groups. More preferably, the substituted amine conforms to the formula –NR 4 R 5 , wherein each R 4 and R 5 is independently selected from H, C 1-16 branched alkyl, C 1-16 straight-chain alkyl, C 1-16 substituted branched alkyl, C 1-16 substituted straight-chain alkyl, C 7-16 substituted alkaryl, C 7-16 unsubstituted alkaryl, polyoxyalkylene and mixtures thereof.

[0051] Even more preferably, as described above, the fabric washing and care composition may comprise at least one fabric washing and care component and at least one leuco composition conforming to formula (I), wherein Ar 2 and Ar 3 are each a benzene ring having, covalently bonded to each benzene ring at the para position of the carbon atom connecting the three Ar groups, independently selected substituted amines. The substituted amines may conform to the formula –NR 4 R 5 , wherein each R 4 and R 5 is independently selected from H, C 1-16 branched alkyl, C 1-16 straight-chain alkyl, C 1-16 substituted branched alkyl, C 1-16 substituted straight-chain alkyl, C 7-16 substituted alkaryl, C 7-16 unsubstituted alkaryl, polyoxyalkylene, and mixtures thereof.

[0052] As described above, a fabric washing and care composition comprising at least one fabric washing and care component and at least one leuco composition conforming to formula (I) can resist deposition onto textiles, and thus the composition does not affect the quality or functionality of the fabric washing and care composition during use for washing textiles. The leuco composition can resist deposition onto textiles, for example, by having increased solubility in the wash water. When the leuco composition has a greater affinity for the wash water than for the textile, the leuco composition will have a low affinity for the textile. Thus, the leuco composition may comprise solubility-enhancing substituents. Such polar solubilizing groups can include both nonionic and ionic polar solubilizing groups.

[0053] As described above, the solubility-enhancing substituents can include substituted amines conforming to the formula –NR 4 R 5 , wherein at least one of R 4 and R 5 is polyoxyalkylene. At least two, at least three, and four of R 4 and R 5 can be polyoxyalkylene. One or more polyoxyalkylenes can be a polyethylene oxide polymer having 2 - 300 ethylene oxide repeating units. The polyoxyalkylene is preferably a polyethylene oxide polymer having 2 - 100 ethylene oxide repeating units. More specifically, it is preferably one or more polyethylene oxide polymers having 2 - 50 ethylene oxide repeating units. Preferably, at least one polyoxyalkylene polymer has at least three alkylene oxide repeating units, preferably ethylene oxide repeating units.

[0054] One or more polyoxyalkylenes can also be represented by formula (II):

[0055] -(EO)b (PO) c (II)

[0056] Wherein the polyalkylene oxide comprises b ethylene oxide units and c propylene oxide units in any sequence, wherein one such unit is covalently bonded to the nitrogen atom of the polyalkylene oxide-substituted amine. Preferably, the ethylene oxide (“EO”) unit is covalently bonded to the nitrogen atom of the polyalkylene oxide-substituted amine. The subscript b ranges from 2 to 300, preferably from 2 to 100, and more preferably from 2 to 15; and the subscript c represents the number of propyleneoxy (“PO”) units (if any) in the polyalkylene oxide and ranges from 0 to 60, preferably from 0 to 20, and more preferably from 0 to 10.

[0057] The affinity of the leuco composition for the textile can be measured by the mole % of the leuco composition deposited on the textile during a typical wash cycle. During a typical wash cycle, less than 10 mole %, preferably less than 5 mole %, more preferably less than 1 mole %, and even more preferably less than 0.5 mole % of the leuco composition in the laundry wash care composition is deposited on the textile.

[0058] During a typical wash cycle, it may be acceptable for the leuco composition to be substantially deposited on the textile. In the absence of sufficient trigger, the resistance of the leuco composition to conversion from a colorless or substantially colorless state to a colored state may cause deposition on textiles that are not visible to the user. Thus, the affinity of the leuco composition for the textile can be greater than 10 mole %, greater than 15 mole %, and even greater than 25 mole %.

[0059] The leuco compositions of the present disclosure may include those having formula (III):

[0060]

[0061] Wherein Ar 2 and Ar 3 are each a benzene ring having, covalently bonded to each benzene ring at the para position of the carbon atom connecting the three Ar groups, an independently selected substituted amine –NR 4 R 5 . Ar 1 is preferably an electron-deficient carbocyclic aryl group, wherein the subscript a is an integer from 1 to 5.

[0062] The leuco compositions of the present disclosure more preferably include those having formula (IV):

[0063]

[0064] Wherein Ar 1 is furan, and Ar 2 and Ar3 Each is a benzene ring, and the benzene ring has a substituted amine –NR covalently bonded to each benzene ring at the para position of the carbon atom connecting the three Ar groups 4 R 5 .

[0065] Even more preferably, the leuco compositions of the present disclosure include those having formula (IV):

[0066]

[0067] where each n is independently an integer from 2 to about 300, more preferably from 2 to about 100, even more preferably from 2 to 50, and most preferably each n is independently an integer from 2 to about 25; and each X is independently selected from H, alkyl, alkyl carboxylate, and aryl carboxylate. More preferably, each X is H.

[0068] The amount of the leuco colorant used in the laundry care composition of the present invention can be any content suitable for achieving the purpose of the present invention. In one aspect, the laundry care composition contains from about 0.0001% to about 1.0% by weight, preferably from 0.0005% to about 0.5% by weight, even more preferably from about 0.0008% to about 0.2% by weight, and most preferably from 0.004% to about 0.1% by weight of the leuco colorant.

[0069] In another aspect, the laundry care composition contains from 0.0025 to 5.0 meq / kg, preferably from 0.005 to 2.5 meq / kg, even more preferably from 0.01 to 1.0 meq / kg, and most preferably from 0.05 to 0.50 meq / kg of the leuco colorant, where the unit meq / kg refers to the number of milliequivalents of the leuco portion per kg of the laundry composition. For a leuco colorant containing more than one leuco portion, the number of milliequivalents is related to the number of millimoles of the leuco colorant by the following formula: (number of millimoles of the leuco colorant) x (number of milliequivalents of the leuco portion / number of millimoles of the leuco colorant) = number of milliequivalents of the leuco portion. In the case where only a single leuco portion is present per leuco colorant, the number of milliequivalents / kg will be equal to the number of millimoles of the leuco colorant / kg of the laundry care composition.

