阅读说明：本技术 包含氨基多羧酸盐的成形洗涤剂产品组合物 (Shaped detergent product 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：本发明涉及成形洗涤剂产品,其包含10-100重量％的固体无定形相和0-90重量％的一个或多个其它固体相,所述固体无定形相包含：25-88重量％的游离酸当量的氨基多羧酸盐；10-60重量％的游离酸当量的酸,所述酸不是氨基多羧酸盐；2-30重量％的水,其中所述成形洗涤剂包含至少0.5重量％的表面活性剂。(The present invention relates to a shaped detergent product comprising from 10 to 100 wt% of a solid amorphous phase comprising: 25-88% by weight of free acid equivalent of an aminopolycarboxylate; 10-60% by weight of free acid equivalent of an acid which is not an aminopolycarboxylate; 2-30 wt% water, wherein the shaped detergent comprises at least 0.5 wt% surfactant.)

1. A shaped detergent product comprising from 10 to 100 wt% of a solid amorphous phase comprising:

25-88% by weight free acid equivalent of an aminopolycarboxylate;

10-60% by weight free acid equivalent of an acid which is not an aminopolycarboxylate;

2-30% by weight of water,

wherein the shaped detergent product comprises at least 0.5 wt% surfactant.

2. A shaped detergent product according to claim 1 wherein the product comprises 10-90 wt% of the solid amorphous phase and 10-90 wt% of one or more other solid phases.

3. A shaped detergent product according to claim 1 or 2 wherein the solid amorphous phase comprises an aminopolycarboxylate salt and an acid in a weight ratio of aminopolycarboxylate salt to acid of from 1:2 to 1:0.15 based on the weight of free acid equivalents.

4. A shaped detergent product according to any of the preceding claims wherein the amorphous phase 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.

5. Shaped detergent product according to claim 4, wherein the amorphous phase comprises at least 10 wt% free acid equivalent of di-and/or tri-carboxylic acids having a molecular weight of not more than 300 daltons in their fully protonated form.

6. A shaped detergent product according to claim 5 wherein the amorphous phase comprises at least 10 wt% of citric acid in free acid equivalent.

7. A shaped detergent product according to any of the preceding claims wherein the amorphous phase comprises at least 22 wt% 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.

8. The shaped detergent product of claim 7 wherein the amorphous phase comprises at least 25 wt% of an aminopolycarboxylate selected from the group consisting of GLDA, MGDA, EDDS, and combinations thereof.

9. A shaped detergent product according to any of the preceding claims wherein the amorphous phase comprises 5-25 wt% water.

10. A shaped detergent product according to any of the preceding claims wherein the amorphous phase comprises no more than 30 wt% of ingredients other than aminopolycarboxylate, acid and water.

11. A shaped detergent product according to any of the preceding claims wherein the solid amorphous phase is translucent or transparent.

12. A shaped detergent product according to any of the preceding claims, wherein the product comprises 10-90 wt% of the amorphous phase and 10-90 wt% of a second solid phase, the second solid phase being opaque.

13. A shaped detergent product according to claim 12 wherein the second phase comprises at least 1 wt% surfactant.

14. A shaped detergent product according to any of the preceding claims, wherein the shaped detergent product has a unit weight of from 5 to 50 grams.

15. A shaped detergent product according to any of the preceding claims, wherein at least 10% of the surface area of the shaped detergent product consists of the amorphous solid phase.

Technical Field

The present invention relates to shaped detergent products. In particular, the present invention relates to shaped detergent products comprising a solid amorphous phase comprising an aminopolycarboxylate and water.

Background

Detergent products typically contain several 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 solution. Enzymes help remove stubborn stains from these components by hydrolyzing proteins, starches, and lipids. 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.

Shaped detergent products are known in the art. Detergent tablets are an example of a shaped detergent product. Tablets generally comprise a mixture of a component that is solid at room temperature and a component that is liquid at room temperature. The solid components are usually present in particulate form to facilitate processing and to accelerate dissolution/dispersion. The tablets are typically prepared by mixing the components of the tablet followed by compression into a shaped body.

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, usually in a layered arrangement/body, with an insert formation. The component preparations contained in the multi-phase tablets are usually composed of opaque compressed materials.

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 been benchmarked in the dishwashing 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 (EDTA). A disadvantage of many of these aminopolycarboxylates is that they tend to be hygroscopic.

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 preparing a solid GLDA composition comprising the following successive steps:

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

evaporating water from the phase to produce a precipitate.

