阅读说明：本技术 包含氨基多羧酸盐的固体组合物 (Solid compositions comprising aminopolycarboxylates ) 是由 H·J·M·阿拉博斯瑟 R·J·莫尔 于 2019-02-12 设计创作，主要内容包括：本发明涉及成型洗涤剂产品,所述产品包含固体组合物,所述固体组合物包含：如基于所述固体组合物的总重量计,25至92重量％的游离酸当量的氨基多羧酸盐；和如基于所述固体组合物的总重量计,0.3至50重量％的游离酸当量的聚羧酸盐聚合物；和如基于所述固体组合物的总重量计,2至30重量％的水；其中所述固体组合物是可通过根据本发明的方法获得的。本发明的该固体组合物可以有利地用于生产各种各样的洗涤剂产品。所述固体组合物可以以半透明的或甚至透明的形式提供。本发明进一步涉及一种用于制备根据本发明的固体组合物的方法和包含根据本发明的固体组合物的洗涤剂产品。(The present invention relates to a shaped detergent product comprising a solid composition comprising: 25 to 92 wt% free acid equivalent of an aminopolycarboxylate, based on the total weight of the solid composition; and 0.3 to 50 weight percent, based on the total weight of the solid composition, of a free acid equivalent amount of a polycarboxylate polymer; and 2 to 30 wt% of water, as based on the total weight of the solid composition; wherein said solid composition is obtainable by the process according to the invention. The solid compositions of the present invention can be advantageously used to produce a wide variety of detergent products. The solid composition may be provided in a translucent or even transparent form. The invention further relates to a process for preparing the solid composition according to the invention and to a detergent product comprising the solid composition according to the invention.)

1. A shaped detergent product comprising a solid composition comprising:

25 to 92 wt% free acid equivalent of aminopolycarboxylate, as based on the total weight of the solid composition; and

0.3 to 50 wt% free acid equivalent of a polycarboxylate polymer, as based on the total weight of the solid composition; and

2 to 30 wt% of water, as based on the total weight of the solid composition;

wherein the solid composition is obtainable by a process according to any one of claims 9 to 11.

2. The shaped detergent product of claim 1, wherein the solid composition is amorphous.

3. The shaped detergent product of claim 11 or 2, wherein the solid composition comprises at least 30 wt% of free acid equivalent of an aminopolycarboxylate selected from the group consisting of: glutamic acid N, N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediamine disuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), and combinations thereof.

4. The shaped detergent product according to any of the preceding claims, wherein the solid composition comprises at least 0.3 wt% of free acid equivalent of a polycarboxylate polymer selected from the group consisting of: polyacrylates, copolymers of polyacrylates, polymaleates, copolymers of polymaleates, polymethacrylates, copolymers of polymethacrylates, polymethyl methacrylate, copolymers of polymethyl-methacrylate, polyaspartate, copolymers of polyaspartate, polylactates, copolymers of polylactates, and combinations thereof.

5. The shaped detergent product of any one of the preceding claims, wherein the solid composition comprises from 10 to 60 wt% of free acid equivalents of an acid other than an aminopolycarboxylate or polycarboxylate polymer, as based on the total weight of the solid composition.

6. The shaped detergent product of claim 5, wherein the solid composition comprises at least 10 wt% of free acid equivalent of an acid selected from the group consisting of: acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, sulfuric acid, hydrochloric acid, and combinations thereof.

7. The shaped detergent product of any one of the preceding claims, wherein the solid composition comprises from 5 to 25 wt% water, as based on the total weight of the solid composition.

8. The shaped detergent product according to any of the preceding claims, wherein the solid composition comprises no more than 30 wt% of ingredients other than: an aminopolycarboxylate, a polycarboxylate polymer, an acid other than an aminopolycarboxylate or polycarboxylate polymer, and water.

9. A process for preparing the solid composition of any one of the preceding claims, the process comprising:

I. providing an aqueous solution comprising an aminopolycarboxylate salt and a polycarboxylate polymer; and

removing water from the aqueous solution.

10. The method of claim 9, wherein the method comprises:

removing water from the aqueous solution by evaporation at a temperature of at least 70 ℃ to produce a liquid dry mixture having a water content of no more than 30 wt%, as based on the total weight of the liquid dry mixture; and

reducing the temperature of the dried mixture to below 30 ℃ to obtain the solid composition.

11. The method of claim 10, wherein water is removed from the aqueous solution by evaporation at a temperature of at least 95 ℃.

12. A shaped detergent product comprising the solid composition according to any one of claims 1 to 8 in an amount of from 1 to 90 wt. -%, based on the total weight of the shaped detergent product.

13. The shaped detergent product of claim 12, wherein at least part of the solid composition is visually distinct from the remainder of the detergent product portion.

14. The shaped detergent product of any one of claims 12 or 13, wherein the detergent product is a dish washing machine detergent product, a laundry detergent product, or a toilet seat bar detergent product.

15. The shaped detergent product of any one of claims 12 to 14, wherein the detergent product is a unit dose detergent product.

Technical Field

The present invention relates to shaped detergent products comprising a solid composition, wherein the solid composition comprises an aminopolycarboxylate. In particular, the present invention relates to solid compositions comprising an aminopolycarboxylate, a polycarboxylate polymer and water.

Background

Detergent products typically contain a variety of different active ingredients including builders, surfactants, enzymes and bleaching agents. Surfactants are used to remove stains and soils and to disperse the released components into the cleaning liquid. Enzymes help remove stubborn stains from proteins, starches, and lipids by hydrolyzing these components. Bleaching agents are used to remove stains by oxidizing the components that make up these stains. In order to reduce the adverse effect of especially calcium and magnesium ions on stain/soil removal, so-called "builders" (complexing agents) are often used in detergent products.

Phosphorus-based builders have been used for many years in a wide range of detergent products. Some phosphorus-based builders, such as trisodium phosphate and Sodium Tripolyphosphate (STPP), have set benchmarks in the dishwasher detergent industry for their superior performance. Thus, phosphorus containing builder components are generally considered to be "high performance" builders. The use of phosphorus-based builders in detergent products leads to environmental problems such as eutrophication. To reduce such problems, many jurisdictions have issued or are issuing laws and regulations to limit the maximum amount of phosphorus in detergent products. Thus, there is a need for more environmentally friendly alternative builders that have equivalent (on-par) efficacy and that are also economical. Examples of such alternative builders are aminopolycarboxylates such as glutamic acid N, N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA) and ethylenediaminetetraacetic acid (ethylenediaminetetraacetic acid). A disadvantage of many of these aminopolycarboxylates is that they tend to be water-absorbent.

