Detergent product

Abstract

An outer container suitable for storing and transporting a plurality of detergent containers containing a liquid detergent composition; wherein the outer container has an internal volume of 10 to 500 L; and wherein the outer container material comprises at least 30% by weight cellulose; and wherein the outer container comprises one or more detergent containers wherein at least one of the detergent containers has an internal volume of 0.1 to 10 L; and having an outer surface comprising one or more externally applied layers comprising less than 5% by weight cellulose; and comprising a liquid detergent composition comprising: 5 to 60% by weight of a surfactant; and from 0.00001 to 0.5 wt% of an ethoxylated dye that is free of sulfonic acid groups.

Description

Technical Field

[0001] The present invention relates to an outer container suitable for accommodating a plurality of individual detergent containers and comprising at least one detergent container having an internal volume of 0.1 to 10 L, wherein the at least one detergent container contains liquid detergent. Background Art

[0002] Liquid detergents usually contain a variety of active substances. One of the most common cleaning active substances is a surfactant. Surfactants are important for reducing water tension to ensure that the washing liquid (proper dilution of the clean liquid laundry composition with water) forms a more effective contact with the surface to be cleaned. Surfactants also play a role in more easily suspending / dissolving dirt from the surface into the washing liquid. Dyes are also present in many liquid detergents. Dyes are used for a variety of purposes. One purpose is to optionally provide a color that is attractive to consumers for the detergent liquid, and another purpose is to allow consumers to accurately observe the location of the clean product deposition. This can be used to pre-treat stubborn stains.

[0003] Liquid detergents are stored in detergent containers of suitable size for household use. Such detergent containers are constrained in that they need to accommodate multiple detergent doses, yet still be light enough for the average consumer to handle.

[0004] For logistics purposes, once produced in a factory, the detergent containers themselves can be stored and transported in larger outer containers that are suitable for accommodating multiple individual detergent containers. This makes bulk storage and bulk transport, for example, from a factory to a store or distribution center much more efficient. The outer container can be unpacked in the store, and individual detergent containers can be taken out and arranged on shelves for sale. Of course, the outer container can also be unpacked in a (sub)distribution center to allow smaller amounts of detergent containers to be transported to a single store.

[0005] During batch storage and transportation (either of these two may spend the time of extension), detergent container may experience mechanical and environmental pressure.Detergent container (such as liquid detergent bottle or the box of unit dose with liquid) may lose integrity and leak detergent liquid.For bottle, this may also come from defective lid.Detergent leakage may not only contact outer container, and contact other detergent containers of co-packing.For the personnel of unpacking outer container, it is advantageous to observe quickly whether any single detergent container leaks detergent liquid.Ideally, any undamaged detergent container co-packed in outer container is advantageously hardly affected by any detergent liquid leakage, and in this sense, these can still be easily cleaned.

[0006] An object of the present invention is to provide an outer container suitable for accommodating a plurality of detergent containers, wherein the detergent containers contain liquid detergent with a dye, wherein upon opening the outer container, any detergent leakage from any of the detergent containers contained therein may be more easily identified. Preferably, wherein the exterior of any undamaged detergent container may be cleaned with reduced effort if necessary. Summary of the invention

[0007] In a first aspect of the present invention, one or more of the above objects are achieved by an outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions;

[0008] wherein the outer container has an internal volume of 10 to 500 L; and

[0009] wherein the material of the outer container comprises at least 30% by weight cellulose; and

[0010] wherein the outer container comprises one or more detergent containers,

[0011] wherein at least one of the detergent containers:

[0012] having an internal volume of 0.1 to 10 L; and

[0013] having an outer surface comprising one or more externally applied layers comprising less than 5% by weight cellulose; and

[0014] A liquid detergent composition comprising:

[0015] 5 to 60 wt% of a surfactant; and

[0016] 0.00001 to 0.5% by weight of dyes which do not contain sulfonic acid groups and are ethoxylated.

[0017] When a drop of liquid detergent is placed on a material containing a large amount of cellulose, the drop has a tendency to be adsorbed into the material. When the amount of cellulose in the material is higher, when the material has less waterproofing, and when the drop is allowed to contact the material for a long time, the process is more complete. Due to the presence of dye in the detergent liquid, it will cause visible dyeing, which may be difficult to remove by simply wiping with an absorbent cloth or rinsing under running water. Surprisingly observed, adding 0.00001 to 0.5 weight % of an uncharged and ethoxylated dye at pH 7 can significantly increase the visible dyeing area when overflowing onto the cellulose-containing material.

[0018] Considering that the accidental overflow of liquid detergent container during transportation and storage is actually inevitable, the present invention helps to quickly identify any damaged detergent container when opening an outer container. When a detergent container is damaged, the detergent liquid with dye may overflow onto the surface of any undamaged detergent container. If this overflow occurs particularly on any sticker, sleeve or shrink packaging, then the undamaged detergent container may become unsuitable for sale. This sticker, sleeve or shrink packaging usually keeps other information required by composition information and laws or regulations, and requires to be clearly discernible. It is found that if this sticker, sleeve or shrink packaging is made of a material lower than these by cellulose content, then any overflowing liquid detergent can be more easily removed according to the present invention. Therefore, the present invention allows to more easily identify whether any detergent container has lost integrity when opening an outer container, and reduces the incidental waste of undamaged detergent containers.

[0019] Without wishing to be bound by theory, we have observed that the total wetted spot area on the cellulose containing material is generally larger than the total wetted area where the dye is observed (before any rinsing of the area with tap water).

[0020] It is further surprisingly observed that the presence of certain nonionic surfactants can further increase the size of any visible stain formation on the cellulose. This is especially observed for detergents containing ethoxylated nonionic surfactants with an alkyl portion less than C16 and a molar average ethoxylation degree lower than 10EO. This is in contrast to the use of other ethoxylated nonionic surfactants with an alkyl portion with a higher carbon number and / or with a higher molar average ethoxylation. It is further surprisingly observed that in the case where the surfactant contains a small amount of certain polymers, this can also further increase the size of any visible stain formation. This is especially observed for detergents containing a lower amount of alkoxylated polyamines. All of these findings are individually or collaboratively beneficial to more easily identify detergent overflow from defective / broken detergent containers packaged in certain types of outer containers during batch storage.

[0021] In view of the above, it is clear that the present invention can be used for (bulk) storage and transportation of detergent products according to the invention.

[0022] In a further aspect, the invention relates to the use of an uncharged ethoxylated dye at pH 7 formulated in a liquid detergent to provide improved quality control of any contained detergent container upon opening of the outer container. DETAILED DESCRIPTION

[0023] definition

[0024] Unless otherwise specified or becomes clear from the context, "detergent composition" or "detergent" or "composition" refers to the liquid detergent composition itself, excluding the detergent container; "detergent container" refers to the container itself, excluding any detergent content contained therein; "product" refers to the detergent container + the liquid detergent contained therein. Unless otherwise clearly specified in the context, the terms "outer container" and "detergent container" are used to indicate a container that can hold multiple detergent containers (i.e., an outer container) or a container that can hold multiple detergent usage doses (detergent container, such as a detergent bottle or a unit dose detergent box), respectively.

[0025] Weight percentages (wt%) are based on the total weight of the liquid detergent, container or product, as indicated or as clear from the context. It should be understood that the total weight of the ingredients does not exceed 100 wt%.