It would be desirable to have available shaped detergent products comprising solid aminopolycarboxylates that provide one or more important product benefits, such as attractive appearance, improved stability, and improved dissolution/dispersion properties.

It is an object of the present invention to provide shaped detergent products comprising aminopolycarboxylates which provide such benefits.

Brief description of the invention

In a first aspect of the invention the above object is achieved by a shaped detergent product comprising from 10 to 100 wt% of a solid amorphous phase comprising:

25-88% by weight of free acid equivalent of an aminopolycarboxylate;

10-60% by weight of free acid equivalent of an acid which is not an aminopolycarboxylate;

2-30% by weight of water,

wherein the shaped detergent product comprises at least 0.5 wt% surfactant.

It has surprisingly been found that it is possible to prepare shaped detergent products comprising a solid amorphous phase comprising an aminopolycarboxylate and water. The amorphous phase may be provided in a translucent or even transparent form. Even further advantageously, the amorphous phase may be glossy. Very attractive shaped detergent products can be prepared by incorporating a solid amorphous phase, such as translucent, as the visible element.

The aforementioned solid amorphous phase may also suitably be used as an outer (optionally transparent) coating for shaped detergent products. It has been found possible to incorporate significant amounts of acid into the solid amorphous phase of the shaped detergent product whilst maintaining the amorphous form. The inclusion of an acid significantly reduces the hygroscopicity of the solid amorphous phase. Additionally, an acid such as citric acid may be incorporated into the solid amorphous phase as an additional builder component.

It has surprisingly been found that a solid amorphous phase comprising an aminopolycarboxylate salt, an acid and water can be prepared from an aqueous solution comprising an aminopolycarboxylate salt, an acid and at least 35 wt% water by reducing the water content of the solution to 30 wt% or less while maintaining the liquid mixture at least 50 degrees celsius to produce a liquid dried (solidified) mixture, followed by cooling the dried mixture to a temperature of less than 25 degrees celsius to obtain a solid amorphous phase.

Although the inventors do not wish to be bound by theory, it is believed that the dried liquid formed by reducing the water content of the solution to 30% by weight or less is an amorphous material in a viscous (or rubber-like) state. By cooling the dried liquid, the viscosity increases to a level where the material becomes solid. In case the dried liquid is cooled to a temperature below its glass transition temperature, a hard solid can be obtained. This method provides the advantage of allowing the production of solid amorphous material in the form of (shaped) blocks. Further, the method may be used to coat a solid substrate with a solid amorphous material by coating the substrate with a hot liquid dry mixture and allowing the hot mixture to cool.

Detailed Description

Definition of

Weight percentages (wt.%), unless otherwise indicated, are based on the total weight of the shaped detergent product or solid amorphous phase as indicated. It is understood that the total weight of the ingredients will not exceed 100 weight percent. 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 in the form of an addition solution or 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, an element referred to by the indefinite article "a" or "an" 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 elements and only one of the elements. 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.

The term "distinct" as used herein with respect to a solid amorphous phase means that the phases are visually distinct/distinguishable by the untrained human eye.

Unless otherwise indicated, the term "aminopolycarboxylate" includes both partial and full 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 concentration expressed as weight-% of "free acid equivalents" refers to the concentration of the aminopolycarboxylate or acid expressed as weight-%, assuming that the aminopolycarboxylate or acid is only present 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 pass at least partially through the first solid phase. For quantification, it is preferably evaluated based on a path length of 0.5cm through the first solid phase, thereby measuring the amount of light passing through. A first solid phase of the shaped detergent product is considered translucent if it has a maximum light transmittance of at least 5% under the aforementioned measurement conditions in the wavelength range of 400 to 700 nm. A first solid phase is considered transparent if it has a maximum light transmission of at least 20% in the aforementioned wavelength range. Here, the light transmittance is defined as a ratio between the light intensity measured after light passes through the first solid-phase sample and the light intensity measured when the sample is removed.

The solid amorphous phase may comprise small amounts of (homogeneously dispersed) non-amorphous material (e.g. impurities), but preferably the amount is below 5 wt%, more preferably below 2 wt%, even more preferably below 1 wt%, said weight being based on the total amount of the solid amorphous phase, and most preferably being substantially absent.

Gloss (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 give a "high gloss finish" measurement, 60 degrees to give a "medium gloss finish" measurement, and 85 degrees to give a "matt finish" measurement. Good gloss attributes provide better visual appeal and suggest glass cleaning performance in the solid amorphous phase. 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 amorphous phase, this was done on a (separate, continuous) sample of the solid composition having a thickness of 0.5cm, a flat smooth surface (e.g. shaped like a disc or a plate), and using white paper as background (100% recycled paper, bright white; supplier: Office depth).