Some aminopolycarboxylates are commercially available in solid form. For example,

GL-PD-S is a commercially available GLDA powder consisting essentially of the tetrasodium salt of GLDA.

Solid compositions comprising a variety of detergent components can be used to produce a wide variety of detergent products. Shaped detergent products, such as detergent tablets, are typically prepared by combining components that are solid at room temperature with components that are liquid at room temperature. The solid component is typically present in particulate form to facilitate processing and speed of dissolution/dispersion. The tablets are generally prepared by mixing the tablet components followed by compression molding.

Shaped detergent products in the form of multi-phase tablets are also known in the art. These multi-phase tablets comprise one or more component formulations that are typically present in a layered arrangement/body with insert formation. The component preparations contained in the multi-phase tablets are usually composed of opaque compressed materials.

WO 2014/086662 discloses a solid GLDA (i.e. aminopolycarboxylate) material comprising a combination of GLDA, sulfuric acid and sodium sulfate crystals. Also described is a process for producing a solid GLDA composition comprising the following successive steps:

combining GLDA sodium salt and sulfuric acid in a high water activity phase; and

allowing water to evaporate from the phase to produce a precipitate.

It would be desirable to have available solid aminopolycarboxylate compositions that can be used to prepare detergent products to provide one or more important product benefits, such as attractive appearance, improved stability, improved dissolution/dispersion properties, and moldability.

It is an object of the present invention to provide shaped detergent products comprising solid compositions comprising aminopolycarboxylates which provide one or more of these benefits.

Disclosure of Invention

In a first aspect of the invention, the above object is achieved by a shaped detergent product comprising a solid composition comprising:

25 to 92 wt% free acid equivalent of aminopolycarboxylate, as based on the total weight of the solid composition;

0.3 to 50 wt% free acid equivalent of a polycarboxylate polymer, as based on the total weight of the solid composition;

from 2 to 30% by weight of water, as based on the total weight of the solid composition,

wherein said solid composition is obtainable by the process of the invention.

The process of the present invention relates to a process for preparing said solid composition, said process comprising the steps of:

I. providing an aqueous solution comprising an aminopolycarboxylate salt and a polycarboxylate polymer; and

removing water from the aqueous solution.

The solid compositions of the present invention can be advantageously used to prepare a wide variety of detergent products. The solid composition may be provided in a translucent or even transparent form, and may be glossy. Very attractive detergent products, such as shaped detergent products, can be produced by incorporating such translucent/transparent solid compositions as visible elements.

The solid composition may also be applied as an external coating to the shaped detergent product, thereby protecting the detergent ingredients contained in the core of the product (e.g. by protecting these ingredients from moisture). Surprisingly, it has been found that by preparing a solid composition comprising an aminopolycarboxylate, a polycarboxylate polymer and water in the aforementioned concentrations, a solid composition exhibiting plasticity can be obtained. This plasticity is beneficial because it makes the solid composition easier to handle (mechanically) and makes it easier to prepare detergent products comprising the solid composition.

A second aspect of the invention relates to a method for preparing said solid composition.

Preferably, the shaped detergent product comprises the solid composition in an amount of from 1 to 90 wt%, as based on the total weight of the shaped detergent product.

Detailed Description

Definition of

Weight percentages (wt%) are based on the total weight of the solid composition or shaped detergent product or liquid dried (solidified) mixture as indicated, unless otherwise indicated. It is understood that the total weight of the ingredients is not more than 100% by weight. Whenever an amount or concentration of a component is quantified herein, unless otherwise indicated, the quantified amount or concentration refers to the component by itself, even though such component may conventionally be added in solution or in a blend with one or more other ingredients. It will be further understood that the verb "to comprise" and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. Finally, reference to an element by the indefinite article "a" does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one of the element and only one of the element. Thus, the indefinite article "a" or "an" generally means "at least one". All measurements were made under standard conditions, unless otherwise indicated. Whenever a parameter such as concentration or ratio is considered to be less than a certain upper limit, it is understood that in the absence of a specified lower limit, the lower limit of the parameter is 0.

Unless otherwise indicated, the term "aminopolycarboxylate" includes partial and total acids thereof. Salts of aminopolycarboxylates other than the whole acids are more preferred, and alkali metal salts thereof are particularly preferred.

Unless otherwise indicated, the term "acid" includes partial or full alkali metal salts thereof.

The term "polycarboxylate polymer" includes both fully protonated polycarboxylic acid polymers and their salts.

The term "solid" according to the present invention is according to its conventional usage. For example, while a glass (wineglass) is considered a solid in its conventional usage, it is an extremely viscous liquid in a strict physical sense.

The concentration expressed as% by weight of "free acid equivalents" refers to the concentration of the aminopolycarboxylate or acid expressed as% by weight, assuming that the aminopolycarboxylate or acid is present only in fully protonated form. The following table shows how the free acid equivalent concentration can be calculated for some (anhydrous) aminopolycarboxylates and (anhydrous) acid salts.

The term "transparency" as used herein refers to the ability of light within the visible spectrum to at least partially pass through a solid composition. For quantification, it is preferred that it is based on a path length evaluation of 0.5cm through the solid composition, measuring the amount of light passing through. A solid composition is considered translucent if it has a maximum light transmission of at least 5% in the wavelength range of 400 to 700 nm. A solid composition is considered transparent if it has a maximum light transmission of at least 20% within the aforementioned wavelength range. Here, the light transmittance is defined as the ratio (in%) between the light intensity measured after light passes through a solid composition sample and the light intensity measured when the sample is removed.

Gloss is the fraction of light reflected in the specular (mirror-like) direction. The angle of incident light at which gloss is measured is 20 degrees to obtain a measurement result of "high gloss finish", it is 60 degrees to obtain a measurement result of "medium gloss finish", and it is 85 degrees to obtain a measurement result of "matt finish". Good gloss attributes provide better visual appeal and suggest glass cleaning performance of the solid composition. These gloss values were measured using Rhopoint IQ (Goniophorometers; super Rhopoint Instruments) according to the Supplier's instructions. To measure the gloss of the solid composition, this was done on a (separate, continuous) solid composition sample having a thickness of 0.5cm, a flat, smooth surface (e.g. shaped like a disc or a flat plate), and white paper was used as background (100% recycled paper, bright white; supplier: Office depth).