[0026] Unless otherwise stated, whenever the amount or concentration of a component is quantitatively determined herein, the quantified amount or the quantified concentration relates to the component itself, even if common practice may be to add such a component in the form of a solution or a blend with one or more other ingredients. In addition, it should be understood that the verb "comprise" and its variants are used in a non-restrictive sense to mean to include the items after the word, but do not exclude items not specifically mentioned. Finally, mentioning an element by the indefinite article "a" or "an" does not exclude the possibility of having more than one element, unless the context clearly requires the presence of one and only one element. Therefore, the indefinite article "a" or "an" generally means "at least one". Unless otherwise stated, all measurements are performed under standard conditions. Whenever a parameter (such as concentration or ratio) is referred to as being lower than a specific upper limit, it should be understood that, in the absence of a specified lower limit, the lower limit of the parameter is 0.

[0027] The liquid detergent of the present invention is preferably a hand dishwashing detergent, a machine dishwashing detergent, a dishwashing rinse aid, a laundry detergent, a fabric conditioner or a floor cleaner. Hand dishwashing detergents and laundry detergents are more preferred, and laundry detergents are particularly preferred.

[0028] In the context of the present invention, the term "liquid" means that the continuous phase or major part of the detergent is liquid and the composition is flowable at 15 degrees Celsius or higher. Thus, the term "liquid" may include emulsions, suspensions and compositions with a flowable but harder consistency, known as gels or pastes. The viscosity of the detergent at 25 degrees Celsius and 21 seconds -1The shear rate is preferably 200 to about 10,000 mPa.s. This shear rate is the shear rate normally applied to the liquid when pouring from the bottle. The pourable liquid detergent preferably has a viscosity of 200 to 1,500 mPa.s, preferably 200 to 700 mPa.s.

[0029] The liquid detergent of the present invention is preferably an aqueous liquid detergent.Preferably, the detergent comprises at least 40 wt. %, even more preferably 50 wt. %, yet even more preferably 60 wt. % water, yet more preferably at least 70 wt. % water.

[0030] The detergent of the present invention is preferably a laundry detergent. In the context of the present invention, the term "laundry detergent" means a detergent intended for and capable of wetting and cleaning household laundry (such as clothes, linens and other household textiles), preferably also when diluted in a washing machine to form a wash liquor. Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of an automatic washing machine, as well as liquid fine wash and liquid color care detergents, such as those suitable for washing delicate garments (such as those made of silk or wool) by hand or in the wash cycle of an automatic washing machine.

[0031] Outer container

[0032] The outer container of the present invention has an inner volume of 10 to 500 L, preferably 15 to 300 L, more preferably 20 to 150 L, even more preferably 40 to 100 L. The outer container is suitable for accommodating a plurality of detergent containers during storage and transportation.

[0033] The material of the outer container preferably has a cellulose content of at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, even more preferably at least 75% by weight, and still even more preferably at least 80% by weight to 99.5% by weight. Preferred materials for the outer container that can provide sufficient structural integrity and cellulose content are paperboard and / or wood, with paperboard being more preferred. The paperboard can be of any suitable type, but is preferably a reinforced paperboard type, such as corrugated fiberboard with two flat linerboards.

[0034] When closed and filled to maximum capacity (e.g., it still allows closing of the container lid (if present) and / or still allows easy stacking), the outer container is preferably capable of / holding 2 to 50 detergent containers, more preferably 4 to 30, even more preferably 5 to 20, and yet even more preferably 8 to 15 detergent containers. Preferably, at least a portion of the inner exposed surface of the outer container, preferably the bottom panel and / or the side panels, more preferably the bottom panel, does not have a plastic lining and / or is not wax-coated. In terms of shape, the outer container is preferably a cuboid with a lid configuration, and more preferably has one or more gripper configurations on one or more side panels for easy manual transport.

[0035] At least one of the detergent containers contained in the outer container has an internal volume of 0.1 to 10 L; and an outer surface comprising one or more outer applied layers having less than 5% by weight of cellulose. This preferably applies to at least 50% by number of the detergent containers contained in the outer container, more preferably to all detergent containers contained in the outer container.

[0036] Detergent container

[0037] The detergent container of the present invention has an internal volume of 0.1 to 10 L. The preferred internal volume of the detergent container is 0.2 to 5 L, even more preferably 0.5 to 5 L, and even more preferably 0.5 to 2 L. Therefore, it is suitable for accommodating multiple use doses, whether in a continuous liquid form or in the form of multiple unit doses (such as capsules with water-soluble films). The detergent container can have any suitable shape, such as a bottle or a box (which is a preferred shape). In terms of shape, the bottle is usually characterized by having no sharp-edged corners, while the box usually has one or more sharp-edged corners.

[0038] Detergent containers for holding detergents (having an internal volume of 0.1 to 10 L and being suitably shape-stable and rigid during transport and storage) are still typically constructed of plastic, although paper-based rigid materials such as cardboard (e.g. similar to milk cartons) are gaining interest due to environmental concerns. Regardless of the primary material providing structural strength and shape stability to the detergent container, an outwardly facing surface area of ​​such detergent containers is typically provided with a sticker and / or sleeve to present information. The information may be required by law or regulation, may be marketing information and / or for general aesthetics.

[0039] The present invention is particularly advantageous when the outwardly facing surface area of ​​the detergent container comprises one or more externally applied layers, such as sleeves, shrink wraps and stickers containing 5% cellulose. Typically, stickers and sleeves can be made of various materials. They can be, for example, vinyl-based or paper-based. Paper (usually) has a cellulose content of more than 50% by weight. Therefore, even when the detergent container rigid material is based on a cellulose-containing material, the outwardly facing surface area can also include (substantial) areas with stickers and / or sleeves that contain little or no cellulose. In this case, the present invention still provides benefits because such stickers and / or sleeves typically retain necessary information required by law or regulations and must remain legible (optionally after a wiping action). Preferably, however, the detergent container rigid material itself also contains less than 5% cellulose.

[0040] The detergent container of the present invention comprises one or more externally applied layers, such as stickers, sleeves, shrink packaging or combinations thereof, which comprise less than 5% by weight of cellulose. Preferably, one or more stickers, sleeves, shrink packaging or combinations thereof cover at least 10% of the total surface area of ​​the detergent container facing the outside, more preferably at least 20%, even more preferably at least 40%, and even more preferably 50 to 80%. The total outward-facing detergent container surface is the entire surface area visible to the consumer holding the detergent container in any direction. In doubtful cases, and as applicable according to the type of detergent container, the total outward-facing detergent container surface area is based on a detergent container in a closed configuration (e.g., the lid is in a closed position and / or the lid of the box is closed). Preferred examples of this outward-facing cellulose-containing material include vinyl-containing stickers, plastic-containing sleeves and / or plastic-containing shrink packaging.