Advantageously, to provide even better visual appeal, the solid amorphous phase 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, even more preferably, the solid amorphous phase has a preferred reflectance (i.e., has a good high gloss finish and a good medium gloss finish and a good matte finish) combined at 20, 60 and 85 degrees.

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 amorphous phase is substantially GLDA and/or MGDA. The chiral aminopolycarboxylate may be a mixture of chiral aminopolycarboxylates. 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 amorphous phase of the shaped detergent product of the present invention.

The solid amorphous phase of the present invention preferably comprises 30 to 70% by weight of free acid equivalent of the aminopolycarboxylate. More preferably, the aminopolycarboxylate content is from 32 to 68 wt% free acid equivalents, and even more preferably from 35 to 60 wt% free acid equivalents.

In a preferred embodiment, the amorphous phase comprises at least 25 wt.%, more preferably at least 30 wt.%, even more preferably at least 35 wt.% of GLDA, MGDA, EDDS, IDS, IDM or a mixture thereof in free acid equivalent. In another preferred embodiment, the amorphous phase comprises at least 25 wt.%, more preferably at least 30 wt.%, even more preferably at least 35 wt.% of free acid equivalent GLDA, MGDA, EDDS or mixtures thereof aminopolycarboxylate.

Acid(s)

The solid amorphous phase of the present invention comprises an acid which is not an aminopolycarboxylate.

As explained herein before, it has surprisingly been found possible to prepare a solid amorphous phase comprising an aminopolycarboxylate, water and an acid. The solid amorphous phase was found to be free of aminopolycarboxylate and acid crystals as measured by WAXS using the method listed in the examples. Without wishing to be bound by theory, it is believed that intermolecular interactions of the aminopolycarboxylate salt with the acid (although, not covalently bound thereto) prevent 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.

In a preferred embodiment, the acid is an organic acid. The organic acid used in the solid amorphous phase according to the invention may be any organic acid. Particularly good results are obtained with organic acids as polybasic acids (i.e. acids having more than one carboxylic acid group), more particularly with organic acids as 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 user acceptance, the organic acids used may preferably be those which occur naturally (such as 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 these, 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 its salts are particularly beneficial because, in addition to acting as a builder, they are also highly biodegradable. Thus, a more preferred solid amorphous phase of the invention comprises (and is essentially) 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 amorphous phase 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 were obtained with certain weight ratios of aminopolycarboxylate and acid in the solid amorphous phase. Thus, it is preferred that the weight ratio of aminopolycarboxylate to acid is from 1:2 to 1:0.15, 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 amorphous phase comprises at least 10 wt%, more preferably at least 15 wt%, even more preferably at least 20 wt%, most preferably at least 25 wt% 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 amorphous phase 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 dicarboxylic and/or tricarboxylic acids having a free acid equivalent weight of less than 500 daltons, more preferably less than 400 daltons, and most preferably less than 300 daltons.

In a particularly preferred embodiment of the invention, the amorphous phase 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.

It was found that the solid amorphous phase of the present invention can be made substantially more plastic (less solid) by heating the amorphous phase to a temperature of at least 50 degrees celsius. The thermoplastic properties may suitably be used to prepare shaped detergent products, for example by introducing a plasticized amorphous phase into a mould and solidifying the plasticized amorphous phase in the mould by cooling. Also, the plasticized amorphous phase may be spread as a layer on a solid substrate, followed by cooling to solidify the layer of amorphous phase.

Water (W)

The solid amorphous phase of the shaped detergent product comprises from 2 to 30 wt% water. It has surprisingly been found that such a water content provides a solid amorphous phase with a good balance between hardness and plasticity. Depending on the water content, the solid amorphous phase may be a hard solid (water content of 2 to 20% by weight) or a cartilaginous body (water content higher than 20 to 30% by weight). Typically, solid amorphous phases having a water content of 2 to 30 wt.% are generally plastic (especially at higher water contents). This provides a significant practical advantage, as the solid amorphous phase can be more easily processed (factory machinery) with a low probability of breaking or forming cracks. Also, not inconsequential, it may provide an improved sensory experience when operated by a consumer. Better results were obtained with 5 to 25 wt% water and still with 6 to 20 wt% water. The latter range provides further optimum results between suitable hardness, reduced brittleness and plasticity.