Advantageously, in order to provide even better visual appeal, the solid composition has the following gloss properties:

a specular reflectance of at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, and even more preferably at least 60% at 20 degrees of incident light. Preferably, at most 95%, 90%, 85%, 80% and more preferably at most 75% of reflectance at 20 degrees. The most advantageous 20 degrees reflectance is from 40 to 85%, more preferably from 50 to 80%, and even more preferably from 55 to 75%.

A specular reflectance of at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% at 60 degrees of incident light. Preferably, a reflectance at 60 degrees of at most 99.5%, 99.0%, 98.5% and more preferably 98.0%. The most advantageous 60 degrees is a reflectance of 50 to 99.5%, more preferably 70 to 99.0%, and even more preferably 80 to 98.5%.

A specular reflectance of at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, and even more preferably at least 60% at 85 degrees of incident light. Preferably, a reflectance at 85 degrees of at most 95%, 90%, 85%, 80% and more preferably at most 75%. The most advantageous 85 degree reflectance is from 40 to 85%, more preferably from 50 to 80%, and even more preferably from 55 to 75%.

Of course, it is even more advantageous that the solid composition has a preferred reflectance at 20, 60 and 85 degrees in combination (i.e., has a good high gloss finish and a good medium gloss finish and a good matte finish).

Aminopolycarboxylates

Aminopolycarboxylates are well known in the detergent industry and are sometimes referred to as aminocarboxylate chelants. They are generally considered to be strong builders.

According to a preferred embodiment, the aminopolycarboxylate used according to the present invention is a chiral aminopolycarboxylate. Chirality is the geometric property of a molecule caused by the molecule having at least one chiral center. Chiral molecules are not superimposable with their mirror image. The chiral aminopolycarboxylate as used in the present invention may include all molecular mirror images thereof.

Chiral and preferred aminopolycarboxylates are glutamic acid N, N-diacetic acid (GLDA), methylglycine diacetic acid (MGDA), ethylenediamine disuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM) or mixtures thereof, more preferably GLDA, MGDA, EDDS or mixtures thereof, and even more preferably GLDA and MGDA or mixtures thereof. Preferably, the aminopolycarboxylate as used in the solid composition is substantially GLDA and/or MGDA. In the case of GLDA, it is preferably present predominantly (i.e. more than 80 mole%) in one of its chiral forms.

Examples of achiral aminopolycarboxylates are ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA), aspartic acid diethoxysuccinic Acid (AES), aspartic acid-N, N-diacetic acid (ASDA), hydroxyethylethylenediaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), iminodifumaric acid (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), ethylenediamine difumaric acid (EDDF), ethylenediamine dimalic acid (EDDM), ethylenediamine ditartaric acid (EDDT), ethylenediamine dimaleic acid and (EDDMAL), dipicolinic acid. The achiral aminopolycarboxylate is preferably present in an amount of up to 10 wt%, more preferably up to 5 wt%, and even more preferably is substantially absent from the solid composition of the present invention.

The solid composition of the present invention preferably comprises 30 to 80% by weight of free acid equivalent of the aminopolycarboxylate. More preferably, the aminopolycarboxylate content is from 32 to 70 weight percent free acid equivalents, and even more preferably from 35 to 65 weight percent free acid equivalents.

In a preferred embodiment, the solid composition contains at least 25 wt.%, more preferably at least 30 wt.%, even more preferably at least 32 wt.%, the composition comprising at least 35 wt.% of free acid equivalents of an aminopolycarboxylate selected from the group consisting of: glutamic acid N, N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediamine disuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), and combinations thereof.

In another preferred embodiment, the solid composition comprises at least 25 wt.%, more preferably at least 30 wt.%, even more preferably at least 35 wt.% free acid equivalent of an aminopolycarboxylate selected from GLDA, MGDA, EDDS and combinations thereof.

Polycarboxylate polymers

The solid composition of the present invention comprises 0.3 to 50% by weight of free acid equivalent polycarboxylate polymer. More preferably, the solid composition comprises 0.6 to 25 wt% polycarboxylate polymer, still more preferably in an amount of 1 to 8 wt%, such as based on free acid equivalents. Particularly preferred are solid compositions comprising 1.8 to 6% by weight of the polycarboxylate polymer in free acid equivalent.

Suitable polycarboxylate polymers have an average molar mass Mw of from 500 to 500000. They may be modified unmodified, but are preferably unmodified. Moreover, they may be copolymers or homopolymers, although homopolymers are considered more beneficial.

Surprisingly, it was observed that the hygroscopicity is reduced if the solid composition comprises a polycarboxylate polymer. This reduction is more pronounced if the polycarboxylate polymer used has a lower molecular weight. Having reduced hygroscopicity is of course beneficial as it helps to improve the stability of the shaped detergent product and generally increases shelf life. Polycarboxylate polymers having an average molar mass (Mw) of 900 to 100000, more preferably 1100 to 10000, give particularly good results.

In a preferred embodiment, the solid composition comprises at least 0.3 wt%, more preferably at least 0.6 wt%, even more preferably at least 1 wt% and most preferably at least 1.8 wt% free acid equivalent polycarboxylate polymer selected from the group consisting of polyacrylates, copolymers of polyacrylates, polymaleates, copolymers of polymaleates, polymethacrylates, copolymers of polymethacrylates, polymethylmethacrylates, copolymers of polymethylmethacrylates, polyaspartates, copolymers of polyaspartates, polylactates, copolymers of polylactates, polyitaconates, copolymers of polyitaconates and combinations thereof.

Even more preferably, the composition comprises at least 0.3 wt%, more preferably at least 0.6 wt%, even more preferably at least 1 wt% and most preferably at least 1.8 wt% of free acid equivalent of a polycarboxylate polymer selected from the group consisting of: polyacrylates, copolymers of polyacrylates, polymethacrylates, copolymers of polymethacrylates, and combinations thereof.

A highly preferred polycarboxylate polymer is polyacrylate. Suitable polyacrylates are commercially available, such as from BASF under the following trade names: sokalan PA 13 PN, Solakan PA 15, Sokalan PA 20 PN, Sokalan PA 20, Sokalan PA 25 PN, Sokalan PA 30, Sokalan 30 CL, Sokalan PA 40, Sokalan PA 50, Sokalan PA 70 PN, Sokalan PA 80S and Sokalan PA 110S.

Preferred are partially or fully neutralized polyacrylates.

Thus, highly preferred for use in the solid compositions of the present invention are polyacrylates having the following combination of properties:

present in an amount of from 1 to 25% by weight, based on free acid equivalents; and

it is partially or fully neutralized; and

it has an average molar mass (Mw) of 500 to 500000; and

it is a homopolymer.