[0041] Advantageously, the outward-facing detergent container surface area that is not covered by one or more layers (such as sleeves, stickers and shrink wrap) of non-cellulose-containing or low-cellulose-containing also has at least a certain degree of resistance to liquid detergent absorption. Simple test is enough to understand the resistance of surface area part to liquid detergent absorption: 50 microliters of droplets of 10 % by weight LAS (linear alkyl sulfonate) aqueous solution are placed on the selected detergent container surface area (or its representative area), wherein the surface area to be tested is horizontally oriented so that the droplet does not roll off. The droplet is incubated under 20 degrees Celsius and other standard conditions. After 10 minutes, wipe off the droplet. This process repeats up to 5 times or until the area under the droplet becomes soaked obviously. This is usually represented by darkening of color and / or wrinkling of material. If the material is affected by the surfactant solution droplet in this process, it shows that at least a portion of the droplet is adsorbed in the surface-treated region. If this is the case, any dye present will be difficult to remove. Preferably, the detergent container comprises an outwardly facing cellulose-containing surface area which shows no visible signs of soaking in the above test after at most 1 repetition, preferably at most 2 repetitions, more preferably at most 4 repetitions, even more preferably at most 5 repetitions, and still even more preferably does not show any visible signs of soaking after at most 6 repetitions.

[0042] In the case of a bottle, the detergent container advantageously has a pouring neck with a resealable screw cap, wherein the maximum dimension of the pouring neck of the detergent container is at least 3 times smaller than the maximum dimension of the detergent container. Preferably, the detergent container has a minimum width of 3 cm, more preferably 4 cm at its base. The width is measured parallel to a flat surface on which the detergent container rests in an upright position. At the time of initial sale, the detergent container is preferably filled to more than 95% of the detergent container capacity by weight.

[0043] In the case where the detergent container rigid material is based on plastic, the plastic of the detergent container can be colored, although it is preferably at least partially transparent. This can be easily achieved by reducing the amount of colorant in the plastic as required and / or by changing the detergent container wall thickness. Advantageously, the plastic of the detergent container is substantially free of added colorants (e.g., dyes or pigments) and does not have a color that is perceptible to the untrained human eye (i.e., non-white, non-grey). Plastics with little or no added colorants are preferred because they have higher recyclability.

[0044] The main benefit of using cellulose-based materials is their higher bio-source and bio-renewability. In the case where the detergent container contains plastic, preferably based on the total amount of plastic (raw material), the plastic of the detergent container contains at least 30% by weight, preferably at least 50% by weight, more preferably 70% by weight, and even more preferably at least 90% by weight of recycled plastic, preferably post-consumer recycled plastic, or can be obtained by using such a method of recycled plastic, wherein the remainder can be virgin plastic. Information on recycled plastics and their use in making detergent containers is discussed in the literature, such as in Methods of Recycling, Properties and Applications of Recycled Thermoplastic Polymers. MEGrigore, Recycling 2017, 2, 24. Typically, in order to convert recycled post-use plastics into usable raw materials to make new plastic detergent containers, the plastics are washed, dried and appropriately granulated.

[0045] Surfactants

[0046] The liquid detergent of the present invention comprises from 5 to 60 wt%, most preferably from 10 to 30 wt% of surfactant.Preferably greater than 95% of the surfactant is selected from anionic and nonionic surfactants and mixtures thereof.

[0047] Typically, the anionic surfactant and nonionic surfactant of the surfactant system can be selected from the surfactants described in the following literature: Liquid Detergent Detergents, edited by E. Smulders (Wiley VCH 2002), Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, published by CRC Press, and Non-Ionic Surfactants: Organic Chemistry, edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series, published by CRC Press.

[0048] Preferred amounts of total nonionic surfactants are from 0.1 to 25 wt%, more preferably from 2 to 20 wt%, even more preferably from 4 to 16 wt%, still even more preferably from 5 to 12 wt%.

[0049] Suitable nonionic surfactants may include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom (e.g. aliphatic alcohols, acids, amides) with alkylene oxides (especially ethylene oxide alone or with propylene oxide). Specific nonionic surfactants are aliphatic C 8 To C 18 Condensation products of linear or branched primary or secondary alcohols with ethylene oxide (typically 5 to 40 EO, preferably 7 to 9 EO). For nonionic surfactants with C16 / 18 alcohol ethoxylates and C16 / 18 methyl ester ethoxylates, it is preferred that the major C18 portion is C18:1, more preferably C18:1 (Δ9). Preferably, the polyunsaturated chains are present at less than 11 wt%.

[0050] Suitable anionic surfactants that can be used are generally water-soluble alkali metal salts of organic sulfuric and sulfonic acids having an alkyl group containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of the higher acyl group. Examples of suitable synthetic anionic surfactants are sodium and potassium alkyl sulfates, especially those obtained by sulfation of higher C8 to C18 alcohols such as those produced from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulfonates, especially linear secondary alkyl C10 to C15 sodium benzene sulfonates; and sodium alkyl glyceryl ether sulfates, especially those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. Preferred anionic surfactants are sodium C11 to C15 alkylbenzene sulfonates and sodium C12 to C18 alkyl sulfates. Highly preferred are anionic alkylbenzene sulfonates, which are more advantageously linear alkylbenzene sulfonates. Also suitable are surfactants such as those described in EP-A-328 177 (Unilever), which exhibit resistance to salting out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides. Rhamnolipids may also be used.

[0051] Preferred surfactant systems are mixtures of anionic and nonionic surfactants, in particular the groups and examples of anionic and nonionic surfactants indicated in EP-A-346995 (Unilever). Particularly preferred as C 16 -C 18 Alkali metal salts of primary alcohol sulfates and C 12 -C 15 More preferably, the surfactant system is a mixture of anionic and nonionic surfactants.

[0052] Preferably, the weight ratio of total nonionic surfactant to total anionic surfactant is 9:1-1:9, more preferably 3:1-1:3.

[0053] If alkyl ether sulfate surfactant is present, preferably the weight ratio of total nonionic surfactant to total alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate surfactant) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0054] If linear alkylbenzene sulfonate is present, preferably the weight ratio of total nonionic surfactant to linear alkylbenzene sulfonate (weight of nonionic surfactant / weight of linear alkylbenzene sulfonate) is from 0.1 to 2, preferably from 0.3 to 1, most preferably from 0.45 to 0.85.

[0055] As indicated, the presence of certain types of nonionic surfactants can be beneficial for improving visibility / detection of detergent container leakage onto the inner surface of the outer container. Therefore, the detergent preferably comprises an ethoxylated nonionic surfactant having an alkyl moiety less than C16 and a molar average degree of ethoxylation below 10EO. Preferably, the nonionic surfactant has an alkyl moiety of C8-C15 and a molar average degree of ethoxylation of 4-9, more preferably the nonionic surfactant has an alkyl moiety of C10-C15 and a molar average degree of ethoxylation of 5-8, even more preferably the nonionic surfactant has an alkyl moiety of C12-C15 and a molar average degree of ethoxylation of 6-7, wherein even more preferably the molar average degree of ethoxylation is 7.

[0056] Based on the total amount of nonionic surfactants, the amount of nonionic surfactants having an alkyl portion less than C16 and a molar average degree of ethoxylation below 10 EO is preferably at least 20 wt%, more preferably at least 40 wt%, even more preferably at least 60 wt%, and even more preferably at least 80 wt%.

[0057] The preferred amount of nonionic surfactant having an alkyl portion less than C16 and a molar average degree of ethoxylation below 10 EO is 0.1-25 wt%, more preferably 2-20 wt%, even more preferably 4-16 wt%, yet even more preferably 5-12 wt%.