[0070] The molar extinction coefficient of the colored state at the maximum absorbance at wavelengths in the range of 200 to 1,000 nm (more preferably 400 to 750 nm) is preferably at least five times, more preferably 10 times, even more preferably 25 times, and most preferably at least 50 times the molar extinction coefficient of the colorless state at the wavelength of the maximum absorbance of the colored state. Preferably, the molar extinction coefficient of the colored state at the maximum absorbance at wavelengths in the range of 200 to 1,000 nm (more preferably 400 to 750 nm) is at least five times, preferably 10 times, even more preferably 25 times, and most preferably at least 50 times the maximum molar extinction coefficient of the colorless state in the corresponding wavelength range. Those of ordinary skill in the art will recognize that these ratios can be much higher. For example, the colorless state may have a maximum molar extinction coefficient as low as 10 M -1 cm -1 in the wavelength range of 400 to 750 nm, and the colored state may have a maximum molar extinction coefficient of up to 80,000 M -1 cm -1 or greater in the wavelength range of 400 to 750 nm, in which case the ratio of the extinction coefficients will be 8,000:1 or greater.

[0071] The maximum molar extinction coefficient of the colorless state at wavelengths in the range of 400 to 750 nm is less than 1000 M -1 cm -1 and the maximum molar extinction coefficient of the colored state at wavelengths in the range of 400 to 750 nm is greater than 5,000 M -1 cm -1 , preferably greater than 10,000, 25,000, 50,000 or even 100,000 M -1 cm -1 . Those skilled in the art will recognize and understand that polymers containing more than one leuco moiety may have significantly higher maximum molar extinction coefficients in the colorless state (e.g., due to the additive effect of the multiplicity of leuco moieties or the presence of one or more leuco moieties that convert to the colored state).

[0072] The colored state of the leuco composition may have a maximum absorbance at wavelengths of 400–700 nm (λ max) . Preferably, the λ max of the colored state of the leuco composition can be outside the range of 520 - 620 nm. More preferably, the λ max of the colored state of the leuco composition can be 625 - 655 nm.

[0073] Trigger

[0074] As used herein, a trigger is a reactant suitable for converting a leuco composition from a colorless or substantially colorless state to a colored state. Suitable triggers are any oxidizing agents known in the art other than molecular oxygen at atmospheric concentrations in its natural (triplet) state. Commercial products such as laundry care compositions will be exposed to such concentrations of molecular oxygen during manufacture, distribution through the supply chain (including shipping by car, truck, rail, boat, and airplane, with or without temperature control), shelf-life storage, or normal use as directed by the package instructions. The term "sufficient trigger" also does not refer to the concentration of oxidizing agent present in municipal water supplies that will be in contact with the laundry care composition during normal use.

[0075] The trigger can be a halogen bleaching compound that is in a solid state at 25 °C. Suitable hypochlorite-generating compounds are those water-soluble dry solid materials that generate hypochlorite ions upon contact with water or when dissolved in water. Non-limiting examples thereof are dry granular heterocyclic N-chloroimides such as trichlorocyanuric acid, dichlorocyanuric acid, and their salts such as sodium dichlorocyanurate and potassium dichlorocyanurate. Other N-chloroimides can be used, such as N-chlorosuccinimide, N-chloromaleimide, N-chlorophthalimide, and N-chloronaphthalimide. Other suitable N-chloroimides are hydantoins such as: 1,3-dichloro-5,5-dimethylhydantoin; N-monochloro-C,C-dimethylhydantoin; methylene-bis(N-chloro-C,C-dimethylhydantoin); 1,3-dichloro-5-methyl-5-isobutylhydantoin; 1,3-dichloro-5-methyl-5-ethylhydantoin; 1,3-dichloro-5,5-diisobutylhydantoin; 1,3-dichloro-5-methyl-5-n-pentylhydantoin; and so on. Other available hypochlorite-releasing agents are trichloromelamine and dry granular water-soluble anhydrous inorganic salts such as calcium hypochlorite, calcium hypochlorite tetrahydrate, and lithium hypochlorite.

[0076] The trigger can be selected from dichloroisocyanuric acid, alkali metal dichloroisocyanurates (which can be anhydrous or can be used in the form of their monohydrate and / or dihydrate), 1,3,5-trichloroisocyanuric acid, alkali metal 1,3,5-trichloroisocyanurates, N-chlorosulfonamides such as alkali metal N-chloro(4-toluene)sulfonamide ( T), N-chloroaminosulfonates, N-halogenosuccinimides such as N-chlorosuccinimide and / or N-bromosuccinimide, calcium hypochlorite (which can also be used in the form of its mixed salt with calcium chloride and calcium hydroxide, such as 3CaCl(OCl)·Ca(OH) 2 ·5H 2 O), and mixtures thereof. A preferred solid halogen bleaching compound suitable for use as a trigger is an alkali metal dichloroisocyanurate. Sodium is the preferred alkali metal, but lithium salts and potassium salts can also be used.

[0077] Hydride donors can be used as initiators. Suitable hydride donors can be selected from chloroquinones (tetrachloro-1,4-benzoquinone), tetrachloro-1,2-benzoquinone, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone), and mixtures thereof.

[0078] Highly preferred initiators for use in the present invention include sodium hypochlorite, calcium hypochlorite, sodium dichloroisocyanurate, alkali metal N-chloro(4-toluene)sulfonamide ( T), N-chloroaminosulfonates, N-bromosuccinimide, tetrachloro-1,2-benzoquinone, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone), and mixtures thereof.

[0079] The initiator can be liquid or solid. The initiator can be pre-packaged in single-dose aliquots. The initiator can also be in the form of tablets.

[0080] Product form

[0081] Liquid

[0082] When in liquid form, the fabric washing and care composition can be aqueous (usually more than 2% by weight, or even more than 5% or 10% by weight of total water, up to 90% by weight or up to 80% or 70% by weight of total water) or non-aqueous (usually less than 2% by weight of total water content). The composition can be in the form of an aqueous solution or a homogeneous dispersion or suspension of surfactants, leuco compositions, and certain optional other ingredients. Some of the ingredients are usually in solid form and can be mixed with the usually liquid components of the composition (such as liquid alcohol ethoxylate non-ions and aqueous liquid carriers). Such a solution, dispersion, or suspension can be acceptably phase-stable. When in liquid form, the viscosity of the fabric washing and care composition can be from 1 to 1500 centipoise (1 - 1500 mPa·s), preferably from 100 to 1000 centipoise (100 - 1000 mPa·s), and most preferably from 200 to 500 centipoise (200 - 500 mPa·s) at 20 s⁻¹ and 21 °C. The viscosity can be determined by conventional methods. The viscosity is measured using an AR 550 rheometer from TA Instruments, with a 40 mm diameter plate steel spindle and a gap size of 500 μm. The high shear viscosity at 20 s⁻¹ and the low shear viscosity at 0.05 - 1 can be obtained by a logarithmic shear rate sweep from 0.1 - 1 to 25 - 1 over a 3-minute period at 21 °C. Among them, the preferred rheological properties described herein can be achieved using the existing internal structure with detergent ingredients or by employing external rheology modifiers. The liquid detergent composition can have a high shear rate viscosity of about 100 centipoise to 1500 centipoise, more preferably 100 to 1000 cps. The fabric washing and softening composition can have a high shear rate viscosity of 10 to 1000, more preferably 10 to 800 cps, and most preferably 10 to 500 cps.