From the above, it follows that even more preferred are polyacrylates having the following combination of properties:

present in an amount of 1.8 to 10% by weight, based on free acid equivalents; and

it is partially or fully neutralized; and

it has an average molar mass (Mw) of from 900 to 100000; and

it is a homopolymer.

Water (W)

The solid composition according to the invention comprises from 2 to 30% by weight of water. It has surprisingly been found that the use of such a water content provides a good balance of hardness and plasticity to the solid composition. Depending on the water content, the solid composition may be a hard solid (water content of 2 to 20 wt.%), or a soft solid (water content above 20 to 30 wt.%). The general plastic and thermoplastic properties offer significant practical advantages, since the solid composition can be processed with a low probability of failure or crack formation (machine). Also, not inconsequential, it may provide an improved sensory experience when operated by a user. Better results were obtained with 5 to 25 wt% water and still better results with 6 to 20 wt% water. The latter range provides further optimal results between suitable hardness, reduced brittleness and plasticity. Water-Activity a of the solid composition according to the invention_wAnd may be 0.7 or less. Water activity a of at most 0.6 is preferred_wFurther preferred is a water activity a of at most 0.5_w. Water Activity a_wA preferred lower limit of (d) may be 0.15.

Acid(s)

According to a particularly preferred embodiment, the solid composition comprises 10 to 60% by weight of free acid equivalent of an acid which is not an aminopolycarboxylate or polycarboxylate polymer.

The inclusion of an acid provides the advantage that the hygroscopicity of the solid composition can be further reduced.

In a preferred embodiment, the acid is an organic acid. The organic acid used in the solid composition according to the invention may be any organic acid. Particularly good results are achieved with organic acids which are polybasic acids (i.e. acids having more than one carboxylic acid group), more particularly with organic acids which are di-or tricarboxylic acids.

The organic acid used according to the present invention preferably comprises from 3 to 25 carbon atoms, more preferably from 4 to 15 carbon atoms.

In general, any organic acid may be used, but in view of consumer acceptance, the organic acids are preferably those which are also found naturally, for example in plants. Thus, organic acids of note are acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, salts thereof, or mixtures thereof. Of particular interest are citric acid, aspartic acid, acetic acid, lactic acid, succinic acid, glutaric acid, adipic acid, gluconic acid, salts thereof or mixtures thereof. Citric acid, lactic acid, acetic acid and aspartic acid are even more preferred. Citric acid and/or salts thereof are particularly beneficial because, in addition to being a builder, they are also highly biodegradable. Thus, a more preferred solid composition of the invention comprises (or consists essentially of) citric acid, a citrate salt or a mixture thereof. Generally, acids of organic acids are preferred over their alkali metal salt equivalents.

In a preferred embodiment, the solid composition comprises 15 to 55% by weight of free acid equivalent of acid. More preferably the total amount of acid is from 20 to 52% by weight free acid equivalents, more preferably from 25 to 50% by weight free acid equivalents.

Better results have been achieved with certain weight ratios of aminopolycarboxylate and acid in the solid composition. Thus, it is preferred that the weight ratio of aminopolycarboxylate to acid is from 1:2 to 1:0.15, more preferably from 1:1.5 to 1:0.4, more preferably from 1:1.4 to 1:0.5, based on the weight of free acid equivalents.

Preferably, the solid composition comprises at least 10 wt%, more preferably at least 15 wt%, even more preferably at least 20 wt%, most preferably at least 25 wt% of free acid equivalent of an acid selected from the group consisting of: acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, sulfuric acid, hydrochloric acid, and combinations thereof.

In a particularly preferred embodiment, the solid composition comprises at least 10 wt.%, more preferably at least 15 wt.%, even more preferably at least 20 wt.% of dicarboxylic and/or tricarboxylic acids having a free acid equivalent weight of less than 500 dalton, more preferably less than 400 dalton and most preferably less than 300 dalton.

In a particularly preferred embodiment of the invention, the solid composition comprises at least 10 wt.%, more preferably at least 15 wt.%, even more preferably at least 20 wt.%, most preferably at least 25 wt.% of citric acid in free acid equivalent.

The most preferred combination of aminopolycarboxylate salt and acid comprises a chiral aminopolycarboxylate salt and an organic acid.

Particularly preferred is a composition comprising GLDA and citric acid; or a combination of MGDA and citric acid.

pH profile

The solid composition of the invention preferably has the following pH profile: the pH of a solid composition solution prepared by dissolving the solid composition in water at a 1:1 weight ratio was at most 10.0 as measured at 25 degrees celsius. Such a pH profile improves the stability of the solid composition. Particularly good results are obtained for a pH profile of at most 9.0, more preferably at most 8.0. Many detergent products are generally alkaline. Thus, for practical reasons and to increase the formulation freedom, it is preferred that the pH of a solution prepared by dissolving 1 wt% of the solid composition in water is at least 5.0, more preferably at least 6.0, most preferably at least 6.5.

Solid composition

According to a particularly preferred embodiment of the present invention, the solid composition is a solid amorphous composition. The aminopolycarboxylate salt, polycarboxylate polymer and water are present in the solid amorphous phase in a non-crystalline form. The solid amorphous phase may contain other components in crystalline form but only in such small amounts that the solid amorphous phase has a maximum transmittance of at least 2% in the wavelength range of 400 to 700 nm. Most preferably, the solid amorphous phase is free of crystalline components.

It has been unexpectedly found that solid amorphous compositions containing aminopolycarboxylate salts, polycarboxylate polymers and water can be prepared. The solid composition was found to be free of crystals of aminopolycarboxylate and of polycarboxylate polymer as measured by WAXS using the method listed in the examples. Without wishing to be bound by theory, it is believed that the molecular interaction of the aminopolycarboxylate with the acid (although not covalently bound thereto) prevents crystallization of either of these components. Thus, another benefit of the composition according to the invention is that the composition may be free of further added crystal formation inhibitors.

The solid composition of the invention is preferably translucent/transparent, more preferably also glossy. According to a particularly preferred embodiment, the translucent/transparent solid composition is amorphous, more preferably also glossy. The solid composition preferably has a maximum light transmission of at least 5%, more preferably at least 10%, even more preferably at least 20%, still more preferably at least 25% and most preferably at least 30% in the wavelength range of 400 to 700 nm. According to another preferred mode, the solid composition has an average light transmission in the wavelength range of 400 to 700nm of at least 5%, more preferably at least 10%, even more preferably at least 20% and most preferably at least 25%.