[0058] Alkoxylated polyamine

[0059] As shown, the addition of alkoxylated polyamines can reduce the visibility / detection of detergent container leakage onto the inner surface of the outer container. Typically, such anti-redeposition polymers stabilize soil in the wash liquor, thereby preventing redeposition of soil. Soil release polymers suitable for use in the present invention include alkoxylated polyamines, preferably alkoxylated polyethyleneimines. Polyethyleneimines are composed of ethyleneimine units -CH 2 CH 2The preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (MW) of about 300 to about 10,000. w ). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may generally be ethoxylation or propoxylation or a mixture of the two. When the nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10 to 30, preferably 15 to 25 alkoxy groups per modification. The preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation is 10 to 30, preferably 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone. Mixtures of any of the above materials may also be used.

[0060] The detergents of the present invention preferably comprise from 0.025 to 8% by weight of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines described above. More preferably, the polyamine is an alkoxylated cationic or zwitterionic diamine or polyamine polymer in which the positive charge is provided by quaternization of the amine nitrogen atoms and the anionic groups, if present, are provided by sulfation or sulfonation of the alkoxylated groups.

[0061] Preferably, the alkoxylate is selected from butoxy, propoxy and ethoxy, most preferably ethoxy.

[0062] Preferably, greater than or equal to 50 mol % of the nitrogen amines are quaternized, preferably with methyl groups.Preferably, the polymer contains 2 to 10, more preferably 2 to 6, most preferably 3 to 5 quaternized nitrogen amines.

[0063] Preferably, the polymer contains ester (COO) or amide (CONH) groups within the structure, preferably these groups are arranged so that when all ester or amide groups are hydrolyzed, at least one, preferably all, of the hydrolyzed fragments have a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.

[0064] Preferably, the polymer has the following form:

[0065]

[0066] Where R 1 is a C3 to C8 alkyl group, X is (C 2 H 4 O) n Y group, wherein n is 15 to 30, wherein m is 2 to 10, preferably 2, 3, 4 or 5, and wherein Y is selected from OH and SO 3 - , and preferably SO 3 -The number of X and R groups is greater than the number of OH groups. Preferably, there are 0, 1 or 2 OH groups. 1 X may contain an ester group. X may contain a carbonyl group, preferably an ester group. Preferably there is one C separating the ester group from the N 2 H 4 O unit, making the structural unit NC 2 H 4 O-ester-(C 2 H 4 O) n-1 Y is preferred. Such polymers are described in WO2021239547 (Unilever). Exemplary polymers are sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. Amide and ester groups can be included using lactones or sodium chloroacetate (modified Williamson synthesis), respectively, added to the OH or NH groups and then ethoxylated.

[0067] An exemplary reaction scheme for inclusion of an ester group is

[0068]

[0069] The addition of lactones is discussed in WO2021 / 165468.

[0070] On the one hand, the alkoxylated polyamine provides benefits for cleaning. On the other hand, its presence can reduce detergent visibility of detergent leakage onto the interior of the outer container. Therefore, when the detergent comprises an alkoxylated polyamine, it is included in a relatively low amount. In this case, the amount of alkoxylated polyamine in the liquid detergent is preferably, in increasing order of preference, at most 4 wt%, at most 2.0 wt%, at most 1.0 wt%, at most 0.5 wt%, at most 0.3 wt%, and even more preferably substantially absent from the detergent liquid.

[0071] Further polymers of this type are discussed in WO 2022 / 136389 A1.

[0072] dye

[0073] Dyes are described in Industrial Dyes, K. Hunger edited 2003 Wiley-VCH ISBN 3-527-30426-6. Dyes used for the present invention are selected from cationic dyes, anionic dyes and nonionic dyes, and are preferably selected from anionic dyes and nonionic dyes. Anionic dyes are negatively charged in aqueous media at pH 7. Examples of anionic dyes are found in the acid and direct dye categories in Color Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists). Anionic dyes preferably contain at least one sulfonic acid or carboxylic acid group. Nonionic dyes are uncharged in aqueous media at pH 7, and examples are found in the disperse dye category of Color Index.

[0074] The dye may be any color, preferably the dye is blue, violet, green or red. Most preferably, the dye is blue or violet. The dye may be alkoxylated. The alkoxylated dye preferably has the following general form: Dye-NR 1 R 2 NR 1 R 2 The group is attached to the aromatic ring of the dye. 1 and R 2 Independently selected from polyoxyalkylene chains having 2 or more repeating units and preferably having 2 to 20 repeating units. Examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidyl ether, butylene oxide and mixtures thereof.

[0075] The preferred polyoxyalkylene chain is [(CH 2 CR 3 HO) x (CH 2 CR 4 HO) y R 5 ], where x+y≤5, where y≥1 and z=0 to 5, R 3 Selected from: H; CH 3 ; CH 2 O(CH 2 CH 2 O) z H and mixtures thereof; R 4 Selected from: H; CH 2 O(CH 2 CH 2 O) z H and mixtures thereof, and R 5 Selected from: H and CH 3Preferred alkoxylated dyes for use in the present invention are:

[0076]

[0077] Preferably, the dye is selected from acid dyes; disperse dyes and alkoxylated dyes. Most preferably, the dye is a nonionic dye. Preferably, the dye is selected from those having: anthraquinone; monoazo; disazo; xanthene; phthalocyanine; and phenazine chromophores. More preferably, the dye is selected from those having phenazine, anthraquinone and monoazo chromophores.

[0078] Preferably, the dye is selected from the group consisting of acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid blue 59, acid blue 98, direct violet 9, direct violet 99, direct violet 35, direct violet 51, acid violet 50, acid yellow 3, acid red 94, acid red 51, acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, acid violet 9, acid red 52, food black 1, food black 2, acid red 16 3, Acid Black 1, Acid Orange 24, Acid Yellow 23, Acid Yellow 40, Acid Yellow 11, Acid Red 180, Acid Red 155, Acid Red 1, Acid Red 33, Acid Red 41, Acid Red 19, Acid Orange 10, Acid Red 27, Acid Red 26, Acid Orange 20, Acid Orange 6, Sulfonated Aluminum and Zinc Phthalocyanine, Solvent Violet 13, Disperse Violet 26, Disperse Violet 28, Solvent Green 3, Solvent Blue 63, Disperse Blue 56, Disperse Violet 27, Solvent Yellow 33, Disperse Blue 79:1.

[0079] The dye is preferably a hueing dye for imparting a sense of whiteness to laundry textiles, preferably acid violet 50, solvent violet 13, disperse violet 27, disperse violet 28, alkoxylated thiophene or cationic phenazine, as described in WO 2009 / 141172 and WO 2009 / 141173. When a hueing dye is present, preferably a further green dye is present to convert the color from purple to blue-green. The dye may be covalently bound to a polymeric substance. Also contemplated are leuco-based hueing dyes as described in WO2020 / 023812, most preferably triphenylmethane leuco colorants. Such leuco dyes are included in the term hueing dyes, although preferably, the hueing dyes according to the present invention are non-leuco hueing dyes.

[0080] Combinations of dyes may be used.

