阅读说明：本技术 洗涤剂组合物 (Detergent composition ) 是由 G·S·米瑞科 丹尼尔·戴尔·迪图利奥 于 2019-03-18 设计创作，主要内容包括：本发明公开了包含水溶性膜和隐色着色剂的洗涤剂组合物。将至少约10％的隐色着色剂掺入水溶性膜中。也公开了制备此类洗涤剂组合物的方法。一种洗涤剂组合物包含(a)至少一种衣物洗涤护理成分,和(b)隐色组合物。所述隐色组合物具有第一颜色状态和第二颜色状态,并且第二颜色状态与第一颜色状态的摩尔比为2:98至5:95。还公开了确定洗涤剂组合物的近似功能年龄的方法,所述方法包括以下步骤：(a)提供包含至少一种衣物洗涤护理成分和隐色组合物的洗涤剂组合物,(b)提供包含多种不同颜色的功能年龄标度,所述多种不同颜色对应于独特的功能年龄,以及(c)将所述洗涤剂组合物的颜色与所述功能年龄标度进行比较。(Detergent compositions comprising a water-soluble film and a leuco colorant are disclosed. At least about 10% of the leuco colorant is incorporated into the water-soluble film. Also disclosed are methods of making such detergent compositions. A detergent composition comprises (a) at least one laundry care ingredient, and (b) a leuco composition. The leuco composition has a first color state and a second color state, and the molar ratio of the second color state to the first color state is from 2:98 to 5: 95. Also disclosed is a method of determining the approximate functional age of a detergent composition, the method comprising the steps of: (a) providing a detergent composition comprising at least one laundry care ingredient and a leuco composition, (b) providing a functional age scale comprising a plurality of different colors, said plurality of different colors corresponding to distinct functional ages, and (c) comparing the color of said detergent composition to said functional age scale.)

1. A detergent composition comprising:

a) a first composition;

b) a water-soluble film; and

c) leuco colorants

Wherein the first composition is selected from a liquid detergent, a granular detergent or a tablet detergent, and

wherein at least about 10% of the leuco colorant is incorporated into the water-soluble film.

2. The detergent composition according to any preceding claims, wherein the leuco colorant is selected from the group consisting of diarylmethane leuco colorants, triarylmethane leuco colorants, oxazine leuco colorants, thiazine leuco colorants, hydroquinone leuco colorants, aryl aminophenol leuco colorants, and mixtures thereof.

3. The detergent composition according to any preceding claims, wherein the leuco colorant is selected from one or more compounds selected from the group consisting of:

(f) mixtures thereof;

wherein the ratio of formula I-V to its oxidized form is at least 1: 3; wherein each individual R on each of rings A, B and C_o、R_mAnd R_pThe radicals are independently selected from hydrogen, deuterium and R⁵(ii) a Wherein each R⁵Independently selected from halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, -C (O) R¹、-C(O)OR¹、-C(O)O^-、-C(O)NR¹R²、-OC(O)R¹、-OC(O)OR¹、-OC(O)NR¹R²、-S(O)₂R¹、-S(O)₂OR¹、-S(O)₂O^-、-S(O)₂NR¹R²、-NR¹C(O)R²、-NR¹C(O)OR²、-NR¹C(O)SR²、-NR¹C(O)NR²R³、-OR¹、-NR¹R²、-P(O)₂R¹、-P(O)(OR¹)₂、-P(O)(OR¹)O^-and-P (O)^-)₂(ii) a (ii) a Wherein said R on at least one of three rings A, B or C_oAnd R_mAt least one of the radicals is hydrogen; each R_pIndependently selected from hydrogen, -OR¹and-NR¹R²；

Wherein G is independently selected from hydrogen, deuterium, C₁-C₁₆Alkoxides, phenoxides, biphenoxides, nitrites, nitriles, alkylamines, imidazoles, arylamines, polyalkylene oxides, halides, alkyl sulfides, aryl sulfides and phosphine oxides;

wherein R is¹、R²And R³Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R⁴；R⁴Is an organic group consisting of one or more organic monomers, wherein the monomer molecular weight is in the range of 28 to 500;

wherein e and f are independently integers from 0 to 4;

wherein each R²⁰And R²¹Independently selected from halogen, nitro group, alkyl group, substituted alkyl group, -NC (O) OR¹、-NC(O)SR¹、-OR¹and-NR¹R²；

Wherein each R²⁵Independently selected from the group consisting of monosaccharide moiety, disaccharide moiety, oligosaccharide moiety, polysaccharide moiety, -C (O) R¹、-C(O)OR¹、-C(O)NR¹R²；

Wherein each R²²And R²³Independently selected from hydrogen, alkyl groups and substituted alkyl groups;

wherein R is³⁰Positioned ortho OR para to the bridging amine moiety and selected from-OR³⁸and-NR³⁶R³⁷Wherein each R is³⁶And R³⁷Independently selected from hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group, acyl group, R⁴、-C(O)OR¹、-C(O)R¹and-C (O) NR¹R²；

Wherein R is³⁸Selected from hydrogen, acyl groups, -C (O) OR¹、-C(O)R¹and-C (O) NR¹R²；

Wherein g and h are independently integers from 0 to 4;

wherein each R³¹And R³²Independently selected from the group consisting of alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, alkaryl groups, substituted alkaryl groups, -C (O) R¹、-C(O)OR¹、-C(O)O^-、-C(O)NR¹R²、-OC(O)R¹、-OC(O)OR¹、-OC(O)NR¹R²、-S(O)₂R¹、-S(O)₂OR¹、-S(O)₂O^-、-S(O)₂NR¹R²、-NR¹C(O)R²、-NR¹C(O)OR²、-NR¹C(O)SR²、-NR¹C(O)NR²R³、-OR¹、-NR¹R²、-P(O)₂R¹、-P(O)(OR¹)₂、-P(O)(OR¹)O^-and-P (O)^-)₂；

wherein-NR³⁴R³⁵Positioned ortho or para to the bridging amine moiety, and R³⁴And R³⁵Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R⁴；

Wherein R is³³Independently selected from hydrogen, -S (O)₂R¹、-C(O)N(H)R¹；-C(O)OR¹(ii) a and-C (O) R¹(ii) a Wherein when g is 2 to 4, any two adjacent R³¹Groups can be combined to form five or more membered fused rings, wherein no more than two atoms in the fused rings can be nitrogen atoms;

wherein X⁴⁰Selected from oxygen atom, sulfur atom and NR⁴⁵(ii) a Wherein R is⁴⁵Independently selected from hydrogen, deuterium, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, -S (O)₂OH、-S(O)₂O^-、-C(O)OR¹、-C(O)R¹and-C (O) NR¹R²；

Wherein R is⁴⁰And R⁴¹Independently selected from-OR¹and-NR¹R²；

Wherein j and k are independently integers from 0 to 3;

wherein R is⁴²And R⁴³Independently selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, -S (O)₂R¹、-C(O)NR¹R²、-NC(O)OR¹、-NC(O)SR¹、-C(O)OR¹、-C(O)R¹、-OR¹、-NR¹R²(ii) a Wherein R is⁴⁴is-C (O) R¹、-C(O)NR¹R²and-C (O) OR¹(ii) a Wherein any charge present in any one of the compounds is balanced with a suitable independently selected internal or external counterion.

4. The detergent composition according to any preceding claims, wherein the leuco colorant conforms to the structure of formula VI,

wherein each R⁴Independently selected from H, methyl, ethyl, ((CH)₂CH₂O)_a(C₃H₆O)_b) H, and mixtures thereof; preferably at least one R⁴The radical being ((CH)₂CH₂O)_a(C₃H₆O)_b) H; wherein each index a is independently an integer from 1 to 100, each index b is independently an integer from 0 to 50, and wherein all R's are⁴The sum of all independently selected integers a in the group does not exceed 200, preferably 100, and all R⁴The sum of all independently selected integers b in the group does not exceed 100, preferably 50, preferably at least two R⁴The groups are selected from methyl and ethyl, most preferably at least one N in structure VI is substituted with two R4 groups, said two R4 groups being selected from methyl and ethyl, preferably Me.

5. The detergent composition according to any preceding claims, wherein the leuco colorant conforms to the structure of formula VII

Wherein each index c is independently 0, 1 or 2, preferably each c is 1; each R⁴Independently selected from H, Me, Et, ((CH)₂CH₂O)_a(C₃H₆O)_b) H, and mixtures thereof; preferably each R⁴Is ((CH)₂CH₂O)_a(C₃H₆O)_b) H, wherein each index a is independently an integer from 1 to 50, more preferably from 1 to 25, even more preferably from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 5 or even from 1 to 2; each index b is independently an integer from 0 to 25, more preferably from 0 to 15, even more preferably from 1 to 5 or even from 1 to 3, and wherein the sum of all independently selected integers a in the leuco colorant does not exceed 100, more preferably does not exceed 80, most preferably does not exceed 60, 40, 20, 10 or even does not exceed 5, and the sum of all independently selected integers b in the leuco colorant does not exceed 50, more preferably does not exceed 40, most preferably does not exceed 30, 20 or even 10.

6. The detergent composition of any preceding claim, wherein the leuco colorant conforms to the structure of formula VIII

Wherein R is⁸Is H or CH₃And each index b is independently averaged to about 1 to 2.

7. The detergent composition of any preceding claim, wherein at least about 50% of the leuco colorant is incorporated into the water-soluble film.

8. The detergent composition according to any preceding claims, wherein the detergent composition is in the form of a unit dose article.