[0083] A laundry care composition can be prepared by combining its components in any convenient order and by mixing, for example, stirring the resulting combination of components to form a phase-stable liquid laundry care composition. In a method for preparing such a composition, a liquid matrix is formed that contains at least most or even substantially all of the liquid components, such as nonionic surfactants, surfactant-free liquid carriers, and other optional liquid components, while thoroughly mixing the liquid components by applying shear stirring to the liquid combination. For example, rapid stirring with a mechanical stirrer can be effectively employed. While maintaining the shear stirring, substantially all of any anionic surfactant and ingredients in solid form can be added. Stirring of the mixture can be continued, and if desired, stirring can be enhanced at this time to form a uniform dispersion of a solution or insoluble solid phase particles within the liquid phase. After some or all of the solid-like materials have been added to this stirred mixture, any enzyme-containing particulate matter such as enzyme pellets can be incorporated. As a variation of the composition preparation procedure described above, one or more of the solid components can be added to the stirred mixture as a solution or particulate slurry premixed with a minor portion of one or more of the liquid components. After adding all of the composition components, stirring of the mixture can be continued for a period of time sufficient to form a composition having the desired viscosity and phase-stable characteristics. Typically, this will involve a stirring time of about 30 to 60 minutes.

[0084] The liquid laundry detergent composition can contain less than about 50% by weight, or even less than about 40% or even less than about 30% water. The liquid laundry detergent composition can contain from about 1% to about 30% by weight of the composition, or even from about 2% to about 20%, or even from about 3% to about 15% water. The water and other components in the laundry care composition can be free of any triggering agents.

[0085] Sachet

[0086] The laundry care composition can be provided in a combined dosage form, which is in the form of a tablet or preferably in the form of a liquid / solid (optionally particulate) / gel / paste retained within a water-soluble film, which is referred to as a sachet or pouch. The laundry care composition can be encapsulated in a single-compartment or multi-compartment sachet or pouch. Multi-compartment sachets are described in more detail in EP-A-2133410. When the laundry care composition is present in a multi-compartment sachet, it can be located in one or two or more compartments, so that the leuco composition can be present in one or more compartments, optionally in all compartments. Non-tonal dyes or pigments or other aesthetic agents can also be used in one or more compartments. The composition can be present in a single compartment of a multi-compartment sachet. The leuco composition can also be incorporated into the film material of the sachet.

[0087] The preferred membrane material is a polymeric material. As is known in the art, the membrane material can be obtained, for example, by casting, blow molding, extrusion, or coextrusion of a polymeric material. Preferred polymers, copolymers, or derivatives thereof suitable for use as sachet materials are selected from polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and polycarboxylates, polyamino acids or peptides, polyamides, polyacrylamides, maleic acid / acrylic acid copolymers, polysaccharides (including starch and gelatin), natural gums (such as xanthan gum and carrageenan). More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and most preferably from polyvinyl alcohol, polyvinyl alcohol copolymers, and hydroxypropylmethylcellulose (HPMC), and combinations thereof. Preferably, the content of the polymer such as the PVA polymer in the sachet material is at least 60% by weight. The polymer can have any weight average molecular weight, preferably about 1,000 to 1,000,000, more preferably about 10,000 to 300,000, still more preferably about 20,000 to 150,000. Mixtures of polymers can also be used as sachet materials. This may be beneficial for controlling the mechanical and / or dissolution properties of the compartments or sachets according to their applications and the required requirements. Suitable mixtures include, for example, mixtures in which one polymer has a higher water solubility than the other polymer, and / or one polymer has a higher mechanical strength than the other polymer. Also suitable are mixtures of polymers having different weight average molecular weights, such as mixtures of PVA or its copolymers having a weight average molecular weight of about 10,000 - 40,000, preferably about 20,000, and mixtures of PVA or its copolymers having a weight average molecular weight of about 100,000 to 300,000, preferably about 150,000. Also suitable for the present invention are polymer blend compositions, which, for example, comprise a hydrolyzable and water-soluble polymer blend, such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, and generally contain about 1% to 35% by weight of polylactide and about 65% to 99% by weight of polyvinyl alcohol. Preferred for the present invention are polymers hydrolyzed from about 60% to about 98%, preferably from about 80% to about 90%, to improve the material dissolution properties.

[0088] Different membrane materials and / or membranes of different thicknesses can be employed in the preparation of the compartments. The advantage of selecting different membranes is that the resulting compartments can exhibit different solubility or membrane release properties.

[0089] The most preferred membrane materials are PVA membranes named MonoSol commercial references M8630, M8900, H8779, those described in U.S. Patent No. 6,166,117 and U.S. Patent No. 6,787,512, and PVA membranes having corresponding solubility and deformability characteristics.

[0090] Laundry care component 。

[0091] Laundry care compositions can contain surfactants, anionic surfactants, nonionic surfactants, cationic surfactants, polyethylene glycol polymers, ethoxylated polyethyleneimine, rheology modifiers, color dyes, dye transfer inhibitors, aesthetic colorants, encapsulates, fragrances, fragrance microcapsules, fragrance delivery systems, odor reducing substances, fabric softeners, chelating agents, enzymes, enzyme stabilizers, catalytic substances, tannic acid, detergency polymers, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids, enzyme stabilizing systems, antioxidants, light blockers, pearlescents, deposition aids, builders, dispersants, bleaches, bleach activators, bleach catalysts, organic gloss polymers, surface modified polymers, foam suppressants, metal care agents, metal salts, preservatives, and mixtures thereof.

[0092] Laundry care compositions can contain from about 1% to about 80% surfactant, by weight of the detergent or cleaning composition. The surfactant can be selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, ampholytic surfactants, semi-polar surfactants, cationic surfactants, or mixtures thereof. The surfactant can be selected from: anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof. The surfactant system typically contains a certain weight ratio of anionic surfactant and nonionic surfactant. The weight ratio of anionic surfactant to nonionic surfactant can be from about 1.1:1 to 4:1, or preferably from about 1.2:1 to about 3:1, or preferably from about 1.5:1 to about 2.5:1, or even more preferably about 2:1.

[0093] Laundry care compositions can contain enzymes. The enzymes are selected from hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, cutinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, melanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof.