[0081] Hueing dyes are particularly advantageous for laundry detergents, where they can impart a hue to white fabrics, and preferably provide a blue or purple hue to white fabrics. In this regard, the hueing dye imparts a blue or purple hue to white cloth, with a hue angle of 240 to 330, more preferably 260 to 320, and most preferably 265 to 300. The white cloth used is a bleached non-mercerized woven cotton sheet. Preferably, a 10×10 cm piece of white bleached non-mercerized woven cotton cloth is stirred at room temperature for 30 minutes in a 2 g / L aqueous solution (6° French hardness water, liquid 298K: cloth 30:1) of a basic detergent (10 wt % linear alkylbenzene sulfonate, 5 wt % primary alcohol ethoxylate (C12-15, with 7 moles of ethoxy groups), pH=8). The cloth is removed, rinsed and drum dried. The experiment is repeated with and without the addition of hueing dye. The color of the cloth is measured using a reflectometer and expressed as CIE L*a*b* values. The experiment is repeated with 0.001 wt % of dye added to the formulation.

[0082] The total color added to the cloth is calculated as the ΔE value, such that ΔE = (ΔL 2 +Δa 2 +Δb 2 ) 0.5 , where ΔL=L(control)-L(dye); Δa=a(control)-a(dye); ΔB=b(control)-b(dye).

[0083] The actual color of the cloth is calculated as the hue angle, which for the current color range is given by: Hue angle = 270 + 180 / π x atan (-Δa / Δb). A hue angle of 360 / 0 is red, 270 is blue, and 180 is green.

[0084] A hueing dye according to the invention is advantageously a hueing dye meaning that it is capable of being deposited onto textiles under domestic washing conditions in the presence of a wash liquor comprising a surfactant. This can be assessed using the test described above, where the hueing dye gives a non-zero ΔE value.

[0085] The total amount of dyes in the detergent according to the invention is preferably from 0.00001 to 0.5% by weight, more preferably from 0.0001 to 0.1% by weight, even more preferably from 0.0005 to 0.05% by weight.

[0086] As shown, the nature of the dye can affect the dye-stained area when detergent leaks from the detergent container onto the inner surface of the outer container. It was found that the use of anthraquinone dyes having the following structure produced larger dye-stained areas when compared to the use of acid violet 50:

[0087]

[0088] Acid Violet 50 has the following structure:

[0089]

[0090] Thus, preferably, the detergent comprises a dye which is an alkoxylated anthraquinone according to the following structure:

[0091]

[0092] wherein the anthraquinone chromophore contains an amine or amide group at the 1-position, the 4-position, or both the 1-position and the 4-position; and

[0093] The chromophore contains at least one [alkoxy] n Part of the group;

[0094] wherein at least one of the n The moiety may be covalently attached at any numbered position, either directly or via an amine or amide group; and

[0095] wherein at least one of the n n of the moiety of the groups is from 2 to 20. More preferred anthraquinone dyes of the present invention have an amine group or an amide group in both the 1- and 4-positions.

[0096] Preferably, the number of alkoxy monomers in the anthraquinone dye as a whole is 2 to 40, preferably 3 to 30, and more preferably 4 to 20. The anthraquinone dye may have more than one [alkoxy]-containing n The anthraquinone dye of the present invention contains [alkoxy] n The number of groups may suitably be from 1 to 8, but is preferably from 1 to 4, more preferably 1 or 2 or 3, and even more preferably 2.

[0097] Advantageously, at least one [alkoxy]-containing n The group is covalently linked to any of the 1 to 4 positions of the anthraquinone dye of the present invention, either directly or via the N atom of the amine or acid group.

[0098] Anthraquinone dyes having the following structure are of interest:

[0099]

[0100] Where R 2 , R 3 , X and Y are H or an organic group, and the group R 2 , R 3 , at least one of X and Y contains -[CH 2 CH 2 O] n R 1 Group, where

[0101] n is 2 to 20; and

[0102] ·R 1 is an organic group or H, preferably R 1 Yes CH 3 or H, and more preferably R 1 is H; and

[0103] Preferably, X and Y represent the same group, more preferably H; and

[0104] Preferably, R 2 and R 3 -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 R 1 , more preferably R 1 is -H.

[0105] Preferred examples of dyes are 1-amino-2-polyethyleneoxy-4-phenylamino-anthraquinone, 1-amino-2-methoxy-4-[-4-polyethyleneoxy-anisyl]anthraquinone, 1-amino-2-polyethyleneoxy-4-(2,4,6-trimethylphenylamino)anthraquinone and N,N'-dialkylenoxy-substituted 1,4-diaminoanthraquinone. More preferred is N,N'-dialkylenoxy-substituted 1,4-diaminoanthraquinone.

[0106] (Further) useful alkoxylated anthraquinone dyes are as follows:

[0107]

[0108] It is preferred that the anthraquinone dye contains no sulphate or sulphonate groups, more preferably no charged groups. In case of doubt, the presence of charged groups is determined in water at pH 7.0 under otherwise standard conditions.

[0109] It will be apparent that if a further dye which does contain one or more sulfonic acid groups and which is not ethoxylated is present, it is present in an amount of less than 0.05 wt%, more preferably less than 0.01 wt%, even more preferably less than 0.005 wt%, and still even more preferably it is substantially absent from the detergent.

[0110] Further ingredients

[0111] The detergent of the present invention may contain further optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include foam boosters, polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosive agents, drape imparting agents, antistatic agents, ironing aids, other colorants such as pigments, pearlescent agents and / or sunscreens. Each of these ingredients is present in an amount that effectively achieves its purpose. Typically, these optional ingredients are included individually in an amount of up to 5% (based on the total weight of the diluted composition by weight), and are adjusted accordingly according to the dilution ratio with water.

[0112] Co-surfactant

[0113] In addition to the non-soap anionic and / or nonionic detersive surfactants described above, the detergents of the present invention may contain one or more co-surfactants (e.g., amphoteric (zwitterionic) and / or cationic surfactants). Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof, in which one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. When included, the cationic surfactant may be present in an amount ranging from 0.1 to 5% by weight. Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sulfobetaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycocinates, alkyl amidopropyl hydroxysulfobetaines, acyltaurates and acylglutamates, which have an alkyl group containing from about 8 to about 22 carbon atoms, preferably selected from C12:0, C14:0, C16:0, C18:0 and C18:1, the term "alkyl" being used to include the alkyl portion of the higher acyl group. When included, the amphoteric (zwitterionic) surfactant can be present in an amount ranging from 0.1 to 5% by weight. Mixtures of any of the above materials can also be used.

[0114] pH

[0115] The suitable pH of the liquid detergent depends on the type of detergent. Preferably, the liquid detergent has a pH of 5 to 9, preferably 6 to 8, as measured at 293 K, in the case where it is a laundry detergent. In the case where the liquid detergent is a machine dishwashing detergent, the preferred pH is 7 to 10.

[0116] Fluorescent agent

[0117] Liquid detergents of the present invention preferably include fluorescent agents (also referred to as fluorescent whitening agents), particularly when they are laundry detergents. Fluorescent agents are well known, and many such fluorescent agents are commercially available. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts (e.g., sodium salts). The total amount of one or more fluorescent agents used in the detergents of the present invention is typically 0.005 to 2 weight percent, more preferably 0.01 to 0.1 weight percent. Preferred classes of fluorescent agents are: distyryl biphenyl compounds, such as Tinopal (trademark) CBS-X, diamine stilbene disulfonic acid compounds, such as Tinopal DMS pureXtra and Blankophor (trademark) HRH, and pyrazoline compounds, such as Blankophor SN. Preferred fluorescent agents are: sodium 2-(4-phenylvinyl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'-disulfonate, disodium 4,4'-bis{[(4-phenylvinyl-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'-disulfonate and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

[0118] It is preferred that the liquid detergent according to the invention comprises a fluorescent agent. When the liquid detergent of the invention is used to prepare a dilute wash liquor in a household method for treating textiles, the fluorescent agent is preferably present in the dilute wash liquor in the range of 0.0001 g / L to 0.1 g / L, preferably 0.001 to 0.02 g / L.