9. The detergent composition according to any preceding claims, wherein the unit dose article comprises a first film and a second film.

10. The detergent composition according to any preceding claims, wherein the leuco colorant is incorporated into the first film.

11. The detergent composition according to any preceding claims, wherein the leuco colorant is incorporated into both the first film and the second film.

12. The detergent composition according to any preceding claims, wherein substantially all of the leuco colorant is incorporated into the first film.

13. The detergent composition according to any preceding claims, wherein the unit dose article comprises a first film, a second film, and a common wall.

14. The detergent composition according to any preceding claims, wherein the first composition comprises an adjunct selected from the group consisting of: surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal agents, anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, pigments and mixtures thereof.

15. The detergent composition according to any preceding claims, further comprising an antioxidant incorporated into at least a portion of the water-soluble film, wherein the antioxidant is selected from the group consisting of hindered phenols, diarylamines, and mixtures thereof.

Technical Field

The present disclosure is directed, in part, to detergent compositions comprising a water-soluble or water-dispersible film and a leuco colorant. These types of colorants are provided in a stable, substantially colorless state, and can then be converted to a strongly colored state upon exposure to certain physical or chemical changes, such as exposure to oxygen, ionic addition, exposure to light, and the like. The present application also relates to methods for determining the approximate functional age of a detergent composition comprising a leuco composition. The invention also relates to a process for preparing such detergent compositions.

Background

Currently, detergents are available in a variety of forms, such as powders, granules, liquids, and gels. Unit dose and concentrated (or compact) detergent forms are becoming increasingly popular because they provide convenience to the consumer at a lower weight and simplified dosing in the case of unit doses. The highly concentrated nature of these forms provides additional sustainability advantages, such as reduced shipping costs and environmental impact (e.g., carbon footprint).

As detergent compositions age, it is known that they may become more yellow for any of a variety of reasons, including, for example, exposure to light, heat, air permeating through the package, natural degradation of composition components, or reactions involving the formulated components. In addition, as many laundry compositions age, their efficacy tends to decrease as certain components may degrade and lose efficacy with aging. Consumers who are accustomed to the useful life of the goods understand that the formulations have some limited time during which they will function as intended, after which they expect some reduction in the efficacy of the product. However, few, if any, products provide consumers with a way in which they can assess the product they own as to its expected useful life, even when the date of manufacture is on the package. The manufacturing date does not provide any information about the effect of the conditions to which the product is exposed between the manufacturing date and the point of purchase. The date of manufacture merely indicates the maximum possible freshness and/or function of the product at any point in time, but adverse storage conditions lead to a deterioration that reduces the efficacy of certain ingredients (such as enzymes), and there is no way in which a consumer can estimate the functional age of the formulation.

It is also known that as textile substrates age, their color tends to fade or yellow due to exposure to light, air, dirt, and natural degradation of the fibers making up the substrate. Thus, to visually enhance these textile substrates and counteract fading and yellowing, the use of polymeric colorants to color consumer products is well known in the art. For example, the use of brighteners (optical brighteners or bluing agents) in textile applications is well known. However, due to the blue or violet hue of traditional bluing agents, formulators have been limited to using traditional bluing agents in deep blue detergent compositions that exhibit little, if any, color change over time.

Leuco dyes are also known in the prior art to exhibit a change from a colorless or pale colored state to a colored state upon exposure to a particular chemical or physical trigger. The resulting change in coloration is typically visually perceptible to the human eye. Most organic compounds have some absorbance in the visible light region (400nm-750nm) and thus more or less some color. As referred to herein, a dye is considered to be a "leuco dye" if it does not exhibit significant color at its applied concentration and conditions, but does exhibit significant color in its triggered form. The color change upon triggering results from a change in the molar attenuation coefficient (also referred to in some literature as molar extinction coefficient, molar absorption coefficient and/or molar absorption) of the leuco dye molecule in the range 400-750nm, preferably in the range 500-650nm, and most preferably in the range 530-620 nm. The increase in the molar decay coefficient of the leuco dye before and after triggering should be greater than 50%, more preferably greater than 200%, and most preferably greater than 500%.

Thus, there remains a need for consumers to evaluate the estimated functional age of a unit dose composition, and thereby the estimated efficacy of the composition.

It has now been surprisingly found that the leuco colorants claimed at the present time incorporated into the film of a unit dose composition develop their color over time in response to environmental factors such as the temperature to which they are exposed, thereby providing the consumer with an estimated functional age of the composition. Furthermore, where the leuco colorants appear blue, they can be used to counteract the natural yellowing of aged detergent compositions, and will generally be designed to deposit on fabrics in their leuco form or in their oxidized form by washing, thereby providing whiteness enhancement to aged fabrics.

Disclosure of Invention

The present disclosure relates to detergent compositions comprising a first composition, a water-soluble film, and a leuco colorant. The first composition is selected from a liquid detergent, a granular detergent, or a tablet detergent, and at least about 10% of the leuco colorant is incorporated into the water-soluble film.

In another aspect, the present invention relates to a method of determining the approximate functional age of a detergent composition, said method comprising the steps of: (a) providing a detergent composition comprising (i) a water-soluble film, (ii) at least one laundry care ingredient, and (iii) a leuco composition; (b) providing a functional age scale comprising a plurality of different colors, wherein each different color corresponds to a unique functional age; and (c) comparing the color of the detergent composition to the functional age scale.

The present disclosure also relates to a process for making a detergent composition comprising a first composition, a water-soluble film, and a leuco colorant. The method comprises the following steps: incorporating a leuco colorant into the film, optionally incorporating an antioxidant into the film, and encapsulating the first composition in a water-soluble film.

The present disclosure also relates to detergent compositions comprising (a) a water-soluble film, (b) at least one laundry care ingredient, and (c) a leuco colorant. The leuco colorant has a first color state and a second color state, and the molar ratio of the second color state to the first color state is from 2:98 to 25:75, preferably from 2:98 to 15:85, or to 10:90, or even to 5: 95.

The present disclosure also relates to a unit dose detergent composition comprising: at least one compartment, a water-soluble film, and a leuco colorant. At least about 10% of the leuco colorant is incorporated into the water-soluble film.

Drawings

FIG. 1 is a side view of a unit dose article according to the present invention;

FIG. 2 is a side view of another embodiment of a unit dose article according to the present invention;

FIG. 3 is a side view of another embodiment of a unit dose article according to the present invention;

FIG. 4 is a side view of another embodiment of a unit dose article according to the present invention.

Detailed Description

The present disclosure relates to detergent compositions comprising a water-soluble film and a leuco colorant.

Definition of

The features and advantages of various embodiments of the present invention will become apparent from the following description, which includes examples intended to give a broad representation of specific embodiments of the invention. Various modifications will be apparent to those skilled in the art from this description and from practice of the invention. The scope is not intended to be limited to the particular forms disclosed, and the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.

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

As used herein, the terms "comprising," "including," and "containing" are intended to be non-limiting. The term "comprising" is intended to include the more restrictive phrases "consisting essentially of … …" and "consisting of … …". Thus, a composition comprising a component may consist essentially of, or consist of, the component.

As used herein, the terms "substantially free of and/or" substantially free of "mean that the referenced material is present in the minimum amount not intentionally added to the composition to form a part of the composition, or preferably not present in an analytically detectable amount. This is meant to include compositions in which the material referred to is present only as an impurity in one of the other materials intentionally added.

As used herein, the term "soiled material" is used non-specifically and may refer to any type of flexible material composed of a network of natural or synthetic fibers, including natural, artificial, and synthetic fibers such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations. Soiled material may also refer to any type of hard surface, including natural, man-made, or synthetic surfaces, such as, but not limited to, brick, granite, mortar, glass, composites, vinyl, hardwood, metal, cooking surfaces, plastics, and the like, as well as blends and combinations.

As used herein, the term "alkoxy" is intended to include alkoxy derivatives of polyols and C₁-C₈Alkoxy groups, the polyol having a repeating unit such as butylene oxide, glycidyl oxide, ethylene oxide or propylene oxide.

As used herein, the interchangeable terms "alkylene oxide" and "alkylene oxide", and the interchangeable terms "polyalkylene oxide" and "polyoxyalkylene" generally refer to the molecular structure-C comprising one or more than one repeating unit, respectively₂H₄O-、-C₃H₆O-、-C₄H₈O-, and any combination thereof. Non-limiting structures corresponding to these groups include, for example, -CH₂CH₂O-、-CH₂CH₂CH₂O-、-CH₂CH₂CH₂CH₂O-、-CH₂CH(CH₃) O-and-CH₂CH(CH₂CH₃) O-is formed. Furthermore, the polyoxyalkylene component may be selected from one or more monomers selected from C_2-20Alkylene oxide groups, glycidyl groups, or mixtures thereof.

The terms "ethyleneoxy", "propyleneoxy" and "butyleneoxy" may be illustrated herein by their typical labels "EO", "PO" and "BO", respectively.

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 hydrocarbyl moieties including C₁-C₁₈An alkyl group, and in one aspect, C₁-C₆An alkyl group.

As used herein, unless otherwise indicated, the term "aryl" is intended to include C₃-C₁₂An aryl group. The term "aryl" refers to both carbocyclic and heterocyclic aryl groups.

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_7-16Alkyl-substituted aryl substituents and C_7-16Aryl-substituted alkyl substituents, which may or may not comprise additional substituents.