[0094] A detergent or cleaning composition may comprise a polymer. The polymer may be selected from carboxylate polymers, polyethylene glycol polymers, terephthalate polymers, amine polymers, cellulose polymers, dye transfer inhibiting polymers, dye fixing polymers such as condensation oligomers formed by the optional condensation of imidazole and epichlorohydrin in a ratio of 1:4:1, hexamethylene diamine derivative polymers, ethoxylated polyethyleneimine, and any combination thereof.

[0095] A fabric washing and care composition may comprise other suitable components, and in some aspects, these components may be incorporated in whole or in part. The components may be selected according to the intended function of the fabric washing and care composition. In some aspects, for a multi-compartment unit dose article, the fabric washing and care components may be part of a non-first (e.g., second, third, fourth, etc.) composition encapsulated in a compartment separate from the first fabric washing and care composition. The non-first composition may have any suitable composition. The non-first composition may be in the form of a solid, liquid, dispersion, gel, paste, or a combination thereof. Wherein the unit dose comprises a plurality of compartments, the leuco composition may be added to or present in one, two, or even all of the compartments. Concentrating the antioxidant with the leuco composition in a smaller volume compartment may result in a higher local concentration of the antioxidant, which may provide enhanced stability. Thus, as will be understood by those skilled in the art, the formulator may select the location and amount of the leuco composition according to the desired properties of the unit dose.

[0096] Method of use

[0097] The present disclosure also relates to a method for determining a genuine fabric washing and care composition. The method may comprise the steps of: a) providing a fabric washing and care composition having a first color, the fabric washing and care composition comprising at least one fabric washing and care ingredient; b) adding a trigger to the fabric washing and care composition; and c) detecting a change in the fabric washing and care composition from the first color to a second color. The presence of the leuco composition of the present invention protected by the claims in a genuine fabric washing and care composition may distinguish the genuine fabric washing and care composition from a counterfeit composition. The presence of the leuco composition of the present invention protected by the claims does not affect the quality or functionality of the fabric washing and care composition during manufacture, shipping, shelf storage, or use. Additionally, when incorporated into a fabric washing and care composition and used to wash fabrics, the leuco composition may substantially not deposit onto the fabrics, thus maintaining the suitability of the composition for use with a variety of fabric types and colors. If the washing solution contains an additive or a trigger, the appearance of the fabric washing and care composition may change during use. In such a case, a visual change in appearance (color) may occur during use, but the performance of the fabric washing and care composition is not reduced, and the leuco composition may substantially not deposit onto the fabrics.

[0098] Upon exposure to a sufficient triggering agent, the leuco composition changes from a colorless or substantially colorless state to a colored state. This change in the leuco composition is sufficient to affect the color of the laundry care composition such that it changes from a first color to a second color. The user can detect the color change of the laundry care composition visually or by spectrophotometry to demonstrate that the laundry care composition is authentic. The color change of the laundry care composition can be determined according to the methods provided in the following test methods section. The lack of a color change can indicate that the laundry care composition is not authentic.

[0099] For a laundry care preparation having a first color that is substantially colorless or only lightly colored, a lower content of the leuco composition can be employed. In the case where the first color is darker, a higher content of the leuco composition may be required to achieve a discernible appearance change after addition of the triggering agent. If the color of the first color state is particularly dark, it may be advantageous to dilute the laundry care composition with, for example, deionized water before addition of the triggering agent so that the appearance change from the diluted first color state to the second color state is more easily discernible. The change in appearance is more easily discernible when two samples are compared side by side, and the instructions for detecting the color change can include ensuring that a side-by-side comparison of the first color and the second color is performed. In other cases, a side-by-side comparison will not be required, and a visual inspection after addition of the triggering agent will be sufficient to convince the person performing the detection that a significant appearance change has occurred, thereby determining that the product is authentic.

[0100] The method can include the following steps: a) providing a laundry care composition having a first color, the laundry care composition comprising at least one laundry care ingredient and at least one leuco composition; b) adding a triggering agent to the laundry care composition, wherein the triggering agent is sufficient to effect the change of the leuco composition from a colorless state to a colored state in accordance with formula (I) as described above; and c) detecting the change of the laundry care composition from the first color to the second color.

[0101] Verification test kit

[0102] A test kit can be used to detect whether a laundry care composition is authentic or counterfeit. The kit can be configured for on-site use at various facilities, such as at one or more of customs warehouses, retail locations, wholesale supply stores, manufacturing plants, distributors, shipping and receiving facilities, consumer residences, or any other location where a suspected counterfeit product may be found. The kit allows for rapid and efficient on-site detection of counterfeit consumer goods without the need for expensive analytical instruments, highly trained test technicians, or complex experimental procedures.

[0103] A test kit for detecting a genuine laundry care composition preferably comprises: (a) a container for containing a quantity of a laundry care product; (b) a trigger agent, wherein the trigger agent converts a leuco composition conforming to formula (I) as described above, wherein Ar 2 and Ar 3 are independently a carbocyclic aryl or a heteroaryl, and Ar 1 is selected from: an unsubstituted phenyl, an electron-deficient carbocyclic aryl and a heteroaryl; and (c) instructions for mixing the laundry care product and the trigger agent to detect a genuine laundry care composition. The test kit may include two containers for containing a quantity of a laundry care composition. The second container may be used to contain a quantity of a laundry care composition that can be used as a negative control, thereby allowing side-by-side comparison and making the visual determination of color change easier.

[0104] The instructions of the test kit may take the form of a set of written instructions, illustrated instructions, audio instructions, video instructions, or various combinations of these types of instructions. The instructions of the kit may include a color index. The color index may show a series of colors indicating a genuine laundry care composition after mixing the laundry care composition with the trigger agent. The color range indicating a genuine laundry care composition will depend on the first color of the laundry care composition and the particular leuco composition selected. In one non-limiting example, a color index with a series of green hues may be included in the instructions of the kit, the kit being configured to detect the authenticity of a laundry care composition having a first color, the laundry care composition being substantially colorless and containing a furfural leuco composition, such as a leuco composition conforming to formula IV above, which exhibits green after triggering.

[0105] The instructions may also include sample preparation guidance. The sample preparation guidance may instruct the user to dilute a sample of the laundry care composition before adding the trigger agent. For example, the instructions may include guidance for the user to dilute one part of the laundry care composition with nine parts of distilled water or non-chlorinated water.

[0106] Combination

[0107] A. A laundry care composition, the laundry care composition comprising at least one laundry care ingredient and at least one leuco composition conforming to formula (I):

[0108] Ar 1 Ar 2 Ar 3 CH (I)

[0109] wherein Ar 2 and Ar 3 are independently a carbocyclic aryl or a heteroaryl, and wherein Ar1 Selected from:

[0110] unsubstituted phenyl, electron-deficient carbocyclic aryl, and heteroaryl.