Preferably, the glass transition temperature (T) of the solid composition_g) Less than 80 degrees celsius, more preferably 10 to 60 degrees celsius, even more preferably 15 to 50 degrees celsius, and most preferably 20 to 40 degrees celsius.

Depending on the aminopolycarboxylate and the acid used, the solid compositions of the present invention may be colored and, for example, have a pale yellow hue. The transparency of such solid compositions can be further improved by the addition of a relatively coloring agent, preferably a dye, to the color wheel. For example, on a color wheel, yellow is opposite to blue, and purple is opposite to green. This will make the solid composition substantially more colorless, which may be preferred. It is noted that typical dyes need to be added in relatively small amounts to be effective. Therefore, it is recommended that their level is not higher than 0.5% by weight, preferably at most 0.2% by weight.

Preferably, the solid composition comprises no more than 30 wt% of ingredients other than the aminopolycarboxylate, polycarboxylate polymer, acid, colorant and water, more preferably no more than 20 wt%, still even more preferably no more than 10 wt%, still even more preferably no more than 5 wt%, still even more preferably no more than 2 wt%, and still even more preferably substantially no additional ingredients are present.

Process for preparing solid compositions

A second aspect of the present invention relates to a process for preparing the solid composition of the present invention, said process comprising the steps of:

I. providing an aqueous solution comprising an aminopolycarboxylate salt and a polycarboxylate polymer; and

removing water from the aqueous solution.

Preferably, the aqueous solution comprises:

5 to 45% by weight of free acid equivalent of an aminopolycarboxylate;

0.2 to 1% by weight of a free acid equivalent of a polycarboxylate polymer;

at least 35% by weight of water;

in a preferred embodiment, the method according to the invention comprises:

removing water from the aqueous solution by evaporation at a temperature of at least 50 ℃ to produce a liquid dry mixture having a water content of no more than 30 wt%, such as based on the total weight of the liquid dry mixture; and

reducing the temperature of the dried mixture to below 25 ℃ to obtain the solid composition.

The combination of ingredients in step i. The amount of water used to provide the aqueous solution is advantageously sufficient to completely dissolve components a) and b) at boiling temperatures to simplify processing. Both the aminopolycarboxylate and polycarboxylate polymers can be added as separate pre-prepared aqueous solutions, which is preferred for further simplification of processing.

Heat may be applied to (more quickly) dissolve components a) and b). Applying heat in step i. is preferred as it not only reduces the time to dissolve (if necessary) components a) and b), but also reduces the amount of water required to provide the solution, thereby saving costs. Also, having less water in the solution provided in step I may save time for completing step ii. Preferably, in step i.an aqueous solution having a temperature of at least 50, more preferably at least 70, even more preferably at least 90 degrees celsius, and still even more preferably at least 100 degrees celsius is provided.

The aqueous solution in step i. should be homogeneous at least with respect to the aminopolycarboxylate, polycarboxylate polymer and water. More preferably, the aqueous solution is completely homogeneous. Thus, it is particularly preferred that the aqueous solution of step i. The aqueous solution provided in step i.

Adding a large amount of water in step i. means that more water needs to be removed in step II, requiring additional time and/or energy. Thus, preferably, the aqueous solution provided in step I comprises 40 to 95 wt% water, preferably 45 to 85 wt% water.

Particularly good results may be obtained when the aqueous solution applied in step i. of the process of the invention further comprises an acid as defined herein before. The acid may be introduced into the aqueous solution in pure form or as an aqueous solution. Preferably, the acid is introduced as an aqueous solution.

In step ii. of the process, water is removed from the aqueous solution provided in step i. by evaporation at a temperature of at least 50 degrees celsius to provide a water content of 2 to 30% by weight. Preferably, the water is removed from the aqueous solution by evaporation at a temperature of at least 70 degrees celsius, more preferably at least 90 degrees celsius and most preferably at least 100 degrees celsius.

A preferred way of removing water in step ii. is by applying sufficient heat to boil the aqueous solution provided in step i. This allows for a fast removal of water, which is advantageous for obtaining the benefits of the solid composition according to the invention. Thus, the removal of water may be performed by any suitable method, but preferably such that the removal of water is equivalent to (on-par), or faster than, boiling under otherwise standard environmental conditions.

Preferably step ii. In particular, spray drying is believed to promote crystal formation, thereby reducing the clarity of the resulting solid composition.

The temperature of the dried mixture is reduced to below 25 ℃ to obtain a solid composition. Preferably, the temperature is reduced from 20 to 25 degrees celsius by passive or active cooling. Active cooling may be performed using any conventional means, such as by refrigeration. It is particularly preferred that the cooling of the dry mixture is effected by heat exchange with the remainder of the detergent product portion. In this sense it is particularly preferred that the "solid composition" is applied to the remainder of the detergent product in liquid/viscous form having an elevated temperature and allowed to cure (further) in situ. Further surprising benefits conferred by the solid compositions of the invention are: it can be reheated to improve its plasticity for machining.

Preferably, the solid composition according to the invention is obtainable by the process according to the invention. In view of the properties indicated previously, solid compositions prepared according to the process of the present invention appear to be highly beneficial.

Detergent product

The present invention relates to shaped detergent products, such as comprising the solid composition according to the invention in an amount of from 1 to 90 wt. -%, based on the total weight of the shaped detergent product. Preferably, the detergent product comprises the solid composition according to the invention in an amount of from 2 to 85 wt%, more preferably from 5 to 80 wt%, even more preferably from 10 to 85 wt%.

The solid composition may be present in the detergent product of the invention in any one or more suitable shapes, such as one or more layers, threads (e.g., rods, sticks), spherical or cubic shapes, or combinations thereof. Preferred shapes are as follows: cubes, cylinders, spheres, bars, X-bars, pyramids, prisms, cones, domes and (circular) tubes. Among these, the more preferred shapes are strips, X-strips, cylinders, cubes, (round) tubes and spheres.

Regardless of the geometric arrangement of the solid composition of the invention within the overall detergent product, it is preferred that at least part of the solid composition forms part of the surface of the detergent product. More preferably, at least 10%, 20%, 30%, 40%, more preferably at least 50% of the surface area of the detergent product is formed by the solid composition. Preferably, at most 95%, 90% and more preferably at most 85% of the surface area of the detergent product is formed by the solid composition.