As used herein, unless otherwise indicated, the term "laundry care composition" includes granular, powder, liquid, gel, paste, unit dose bar form and/or flake type detergent and/or fabric treatment compositions, including but not limited to products for laundering fabrics, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, and other products for fabric care and maintenance, and combinations thereof. Such compositions may be pre-treatment compositions used prior to the washing step, or may be rinse-added compositions as well as cleaning adjuvants, such as bleach additives and/or "stain-stick" or pre-treatment compositions, or substrate-borne products such as dryer paper.

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 portion thereof) that undergoes one or more chemical and/or physical changes upon exposure to a particular chemical or physical trigger that results in a transition from a first color state (e.g., uncolored or substantially colorless) to a second, higher colored state. Suitable chemical or physical triggers include, but are not limited to, oxidation, pH change, temperature change, and change in electromagnetic radiation (e.g., light) exposure. Suitable chemical or physical changes that occur in the leuco entity include, but are not limited to, oxidative and non-oxidative changes, such as intramolecular cyclization. Thus, in one aspect, a suitable leuco entity may be a reversibly reduced form of a chromophore. In one aspect, the leuco moiety preferably comprises at least first and second pi-systems that are capable of converting to a third combined conjugated pi-system that binds the first and second pi-systems upon exposure to one or more of the above-described chemical and/or physical triggers.

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.

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: because of its manufacturing process, the leuco colorants disclosed herein may contain a distribution of repeating units in their polymer portion.

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.

As used herein, the term "conversion agent" refers to any oxidizing agent as known in the art, in addition to molecular oxygen in any of its known forms (singlet and triplet).

As used herein, the term "trigger" refers to a reactant suitable for converting a leuco composition from a colorless or substantially colorless state to a colored state.

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

As used herein, "cellulosic substrate" is intended to include any substrate that is at least largely composed of cellulose by weight. Cellulose may be present in wood, cotton, flax, jute, and hemp. The cellulosic substrate may 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.

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

As used herein, the terms "include" and "comprise" are intended to be non-limiting.

As used herein, the term "solid" includes granular, powder, bar, and tablet product forms.

As used herein, the term "fluid" includes liquid, gel, paste, and gaseous product forms.

Unless otherwise specified, all components or compositions are on average with respect to the active portion of that component or composition, and do not include impurities, such as residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

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

In one aspect, the molar extinction coefficient of the second colored state at the maximum absorbance at a wavelength in the range of 200 to 1,000nm (more preferably 400 to 750nm) is preferably at least five times, more preferably 10 times, even more preferably 25 times, most preferably at least 50 times the molar extinction coefficient of the first colored state at the wavelength of the maximum absorbance of the second colored state. Preferably, the molar extinction coefficient of the second coloured state at maximum absorbance at a wavelength in the range of 200 to 1,000nm (more preferably 400 to 750nm) is at least five times, preferably 10 times, even more preferably 25 times, most preferably at least 50 times, the molar extinction coefficient of the first coloured state at the corresponding wavelength range. One of ordinary skill will recognize that these ratios can be much higher. For example, the first color state may have a color as small as 10M^-1cm^-1And the second tinting state can have a maximum molar extinction coefficient in the wavelength range of 400 to 750nm of up to 80,000M^-1cm^-1Or a greater maximum molar extinction coefficient in the wavelength range of 400 to 750nm, in which case the ratio of the extinction coefficients may be 8,000:1 or greater.

In one aspect, the maximum molar extinction coefficient of the first color state at a wavelength in the range of 400 to 750nm is less than 1000M^-1cm^-1And the maximum molar extinction coefficient of the second colored state is greater than 5,000M at a wavelength in the range of 400 to 750nm^-1cm^-1Preferably greater than 10,000, 25,000, 50,000 or even 100,000M^-1cm^-1. The skilled artisan will recognize and appreciate that polymers comprising more than one leuco moiety may have significantly higher maximum molar extinction coefficients in a first color 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 a second color state).

Detergent composition

As used herein, the term "detergent composition" includes compositions and formulations designed to clean soiled materials. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-washes, laundry pre-treatments, laundry additives, spray-on products, dry washes or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or within a porous substrate or nonwoven sheet, and other suitable forms apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as laundry pre-treatment agents, laundry post-treatment agents, or may be added during the rinse cycle or wash cycle of a laundry washing operation. The detergent composition may have a form selected from: a liquid, powder, slurry, single or multi-phase unit dose article, sachet, tablet, gel, paste, stick or sheet.

In some aspects, the detergent composition comprises a first composition, wherein the first composition is selected from a liquid detergent, a granular detergent, or a tablet detergent. Preferably, when the first composition is a granular detergent or a tablet detergent, the first composition is encapsulated in a water-soluble film or a water-soluble coating.

Liquid detergent compositions and other detergent composition forms containing liquid components, such as liquid-containing unit dose detergent compositions, may contain water and other solvents as fillers or carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols may be used in some examples to solubilize the surfactant, and polyhydric alcohols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., 1, 3-propanediol, ethylene glycol, glycerol, and 1, 2-propanediol) may also be used. Amine-containing solvents may also be used. Solvents particularly useful in unit dose articles are described below.

Detergent compositions may comprise from about 5% to about 90%, and in some examples from about 10% to about 50%, by weight of the composition, of such carriers. For compact or ultra-compact heavy duty liquid or other detergent composition forms, water may be used at less than about 40%, or less than about 20%, or less than about 5%, or less than about 4% free water, or less than about 3% free water, or less than about 2% free water, or substantially free of free water (i.e., anhydrous), by weight of the composition.

The liquid detergent composition may comprise water. However, when the liquid composition is to be contacted with a water-soluble film, for example in a unit dose article, it is often desirable to limit the amount of water in order to preserve the integrity of the film and prevent a sticky feel of the pouch. Thus, in some embodiments, a liquid detergent composition comprises less than about 50% water by weight of the liquid composition, or less than about 40% water by weight of the liquid composition, or from about 1% to about 30%, or preferably from about 2% to about 20%, or from about 5% to about 13% water by weight of the liquid composition.

For powder or bar detergent compositions, and forms containing solid or powder components (such as powder-containing unit dose detergent compositions), suitable fillers may include, but are not limited to, sodium sulfate, sodium chloride, clays, or other inert solid ingredients. The filler may also comprise biomass or bleached biomass. Fillers may be present in granular, bar, or other solid detergent compositions at levels of less than about 80% by weight of the detergent composition, and in some examples less than about 50% by weight of the detergent composition. Compact or ultra-compact powder or solid detergent compositions may comprise less than about 40%, or less than about 20% or less than about 10% filler by weight of the detergent composition.

For compact or ultra-compact liquid or powder detergent compositions, or other forms, the level of liquid or solid filler in the product can be reduced such that the same amount of active chemical is delivered to the wash liquid as compared to a non-compact detergent composition, or in some examples, the detergent composition is more effective such that less active chemical is delivered to the wash liquid as compared to a non-compact composition. For example, the wash liquor may be formed by contacting the detergent composition with water in an amount such that the concentration of the detergent composition in the wash liquor is from above 0g/l to 4 g/l. In some examples, the concentration may be from about 1g/l to about 3.5g/l, or to about 3.0g/l, or to about 2.5g/l, or to about 2.0g/l, or to about 1.5g/l, or from about 0g/l to about 1.0g/l, or from about 0g/l to about 0.5 g/l. These dosages are not intended to be limiting, and other dosages may be used as will be apparent to those of ordinary skill in the art.

In some aspects, referring to the embodiments of fig. 1-4, the detergent composition is in the form of a unit dose article 10. The unit dose article 10 comprises at least one compartment, wherein the compartment comprises a composition, such as the first composition 20. The unit dose article 10 is intended to provide a single, easy to use dose of the composition contained within the article for a particular application. In some aspects, the detergent composition is in unit dose form 10 and comprises a water-soluble film encapsulating a liquid detergent.

The compartment is understood to mean a closed interior space within the unit dose article, which contains the composition. Preferably, the unit dose article comprises a water-soluble film. The unit dose article is manufactured such that the water-soluble film completely surrounds the composition and in so doing defines a compartment in which the composition is present. The unit dose article may comprise two films. The first film 40 may be shaped to include an open compartment to which the composition is added. A second film 50 is then overlaid over the first film 40 in an orientation proximate the opening of the compartment. The first film 40 and the second film 50 are then sealed together along the seal area 70. The sealing area 70 may comprise a flange. The flange is comprised of excess sealing film material that protrudes beyond the edges of the unit dose article and provides increased surface area for sealing the first and second films 40, 50. The membrane is described in more detail below. In some aspects, the unit dose article 10 comprises three, four, five or more films.

The unit dose article 10 may comprise more than one compartment, even at least two compartments, or even at least three compartments. In some aspects, the unit dose article 10 comprises 1, or 2, or 3, or 4, or 5 compartments. The compartments may be arranged in a stacked orientation, i.e. positioned one on top of the other, as shown in fig. 3, where they may share a common wall 60. In one aspect, at least one compartment is stacked on another compartment. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e., one immediately adjacent to the other, as shown in fig. 4. The compartments may even be oriented in a "tire and rim" arrangement, i.e., a first compartment is positioned adjacent to, but at least partially surrounds, but does not completely enclose, a second compartment. Alternatively, one compartment may be completely enclosed within another compartment.

When the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment. When the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are superposed on the larger compartments. The smaller stacked compartments are preferably oriented side-by-side.

When the unit dose article comprises at least two compartments, each compartment may comprise the same composition, or each compartment may independently comprise a different composition. The compartments may be organoleptically distinct; for example, the compartments may have different shapes, or they may be different colors.