Water activity of the solid amorphous phase a_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. As to water activity a_wThis may be 0.15.

pH profile

The solid amorphous phase of the invention preferably has the following pH profile: the pH of a solid amorphous phase solution prepared by dissolving the solid amorphous 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 amorphous phase. Particularly good results are obtained for said 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, preferably the pH of the solution prepared by dissolving 1 wt% of the solid amorphous phase in water is at least 5.0, more preferably at least 6.0, and most preferably at least 6.5.

Other ingredients

The solid amorphous phase of the present invention may contain other ingredients, such as other detergent active ingredients.

Particularly good results are observed when the solid amorphous phase further comprises polycarboxylate polymers in an amount of 1 to 50 wt% (the weight being based on free acid equivalents). Here, the term "polycarboxylate polymer" is also used to cover the acid form and is different from the acid present in the solid amorphous phase. The addition of polycarboxylate polymer has been shown to surprisingly further increase the plasticity of the solid amorphous phase, as well as increase the glass transition temperature (T) of the solid amorphous phase_g). The increased plasticity is beneficial because it makes the solid amorphous phase easier to process (mechanically) and makes it easier to prepare detergent products comprising a solid amorphous phase. A higher glass transition temperature is beneficial as it contributes to the stability of the solid amorphous phase during storage and handling, especially in view of temperature stress. That is, the glass transition temperature (which is not too high) will help the product dissolve rapidly in warm water, as it helps to liquefy the solid amorphous phase during use by increasing the surface area.

Preferably, the glass transition temperature (T) of the solid amorphous phase_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. Further improvement is observed when the solid amorphous phase comprises polycarboxylate polymer in an amount of 1.5 to 15 wt%, still more preferably 1.8 to 8 wt% (as based on free acid equivalents).

Suitable polycarboxylate polymers have an average molar mass Mw of from 500 to 500000. They may be modified or 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 amorphous phase of the shaped detergent product comprises a polycarboxylate polymer. This reduction is more pronounced if the polycarboxylate polymer used has a lower molecular weight. Reduced hygroscopicity is of course beneficial as it helps to improve the stability of the shaped detergent product and generally increases shelf life. In further improving the glass transition temperature (T)_g) Good results are obtained with polycarboxylate polymers having an average molar mass (Mw) of 900 to 100000, more preferably of 1100 to 10000, in terms of plasticity and hygroscopicity.

In a preferred embodiment, the solid amorphous phase 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 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, polylactate, copolymers of polylactate, polyitaconates, copolymers of polyitaconates, 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 13PN, Solakan PA 15, Sokalan PA 20PN, Sokalan PA 20, Sokalan PA 25PN, Sokalan PA 30, Sokalan 30CL, Sokalan PA 40, Sokalan PA 50, Sokalan PA 70PN, Sokalan PA 80S and Sokalan PA 110S.

Preferred are partially or fully neutralized polyacrylates.

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

present in an amount of from 2 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 polyacrylate salts having the following combination of properties are still more preferred:

used in an amount of 3 to 15% 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.

Depending on the aminopolycarboxylate and the acid used, the solid amorphous phase of the present invention may be colored and, for example, have a pale yellow hue. The transparency of such a solid amorphous phase 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 amorphous phase 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.

The amorphous phase preferably comprises no more than 30 wt% of ingredients other than aminopolycarboxylates, acids, polyacrylates, colorants and water, more preferably no more than 20 wt%, still 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 other ingredients are present.

Process for preparing solid amorphous phase

Another aspect of the invention relates to a process for preparing a solid amorphous phase comprising the steps of:

providing an aqueous solution of an aminocarboxylate and one or more water soluble components, the aqueous solution comprising:

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

-2-40% by weight of free acid equivalent of acid;

-at least 35 wt% water;

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% by weight; and

reducing the temperature of the dried mixture to less than 25 ℃ to obtain a solid amorphous phase.

The process for preparing the solid amorphous phase according to the invention has the advantage of being simple, economical and of omitting the need to add an additional crystal formation inhibitor.

The combining of the components in the first step (i.e., step I.) may be performed in any order. The amount of water used in providing the aqueous solution is advantageously sufficient to completely dissolve components a) and b) at the boiling temperature to simplify the process. Both the aminopolycarboxylate and the mineral acid may be added as separate pre-prepared aqueous solutions, which is advantageous for further process simplification. As indicated, preferred step i. addition of a) as (part of) the alkali metal salt and b) as the acid. When the aminopolycarboxylate is combined with the acid, additional water may need to be added and/or heat applied to completely dissolve the ingredients, as a precipitate may form.