[0119] spices

[0120] Preferably, the liquid detergent contains perfume. The perfume is preferably present in the detergent in an amount of 0.001 to 3% by weight, most preferably 0.1 to 1% by weight. Examples of many suitable perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide published by CFTA Publications and the OPD 1993 Chemicals Buyers Directory 80th Annual Edition published by Schnell Publishing Co.

[0121] It is common to have multiple perfume components in detergents. In the detergents of the present invention, it is envisaged that there will be four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components. In a perfume mixture, preferably 15 to 25% by weight are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80

[1955] ). Preferred top notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Perfumes and top notes are advantageously used to indicate the decontamination benefits provided by the detergents of the present invention.

[0122] Soil Release Polymers

[0123] Soil release polymers (SRPs) help improve the release of soil from surfaces by modifying the surface to be cleaned, such as fabrics or hard surfaces, during the washing process. The SRPs used in the present invention can include a variety of charged (e.g., anionic) and uncharged monomer units, and the structure can be linear, branched, or star-shaped. The SRP structure can also include end-capping groups to control molecular weight or change polymer properties, such as surface activity. The weight average molecular weight (M) of the SRP is w ) may suitably be in the range of about 1000 to about 20,000, preferably in the range of about 1500 to about 10,000.

[0124] The SRP used in the present invention can be suitably selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units substituted with anionic groups, such as, for example, sulfonated isophthaloyl units.

[0125] Other types of SRPs useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, C 1 -C 4 Alkyl cellulose and C 4 Hydroxyalkyl cellulose; polymers having poly(vinyl ester) hydrophobic segments, such as graft copolymers of poly(vinyl esters), for example C 1 -C 6 Vinyl esters such as poly(vinyl acetate); poly(vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam and polyethylene glycol.

[0126] When included, overall levels of SRP may range from 0.1 to 10%, depending upon the level of polymer intended for use in the final letdown composition, and ideally is 0.3 to 7%, more preferably 0.5 to 5% (by weight based on the total weight of the letdown composition).

[0127] Suitable soil release polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007 / 079850 and WO 2016 / 005271. If used, soil release polymers are typically incorporated into liquid detergents at concentrations ranging from 0.01 to 10 wt%, more preferably 0.1 to 5 wt%.

[0128] Hydrotrope

[0129] The compositions of the present invention may include non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n-propanol or isopropanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); weight average molecular weight (M w ) range of about 200 to 600; C1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as xylene, toluene, ethylbenzene and sodium and potassium cumene (cumene) sulfonates). Mixtures of any of the above materials may also be used. The non-aqueous carrier (when included) may be present in an amount ranging from 0.1 to 20% by weight, preferably 2 to 15% by weight, and more preferably 10 to 14% by weight. The level of hydrotrope used is associated with the level of surfactant, and it is desirable to use the hydrotrope content to control the viscosity in such detergents. Preferred hydrotropes are monopropylene glycol and glycerol. Preferably, the detergent contains less than 2% by weight ethanol, more preferably less than 0.5% by weight ethanol, and preferably it is substantially free of ethanol.

[0130] Builders and Chelating Agents

[0131] The detergents of the present invention preferably contain an organic detergent builder or chelating agent material. Examples include alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid. Other examples are DEQUEST TM , an organic phosphonate-type chelating agent marketed by Monsanto, and an alkylhydroxyphosphonate.

[0132] Other suitable organic builders include the high molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acids, polymaleic acids and polyacrylic acid / polymaleic acid copolymers and their salts, such as those marketed by BASF under the name SOKALAN TM The organic detergent materials may be those materials sold as such. If used, organic builder materials may comprise from about 0.5% to 20% by weight of the detergent, preferably from 1% to 10% by weight. Preferred builder levels are less than 10% by weight of the detergent, and preferably less than 5% by weight. More preferably, the liquid detergent is a non-phosphate-built detergent formulation, i.e., containing less than 1% by weight of phosphate. Most preferably, the detergent formulation is non-built, meaning that it contains less than 1% by weight of builder. A preferred chelating agent is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), such as that sold as Dequest 2010. Dequest (R) 2066 (diethylenetriamine penta (methylenephosphonic acid) or DTPMP heptasodium) is also suitable, but less preferred because its cleaning effect is poor.

[0133] In view of reducing environmental eutrophication problems, it is preferred that the detergent contains less than 1 wt. % phosphate, phosphonate or a mixture thereof, more preferably it contains less than 0.8 wt. %, even more preferably less than 0.5 wt. %, and even more preferably less than 0.15 wt. % phosphate, phosphonate or a mixture thereof.

[0134] The following builders are particularly preferred: 2,2',2"-nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), iminodisuccinic acid (IDS), ethylenediamine-N,N'-disuccinic acid (EDDS), methylglycine-N,N-diacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), N-(2-hydroxyethyl)iminodiacetic acid (EDG), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDA), N-(sulfomethyl)aspartic acid (SMAS), N-(2-sulfoethyl)-aspartic acid (SEAS), N-(sulfomethylglutamic acid) (SMGL), N-(2-sulfoethyl)-aspartic acid (SMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDA), N-(sulfomethyl)aspartic acid (SMAS), N-(2-sulfoethyl)-aspartic acid (SEAS), N-(sulfomethylglutamic acid) (SMGL), N-(2-sulfoethyl)-aspartic acid (SMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), )-glutamic acid (SEGL), N-methyliminodiacetic acid (MIDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diacetic acid (ANDA), p-aminobenzenesulfonic acid-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA) and N'-(2-hydroxyethyl)ethylenediamine-N,N,N'-triacetic acid (HEDTA), diethanolglycine (DEG). Although these builder substances are referred to using their acid form, it should be understood that their partial or complete salt forms are included in the name. Preferred are the acid forms of the builders. These builders are preferably present in an amount of 0.01 to 10 wt %, more preferably 0.2 to 5 wt %.

[0135] In particular, for machine dishwashing detergents it is advantageous if they contain MGDA, GLDA, citric acid or a combination thereof.

[0136] Polymer thickener

[0137] The detergents of the present invention may contain one or more polymeric thickeners. Suitable polymeric thickeners for use in the present invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture including at least one acidic vinyl monomer such as (meth)acrylic acid (i.e., methacrylic acid and / or acrylic acid) and at least one associative monomer. The term "associative monomer" in the context of the present invention refers to a monomer having an ethylenically unsaturated segment (for addition polymerization with other monomers in the mixture) and a hydrophobic segment. Preferred types of associative monomers include a polyolefin segment between the ethylenically unsaturated segment and the hydrophobic segment. Preferred HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization of (meth)acrylic acid with (i) a linear or branched C 8 -C40 Alkyl (preferably straight chain C 12 -C 22 (ii) at least one associative monomer selected from C 1 -C 4 The associative monomer (i) is prepared by addition polymerization of at least one other monomer of an alkyl (meth) acrylate, a polyacid vinyl monomer (such as maleic acid, maleic anhydride and / or its salts) and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally comprises from about 5 to about 100, preferably from about 10 to about 80, more preferably from about 15 to about 60 oxyethylene repeating units. Mixtures of any of the above materials may also be used.