The encapsulated composition can be any suitable composition. The composition may be in the form of a solid, liquid, dispersion, gel, paste, or combination thereof. The composition in each compartment of the multi-compartment unit dose article may be different. However, typically at least one compartment, preferably each compartment, of the unit dose article contains a liquid. The compositions are described in more detail below.

Water-soluble or water-dispersible film

In some aspects, the detergent compositions of the present disclosure comprise a water-soluble or water-dispersible film. The film may encapsulate a detergent composition, preferably a first composition. The film may encapsulate a liquid composition, a granular detergent, a tablet detergent, or a mixture thereof. The terms water soluble and water dispersible are used interchangeably in this application.

The membranes of the invention are soluble or dispersible in water. The water-soluble film preferably has a thickness of about 20 to about 150 microns, preferably about 35 to about 125 microns, even more preferably about 50 to about 110 microns, most preferably about 76 microns.

Preferably, the membrane has a water solubility of at least 50%, preferably at least 75%, or even at least 95%, after use of a glass filter having a maximum pore size of 20 microns, as measured by the method set forth herein:

50 g. + -. 0.1 g of membrane material was added to a pre-weighed 400ml beaker and 245 ml. + -.1 ml of distilled water was added. It was vigorously stirred for 30 minutes at 24 ℃ on a magnetic stirrer Lab-Line (model No.1250) or an equivalent and a 5cm magnetic stirrer (set at 600 rpm). The mixture was then filtered through a folded qualitative porous glass filter with the specified pore size (maximum 20 microns) described above. The moisture in the collected filtrate was dried by any conventional method and the weight of the remaining material (dissolved or dispersed portion) was determined. Then, the percentage of solubility or dispersity can be calculated.

Preferred membrane materials are preferably polymeric materials. As known in the art, film materials may be obtained by, for example, casting, blow molding, extrusion or blow extrusion of polymeric materials. Preferably, the membrane is obtained by an extrusion process or by a casting process.

Preferred polymers, including copolymers, terpolymers, or derivatives thereof, suitable for use as the film material are selected from the group consisting of polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamides, maleic/acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan gum and carrageenan. More preferred polymers are selected from the group consisting of polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and most preferably selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymers and Hydroxypropylmethylcellulose (HPMC), and combinations thereof. Preferably, the polymer of the membrane material is free of carboxylate groups.

Preferably, the content of polymer, such as PVA polymer, in the membrane material is at least 60%. The polymer may have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000, still more preferably from about 20,000 to 150,000.

Mixtures of polymers may also be used as membrane materials. This may be beneficial for controlling the mechanical and/or dissolution properties of the compartment or pouch according to its application 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, for example mixtures of PVA or copolymers thereof having a weight average molecular weight of from about 10,000 to about 40,000, preferably about 20,000 with PVA or copolymers thereof having a weight average molecular weight of from about 100,000 to about 300,000, preferably about 150,000. Also suitable for use herein are polymer blend compositions, for example comprising hydrolytically degradable and water soluble polymer blends, such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35% by weight polylactide and about 65% to 99% by weight polyvinyl alcohol. Preferred for use herein are polymers, preferably polyvinyl alcohol, having a degree of hydrolysis of from about 60% to about 99%, preferably from about 80% to about 99%, even more preferably from about 80% to about 90% to improve the dissolution characteristics of the material. As used herein, the degree of hydrolysis is expressed as a percentage of vinyl acetate units converted to vinyl alcohol units.

Preferred films exhibit good solubility in cold water (which means unheated distilled water). Preferably, such films exhibit good solubility at a temperature of 24 ℃, even more preferably at 10 ℃. By good solubility, it is meant that the membrane exhibits a water solubility of at least 50%, preferably at least 75%, or even at least 95%, as described above, using a glass filter having a maximum pore size of 20 microns, as measured by the method set forth herein. The water solubility can be measured at 24 ℃ or, preferably, at 10 ℃.

Preferred membranes are those described in US 6166117 and US6787512, provided by Monosol (Merrillville, Indiana, USA) under trade references M8630, M8900, M8779 and M8310, as well as PVA membranes having corresponding solubility and deformability characteristics. Other suitable membranes may include the so-called membrane available from Aicello Chemical Europe GmbHPT、GA、KC orKL, membrane VF-HP from Kuraray, or membranes from Nippon Gohsei, such as Hi Selon. Further preferred films are those described in US2006/0213801, US2011/0188784, WO2010/119022 and US 6787512. In some aspects, it is preferred to use a membrane that exhibits better solubility than the M8630 membrane provided by Monosol at a temperature of 24 ℃, even more preferably at 10 ℃.

Preferred water-soluble films are those derived from resins comprising a blend of polymers, preferably wherein at least one polymer in the blend is polyvinyl alcohol. Preferably, the water-soluble film resin comprises a blend of PVA polymers. For example, the PVA resin may comprise at least two PVA polymers, wherein as used herein, the first PVA polymer has a viscosity that is less than the second PVA polymer. The first PVA polymer may have a viscosity of at least 8 centipoise (cP), 10cP, 12cP, or 13cP, and at most 40cP, 20cP, 15cP, or 13cP, for example in a range of about 8cP to about 40cP, or 10cP to about 20cP, or about 10cP to about 15cP, or about 12cP to about 14cP, or 13 cP. Further, the second PVA polymer may have a viscosity of at least about 10cP, 20cP, or 22cP and at most about 40cP, 30cP, 25cP, or 24cP, for example, in a range of about 10cP to about 40cP, or 20 to about 30cP, or about 20cP to about 25cP, or about 22cP to about 24cP, or about 23 cP. The viscosity of the PVA polymer was determined by measuring the freshly prepared solution using a Brookfield LV type viscometer with a UL adapter as described in the British Standard EN ISO15023-2:2006Annex E Brookfield test method. It is an international practice to describe the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20 ℃. Unless otherwise indicated, all viscosities recited herein in cP are understood to refer to the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20 ℃. Similarly, when a resin is described as having (or not having) a particular viscosity, unless otherwise indicated, this means that the viscosity recited is the average viscosity of the resin, which inherently has a corresponding molecular weight distribution.

The PVA polymer alone may have any suitable degree of hydrolysis, so long as the degree of hydrolysis of the PVA resin is within the ranges described herein. Additionally or alternatively, the PVA resin may optionally comprise a first PVA polymer having a molecular weight in the range of about 50,000 to about 300,000 daltons, or about 60,000 to about 150,000 daltons; and a second PVA polymer having a molecular weight in the range of about 60,000 to about 300,000 daltons, or about 80,000 daltons to about 250,000 daltons.

Different membrane materials and/or different thickness membranes may be used in the preparation of the compartments of the present invention. The benefit of selecting different membranes is that the resulting compartments may exhibit different solubility or release characteristics.

In some aspects, hydrophobically modified polymers are employed. Polymers suitable for use as all or part of the backbone of the hydrophobically modified polymer are preferably selected from: polyvinyl alcohol, polyvinyl acetate, cellulose ether, polyethylene oxide, starch, polyvinyl pyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene maleic anhydride, hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, carboxymethyl cellulose, polyacrylate, alginate, acrylamide copolymer, guar gum, casein, ethylene-maleic anhydride resin series, polyethyleneimine, ethyl hydroxyethyl cellulose, ethyl methyl cellulose, and hydroxyethyl methyl cellulose. Copolymer mixtures of polymers derived from the above-described backbones are also suitable. Preferably, the polymer has a backbone comprising pendant hydroxyl groups, more preferably pendant hydroxyl groups located on carbon atoms spaced 1,2 or 1,3 apart from each other.

In one aspect, the preferred backbone for the hydrophobic modification comprises polyvinyl alcohol, and the polymer preferably has an average molecular weight of 1,000 to 300,000 daltons, preferably 2,000 to 100,000 daltons. Such polyvinyl alcohols generally comprise at least some polyvinyl acetate (PVAc). The PVOH material before or after the hydrophobic modification may comprise 0.01 to 40%, preferably 0.01 to 29%, more preferably 0.1 to 15%, most preferably 0.5 to 10%, based on the percentage of the total number of monomers making up the polymer. As used herein, the term polyvinyl alcohol (PvOH) includes PvOH compounds having PVAc levels as defined above.

The polymer is modified to include hydrophobic substituents. Preferred derivatising groups include those based on a parent group selected from acetals, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes and aromatics. Highly preferred hydrophobic substituents are hydrocarbyl groups having a carbon chain length of C4 to C22, wherein the hydrocarbyl group can be alkyl or alkenyl, and can be linear or branched, can contain rings, can optionally incorporate aromatic moieties, and combinations thereof. Additional modifying groups such as amines may be present on the polymer backbone.

More preferably, the hydrocarbyl group has C₄To C₂₀Even more preferably C₄To C₁₅Most preferably C₄To C₁₀E.g. C₄To C₈The chain length of (a). Preferred materials suitable for introducing hydrophobic derivatizing groups onto the polymer are aldehydes such as butyraldehyde, octanal, dodecanal, 2-ethylhexanal, cyclohexanecarboxaldehyde, citral and 4-aminobutyraldehyde dimethyl acetal. In one aspect, butyraldehyde is most preferred. Methods for preparing such hydrophobically modified polymers are disclosed in the public and are readily available to those skilled in the art。

The hydrophobic material is preferably present in the hydrophobically modified polymer in a content of from 01 weight% to 40 weight%, more preferably from 2 weight% to 30 weight%, most preferably from 5 weight% to 15 weight%, based on the total weight of the polymer.