Heat may be applied to (more quickly) dissolve the components a) and b). The application of heat in step i. is preferred because it not only reduces the time to dissolve (if necessary) components a) and b), but it 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, and still even more preferably at least 100 degrees celsius is provided.

The aqueous solution in step i. should be homogeneous, at least in terms of aminopolycarboxylate, acid 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.

The final solid amorphous phase is characterized by a solid amorphous phase ratio of 1:1 in water based on the solid amorphous phase: water weight ratio solution, pH profile of up to 10.0, as measured at 25 degrees celsius. Thus, according to conventional methods, this can be easily achieved by suitably adjusting the pH of the aqueous solution, preferably in step I. For example, the balanced use of the acid or (partially) neutralized salt forms of components a) and b) can be applied.

In a second step of the process (i.e. step II.), water is removed from the aqueous solution provided in step i. by evaporation at a temperature of at least 50 degrees celsius to obtain 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 amorphous phase according to the invention. Thus, this water removal may be performed by any suitable means, but preferably is made equivalent to (on-par) boiling under otherwise standard environmental conditions, or faster.

Preferably, step ii. Spray drying is believed to promote crystal formation and thus reduce the transparency of the resulting solid amorphous phase.

In a third step of the process (i.e., step III), the temperature of the dried mixture is reduced to less than 25 ℃ to obtain a solid amorphous phase. Preferably, the temperature is reduced to 20-25 degrees Celsius. Step iii can be performed using passive cooling or active cooling. Active cooling may be performed using any conventional method, such as by refrigeration.

In a particularly preferred step iii, the cooling of the dried mixture is effected by heat exchange with the remainder of the detergent product portion. In this sense it is particularly preferred that the "solid amorphous phase" is applied to the remainder of the detergent product in liquid/viscous form with elevated temperature and allowed to cure in situ to (further) cure.

Preferably, the solid amorphous phase according to the invention is obtainable by the process according to the invention. In view of the indicated properties, the solid amorphous phase prepared according to the process of the present invention appears to be highly beneficial.

Shaped detergent product

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.

Preferably, the solid amorphous phase present in the shaped detergent product is in the range of 0.1 to 20cm³More preferably at least 0.2 to 15cm³Even more preferably 0.4 to 10cm³Most preferably 0.5 to 5cm³Is present in at least one continuous volume. The preferred volume renders the distinguishing solid amorphous phase of the present invention readily visible to the naked eye, thereby making it better perceived for its visual appeal. The solid amorphous phase may be present in any suitable shape.

The solid amorphous phase 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 amorphous phase 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%.

The shaped detergent products of the invention comprise from 10 to 100 wt% of a solid amorphous phase and from 0 to 90 wt% of one or more other solid phases. Preferably, the shaped detergent product comprises from 10 to 90 wt% of a solid amorphous phase and from 10 to 90 wt% of a second solid phase. An example of a shaped detergent product comprising a solid amorphous phase in combination with a second solid is a tablet coated with the solid amorphous phase. Another example is a multilayer tablet comprising one or more solid amorphous phase layers and one or more second solid phase layers.

Preferably, the second solid phase is visually distinct from the solid amorphous phase. Advantageously the solid amorphous phase is translucent or 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 dish washing machine detergent product.

In the case of a dishwashing machine detergent product, a particularly preferred amount of the solid amorphous phase 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 amorphous phase of the present invention are from 10 to 60 wt%, more preferably from 20 to 50 wt%, and even more preferably from 25 to 35 wt%.

In the case of toilet seat detergent products, particularly preferred amounts of the solid amorphous phase 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 amorphous phase of the shaped detergent product may be 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 transparency is maintained to an appreciable extent when colouring is applied. Generally, colorants such as dyes and/or pigments are effective at low amounts, and thus this is generally not a problem. In any event, the solid amorphous phase of the present invention is specifically contemplated for use in detergent products and increases its visual appeal.

The detergent product of the invention may be present in any suitable shape, such as the shape of a tablet. The solid amorphous phase may be present in the detergent product of the invention in any one or more suitable shapes, such as one or more layers, wires (e.g., rods, bars), spheres, or cube 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.

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.

Preferably, the shaped detergent product is a tablet.

Regardless of the geometric arrangement of the detergent product, it is preferred that at least part of the solid amorphous phase 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 amorphous phase. Preferably at most 95%, 90% and more preferably at most 85% of the surface area of the detergent product is formed by the solid amorphous phase.