[0138] When included, detergents of the present invention preferably comprise from 0.01 to 5% by weight (but depending on the amount intended for use in the final diluted product) and ideally, from 0.1 to 3% by weight, based on the total weight of the diluted composition.

[0139] Enzymes

[0140] One or more enzymes are preferably present in the liquid detergent of the present invention. Preferably, the level of each enzyme in the detergent is from 0.0001 wt % to 0.1 wt % protein. Unless otherwise stated, the amount of enzyme in the liquid detergent in wt % refers to the wt % of active protein level.

[0141] Preferably, the detergent may comprise an effective amount of one or more lipases, cellulases, proteases, amylases, hemicellulases, peroxidases, hemicellulases, xylanases, xanthanases, lipases, phospholipases, esterases, cutinases, pectinases, carrageenase, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malasases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, tannases, nucleases (e.g., deoxyribonucleases and / or ribonucleases), phosphodiesterases, or mixtures thereof.

[0142] Examples of preferred enzymes are sold under the following trade names: Purafect (DuPont), Stainzyme (Novozymes), Biotouch (AB Enzymes), (BASF).

[0143] Detergent enzymes are discussed in WO 2020 / 186028 (Procter and Gamble), WO 2020 / 200600 (Henkel), WO 2020 / 070249 (Novozymes), WO 2021 / 001244 (BASF) and WO 2020 / 259949 (Unilever).

[0144] Nucleases are enzymes capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids, and are preferably deoxyribonucleases or ribonucleases. Preferably, the nuclease is a deoxyribonuclease, preferably selected from any of the classes EC3.1.21.x, wherein x=1, 2, 3, 4, 5, 6, 7, 8 or 9, EC3.1.22.y, wherein y=1, 2, 4 or 5, or EC3.1.30.Z, wherein z=1 or 2, EC3.1.31.1, and mixtures thereof.

[0145] preservative

[0146] Food preservatives are discussed in Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th edition Springer. Isothiazolone-based preservatives may also be used. The detergent preferably contains a preservative or a mixture of preservatives selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and their salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, most preferably sodium benzoate. The preservative is preferably present in 0.1 to 3% by weight, preferably 0.3% to 1.5% by weight, wherein the weight is calculated for the protonated form of the preservative.

[0147] External structurants

[0148] The detergents of the present invention can further modify their rheology by using one or more external structurants that form a structured network within the detergent. Examples of such materials include hydrogenated castor oil, microfiber cellulose, and citrus pulp fibers. The presence of an external structurant can provide shear-thinning rheology and can also enable materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0149] The liquid detergent according to the present invention preferably does not contain tocopherols in an amount of 0.001 to 2% by weight. Omitting these antioxidants from the detergent reduces the ingredient list and simplifies the manufacture. For the same reason, the liquid composition according to the present invention also preferably does not contain pearlescent agents as disclosed in US2008 / 0234169. These pearlescent agents are crystalline or glassy solids that can reflect and refract light to produce a pearlescent effect. Such pearlescent agents complicate the manufacture. Although not preferred, such tocopherols and pearlescent agents may be present in the liquid detergent according to the present invention.

[0150] Where the liquid detergent is a laundry detergent it is further preferred that it does not contain peroxygen bleaches such as sodium percarbonate, sodium perborate and peracids.

[0151] An exemplary detergent of the present invention is an aqueous liquid detergent containing a surfactant system (including the nonionic surfactant of the present invention), a dye, an alkoxylated polyamine, a chelating agent, a builder, a perfume, a preservative and one or more enzymes, and contained in a detergent container having an internal volume of 0.5 to 5 L, wherein at least 15% of the outwardly facing surface area is composed of a cellulose-containing material.

[0152] Detergent form

[0153] The liquid detergent product can be in any suitable form, such as a unit dose liquid in a multi-dose (continuous) liquid and / or a water-soluble film. In either case, leakage from a detergent container to the inside of an outer container surface may occur. This can occur by tearing (including, for example, a defective lid) of a detergent container wall. With regard to unit dose, it can occur by the accidental rupture of one or more unit dose capsules and liquid, thereby causing a large amount of liquid accumulation, which then seeps out or reduces its integrity therewith by, for example, a container-box. Preferably, the product is in the form of a detergent container comprising a multi-dose detergent liquid.

[0154] Liquid detergents according to the present invention can be prepared by using conventional techniques known in the field of liquid detergent manufacturing. Typically, the method includes the steps of adding ingredients in any suitable order and mixing the ingredients to the desired homogeneity before filling the detergent container. The detergent container can be directly filled with liquid, such as in the case of a plastic bottle or a detergent container with a plastic liner, or can be filled with a single unit dose containing a liquid detergent. Preferred unit doses are those with a water-soluble film and having more than one compartment.

[0155] In a preferred embodiment, the liquid detergent is isotropic.The detergent is preferably aqueous.Preferably, the liquid detergent is a laundry detergent.

[0156] Unless otherwise stated, preferences in the context of one aspect of the invention (e.g. a detergent product) also apply mutatis mutandis as preferences in the context of one of the other aspects (e.g. use of an ethoxylated nonionic surfactant having an alkyl moiety of C16 to C22 and a molar average degree of ethoxylation of at least 8 EO to reduce staining).

[0157] The invention will now be illustrated by the following non-limiting examples.

[0158] Example

[0159] Example 1 - Effect of Including Ethoxylated Polyamine Polymers.

[0160] A4 Card White Silkweave Linen Textured Matt was obtained from Amazon. The paperboard is recyclable, acid-free, and elemental chlorine-free. Paperboard dye staining was compared with detergent formulations with and without the addition of ethoxylated polyamine polymers.

[0161] A detergent formulation was prepared by dissolving the following dye, which was a blue ethoxylated anthraquinone dye:

[0162]

[0163] 0.5mg dye is dissolved in 2g of clean C16-18, C18 unsaturated methyl ester ethoxylate, which has a molar average of 10 EO groups. Surfactant-dye solution is divided into two parts, one of which adds 1% by weight of ethoxylated polyamine polymer as described in WO2021118814 (Unilever). 50 microliters of surfactant-dye solution (one with added ethoxylated polyamine polymer, and one without adding ethoxylated polyamine polymer) are pipetted onto the separate part of the card, and placed on a flat surface for 1 hour at room temperature. After this incubation period, the card is rinsed under the tap of running water for 10 seconds, dried, and the area of ​​the residual dye spot is measured using a ruler, and the results are provided in Table 1 below.

[0164] Table 1: Effect of ethoxylated polyamines on dye-stained area.

[0165]

[0166] The results of this experiment surprisingly show that the addition of 1 wt% of the ethoxylated polyamine polymer significantly reduces the area of ​​dye on the card.

[0167] Example 2 - Comparison of Surfactant Types.