In one aspect, the film may be in the form of polymer particles, preferably having a size greater than or equal to 50 μm. Preferably the particle size is from 50 μm to 2cm, preferably from 50 μm to 1 cm. Alternatively, the polymer particles may have a particle size of, for example, 0.1mm to 50 mm; or 0.5mm to 10mm or 1mm to 10 mm. The size of the particles means the maximum of the largest dimension of the particles.

When hydrophobically modified polymer particles are used, the dimensions may be at the lower end of the range defined above such that the particles are not readily visible, or if the particles are intended to be visible, they may have dimensions approaching the upper end of the range defined above.

For hydrophobically modified polyvinyl alcohol films, as used herein, the term "insoluble" means that the polymer should not be dissolved in a solution having greater than 5,000ppm surfactant. In particular, when 1g/L of the modified polymer is placed in an aqueous surfactant solution comprising 50:50 wt% Linear Alkylbenzene Sulphonate (LAS) and non-ionic surfactant (aliphatic C) having a total surfactant concentration of greater than 5g/L₁₂-C₁₅Reaction product of linear alcohol with 7 molar equivalents of ethylene oxide (7EO) and shaken on a rotary shaker at 100RPM for 2 hours at 293K, then removed from solution by filtration through a suitably sized sieve or filter paper and dried, then the weight of the modified polymer removed is within 95% of the weight of the initial addition. Preferably the modified polymer is insoluble in the aqueous surfactant mixture, with a surfactant concentration of from 5 to 800g/L, more preferably from 5 to 500g/L, for example from 50 to 500 g/L.

The film material herein (whether hydrophobically modified or not) may further comprise one or more additive components. For example, the film preferably comprises a plasticizer. The plasticizer may comprise water, glycerin, ethylene glycol, diethylene glycol, dipropylene glycol, sorbitol, or mixtures thereof. In some aspects, the film comprises from about 2% to about 35%, or from about 5% to about 25%, by weight of the film, of a plasticizer selected from the group consisting of water, glycerin, diethylene glycol, sorbitol, and mixtures thereof. In some aspects, the film material comprises at least two, or preferably at least three, plasticizers. In some aspects, the film is substantially free of ethanol, by which is meant that the film comprises from 0% (including 0%) to about 0.1% ethanol by weight of the film. In some aspects, the plasticizer is the same as the plasticizing solvent in the liquid composition, as described below.

Other additives may include water to be delivered to the wash water and functional detergent additives, including surfactants, such as organic polymeric dispersants and the like.

Leuco colorants

The detergent composition comprises a leuco colorant. Preferably, at least about 10%, 30%, 50%, 70%, 90%, or even about 95% of the leuco colorant is incorporated into the water-soluble film. In a preferred embodiment, substantially all of the leuco colorant is incorporated into the water-soluble film. It should be understood that the leuco colorant may be incorporated into any portion of the film, as described above. For example, in one embodiment, a leuco colorant is incorporated into one or both of the first film and/or the second film. In another embodiment, the leuco colorant is incorporated into the common wall, and in a particularly preferred embodiment, substantially all of the leuco colorant is incorporated into the common wall. The antioxidant may be incorporated in any part or all of the water-soluble film.

Leuco colorants typically provide a blue or violet shade to the fabric. Leuco colorants may be used alone or in combination with additional leuco colorants or conventional shading dyes to produce specific hues of hues and/or different fabric types of hues. This may be provided, for example, by mixing red and blue-green dyes to produce a blue or violet hue. Preferably, the hueing dye is a blue or violet hueing dye, thereby providing a blue or violet tint to the white cloth or fabric. Such white cloth treated with the composition will have a hue angle of 210 to 345, or even a relative hue angle of 240 to 320, or even a relative hue angle of 250 to 300 (e.g., 250 to 290).

In one aspect, the present invention relates to a leuco composition selected from the group consisting of: diarylmethane leuco compositions, triarylmethane leuco compositions, oxazine leuco compositions, thiazine leuco compositions, hydroquinone leuco compositions, arylaminophene leuco compositions, and mixtures thereof.

Diarylmethane leuco compounds suitable for use herein include, but are not limited to, diarylmethylene derivatives capable of forming a second colored state as described herein. Suitable examples include, but are not limited to, Michler methane, diarylmethylene substituted with-OH groups (e.g., Michler hydrolysates) and ethers and esters thereof, diarylmethylene substituted with photocleavable moieties such as-CN groups (di (p-N, N-dimethyl) phenyl) acetonitrile), and similar such compounds.

In one aspect, the present invention relates to a composition comprising one or more leuco compounds conforming to a group selected from:

(f) mixtures thereof;

wherein the ratio of formula I-V to its oxidized form is between 98:2 and 75:25, preferably between 98:2 and 85:15, or between 98:2 and 90:10, or even between 98:2 and 95: 5.

In the structure of formula (I), each individual R on each of rings A, B and C_o、R_mAnd R_pThe radicals are independently selected from hydrogen, deuterium and R⁵(ii) a Each R⁵Independently selected from halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, - (CH)₂)_n-O-R¹、-(CH₂)_n-NR¹R²、-C(O)R¹、-C(O)OR¹、-C(O)O^-、-C(O)NR¹R²、-OC(O)R¹、-OC(O)OR¹、-OC(O)NR¹R²、-S(O)₂R¹、-S(O)₂OR¹、-S(O)₂O^-、-S(O)₂NR¹R²、-NR¹C(O)R²、-NR¹C(O)OR²、-NR¹C(O)SR²、-NR¹C(O)NR²R³、-P(O)₂R¹、-P(O)(OR¹)₂、-P(O)(OR¹)O^-and-P (O)^-)₂(ii) a Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; wherein A, B and two R on the C ring are different_oFused rings that can be combined to form five or more members; when the condensed ring is six-membered or more, two R groups on different A, B and C rings_oCan be combined to form an organic linking group optionally containing one or more heteroatoms; in one embodiment, A, B and two R on the C ring are different_oCombine to form a heteroatom bridge selected from-O-and-S-, thereby forming a six-membered fused ring; r on the same ring_oAnd R_mOr R on the same ring_mAnd R_pCan be combined to form a fused aliphatic ring or a fused aromatic ring, any of which can contain heteroatoms; at least one, preferably at least two, more preferably at least three, and most preferably all four R's on at least one of the three rings A, B or C_oAnd R_mThe radicals being hydrogen, preferably all four R on at least two of rings A, B and C_oAnd R_mThe radicals are hydrogen; in some embodiments, all R on rings A, B and C_oAnd R_mThe radical is hydrogen; preferably, each R_pIndependently selected from hydrogen, -OR¹and-NR¹R²(ii) a Not more than two, preferably not more than one R_pIs hydrogen, preferably R_pAre not all hydrogen; more preferably at least one, preferably two, most preferably all three R_pis-NR¹R²(ii) a In some embodiments, one or even both of rings A, B and C can be with independently selected C₃-C₉Heteroaryl ring replacement, said heteroaryl ring comprising one or two independently selected substituentsA heteroatom from O, S and N, optionally substituted with one or more independently selected R⁵Substituted by groups; g is independently selected from hydrogen, deuterium, C₁-C₁₆Alkoxides, phenoxides, biphenoxides, nitrites, nitriles, alkylamines, imidazoles, arylamines, polyalkylene oxides, halides, alkyl sulfides, aryl sulfides or phosphine oxides; in one aspect, the fraction of G [ (deuterium)/(deuterium + hydrogen)]Is at least 0.20, preferably at least 0.40, even more preferably at least 0.50 and most preferably at least 0.60 or even at least 0.80; wherein R is attached to the same heteroatom¹、R²And R³Can be combined to form a five-or more-membered ring, optionally containing one or more members selected from the group consisting of-O-, -NR¹⁵-and-S-additional heteroatoms.

In the structures of formulae (II) - (III), e and f are independently integers from 0 to 4; each R²⁰And R²¹Independently selected from halogen, nitro group, alkyl group, substituted alkyl group, -NC (O) OR¹、-NC(O)SR¹、-OR¹and-NR¹R²(ii) a Each R²⁵Independently selected from the group consisting of monosaccharide moieties, disaccharide moieties, oligosaccharide moieties, and polysaccharide moieties, -C (O) R¹、-C(O)OR¹、-C(O)NR¹R²(ii) a Each R²²And R²³Independently selected from hydrogen, alkyl groups and substituted alkyl groups.

In the structure of formula (IV), wherein R³⁰Positioned ortho OR para to the bridging amine moiety and selected from-OR³⁸and-NR³⁶R³⁷Each R³⁶And R³⁷Independently selected from hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group, acyl group, R⁴、-C(O)OR¹、-C(O)R¹and-C (O) NR¹R²；R³⁸Selected from hydrogen, acyl groups, -C (O) OR¹、-C(O)R¹and-C (O) NR¹R²(ii) a g and h are independently integers from 0 to 4; each R³¹And R³²Independently selected from the group consisting of alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, alkaryl groups, substituted alkaryl groups、-(CH₂)_n-O-R¹、-(CH₂)_n-NR¹R²、-C(O)R¹、-C(O)OR¹、-C(O)O^-、-C(O)NR¹R²、-OC(O)R¹、-OC(O)OR¹、-OC(O)NR¹R²、-S(O)₂R¹、-S(O)₂OR¹、-S(O)₂O^-、-S(O)₂NR¹R²、-NR¹C(O)R²、-NR¹C(O)OR²、-NR¹C(O)SR²、-NR¹C(O)NR²R³、-P(O)₂R¹、-P(O)(OR¹)₂、-P(O)(OR¹)O^-and-P (O)^-)₂(ii) a Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; -NR³⁴R³⁵Positioned ortho or para to the bridging amine moiety, and R³⁴And R³⁵Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R⁴；R³³Independently selected from hydrogen, -S (O)₂R¹、-C(O)N(H)R¹；-C(O)OR¹(ii) a and-C (O) R¹(ii) a When g is 2 to 4, any two adjacent R³¹Groups can combine to form fused five or more membered rings, wherein no more than two atoms in the fused ring can be nitrogen atoms.