[0111] B. The laundry washing and care composition according to paragraph A, wherein Ar 1 is selected from unsubstituted phenyl, nitro-substituted carbocyclic aryl, furan, thiophene, pyridine, and indole, preferably furan.

[0112] C. The laundry washing and care composition according to any one of paragraphs A or B, wherein at least one of Ar 2 and Ar 3 , preferably both Ar 2 and Ar 3 are benzene rings substituted with electron-donating groups.

[0113] D. The laundry washing and care composition according to paragraph C, wherein the electron-donating group is a substituted amine covalently bonded to the benzene ring at the para position of the carbon atom connecting the three Ar groups.

[0114] E. The laundry washing and care composition according to paragraph D, wherein the substituted amine conforms to the formula –NR 4 R 5 , and wherein each R 4 and R 5 is independently selected from: H, C 1-16 branched alkyl, C 1-16 linear alkyl, C 1-16 substituted branched alkyl, C 1-16 substituted linear alkyl, C 7-16 substituted alkaryl, C 7-16 unsubstituted alkaryl, polyoxyalkylene, and mixtures thereof.

[0115] F. The laundry washing and care composition according to paragraph E, wherein at least one R 4 or R 5 is a polyoxyalkylene containing 3 to 60 ethylene oxide repeating units.

[0116] G. The laundry washing and care composition according to paragraph E, wherein R 4 and R 5 are polyoxyalkylenes containing 3 to 60, preferably 10 to 25 ethylene oxide repeating units.

[0117] H. A laundry care composition according to any one of paragraphs A, B, C, D, E, F, and G, wherein the laundry care ingredients are selected from surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic substances, bleach activators, polymeric dispersants, clay soil removal agents, anti-redeposition agents, optical brighteners, foam suppressants, dyes, fragrances, fragrance delivery systems, structurants, fabric softeners, carriers, hydrotropes, processing aids, pigments, antioxidants, and mixtures thereof.

[0118] I. A method for determining a true laundry care composition, the method comprising the steps of:

[0119] a. Providing a laundry care composition having a first color, wherein the laundry care composition comprises at least one laundry care ingredient and at least one leuco composition conforming to formula (I):

[0120] Ar 1 Ar 2 Ar 3 CH (I)

[0121] Wherein Ar 2 and Ar 3 are independently carbocyclic aryl or heteroaryl, and Ar 1 is selected from:

[0122] Unsubstituted phenyl, electron-deficient carbocyclic aryl, and heteroaryl;

[0123] b. Adding a trigger to the laundry care composition, wherein the trigger causes the at least one leuco composition to change from a colorless state to a colored state; and

[0124] c. Detecting the change, wherein the change from the first color to the second color is visually perceptible.

[0125] J. The method according to paragraph I, wherein the change from the first color to the second color has a color change score (DE*) of at least 2.

[0126] K. The method according to any one of paragraphs I and J, wherein Ar 1 is selected from unsubstituted phenyl, nitro-substituted carbocyclic aryl, furan, thiophene, pyridine, and indole, preferably furan.

[0127] L. The method according to any one of paragraphs I, J, and K, wherein Ar 2 and Ar 3 are benzene rings, each of which has independently selected -NR covalently bonded to each benzene ring at the para position of the carbon atom connecting the three Ar groups4 R 5 substituted amines, and each R 3 and R 4 is independently selected from H, C 1-16 branched alkyl, C 1-16 straight-chain alkyl, C 1-16 substituted branched alkyl, C 1-16 substituted straight-chain alkyl, C 7-16 substituted alkaryl, C 7-16 unsubstituted alkaryl, polyalkylene oxide, and mixtures thereof.

[0128] M. A method according to any one of paragraphs I, J, K, and L, wherein the triggering agent is selected from: sodium hypochlorite, calcium hypochlorite, sodium dichloroisocyanurate, alkali metal N-chloro(4-toluene)sulfonamide, N-chlorosulfamate, N-bromosuccinimide, tetrachloro-1,2-benzoquinone, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone), and mixtures thereof.

[0129] N. A test kit for detecting a true laundry care composition, the test kit comprising:

[0130] a) A container for holding a quantity of a laundry care product;

[0131] b) A triggering agent, wherein the triggering agent converts the leuco composition of formula (I) in the laundry care product from a colorless state to a colored state:

[0132] Ar 1 Ar 2 Ar 3 CH (I)

[0133] wherein Ar 2 and Ar 3 are independently a carbocyclic aryl or a heteroaryl, and Ar 1 is selected from:

[0134] unsubstituted phenyl, electron-deficient carbocyclic aryl, and heteroaryl; and

[0135] c) Instructions for mixing the laundry care product and the triggering agent to detect a true laundry care composition.

[0136] O. A test kit according to paragraph N, wherein the instructions include a color index.

[0137] Test method

[0138] I. Determination of electron-deficient carbocyclic aryl groups

[0139] In the case where the carbocyclic aryl group has multiple substituents or where the structure of the leuco composition is unknown, the following method can be used to determine whether the carbocyclic aryl is electron-deficient. For the purposes of the present invention, if the rate of color formation of the two substances shown below during storage is in the following order, the carbocyclic aryl is considered electron-deficient:

[0140]

[0141] where the subscript a is from 1 to 5, and R is not H in the sample. If the rate of the sample composition with an independently selected R substituent is not less than the rate of the control composition shown on the right, the carbocycle (Ar 1 ) in the sample composition is not electron-deficient. The control composition is 4,4'-(benzylidene)bis[N,N-dimethylaniline], also known as leucomalachite green, CAS number 129-73-7, and is available from TCI America Research Chemicals, Portland, OR 97203, USA. The sample leuco composition and the control leuco composition are prepared by standard methods from 2 equivalents of N,N-dimethylaniline and the aldehyde shown below.

[0142]

[0143] Alternatively, the control leuco composition as described above can be purchased. Using an AATCC heavy-duty liquid detergent without optical brighteners, liquid detergents are prepared from each leuco composition, incorporating the leuco composition at 3.00×10 -4 mol·kg. Using a cuvette with an optical path length of 1.0 cm, the initial absorption spectra of each detergent are measured between 400 and 750 nm, as well as the initial absorption spectrum of an AATCC heavy-duty liquid detergent sample without any leuco composition and without optical brighteners. The difference in the initial absorption spectra is determined. The initial absorption spectrum difference of the sample detergent is obtained by subtracting the initial absorbance value of the AATCC detergent without the leuco composition from the initial value of the AATCC detergent containing the sample leuco composition. The initial absorption spectrum difference of the control detergent is obtained by subtracting the initial absorbance value of the AATCC detergent without the leuco composition from the initial value of the AATCC detergent containing the control leuco composition.