[0168] A 10% aqueous solution of three different nonionic surfactants was prepared using Acid Violet 50 (5 mg dye / 20 g nonionic surfactant solution). The nonionic surfactants tested were:

[0169] (i) C12-15 alcohol ethoxylates having a molar average of 7EO(ethoxylate)

[0170] (ii) C16-18, C18 unsaturated alcohol ethoxylates having a molar average of 10 EO groups;

[0171] (iii) C16-18, C18 unsaturated methyl ester ethoxylates having a molar average of 10 EO groups

[0172] For cellulose-containing surfaces, the same card type as in Experiment 1 was used. 50 microliters of surfactant-dye aqueous solution were pipetted onto the card and placed on a flat surface at room temperature for 1 hour, then rinsed under a running tap for 10 seconds, dried and the residual dye staining area was measured. The results are given in Table 2 below:

[0173] Table 2: Effect of surfactant type on dye staining area.

[0174]

[0175] The results of this experiment surprisingly showed that different types of nonionic surfactants can affect the size of the stained area on the card.

[0176] Example 3 - Comparison of dye types

[0177] For cellulose-containing surfaces, the same card type as in Experiment 1 or 2 was used. Comparative Example 1 Anthraquinone and Example 2 Acid Violet 50 card dyeing. Solutions of dyes were prepared in neat C16-18, C18 unsaturated methyl ester ethoxylates (having a molar average of 10 EO groups) or in an aqueous solution with 10 wt % of the same surfactant. The same exposure test as in the previous example was carried out: 50 microliters of the (aqueous) surfactant-dye solution was pipetted onto the card and placed on a flat surface at room temperature for 1 hour, then rinsed under a running tap for 10 seconds, dried and the area of ​​residual dye staining was measured. The results are given in Table 3 below:

[0178] Table 3: Effect of dye type in neat or 10% surfactant solution.

[0179] Surfactant-dye solution <![CDATA[in mm 2 calculated dyeing area]]> Neat surfactant + dye of Example 1 8640 Clean surfactant + Acid Violet 50 1520 10% surfactant solution + dye of Example 1 660 10% surfactant solution + acid violet 50 201

[0180] The results of this experiment surprisingly showed that different types of dyes provided different effects on the size of the dyed area on the card.

Claims

1. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions; wherein the outer container has an internal volume of 10 to 500 L; and wherein the material of the outer container comprises at least 30% by weight cellulose; and wherein the outer container comprises one or more detergent containers, wherein at least one of the detergent containers: having an internal volume of 0.1 to 10 L; and having an outer surface comprising one or more externally applied layers comprising less than 5% by weight cellulose; and A liquid detergent composition comprising: 5 to 60 wt% of a surfactant; and 0.00001 to 0.5% by weight of dyes which do not contain sulfonic acid groups and are ethoxylated.

2. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to claim 1, wherein the outer container contains 2 to 50 detergent containers, more preferably 4 to 30, even more preferably 5 to 20, and even more preferably 8 to 15 detergent containers.

3. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to claim 1 or claim 2, wherein the material of the outer container comprises at least 40 wt. %, preferably at least 50 wt. %, more preferably at least 75 wt. %, even more preferably at least 80 to 99.5 wt. % cellulose.

4. An outer container according to any one of the preceding claims suitable for storing and transporting a plurality of detergent containers containing a liquid detergent composition, wherein the detergent comprises at least 40 wt. %, even more preferably 50 wt. %, yet even more preferably 60 wt. % water, yet more preferably at least 70 wt. % water.

5. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to any of the preceding claims, wherein the surfactant comprises a nonionic surfactant in an amount of 0.1 to 25 wt. %, preferably 2 to 20 wt. %, more preferably 4 to 16 wt. %, and even more preferably 5 to 12 wt. %, based on the total weight of the liquid detergent.

6. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to claim 5, wherein the nonionic surfactant comprises a nonionic surfactant having an alkyl portion less than C16 and a molar average ethoxylation degree below 10EO, preferably an alkyl portion of C10 to C15 and a molar average ethoxylation degree of 5 to 8, more preferably an alkyl portion of C12 to C15 and a molar average ethoxylation degree of 6-7.

7. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to claim 6, wherein the nonionic surfactant having an alkyl portion less than C16 and a molar average degree of ethoxylation below 10 EO is present in an amount of at least 20 wt%, more preferably at least 40 wt%, even more preferably at least 60 wt%, and even more preferably at least 80 wt%, based on the total amount of nonionic surfactant.

8. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to any preceding claim, wherein the amount of dye of the detergent is from 0.0001 to 0.1 wt %, and more preferably from 0.0005 to 0.05 wt %, as based on the total weight of the liquid detergent.

9. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to any one of the preceding claims, wherein the detergent dye comprises a dye having the following general structure: wherein R2, R3, X and Y are H or organic groups, and at least one of the groups R2, R3, X and Y contains -[CH2CH2O] n R1 group, wherein n is 2 to 20; and R1 is an organic group or H, preferably R1 is CH3 or H, and more preferably R1 is H; and Preferably, X and Y represent the same group, more preferably H; and • Preferably R2 and R3 are -CH2CH2CH2O(CH2CH2O)2R1, more preferably R1 is -H.

10. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to any preceding claim, wherein the additional dye comprising one or more sulfonic acid groups and being non-ethoxylated, if present in the detergent, is present in an amount of less than 0.05 wt. %, more preferably less than 0.01 wt. %, even more preferably less than 0.005 wt. %, and still even more preferably is substantially absent from the detergent.

11. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to any of the preceding claims, wherein the one or more outer applied layers comprising less than 5 wt. % cellulose covers at least 10 %, more preferably at least 20 %, even more preferably at least 40 %, and still even more preferably 50 to 80 % of the total facing outer surface area of ​​the one or more detergent containers.

12. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to any preceding claim, wherein the container is in the form of a bottle made of a rigid plastic material; or in the form of a carton.

13. An outer container according to any one of the preceding claims suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions, wherein at most 2.0 wt. % of alkoxylated polyamines are present in the detergent, preferably at most 1.0 wt. %, more preferably at most 0.5 wt. %, and even more preferably alkoxylated polyamines are substantially absent from the detergent.

14. An outer container suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions according to any of the preceding claims, wherein at least a portion of the outwardly facing surface of the detergent container not covered by the one or more outer applied layers comprising less than 5 wt % cellulose does not become appreciably wetted if the following procedure is applied on a representative area: applying a 50 microliter droplet of a 10 wt % aqueous solution of a linear alkyl sulfonate to the surface oriented horizontally and facing upward; incubating the droplet for 10 minutes at 20 degrees Celsius and under otherwise standard conditions, wiping off the droplet, and observing whether the area of ​​the droplet is not soaked, wherein the procedure is repeated up to 3 times, preferably up to 5 times, more preferably up to 5 times, and even more preferably up to 6 times.

15. An outer container according to any one of the preceding claims suitable for storing and transporting a plurality of detergent containers containing liquid detergent compositions, wherein at least 50% of the number of detergent containers contained in the outer container have an internal volume of 0.1 to 10 L and have an outer surface comprising one or more outer applied layers having less than 5% by weight of cellulose, and contain a liquid detergent composition comprising: 5 to 60 wt% of a surfactant; and 0.00001 to 0.5% by weight of ethoxylated dyes free of sulfonic acid groups; More preferably, this applies to all detergent containers contained by the outer container.

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