In the structure of formula (V), wherein X⁴⁰Selected from oxygen atom, sulfur atom and NR⁴⁵；R⁴⁵Independently selected from hydrogen, deuterium, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, -S (O)₂OH、-S(O)₂O^-、-C(O)OR¹、-C(O)R¹and-C (O) NR¹R²；R⁴⁰And R⁴¹Independently selected from- (CH)₂)_n-O-R¹、-(CH₂)_n-NR¹R²Wherein subscript n is an integer of from 0 to 4, preferably from 0 to 1, most preferably 0; j and k are independently integers from 0 to 3; r⁴²And R⁴³Independently selected from alkyl, substituted alkyl,Aryl, substituted aryl, alkylaryl, substituted alkylaryl, -S (O)₂R¹、-C(O)NR¹R²、-NC(O)OR¹、-NC(O)SR¹、-C(O)OR¹、-C(O)R¹、-(CH₂)_n-O-R¹、-(CH₂)_n-NR¹R²(ii) a Wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; r⁴⁴is-C (O) R¹、-C(O)NR¹R²and-C (O) OR¹。

In the structures of formulae (I) - (V), any charge present in any of the foregoing groups is balanced with a suitable independently selected internal or external counterion. Suitable independently selected external counterions can be cationic or anionic. Examples of suitable cations include, but are not limited to, one or more metals preferably selected from groups I and II, of which Na, K, Mg and Ca are most preferred, or organic cations such as iminium, ammonium and phosphonium. Examples of suitable anions include, but are not limited to: fluoride, chloride, bromide, iodide, perchlorate, hydrogensulfate, sulfate, aminosulfate, nitrate, dihydrogenphosphate, hydrogenphosphate, phosphate, hydrogencarbonate, carbonate, methylsulfate, ethylsulfate, cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluoroborate, acetate, chloroacetate, cyanoacetate, hydroxyacetate, aminoacetate, methylamoacetate, dichloro-and trichloroacetate, 2-chloropropionate, 2-hydroxypropionate, glycolate, thioglycolate, thioacetate, phenoxyacetate, pivalate, valerate, palmitate, acrylate, oxalate, malonate, crotonate, succinate, citrate, methylenebisthioglycolate, ethylenebisiminoacetate, nitrilotriacetate, Fumarate, maleate, benzoate, methylbenzoate, chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate, indoleacetate, chlorobenzenesulfonate, benzenesulfonate, toluenesulfonate, biphenyl sulfonate and chlorotoluenesulfonate. Those of ordinary skill in the art are well aware of the different counterions that can be used in place of those listed above.

In the structural formulae (I) to (V), R¹、R²、R³And R¹⁵Independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R⁴(ii) a Wherein R is⁴Is an organic group composed of one or more organic monomers, wherein the molecular weight of said monomers is in the range of from 28 to 500, preferably from 43 to 350, even more preferably from 43 to 250, wherein the organic group may be substituted with one or more additional leuco colorant moieties, said leuco colorant moieties conforming to the structure of formula I-V. In one aspect, R⁴Selected from the group consisting of alkyleneoxy (polyether), oxoalkyleneoxy (polyester), oxoalkyleneamine (polyamide), epichlorohydrin, quaternized epichlorohydrin, alkyleneamine, hydroxyalkylene, acyloxyalkylene, carboxyalkylene, alkoxycarbonylalkylene, and saccharide. In one aspect, R⁴Selected from EO, PO, BO, and mixtures thereof, more preferably from EO alone or EO/PO mixtures. Any leuco colorant comprises R having three or more consecutive monomers⁴In the case of a group, the leuco colorant is defined herein as a "polymeric leuco colorant". Those skilled in the art know that the identity of a compound with respect to any of a variety of characteristic attributes such as solubility, partitioning, deposition, removal, staining, and the like, is related to the location, identity, and quantity of such adjacent monomers incorporated therein. Thus, the skilled person may adjust the position, nature and number of such successive monomers to alter any particular property in a more or less predictable manner.

In one aspect, preferred leuco colorants are those that impart a second colored state that is resistant to photobleaching, sometimes referred to as photofugitive leuco colorants. In situations where the detergent composition is exposed to sunlight, such as may occur if the detergent composition is packaged in a transparent or translucent container, the second coloration state of the photobleaching-resistant leuco colorant provides a more accurate indication of the functional age of the product than those with poor photobleaching resistance, and in most cases, the selection of the photobleaching-resistant leuco colorant is not necessary because the detergent composition is shielded from exposure to sunlight, and the packaging is in many cases opaque.

Preferred leuco colorants include those conforming to the structure of formula VI,

wherein each R⁴Independently selected from H, methyl, ethyl, ((CH)₂CH₂O)_a(C₃H₆O)_b) H, and mixtures thereof; preferably at least one R⁴The radical being ((CH)₂CH₂O)_a(C₃H₆O)_b) H; wherein each index a is independently an integer from 1 to 100, each index b is independently an integer from 0 to 50, and wherein all R's are⁴The sum of all independently selected integers a in the group does not exceed 200, preferably 100, and all R⁴The sum of all independently selected integers b in the group is not more than 100, preferably not more than 50. Preferably, at least two R⁴The groups are selected from methyl and ethyl, most preferably at least one N in structure VI is replaced by two R selected from methyl and ethyl, preferably Me⁴And (4) substituting the group.

Highly preferred leuco colorants include those conforming to the structure of formula VII,

wherein each index c is independently 0, 1 or 2, preferably each c is 1; each R⁴Independently selected from H, Me, Et, ((CH)₂CH₂O)_a(C₃H₆O)_b) H, and mixtures thereof; preferably, each R⁴Is ((CH)₂CH₂O)_a(C₃H₆O)_b) H, wherein each index a is independently from 1 to 50, more preferably from 1 to 25, even more preferably from 1 to 20, from 1 to 15, from 1 to 10,1-5 or even 1-2; each index b is independently an integer from 0 to 25, more preferably from 0 to 15, even more preferably from 1 to 5 or even from 1 to 3, and wherein the sum of all independently selected integers a in the leuco colorant does not exceed 100, more preferably does not exceed 80, most preferably does not exceed 60, 40, 20, 10 or even does not exceed 5, and the sum of all independently selected integers b in the leuco colorant does not exceed 50, more preferably does not exceed 40, most preferably does not exceed 30, 20 or even 10. In a particularly preferred aspect, each index c is 1 and each R is⁴Is ((CH)₂CH₂O)_a(C₃H₆O)_b) H, each index a is an integer from 1 to 5, each index b is an integer from 1 to 5, the sum of all independently selected integers a in the leuco compound is from 4 to 10, and the sum of all independently selected integers b in the leuco colorant is from 5 to 15.

In another aspect, highly preferred leuco compounds include those conforming to the structure of formula (VIII),

wherein R is⁸Is H or CH₃And each index b is independently averaged to about 1 to 2.

The leuco triarylmethane compounds described herein can be produced by any suitable synthetic method. For example, such compounds can be prepared via an acid-catalyzed condensation reaction between an aromatic aldehyde and an electron-rich aryl coupling agent (e.g., an amount of about 2 molar equivalents of aryl coupling agent to 1 molar equivalent of aromatic aldehyde). The aromatic aldehyde can be any suitable compound comprising an aromatic moiety (e.g., an aryl moiety, a substituted aryl moiety, a heteroaromatic moiety, or a substituted heteroaromatic moiety) having an aldehyde group covalently attached thereto. In one aspect, the aromatic aldehyde is preferably a substituted benzaldehyde, preferably comprising an aldehyde group having an-OR in the para position relative to the aldehyde group¹or-NR¹R²Groups of the structure. In another aspect, the aromatic aldehyde is preferably a compound comprising a group-NR in para position relative to the aldehyde group¹R²Substituted benzaldehydes of (1), wherein R¹And R²Selected from hydrogen, methyl or ethyl (more preferably methyl).

As mentioned above, the condensation reaction uses an aryl coupling agent in addition to the aromatic aldehyde. To produce leuco triarylmethane compounds, the condensation reaction typically uses at least two molar equivalents of aryl coupling agent per molar equivalent of aromatic aldehyde. In one aspect, a single aryl coupler compound may be used to provide two molar equivalents of aryl coupler used in the reaction. In another aspect, the reaction can be carried out using a mixture of two molar equivalents of two or more different aryl coupling agents. In this embodiment, two or more different aryl coupling agents may be used in any combination or relative ratio, provided that the mixture adds up to at least about two molar equivalents of aryl coupling agent per molar equivalent of aromatic aldehyde. In such embodiments, two or more different aryl coupling agents may differ, for example, in the number and/or nature of substituents attached to the aryl moiety. In one aspect, the reaction can utilize a first aryl coupling agent comprising a first alkylene oxide or polyoxyalkylene moiety having a first distribution of alkylene oxide groups and a second aryl coupling agent comprising a second alkylene oxide or polyoxyalkylene moiety having a second distribution of alkylene oxide groups, the second distribution being different from the first distribution. For example, in one aspect, the first aryl coupling agent may comprise an oxyalkylene moiety consisting of an ethylene oxy group, such as AC-I, below, and the second aryl coupling agent may comprise a polyoxyalkylene moiety consisting of an ethylene oxy group and a propylene oxy group, such as AC-II, below.