[0144] Three samples were stored in a sealed container at 50 °C in the dark for 12 weeks, then the samples were removed, cooled to room temperature, and the final absorption spectra of each of the three detergents were measured. The difference in the final absorption spectra of the samples and the control was determined in a manner similar to that for determining the initial spectral difference described above. The change in the spectral difference from initial to final at the maximum λ for each of the triphenylmethane dyes formed from the corresponding leuco compositions was determined. For the control leuco composition, the triphenylmethane dye formed was malachite green, CAS No. 14426-28-9, available from BOC Sciences, Shirley, NY, 11967. If no distinct local maximum absorbance of at least 0.1 absorbance unit was found in the change in the spectral difference of at least one of the sample detergent or the control detergent at the wavelength of its corresponding maximum λ value, the sample was stored for an additional 4 weeks in the same manner as before and the measurement was repeated. The procedure was repeated as needed until a distinct local maximum absorbance of at least 0.1 absorbance unit was found in the change in the spectral difference of at least one of the sample detergent or the control detergent at the wavelength of its corresponding maximum λ value.

[0145] When there is a distinct local maximum absorbance of at least 0.1 absorbance unit in the change in the absorption spectral difference of at least one of the sample detergent or the control detergent, the two absorbance values at each maximum λ for the triphenylmethane dyes formed from the corresponding leuco compositions are compared. If the absorbance at the maximum λ for the triphenylmethane dye formed from the sample leuco composition in the absorption spectral difference of the detergent containing the sample leuco composition is lower than the absorbance at the maximum λ for the triphenylmethane dye (malachite green) formed from the control leuco colorant composition in the absorption spectral difference of the detergent containing the control leuco colorant composition, then the aromatic ring containing the independently selected R substituent in the sample leuco colorant composition is considered to be electron-deficient.

[0146] II. Detection of color change in laundry care compositions

[0147] Any suitable method can be used to detect the change in color of the laundry washing and care composition of the present disclosure from a first color to a second color, including visual or spectrophotometric methods.

[0148] The color change of the laundry washing and care composition can be detected by spectrophotometric analysis as described below. The L*, a*, and b* values of samples of the laundry washing and care composition before and after the addition of the trigger are collected. The color change score (DE*) is calculated using the following formula:

[0149] DE* = ((L* i - L* f ) 2 + (a* i – a* f ) 2 + (b*i –b* f ) 2 ) 1 / 2

[0150] Where the subscripts i and f refer to the laundry care composition before the addition of the trigger (first or initial (i) color) and the laundry care composition after the addition of the trigger (second or final (f) color), respectively.

[0151] Based on the first color of the laundry care composition, when DE* = 2.0 or greater, especially when the first color and the second color are compared side by side, the color change of the laundry care composition from the first color to the second color can be visually perceptible. In some cases, it may be preferred to adjust the amount of the leuco composition employed in the laundry care composition such that the color change (DE*) between the first color and the second color is at least about 5, or even at least about 10. This ensures that the color change can be easily discerned by visual inspection and enhances the certainty of differentiating between genuine and counterfeit products.

[0152] These factors are well known to those skilled in the art, and formulators typically have to select a leuco composition, incorporate the leuco composition into the laundry care preparation at an appropriate content, select a suitable trigger, and develop instructions for detecting color change that are easy to understand and follow.

[0153] Spectrophotometric analysis for determining L*, a*, b*, chroma (C*), and hue (h*) of laundry care preparations

[0154] The aesthetic appearance of the laundry care preparation is measured on a LabScan XE reflectance spectrophotometer (Hunter Labs, Reston, VA; D65 illumination, 10° observer, excluding ultraviolet light), which utilizes a translucent sample set (part number: LSXE-SC-ASSY) including a sample cup, ring and disk set, sample cup port plug, and opaque cover. Step-by-step instructions can be found in Hunter Labs Applications Note, Volume 11, Issue 3, 2008.

[0155] The purpose of the ring and disk set is to control the liquid properties and additional light interactions (diffusion and transmission) associated with the translucent liquid sample, thereby making these samples more like the opaque samples that the sensor is designed to measure.

[0156] When the ring and disk set is used to measure a liquid, first place the black plastic ring in the sample cup to fix the internal path length of the light passing through the liquid sample to 10 mm while excluding external light that may cause measurement interference. Pour the liquid into the cup until the liquid level is above the top of the black ring.

[0157] Lower the white ceramic disk into the liquid until it is positioned on top of the ring. The disk provides a white background to direct the light that has passed through the liquid back to the detector. Then place the black sample cup cover on the sample cup to prevent any ambient light from outside the instrument from leaking into the detector. The liquid sample is measured through the bottom of an excellent optical quality quartz sample cup that is part of the ring and disk assembly and is used with the accompanying port insert. Step-by-step instructions for using the ring and disk assembly are provided below.

[0158] 1. Orient the instrument so that the sample port is facing up. Replace the regular port insert with the dedicated port insert for the sample cup.

[0159] 2. Standardize the instrument using the dedicated port insert in place.

[0160] 3. Insert the 10-mm black ring into the cup so that it lies flat on the bottom of the cup.

[0161] 4. Fill the cup with the liquid sample until the liquid is above the plane of the ring.

[0162] 5. Float the white ceramic disk down through the liquid sample until it is firmly positioned on top of the black floating ring. The goal is to make the sample appear smooth and opaque through the glass bottom of the sample cup.

[0163] 6. Place the sample cup on the instrument port and cover it with the opaque cover.

[0164] 7. Measure the sample and record the color value.

[0165] 8. Pour the sample out of the sample cup, refill it, and measure again. It is necessary to take the average of three readings by changing the liquid between each reading.

[0166] Preparation examples

[0167] The following are illustrative embodiments of the laundry washing and care compositions according to the present disclosure and are not intended to be limiting.

[0168] Examples 1-7 : Heavy-duty liquid laundry detergent composition.

[0169]

[0170]

[0171] Based on the total weight of the cleaning and / or treatment composition. Report the enzyme level as the raw material.

[0172] Examples 8 to 18 : Unit dose composition

[0173] These examples provide various formulations for unit dose fabric wash and care compositions. Compositions 8 to 12 contain a single unit dose compartment. The film used for encapsulating the composition is a polyvinyl alcohol-based film.

[0174]

[0175]

[0176] Based on the total weight of the fabric wash and care composition, the enzyme level is reported as a raw material.

[0177] In the following examples, the unit dose has three compartments, but similar compositions can be made with any number of compartments. The film used for encapsulating the compartments is polyvinyl alcohol.

[0178]

[0179]

[0180]

[0181] Based on the weight of the total fabric wash and care composition, the enzyme level is reported as a raw material.