Preferably, at least part of the solid composition is visually distinct from the remainder of the detergent product. In this sense, the solid composition of the invention can be used to form a translucent (partial) skin layer. Further, and this is another preferred use, is that the solid composition acts as a translucent matrix, thereby accommodating visually distinct bodies (e.g., spheres, cubes, or other shapes, preferably spheres, more preferably colored spheres). The body is preferably made of detergent active.

Generally, when making more attractive detergent products, the skilled person has the ability to use the solid compositions of the present invention to exert their advantages. In particular, the solid composition may be used to provide a (partially) translucent detergent product and/or to provide a (partially) glossy detergent product. As mentioned above, the manner in which the solid composition is used in a detergent product in which the solid remains visible and can be of interest due to its translucent and/or shiny nature is highly preferred.

In a preferred embodiment, the detergent product is a unit dose detergent product. In a preferred embodiment, the shaped detergent product has a basis weight of from 5 to 50 grams, more preferably from 10 to 30 grams, even more preferably from 12 to 25 grams.

The detergent product is a shaped detergent product, more preferably a tablet. The solid composition is preferably present in the shaped detergent product in the form of a separate solid phase. The solid phase is preferably at 0.1 to 20cm³More preferably 0.2 to 5cm³Is present. The preferred volume makes the differentiated solid compositions of the present invention readily visible to the naked eye, making them better appreciated for their visual appeal. The solid phase consisting of the solid composition of the invention preferably constitutesFrom 1 to 99 wt%, more preferably from 10 to 85 wt% of the shaped detergent product.

The shaped detergent product according to the invention may further comprise one or more further phases, preferably at least one further solid phase. Preferably, one or more phases are present in an amount of 10 to 99 wt.%. Advantageously, the shaped detergent product comprises from 15 to 90 wt% of said solid composition and from 10 to 85 wt% of the second solid phase. An example of a shaped detergent product comprising a solid composition in combination with a second solid phase is a tablet coated with the solid composition. Another example is a multilayer tablet comprising one or more layers of the solid composition and one or more layers of a second solid phase.

Preferably, the second solid phase is visually distinct from the solid composition. According to a particularly preferred embodiment, the solid composition is translucent/transparent and the second solid phase is opaque.

Preferably, the shaped detergent product of the invention is a dishwashing detergent product, a laundry detergent product or a toilet seat bar detergent product. Most preferably, the shaped detergent product is a dishwashing detergent product.

In the case of a dishwashing machine detergent product, a particularly preferred amount of solid composition is from 5 to 60 wt%, more preferably from 10 to 50 wt%, and even more preferably from 15 to 40 wt%.

In the case of laundry detergent products, particularly preferred amounts of the solid composition of the invention are from 10 to 60, more preferably from 20 to 50% by weight, and even more preferably from 25 to 35% by weight.

In the case of toilet seat (toilet bowl rim) detergent products, particularly preferred amounts of the solid composition of the invention are from 10 to 85 wt%, more preferably from 20 to 80 wt%, and even more preferably from 40 to 70 wt%.

The distinctiveness of the solid composition of the shaped detergent product may be further enhanced by suitable distinctive colourings. This may be done by making it more or less intense in color (e.g., colorless). It is of course preferred that the transparency is maintained to a perceptible degree when coloring is applied. Generally, colorants such as dyes and/or pigments are effective at low amounts, and thus this generally does not pose a problem. In any case, the solid compositions of the present invention are specifically contemplated for use in detergent products and to increase their visual appeal.

The detergent product according to the invention comprises the solid composition according to the invention. Thus, due to this, the detergent product (as a whole) will comprise the aminopolycarboxylate, the polycarboxylate and water. The detergent product also preferably comprises, in other parts, at least one further detergent active ingredient and preferably one or more of the following: enzymes, enzyme stabilizers, bleaches, bleach activators, bleach catalysts, bleach scavengers, drying aids, silicates, metal conditioners, colorants, perfumes, lime soap dispersants, anti-foam agents, anti-discoloration agents, anti-corrosion agents, surfactants, and additional builders.

Additional builders

Additional builder materials may be selected from 1) calcium sequestrant materials, 2) deposition materials, 3) calcium ion-exchange materials, and 4) mixtures thereof. Examples of calcium sequestrant builder materials include alkali metal polyphosphates such as sodium tripolyphosphate, and organic sequestrants such as ethylenediamine tetraacetic acid. Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate. Preferably, the detergent product comprises sodium carbonate in the range of 5 to 50 wt%, more preferably in the range of 10 to 35 wt%. Examples of calcium ion exchange builder materials include various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the most well known representatives, such as zeolite ｃA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and the P-type zeolites described in EP- ｃA-0,384,070.

The detergent product may also contain 0-65% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl or alkenyl succinic acid, nitrilotriacetic acid or other builders as described hereinafter. Many builders are simultaneously bleach stabilizers by virtue of their ability to complex metal ions. Zeolites and carbonates (including bicarbonates and sesquicarbonates)) are preferred additional builders.

The builder may be a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt%. Aluminosilicates are materials having the general formula: 0.8-1.5M₂O·Al₂O₃·0.8-6SiO₂Wherein M is a monovalent cation, preferably sodium. These materials contain some bound water and need to have a calcium ion exchange capacity of at least 50mg CaO/g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO in the above formula₂And (4) units. They can be easily prepared by reaction between sodium silicate and sodium aluminate, as fully described in the literature. The ratio of surfactant to aluminosilicate (when present) is preferably greater than 5:2, more preferably greater than 3: 1.

Alternatively, or in addition to aluminosilicate builders, phosphate builders may be used. In the present invention, the term "phosphate" includes diphosphate, triphosphate and phosphonate species. Other forms of builders include silicates, such as soluble silicates, metasilicates, layered silicates (e.g., SKS-6 from Hoechst). Preferably, however, the detergent product is a non-phosphate built detergent product, i.e. contains less than 1 wt% phosphate, and preferably is substantially free of phosphate.

In view of the environmental concerns associated with the use of high levels of phosphorus-based builders in detergent compositions, it is preferred that the detergent products according to the invention comprise up to 5 wt%, more preferably up to 1 wt% of phosphorus-based builder, and in particular are substantially free of phosphorus-based builder. Examples of phosphorus-based builders are 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), diethylenetriaminepentakis (methylenephosphonic acid) (DTPMP), Ethylenediaminetetramethylenephosphonate (EDTMP), tripolyphosphate, pyrophosphate.