Wherein indices a, b, c and d are independently selected from integers from 0 to 5; for a coupling agent selected from AC-I and AC-II, the sum of a and b is from 2 to 10, and in AC-II the sum of c and d is from 2 to 10. In a more specific aspect, for the coupling agent selected from AC-I and AC-II, the sum of a and b is from 2 to 5, and in AC-II the sum of c and d is from 2 to 5. In one embodiment, the sum of indices a and b in AC-I is 2 or 3; the sum of the indices a and b in AC-II is 2 or 3, and the sum of the indices c and d in AC-II is 1 to 5, preferably 2 to 4, or even 2 to 3. The coupling agents AC-I and AC-II may be combined in any ratio, provided that the amount of coupling agent used is sufficient to provide at least two molar equivalents relative to the equivalents of aromatic aldehyde used in the acid-catalyzed condensation reaction to produce the leuco compound.

In one aspect, for example, one equivalent of p-N, N-dimethylbenzaldehyde is condensed with at least two molar equivalents of a mixture of the aryl coupling agents AC-I and AC-II indicated above, wherein for the aryl coupling agent AC-I, the indices a and b total 2 or 3, preferably 2, and wherein preferably a and b are each 1; and wherein for the aryl coupling agent AC-II, the indices a and b total 2 or 3, preferably 2, and wherein preferably a and b are each 1, and the indices c and d total an average of about 2.5 to 3.0, and wherein at least one of c or d is 1.

The detergent compositions of the present disclosure comprise a water-soluble film comprising a leuco colorant, by which is meant that the leuco colorant may be an integral part of the film and/or in contact with the external surface of the film. The leuco colorant may be added to the film-forming polymeric material prior to forming the film, for example, prior to extruding or casting the film. The leuco colorant may be on an exterior surface of the water-soluble film, with an interior surface in contact with the first composition. The leuco colorant may be applied to the exterior surface of the film by any suitable method. For example, the leuco colorant may be applied to the exterior of the film by dusting, powdering, coating, painting, printing, spraying, atomizing, or mixtures thereof. In some aspects, the leuco colorant is applied to the unit dose composition by spraying or atomizing a composition comprising the leuco colorant and a plasticizing solvent, as described below. When the leuco colorant is sprayed or atomized onto the film, the sprayed or atomized composition may be anhydrous, by which is meant it comprises less than 20%, or less than 15%, or less than 10%, or less than 5%, or less than 1%, by weight of the sprayed or atomized composition, of water. The spray or mist composition may even contain zero percent water.

The detergent composition may comprise a coating, wherein the coating comprises a leuco colorant.

In some aspects, the concentration of the leuco colorant on the surface of the film is from about 10ppb to about 10,000ppm, or preferably from about 50ppb to about 200ppm, or more preferably from about 10ppm to about 250 ppm. In some aspects, the concentration of the leuco colorant is determined after storage of the unit dose article at 25 ℃ and 60% relative humidity for at least one month.

In a preferred embodiment, the leuco colorant is encapsulated alone or separated from the other components in the water-soluble film, such as via capsules or microcapsules. It should be understood that the second color state of the leuco colorant may be blocked or otherwise deformed when present in the capsule or microcapsule.

Detergent builder

The detergent composition may comprise other suitable adjuncts, which in some aspects may be incorporated in whole or in part into the film. The adjunct may be selected according to the intended function of the detergent composition. The first composition may comprise an adjuvant. In some aspects, in the case of a multi-compartment unit dose article, the adjuvant may be part of a non-first (e.g., second, third, fourth, etc.) composition encapsulated in a compartment separate from the first 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 combination thereof. Wherein the unit dose comprises a plurality of compartments, a leuco colorant may be added or present in one, two or even all of the compartments.

Non-limiting examples of detergent compositions include cleaning compositions, fabric care compositions, and hard surface cleaners. More specifically, the composition may be a laundry, fabric care or dishwashing composition, including a pretreatment or soaking composition, as well as other rinse additive compositions. The composition may be a fabric detergent composition or an automatic dishwashing composition. The fabric detergent composition may be used in the main wash process or may be used as a pre-treatment or soaking composition.

Fabric care compositions include fabric detergents, fabric softeners, 2-in-1 detergents and softeners, pretreatment compositions, and the like. The fabric care compositions may comprise typical fabric care adjuncts including surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes and enzyme stabilizers, plasticizing solvents, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments and mixtures thereof. The composition may be a laundry detergent composition comprising an adjunct selected from the group comprising: surfactants, polymers, perfumes, encapsulated perfume materials, structurants, and mixtures thereof.

The composition may be an automatic dishwashing composition comprising an adjunct selected from the group consisting of: surfactants, builders, sulfonated/carboxylated polymers, silicone suds suppressors, silicates, metal and/or glass care agents, enzymes, bleaching agents, bleach activators, bleach catalysts, alkalinity sources, perfumes, dyes, solvents, fillers and mixtures thereof.

Preferably, the liquid composition comprises a surfactant. The surfactant may be selected from anionic, cationic, zwitterionic, nonionic, amphoteric surfactants or mixtures thereof. Preferably, the unit dose composition comprises an anionic surfactant, a nonionic surfactant, or a mixture thereof. The detergent composition, preferably the liquid composition, may comprise from about 1% to about 70%, or from about 3% to about 50%, or from about 5% to about 25% by weight of the surfactant system.

The anionic surfactant may be selected from linear alkylbenzene sulfonates, alkyl ethoxylate sulfates, and combinations thereof.

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

Suitable nonionic surfactants useful herein include alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials corresponding to the general formula: r¹(C_mH_2mO)_nOH, wherein R¹Is C₈-C₁₆An alkyl group, m is 2 to 4, and n is in the range of about 2 to 12. In one aspect, R¹Is an alkyl group, which may be a primary or secondary alkyl group containing 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 containing from about 2 to 12 ethylene oxide moieties per molecule, or from about 3 to 10 ethylene oxide moieties per molecule.

The composition may comprise one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, mailanases, β -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is a combination of enzymes conventionally available such as proteases, lipases, cutinases and/or cellulases in combination with amylases.

The compositions of the present invention may comprise one or more bleaching agents. Suitable bleaching agents in addition to bleach catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, and mixtures thereof. Generally, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent by weight of the cleaning composition.

The composition may comprise a whitening agent. A suitable whitening agent is stilbene, such as whitening agent 15. Other suitable whitening agents are hydrophobic whitening agents and whitening agents 49. The whitening agent may be in micronized particulate form having a weight average particle size in the range of from 3 microns to 30 microns, or from 3 microns to 20 microns, or from 3 microns to 10 microns. The whitening agent may be in the alpha or beta crystalline form.

The compositions herein may also optionally comprise one or more copper, iron and/or manganese chelating agents. Chelating agents, if used, are generally present at levels of from about 0.1% to about 15% by weight of the compositions described herein, or even from about 3.0% to about 15% by weight of the compositions described herein. Suitable chelating agents include those selected from the group consisting of: DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethane diphosphonic acid), DTPMP (diethylenetriaminepentamethylenephosphonic acid), ethylenediamine disuccinic acid (EDDS), disodium 1, 2-dihydroxybenzene-3, 5-disulfonate hydrate, and derivatives of such chelating agents.

The composition may comprise a calcium carbonate crystal growth inhibitor, such as a calcium carbonate crystal growth inhibitor selected from the group consisting of: 1-hydroxyethane diphosphonic acid (HEDP) and salts thereof; n, N-dicarboxymethyl-2-aminopentane-1, 5-dioic acid or its salt; 2-phosphonobutane-1, 2, 4-tricarboxylic acid and salts thereof; and any combination thereof.

The compositions of the present disclosure may also comprise one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof. When present in the compositions herein, the dye transfer inhibiting agents are present at a level of from about 0.0001%, from about 0.01%, from about 0.05% by weight of the cleaning composition to about 10%, from about 2%, or even about 1% by weight of the cleaning composition.

The composition may comprise one or more polymers. Suitable polymers include carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulose polymers, dye transfer inhibitor polymers, dye fixing polymers such as condensation oligomers formed by the condensation of imidazole and epichlorohydrin, optionally in a 1:4:1 ratio, hexamethylenediamine derivative polymers, and any combination thereof.

Other suitable cellulosic polymers may have a Degree of Substitution (DS) of from 0.01 to 0.99 and a Degree of Blockiness (DB) such that DS + DB is at least 1.00, or DB +2DS-DS²Is at least 1.20. The substituted cellulosic polymer may have a Degree of Substitution (DS) of at least 0.55. The substituted cellulose polymer may have a blockiness (DB) of at least 0.35. The substituted cellulose polymer may have a DS + DB of 1.05 to 2.00. One suitable substituted cellulose polymer is carboxymethyl cellulose.

Another suitable cellulose polymer is cationically modified hydroxyethyl cellulose.

Suitable perfumes include perfume microcapsules, polymer-assisted perfume delivery systems (including schiff base perfume/polymer complexes), starch-encapsulated perfume accords, perfume-loaded zeolites, blooming perfume accords, and any combination thereof. Suitable perfume microcapsules are based on melamine formaldehyde, which typically comprise a perfume encapsulated by a shell comprising melamine formaldehyde. Such perfume microcapsules are highly suitable for containing cationic and/or cationic precursor materials, such as polyvinyl formamide (PVF) and/or cationically modified hydroxyethylcellulose (catHEC), in the shell.