[0182] AE1.8S is C 12-15 Alkyl ethoxylate (1.8) sulfate

[0183] AE3S is C 12-15 Alkyl ethoxylate (3) sulfate

[0184] AE7 is C 12-13 Alcohol ethoxylate, average degree of ethoxylation 7

[0185] AE8 is C 12-13 Alcohol ethoxylate, average degree of ethoxylation 8

[0186] AE9 is C 12-13 Alcohol ethoxylate, average degree of ethoxylation 9

[0187] Amylase 1 is 15 mg active substance / g, supplied by Novozymes

[0188] Amylase 2 is 29 mg active substance / g, supplied by Novozymes

[0189] AS is C 12-14 Alkyl sulfate

[0190] Xyloglucanase is 20 mg active substance / g, supplied by Novozymes

[0191] Chelating agent 1 is diethylenetriaminepentaacetic acid

[0192] Chelating agent 2 is 1-hydroxyethane-1,1-diphosphonic acid

[0193] Dispersion B is a glycoside hydrolase, reported as 1000 mg active substance / g

[0194] DTI is poly(4-vinylpyridine-1-oxide) (such as Chromabond ) or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as Sokalan ).

[0195] Dye control agent The dye control agent according to the present invention, for example O.IN(M1), P(M2), PM(M3) or HF(M4)

[0196] HSAS is a mid-branched alkyl sulfate, as disclosed in US 6,020,303 and US 6,060,443

[0197] LAS is a linear alkylbenzene sulfonate having a C 9 -C 15 average aliphatic carbon chain length (HLAS is the acid form).

[0198] Leuco colorant Any suitable leuco composition according to the present disclosure or mixtures thereof.

[0199] Lipase is 18 mg active substance / g, provided by Novozymes

[0200] V200 is a thiophene azo dye provided by Milliken

[0201] Mannanase is 25 mg active substance / g, provided by Novozymes

[0202] Nuclease is phosphodiesterase SEQ ID NO 1, reported as 1000 mg active substance / g

[0203] Optical brightener 1 is 4,4'-bis{[4-anilino-6-morpholino- s -triazin-2-yl]-amino}-2,2'-stilbenedisulfonic acid disodium salt

[0204] Optical brightener 2 is 4,4'-bis-(2-sulfostyryl)biphenyl disodium salt (sodium salt).

[0205] Optical brightener 3 is Optiblanc obtained from 3V Sigma

[0206] The fragrance capsule encapsulant is a core-shell melamine formaldehyde fragrance microcapsule.

[0207] The polishing enzyme is p-nitrobenzyl esterase, reported as 1000 mg active substance / g

[0208] Polymer 1 is bis((C 2 H 5 O)(C 2 H 4 O)n)(CH 3 )-N + -C x H 2x -N + -(CH 3 )-bis((C 2 H 5 O)(C 2 H 4 O)n), where n = 20 - 30, x = 3 to 8, or its sulfated or sulfonated variant

[0209] Polymer 2 is ethoxylated (EO 15 ) tetraethylenepentamine

[0210] Polymer 3 is ethoxylated polyethyleneimine

[0211] Polymer 4 is ethoxylated hexamethylenediamine

[0212] Polymer 5 is Acusol 305, provided by Rohm&Haas

[0213] Polymer 6 is a polyethylene glycol polymer grafted with vinyl acetate side chains, provided by BASF.

[0214] The protease is Purafect 40.6 mg active substance / g, provided by DuPont

[0215] The structurant is hydrogenated castor oil

[0216] Application examples

[0217] I. Synthesis of leuco compositions

[0218] The following examples are provided to further illustrate the leuco compositions; however, they should not be construed as limiting. While exemplary routes for synthesizing the leuco compositions are disclosed, the synthesis should not be limited to these examples and synthesis routes. Other starting materials and / or reagents for different synthesis routes and / or different leuco compositions not illustrated herein are also contemplated. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope or essence of the present disclosure. All parts and percentages given in these examples are by weight unless otherwise indicated.

[0219] Synthesis of leuco compositions :

[0220] Exemplary leuco compositions 1-3, 5-7 and comparative example 8 were prepared following the general procedure described below for compositions where the Ar 1 group is derived from Ar 1 -C(O)H but can be readily adapted.

[0221] A four-necked flask was equipped with an overhead stirrer, a condenser, a temperature controller, a heating mantle and a nitrogen inlet. Then, about 2 moles of a coupling agent (which generally gives rise to the groups Ar 2 and Ar 3 ) were added to the flask and heated to about 65 - 71 °C. During heating, about 1 mole of Ar 1 -C(O)H and a catalytic amount (about 0.4 moles) of urea pre-dissolved in a small amount of water were added. After mixing the above chemicals, about 1.2 moles of hydrochloric acid (in the form of Muriatic acid) were added dropwise to control the temperature below 90 - 100 °C. After adding the hydrochloric acid, the reaction was stirred at 95 - 100 °C for about 7 hours.

[0222] Multiple methods can be used to extract the leuco colorants synthesized by the above procedure. One method is to neutralize the reaction product to a pH of about 9 and remove water by rotary evaporation under reduced pressure. The resulting viscous material is diluted with an organic solvent such as isopropanol and filtered to remove inorganic salts. The organic solvent is allowed to evaporate and the final product is obtained.

[0223] Exemplary leuco composition 4 was prepared as described herein. In a 50 mL round-bottom flask, 1.5 g (10.05 mmol) of p-dimethylaminobenzaldehyde and 2.77 g (21.12 mmol) of 1-methylindole were dissolved in 10 mL of acetonitrile. A few drops of methanesulfonic acid were added to the solution. Then the flask was stoppered and the reaction was stirred overnight at room temperature using a magnetic stir bar and plate. During this process, the product formed precipitated out and was collected by filtration. The structure and purity of the substance were confirmed by 1 H-NMR.

[0224] Table 1. Components used in the preparation of leuco compositions 1-7 (Examples) and 8 (Comparative Example) .

[0225]

[0226]

[0227] a represents Ar 1 -C(O)H (Examples 1-3, 5-7) or Ar 2 -H and Ar 3 -H (Example 4).

[0228] b represents Ar 2 -H and Ar 3 -H (Examples 1-3, 5-7) or Ar 3 -C(O)H (Example 4).

[0229] c is the molar equivalent of the reactants used.

[0230] II. Stability of laundry care compositions containing leuco compositions .

[0231] The following examples demonstrate the stability of the leuco compositions as described in the present disclosure. The leuco compositions as described in the present disclosure resist the change from the colorless state to the colored state under conditions that cause other leuco dyes to turn into the colored state.