Alkali metal carbonates are of interest for their dual function as builders and buffers, and are preferably present in detergent products. Preferred amounts of alkali metal carbonate in the detergent product, if present, are from 2 to 75 wt%, more preferably from 3 to 50 wt%, and even more preferably from 5 to 20 wt%. For most types of water hardness levels, such levels of alkali metalsThe carbonate provides good Ca²⁺And Mg²⁺Ion scavenging, and other builder functions, such as providing good buffering capacity. Preferred alkali metal carbonates are sodium carbonate and/or potassium carbonate, with sodium carbonate being particularly preferred. The alkali metal carbonate present in the detergent product of the invention may be present as such or as part of a more complex ingredient (e.g. sodium carbonate in sodium percarbonate).

Surface active agent

The detergent product of the invention comprises 0.5 wt% surfactant, preferably 1 to 70 wt% surfactant, more preferably 2 to 50 wt% surfactant. The surfactant may be nonionic or anionic.

In the case of dishwashing machine detergent products, particularly preferred amounts of surfactants are from 0.5 to 25% by weight, preferably from 2 to 15% by weight. In the case of toilet seat detergent products, particularly preferred amounts of surfactant are from 0.5 to 55 wt%, preferably from 10 to 40 wt%. In the case of laundry detergent products, particularly preferred amounts of surfactant are from 2 to 70 wt%, preferably from 10 to 35 wt%.

The nonionic and anionic surfactants of the surfactant system may be selected from "Surface active Agents", Vol.1, Schwartz & Perry, Interscience 1949; volume 2, Schwartz, Perry & Berch, Interscience 1958; surfactants as described in the current version of "McCutcheon's emulsifiers and Detergents", published by Manufacturing conditioners Company, or "Tenside-Taschenbuch", H.Stache, 2 nd edition, Carl Hauser Verlag, 1981. Preferably, the surfactant used is saturated.

Nonionic surfactant

Suitable nonionic surfactants which may be used include in particular the reaction products of compounds having a hydrophobic group and active hydrogen atoms, such as aliphatic alcohols, acids, amides or alkylphenols, with alkylene oxides, in particular ethylene oxide alone or together with propylene oxide.

Preferably, use is made in particular of compounds from alkoxylationLow foaming nonionic surfactants of the group of alcohols. Alkoxylated (advantageously ethoxylated), in particular primary alcohols, having preferably 8 to 18C atoms and an average of 1 to 12mol of Ethylene Oxide (EO) per mole of alcohol, where the alcohol residues may be linear or preferably methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo-alcohol residues, are preferably used as nonionic surfactants. In particular, however, alcohol ethoxylates having a linear residue prepared from alcohols of natural origin having from 12 to 18C atoms (for example from coconut, palm, tallow fat or oleyl alcohol) and having an average of from 2 to 8mol EO per mol of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C with 3EO to 4EO_12-14Alcohols, C with 7EO_9-12Alcohols, C with 3EO, 5EO, 7EO or 8EO_13-15Alcohols, C with 3EO, 5EO or 7EO_12-18Alcohols and mixtures of these, e.g. C with 3EO_12-14Alcohols and C with 5EO_12-19A mixture of alcohols. Preferred tallow fatty alcohols with more than 12EO have 60 to 100EO, more preferably 70 to 90 EO. A particularly preferred tallow fatty alcohol with more than 12EO is a tallow fatty alcohol with 80 EO.

Likewise particular preference is given to using nonionic surfactants from the group of alkoxylated alcohols, particular preference being given to the group of mixed alkoxylated alcohols, in particular from the group of EO-AO-EO nonionic surfactants. The surfactants preferably used originate from the group comprising alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and also mixtures of these surfactants with surfactants of complex structure, such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) nonionic surfactants also differ by good foam control.

The most preferred nonionic surfactants are according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, and even more preferably wherein n is 0 and m is 18 to 25. Surfactants according to this formula are particularly useful for reducing spotting of dishes treated in a dish washing machine. Preferably, the detergent product of the invention comprises at least 50 wt% of the nonionic surfactant according to this formula. Such nonionic surfactants are commercially available, for example under the trade names Dehypon WET (supplier: BASF) and Genapol EC50 (supplier: Clariant).

The shaped detergent products of the invention preferably comprise from 0.5 to 15 wt% of nonionic surfactant. A more preferred total amount of nonionic surfactant is an amount of from 2.0 to 8 wt%, and even more preferred is from 2.5 to 5.0 wt%. The nonionic surfactant used in the detergent products of the invention may be a single nonionic surfactant or a mixture of two or more nonionic surfactants.

The nonionic surfactant is preferably present in an amount of from 25 to 90 wt%, based on the total weight of the surfactant system. The anionic surfactant may be present, for example, in an amount in the range of 5 to 40 wt% of the surfactant system.

Anionic surfactants

Suitable anionic surfactants which may be used are preferably 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 higher acyl groups. Examples of suitable synthetic anionic surfactants are sodium and potassium alkyl sulfates, especially those obtained by sulfating higher C8 to C18 alcohols (e.g., produced from tallow or coconut oil), sodium and potassium alkyl C9 to C20 benzene sulfonates, especially sodium linear secondary alkyl C10 to C15 benzene sulfonates; and sodium alkyl glyceryl ether sulfates, particularly those derived from higher alcohols of tallow or coconut oil and synthetic alcohols derived from petroleum. Preferred anionic surfactants are sodium C11 to C15 alkyl benzene sulfonates and sodium C12 to C18 alkyl sulfonates. Surfactants such as those described in EP-A-328177 (Unilever) which exhibit resistance to salting out, alkylpolyglycoside surfactants described in EP-A-070074, and alkylmonoglycosides are also suitable.

Bleaching system

It is preferred that the shaped detergent product according to the invention comprises at least 5 wt%, more preferably at least 8 wt%, and even more preferably at least 10 wt% of bleach, based on the total weight of the product. The bleaching agent preferably comprises a chlorine or bromine releasing agent or a peroxy compound. Preferably, the bleaching agent is selected from the group consisting of peroxides (including peroxide salts, such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleaching agent is a peroxide. Most preferably, the bleaching agent is percarbonate.

The shaped detergent products of the present invention may contain one or more bleach activators, such as peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. By way of non-limiting example, mention may be made of N, N, N ', N' -Tetraacetylethylenediamine (TAED), Sodium Nonanoyloxybenzenesulfonate (SNOBS), sodium benzoyloxybenzenesulfonate (SBOBS) and cationic peroxyacid precursors (SPCC), as described in U.S. Pat. No. 4,751,015.