The solid amorphous phase of the shaped detergent product may act as a matrix for additional ingredients in the detergent product and retain part or all of it. In this sense, the solid amorphous phase of the present invention can be used to form a translucent (partial) skin layer. Further, and this is another preferred use, the solid amorphous phase acts as a translucent matrix to hold different visually distinct objects (e.g., spheres, cubes or other shapes, preferably spheres, more preferably colored spheres). The body is preferably made of a detergent active ingredient.

Generally, when preparing more attractive detergent products, the skilled person has the ability to use the solid amorphous phase of the invention to exert its advantages. In particular, the solid amorphous phase 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 amorphous phase is used in a detergent product in which the solid remains visible and can be perceived due to its translucent and/or glossy nature is highly preferred.

The detergent product according to the invention comprises a solid amorphous phase according to the invention. Thus, due to this, the detergent product (as a whole) comprises the aminopolycarboxylate, the acid 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 other builders.

Other builders

Other 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, diethylenetriamine-pentaacetic acid, alkyl-or alkenylsuccinic acid, nitrilotriacetic acid or other builders as described below. Many builders are also 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), ethylenediaminetetra-methylenephosphonate (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%. Such alkali carbonate levels provide good Ca for most types of water hardness levels²⁺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 shaped detergent products of the invention comprise 0.5 wt% surfactant, preferably 1 to 70 wt%, 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, low-foaming nonionic surfactants from the group of alkoxylated alcohols are used in particular. 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 residue may be linear or methyl-branched, preferably in the 2-position, or may contain linear and methyl-branched residues in the mixture, as is usually present in oxoalcohol 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, particularly preferably from 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 mixtures of these surfactants with structurally complex surfactants, such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) nonionic surfactants are also distinguished 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. The surfactants according to this formula are used in particular for reducing spotting of dishes treated in a dishwasher. 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 sulfates. Surfactants such as those described in EP-A-328177 (Unilever) which exhibit resistance to salting out, alkyl polyglycoside surfactants and alkyl monoglycosides as described in EP-A-070074 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 which are 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 dish 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 products of the present invention comprise 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%. Examples of many suitable perfumes are provided in the CTFA published by CFTAPublinations (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide and the OPD 1993chemical 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 products according to the invention, it is preferred that these include hueing dyes. 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

The shaped detergent product comprises at least a solid portion due to the presence of the solid amorphous phase. The remainder of the detergent product may also be non-solid, such as in the form of a liquid or paste, but preferably comprises at least one further solid portion.

The shaped 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 stabilizing 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 within a detergent cup of a conventional household dish washing machine, washing machine or toilet seat, as is known in the art.

The unit dose pouch preferably has more than one compartment. It is particularly preferred that at least one such compartment contains a liquid, such as a liquid surfactant, or a powder.

Advantageous unit dose tablets are those having more than one visually distinct tablet region. Such areas may be formed, for example, by two distinct (colored) layers or tablets having a body and distinct inserts, such as to form 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 wrapping material is advantageously based on a water-soluble film, which is preferably a polyvinyl alcohol (PVA) -based film. Such a package 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 amorphous phase of the invention with the remainder of the detergent ingredients. A particularly preferred combination in view of preparing a tablet is to compress the solid amorphous phase of the invention onto (or into) the remainder of the tablet ingredients and/or by adding a solid amorphous phase in heated (liquid) form.

Preferred detergent product formulations

A highly preferred general purpose detergent product formulation is as follows:

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

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:

in the case of laundry detergent products, these advantageously have the following composition:

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

Examples

Analytical method

X-ray diffraction (XRD)

XRD was used to detect the presence of crystalline material in the solid amorphous phase using wide angle X-ray scattering technique (WAXS). XRD was performed using a D8Discover X-Ray Diffractometer from Bruker AXS (activa No: 114175). XRD measurements were performed using the following settings:

differential scanning calorimetry

The glass transition temperature (Tg) of the solid amorphous phase was measured using Differential Scanning Calorimetry (DSC). The equipment used for DSC analysis was a Perkin Elmer power compensated DSC8000 equipped with Intracololer III as a cooling tool. A stainless steel sample pan provided by the supplier with the apparatus was used and filled with the material to be analyzed according to the supplier's instructions. The amount of material added to the sample pan (sample weight) was 10 to 40 mg. The following settings were used in the running assay:

the Tg of the sample was measured with a second heating (i.e., the last heating step in the DSC temperature protocol).