[0232] Seven different liquid detergent samples (Samples 1-7) were prepared using a dye-free AATCC 2003 liquid reference detergent without a colorant or optical brightener, each of which contained a leuco composition as described in the present disclosure. Sample 8 contained the leuco composition LCV-4EO as a positive control. Liquid detergent Samples 1-7 contained 0.04 wt% of the leuco composition, and Sample 8 contained 0.01 wt% of the leuco composition. The samples were prepared and stored in glass jars at 50 °C for 56 days. The visible absorption spectra of each detergent were measured on Day 0 (the day the detergent was prepared), Day 7, Day 14, Day 28, and Day 56 of storage. During the storage of the samples, the change in absorbance over time (Δλ max = (λ max ) max ) t – (λ max ) 0 ) was tracked for each detergent sample containing a leuco composition at λ max ), where t is the time in days, and (λ 0 ) max is the absorbance of each detergent solution at λ

[0233] Leucomalachite green was purchased from Aldrich Chemical Company, St. Louis, Missouri, USA. Six additional leuco compositions were prepared according to the general methods disclosed herein. The structures of the samples are provided in Table 1 below. The λ max values of the colored states of each leuco composition were determined as follows: An aliquot of each HDL sample was taken, a 1:10 dilution was prepared with deionized water, oxidized to the corresponding triarylmethane dye with an ethanolic solution of 2,3-dichloro-5,6-dicyano-p-benzoquinone, and the visible absorption spectra of each dilution were measured at 400–700 nm using a UV-Vis spectrophotometer.

[0234] In Table 2, the absorbance changes over time of the leuco compositions 1-7 at the λ max values can be seen compared to the absorbance changes of the positive control sample 8. Samples 1-7 showed little absorbance change over time compared to sample 8.

[0235] Table 2. Examples 1-8: The leuco compositions tested and Δλ at each storage time max Value

[0236]

[0237]

[0238] III. Verification tests for laundry care compositions

[0239] The change in color of the laundry care compositions disclosed herein from a first color to a second color was detected using visual or spectrophotometric methods. In this example, the validation tests included the following general procedure for each formulation tested.

[0240] (1) A 1:5 dilution was prepared by mixing 20.0 mL of the laundry care composition with 80.0 mL of deionized water.

[0241] (2) The first color of the diluted formulation from step (1) above was measured by the spectrophotometric method disclosed herein.

[0242] (3) A trigger agent (0.200 mL of an ethanolic solution of 0.031 M N-bromosuccinimide) was added to 50.0 mL of the diluted formulation from step (1) above, and the resulting solution was shaken for 1 minute.

[0243] (4) A visual assessment was made to determine whether the difference between the first and second colors of the diluted formulation was readily distinguishable.

[0244] (5) The second color of the diluted triggered formulation from step (3) above was measured by the spectrophotometric method disclosed herein.

[0245] (6) Calculate the color change score (DE*) for the appearance change between the first color and the second color.

[0246] Verification tests were carried out on the laundry washing and care preparations A1 and C1, each of which was prepared from the AATCC standard reference (HE) liquid detergent WOB (obtained from AATCC in June 2017) without colorants or optical brighteners. Preparation A1 contained 0.04% by weight of the leuco composition according to the invention and represented a genuine product. Preparation C1 did not contain any leuco composition and represented a counterfeit product. The results are shown in the table below.

[0247] Table 3. Verification test results for laundry care compositions

[0248]

[0249] The dimensions and values disclosed herein should not be construed as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to represent that value and the range functionally equivalent thereto. For example, a dimension disclosed as "40 mm" is intended to represent "about 40 mm".

[0250] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of its filing date, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone or in any combination with any one or more other references anticipates, suggests or discloses any such invention. Further, when any meaning or definition of a term in this invention conflicts with the same term's meaning or definition in a document incorporated by reference, the meaning or definition assigned to the term in this invention shall govern.

[0251] Although specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that numerous other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended that all such changes and modifications that fall within the scope of the invention be covered by the appended claims.

Claims

1. A laundry care composition, the laundry care composition comprising at least one laundry care ingredient and at least one leuco composition of formula (I): Ar 1 Ar 2 Ar 3 CH (I) wherein Ar 2 and Ar 3 are independently indolyl, or Ar 2 and Ar 3 is a benzene ring having, at the para position of the carbon atom connecting the three Ar groups, a substituted amine covalently bonded to each benzene ring, independently selected, wherein the substituted amine conforms to the formula –NR 4 R 5 , and wherein each R 4 and R 5 is independently selected from: H, C 1-16 branched alkyl, C 1-16 linear alkyl, C 1-16 substituted branched alkyl, C 1-16 substituted linear alkyl, C 7-16 substituted alkaryl, C 7-16 unsubstituted alkaryl, polyoxyalkylene, and mixtures thereof, and wherein Ar 1 is selected from: unsubstituted phenyl, nitro-substituted carbocyclic aryl, furan, thiophene and pyridine.

2. The laundry and fabric care composition according to claim 1, wherein Ar 1 is furan.

3. The laundry and fabric care composition according to claim 1, wherein R 4 and R 5 is a polyoxyalkylene having 3 to 60 ethylene oxide repeating units.

4. The laundry and fabric care composition according to claim 1, wherein R 4 and R 5 are polyoxyalkylene having 10 to 25 ethylene oxide repeating units.

5. The laundry care composition according to any one of claims 1-4, wherein the laundry care ingredient is selected from builder, chelating agent, dye transfer inhibitor, dispersant, enzyme, enzyme stabilizer, catalytic substance, bleach activator, clay soil removal agent, anti-redeposition agent, optical brightener, foam suppressant, dye, fragrance, fragrance delivery system, structurant, fabric softener, carrier, hydrotrope, processing aid, pigment, antioxidant, and mixtures thereof.

6. The laundry care composition according to any one of claims 1-4, wherein the laundry care ingredient is selected from surfactants.

7. The laundry care composition according to any one of claims 1-4, wherein the laundry care ingredient is selected from polymeric dispersants.

8. A method for determining an authentic laundry care composition, the method comprising the steps of: a) providing a laundry care composition having a first color, wherein the laundry care composition comprises at least one laundry care ingredient and at least one leuco composition according to any one of claims 1-7; b) adding a trigger agent to the laundry care composition, wherein the trigger agent causes the at least one leuco composition to change from a colorless state to a colored state, and the laundry care composition in the colored state has a second color; and c) detecting the change, wherein the change from the first color to the second color is visually perceptible.

9. The method according to claim 8, wherein the change from the first color to the second color has a color change score (DE*) of at least 2.

10. A test kit for detecting an authentic laundry care composition, the test kit comprising: a. a container for holding a quantity of a laundry care product; b. a trigger agent, wherein the trigger agent converts a leuco composition according to any one of claims 1-7; and c. instructions for mixing the laundry care product and the trigger agent to detect an authentic laundry care composition.

11. The test kit according to claim 10, wherein the instructions include a color index.

12. The test kit according to claim 10, wherein the trigger agent is a solid.

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