Preferably, the shaped detergent product comprises a bleach catalyst. Particularly preferred are bleach catalysts as manganese complexes, such as Mn-Me TACN, as described in EP-A-0458397, and/or sulphoimides of US-A-5,041,232 and US-A-5,047,163 (sulphoimines). It is advantageous that the bleach catalyst is physically separated from the bleach in the detergent product (to avoid premature bleach activation). Cobalt or iron catalysts may also be used.

Enzyme

The shaped detergent product of the invention further preferably comprises one or more enzymes selected from the group consisting of: proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases. Particularly preferred are proteases, amylases, or combinations thereof. If present, the level of each enzyme is from 0.0001 to 1.0 wt%, more preferably from 0.001 to 0.8 wt%.

Silicates of acid or alkali

Silicates are known detergent ingredients and are typically included to provide dishwashing care benefits and to reduce dishwashing corrosion. Particularly preferred silicates are sodium disilicate, sodium metasilicate and crystalline layered silicates or mixtures thereof. If present, the total amount of silicate is preferably from 1 to 15 wt%, more preferably from 2 to 10 wt%, and even more preferably from 2.5 to 5.0 wt%, based on the weight of the shaped detergent product.

Perfume

Preferably, the shaped detergent product of the invention comprises one or more colorants, perfumes or mixtures thereof in an amount of from 0.0001 to 8 wt%, more preferably from 0.001 to 4 wt% and even more preferably from 0.001 to 1.5 wt%.

The perfume is preferably present in the range of 0.1 to 1 wt%. Many suitable examples of perfumes are provided in the CTFA published by CFTAPublifications (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide and the OPD 1993 chemical layers Directory 80th annular Edition published by Schnell Publishing Co. In the perfume mixture, preferably 15 to 25% by weight is top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80[1955 ]). Preferred headnotes are selected from the group consisting of citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

Shading dye

In particular, for laundry detergent compositions according to the present invention, it is preferred that they comprise a hueing dye. For example, shading dyes are added to laundry detergent formulations to enhance the whiteness of fabrics. The shading dye is preferably a blue or violet dye which is substantive to the fabric. Mixtures of hueing dyes may be used and, in practice, are preferred for treating mixed fibre fabrics. Preferred amounts of hueing dye are from 0.00001 to 1.0 wt%, preferably from 0.0001 to 0.1 wt%, in particular, amounts of from 0.001 to 0.01 wt% are preferred. Hueing dyes are discussed in WO2005/003274, WO2006/032327, WO2006/032397, WO2006/045275, WO2006/027086, WOO2008/017570, WO 2008/141880, WO2009/132870, WO2009/141173, WO 2010/099997, WO 2010/102861, WO2010/148624, WO2008/087497 and WO 2011/011799.

Shaped detergent product forms

Due to the presence of the solid composition of the present invention, the shaped detergent product comprises at least a solid part. The remainder of the detergent product may also be non-solid, such as in liquid form, but preferably comprises at least one further solid portion.

The detergent product is preferably provided as a water-soluble or water-dispersible unit dose. Particularly preferred unit doses are in the form of sachets containing at least one additional non-forming stable ingredient, such as a liquid and/or a powder; or in the form of tablets. For ease of use, the unit dose is sized and shaped to fit into a detergent cup of a conventional household dish washing machine, washing machine or toilet seat holder, as is known in the art.

An advantageous unit dose bag preferably has more than one compartment.

Advantageous unit dose tablets are those having more than one visually distinct tablet region. Such areas may be formed, for example, by two different (colored) layers or tablets having a body and different inserts, such as to form nested eggs (nested eggs). Regardless of orientation, one benefit of using a multi-compartment pouch/multi-region tablet is that it can be used to reduce/prevent unwanted chemical reactions between two or more ingredients during storage by physical isolation.

Especially in the case where the detergent product is a dishwashing detergent product, a more preferred unit dose is a tablet. Preferably, the unit dose detergent product is packaged for improved hygiene and consumer safety. The wrapper is advantageously based on a water-soluble film, which is preferably a polyvinyl alcohol (PVA) based film. Such a wrapping prevents the detergent product from coming into direct contact with the skin of the consumer when a unit dose is placed in, for example, a detergent cup/holder of a dishwashing machine. Of course, a further benefit is that the consumer does not need to remove the water-soluble wrap prior to use.

The detergent products according to the invention can be prepared using methods and equipment known in the art of detergent preparation. Detergent products according to the invention may be prepared by combining the solid compositions of the invention with the remainder of the detergent ingredients. In view of preparing tablets, a particularly preferred combination is to press the solid composition of the invention onto (or into) the rest of the tablet ingredients and/or by adding the solid composition in heated (liquid) form.

Preferred detergent product formulationsHighly preferred general detergent product formulations are as follows:

composition (I)	Amount (wt%)
		Solid compositions according to the invention	10 to 80
Surface active agent	0.5 to 70
		Phosphate salts	At most 1.0
Preferably, a combined amount of fragrance and colorant	0.0001 to 8.0

In the case of a dishwashing machine detergent product, the product is preferably a unit dose tablet having the following composition:

composition (I)	Amount (wt%)
		Solid compositions according to the invention	15 to 40
Additional builders, preferably alkali metal carbonates	5 to 20
		Nonionic surfactant	0.5 to 15
Enzyme	0.001 to 0.8
		Silicates of acid or alkali	1 to 10
Bleaching agent + bleach activator + bleach catalyst	2 to 20
		Phosphate salts	At most 1.0
Preferably, a combined amount of fragrance and colorant	0.001 to 1.5

In the case of toilet seat detergent products, the product is preferably a solid block composition, e.g. free of liquid parts and/or powder/granular parts, and even more preferably has the following composition:

composition (I)	Amount (wt%)
		Solid compositions according to the invention	40 to 70
Anionic surfactants	10 to 40
		Nonionic surfactant	0.5 to 15
Bleaching agent + bleach activator	2 to 20
		Total amount of phosphate	At most 1.0
Preferably, a combined amount of fragrance and colorant	0.001 to 8

In the case of laundry detergent products, they advantageously have the following composition:

composition (I)	Amount (wt%)
		Solid compositions according to the invention	5 to 35
Surface active agent	10 to 35
		Enzyme	0.001 to 0.8
Phosphate salts	At most 1.0
		Preferably, a combined amount of fragrance and colorant	0.001 to 4

Unless otherwise indicated, preferred aspects in the context of one aspect of the invention (e.g. solid compositions) also apply (mutatis mutandis) to preferred aspects in the context of one other aspect of the invention.

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