Suitable suds suppressors include silicones and/or fatty acids such as stearic acid.

When the detergent composition comprises a liquid composition encapsulated by a water-soluble film, the liquid composition preferably comprises a plasticizing solvent. The liquid composition may comprise from about 10% to about 50%, or from about 15% to about 40%, by weight of the liquid composition, of plasticizing solvent.

The plasticizing solvent in the composition of the present invention may be a plasticizing solvent comprising water, an organic solvent, or a mixture thereof. Suitable organic solvents include low molecular weight alcohols and/or low molecular weight diols, where "low molecular weight" in this context means having a molecular weight of less than about 500. Suitable organic solvents preferably include glycerol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, diethylene glycol, sorbitol, and mixtures thereof. In some aspects, the plasticizing solvent includes water, glycerin, 1, 2-propanediol, 1-3-propanediol, dipropylene glycol, diethylene glycol, sorbitol, or a mixture thereof.

Antioxidant agent

The composition may optionally contain an antioxidant present at about 0.001 wt% to about 2 wt%. Preferably, the antioxidant is present at a concentration in the range of 0.01 to 0.1 wt%. Mixtures of antioxidants may be used, and in some embodiments, mixtures of antioxidants may be preferred. One or more antioxidants can be incorporated into any portion or all of the water-soluble film. In a preferred embodiment, the antioxidant is incorporated into the water-soluble film along with the leuco colorant.

Antioxidants are substances as described In Kirk-Othmer (vol.3, p.424) and In Ullmann's Encyclopedia (vol.3, p.91).

One class of antioxidants useful in the present invention are alkylated phenols having the general formula:

wherein R is C₁-C₂₂Straight or branched alkyl, preferably methyl or branched C₃-C₆Alkyl radical, C₁-C₆Alkoxy, preferably methoxy, or CH₂CH₂C (O) OR ', wherein R' is H, a charge-balancing counterion OR C₁-C₂₂A linear or branched alkyl group; r₁Is C₃-C₆A branched alkyl group, preferably a tert-butyl group; x is 1 or 2. Hindered phenol compounds are the preferred type of alkylated phenols having this formula. A preferred hindered phenol compound of this type is 3, 5-di-tert-butyl-4-hydroxytoluene (BHT).

Further, the antioxidant used in the composition may be selected from the group consisting of α -, β -, gamma-, - -tocopherol, ethoxyquin, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and its salts, and mixtures thereof.Notably ethoxyquin 1, 2-dihydro-6-ethoxy-2, 2, 4-trimethylquinoline) under the trade name Raluquin^TMPrepared by Raschig^TMAnd (5) selling by companies.

Another type of antioxidant that may be used in the composition is 6-hydroxy-2, 5,7, 8-tetramethylchroman-2-carboxylic acid (Trolox)^TM) And 1, 2-benzisothiazolin-3-one (Proxel GXL)^TM)。

Another class of antioxidants that may be suitable for use in the composition are benzofuran or benzopyran derivatives having the formula:

wherein R is₁And R₂Each independently is alkyl, or R₁And R₂Can be taken together to form C₅-C₆A cyclic hydrocarbyl moiety; b is absent or CH₂；R₄Is C₁-C₆An alkyl group; r₅Is hydrogen or-C (O) R₃Wherein R is₃Is hydrogen or C₁-C₁₉An alkyl group; r₆Is C₁-C₆An alkyl group; r₇Is hydrogen or C₁-C₆An alkyl group; x is-CH₂OH or-CH₂A, wherein A is a nitrogen-containing unit, a phenyl group, or a substituted phenyl group. Preferred nitrogen-containing a units include amino, pyrrole, piperidine, morpholine, piperazine, and mixtures thereof.

In one aspect, the most preferred type of antioxidant for use in the composition is 3, 5-di-tert-butyl-4-hydroxytoluene (BHT), α -, β -, gamma-, -tocopherol, 1, 2-benzisothiazolin-3-one (Proxel GXL)^TM) And mixtures thereof. On the other hand, the most preferred type of antioxidant for use in the composition is a hindered phenol, diarylamine (including having less than 1,000M in the wavelength range of 400 to 750nm)^-1cm^-1Maximum molarity ofPhenoxazines of extinction coefficient) and mixtures thereof. In preferred mixtures, the number of equivalents of hindered phenol initially formulated will generally be greater than or equal to the number of equivalents of diarylamine.

Washing method

The present disclosure also relates to a method of washing laundry or dishes, for example with a machine, using a composition according to the present disclosure, comprising the steps of: a detergent composition according to the present disclosure is placed in contact with laundry or dishes to be washed and subjected to a washing or cleaning operation.

Any suitable washing machine may be used. Those skilled in the art will appreciate machines suitable for use in connection with washing operations. The articles of the present invention may be used in combination with other compositions such as fabric additives, fabric softeners, rinse aids, and the like.

Additionally, the detergent compositions of the present disclosure can be used in known hand washing processes.

Preparation method

The present invention relates to a process for making a detergent composition. More specifically, the present disclosure relates to a process for making a detergent composition comprising a first composition, a water-soluble film and a leuco colorant, wherein the process comprises the step of incorporating the leuco colorant into the water-soluble film. The incorporation step can be carried out according to any suitable method known to those of ordinary skill in the art for making detergent compositions, for example by incorporating the leuco colorant into the film by spraying, atomizing or mixtures thereof. In some embodiments, the leuco colorant may be added to the film composition prior to casting or extruding the film.

Where the first composition is a granular detergent or a tablet detergent, the method comprises the step of encapsulating the first composition in a water-soluble film or a water-soluble coating. Alternatively, the method may comprise the step of providing the first composition already encapsulated in a water-soluble film or water-soluble coating.

In some aspects, the present disclosure relates to a method of making a film comprising a leuco colorant, wherein the method comprises the steps of: providing a liquid composition comprising a leuco colorant and a plasticizing solvent; and contacting the water-soluble film with a liquid composition, wherein the film comprises a plasticizer. The film may be formed into a pouch and sealed, thereby forming a sealed pouch. In some aspects, the sealed pouch encapsulates a surfactant. In some aspects, the contacting is caused by filling the pouch with a liquid composition. In some aspects, the contacting is caused by spraying or atomizing the liquid composition onto the film. After spraying or atomizing, the film may be formed into a pouch.

The process for making the unit dose article is described in more detail below.

The process of the present disclosure may be continuous or batch-wise. The method comprises the following general steps: forming an open pouch, preferably by forming a water-soluble film that may comprise a leuco colorant into a mold, filling the open pouch with a composition, preferably closing the composition-filled open pouch with a second water-soluble film that may comprise a leuco colorant to form a unit dose article. The second film may also comprise additional compartments, which may or may not comprise a composition. Alternatively, the second film may be a second closed pouch comprising one or more compartments for closing the open pouch. Preferably, the process is one in which a web of unit dose articles is prepared and then cut to form individual unit dose articles.

Alternatively, the first film may be formed as an open pouch comprising more than one compartment. In this case, the compartments formed by the first pouch may be in a side-by-side or "tire and rim" orientation. The second film may also comprise a compartment, which may or may not comprise a composition. Alternatively, the second film may be a second closed pouch for closing a multi-compartment open pouch.

The unit dose articles may be prepared by thermoforming, vacuum forming or a combination thereof. The unit dose article may be sealed using any sealing method known in the art. Suitable sealing methods include heat sealing, solvent sealing, pressure sealing, ultrasonic sealing, pressure sealing, laser sealing, or combinations thereof. Examples of continuous in-line processes for making water-soluble containers are shown in U.S.7,125,828, U.S.2009/0199877a1, EP 2380965, EP 2380966, U.S.7,127,874, and US2007/0241022 (all issued to Procter & Gamble Company, Ohio, USA). An example of a discontinuous in-line method of making water-soluble containers is shown in U.S.7,797,912 (to Reckitt Benckiser, Berkshire, GB).

The unit dose article may be dedusted with a release agent. The release agent may comprise talc, silica, zeolite, carbonate or mixtures thereof.

An exemplary way to make the unit dose articles of the present disclosure is a continuous process for making the articles, the process comprising the steps of:

a. continuously feeding a first water-soluble film that may comprise a leuco colorant onto a horizontal portion of a continuous and rotationally moving endless surface comprising a plurality of molds, or onto a non-horizontal portion thereof, and continuously moving the film to the horizontal portion;

b. forming a continuously moving, horizontally positioned web of open pouches from the film on a horizontal portion of a continuously moving surface, and in a mold on the surface;

c. filling a continuously moving, horizontally positioned web of open pouches with a product to obtain a horizontally positioned web of open filled pouches;

d. preferably continuously closing the web of open pouches to obtain closed pouches, preferably by feeding a second water-soluble film that can contain a leuco colorant onto the horizontally positioned web of open filled pouches to obtain closed pouches; and

e. optionally sealing the closed pouch to obtain a web of closed pouches.

The second water-soluble film may comprise at least one open or closed compartment.

In one embodiment, a first web of open pouches is combined with a second web of closed pouches, preferably wherein the first and second webs are bonded together and sealed together via suitable means, and preferably wherein the second web is a rotating drum device. In such devices, the pouch is filled at the top of the drum and preferably sealed back with one film layer, the closed pouch meets down with the first web of the pouch (preferably an open pouch), which is preferably formed on a horizontal forming surface. It has been found particularly suitable to place the rotating drum unit above the horizontal forming surface unit.

Preferably, the web of the resulting closed pouch is cut to produce individual unit dose articles.