ES2942916T3 - Solid embossed detergent - Google Patents

Abstract

An embossed solid detergent comprising: a) from 25 to 88 wt. % free acid equivalent of non-crystalline chiral aminopolycarboxylate; and b) from 10 to 60 wt. % free acid equivalent of non-crystalline organic acid other than aminopolycarboxylate; and c) from 0.7 to 25 wt. % water; wherein the organic acid has an average molecular mass of at most 500 Daltons, the molecular mass being based on the free acid equivalent. (Automatic translation with Google Translate, no legal value)

Description

DESCRIPTION

Solid embossed detergent

field of invention

The present invention relates to an embossed detergent solid comprising aminopolycarboxylate, organic acid and water. The invention also relates to a process for the production of the embossed detergent solid.

Background of the invention

Detergent products typically contain a number of different active components, including builders, surfactants, enzymes, and bleaching agents. Surfactants are used to remove stains and soils and to disperse released components in the wash liquor. Enzymes help remove tough protein, starch and lipid stains by hydrolyzing these components. Bleaching is used to remove stains by oxidizing the components that make up these stains. To reduce the negative effects of, in particular, calcium and magnesium ions on stain/soil removal, so-called "builders" (complexing agents) are commonly applied in detergent products.

Phosphorus-containing builder components are generally considered "high performance" builders. However, the use of phosphorus-based builders in detergent products has led to environmental problems such as eutrophication. As such there is a need for alternative adjuvants that are more environmentally friendly, have equal efficacy and are also cost effective. Examples of such alternative builders are based on aminopolycarboxylates. WO 2014/086662 discloses a solid glutamic acid-N,N-diacetic acid (GLDA) comprising a combination of GLDA, sulfuric acid and sodium sulfate crystals.

It would be desirable to have stable, solid aminopolycarboxylate solids that have attractive characteristics such as translucency or transparency. In addition, it would be desirable to have stable, massive aminopolycarboxylate solids that allow the surface to be intricately shaped. This would open up new possibilities for designing detergent products comprising these solids with added visual and tactile appeal.

In fact, visual/tactile appeal is of great importance to the commercial success of a detergent product. Solid detergents which are not according to the present invention are disclosed in US 2016/186098 A1.

Portions of detergents in compressed granules are known. These by their very nature have a granular substructure that makes it difficult to intricately shape the surface without complex and energy-intensive processing. Even so, fine details can be brittle and sensitive to abrasion during manufacturing and transport.

An object of the present invention is to provide a stable aminopolycarboxylate solid, which is neither a compacted granule/powder nor a gel, comprising an intricate surface conformation, preferably further having improved dissolution/dispersion properties.

Summary of the invention

One or more of the above objectives are achieved, in a first aspect of the invention, by means of an embossed solid detergent comprising:

a) from 25 to 88% by weight of non-crystalline chiral aminopolycarboxylate free acid equivalent; and b) from 10 to 60% by weight of free acid equivalent of non-crystalline organic acid other than aminopolycarboxylate; and

c) from 0.7 to 25% by weight of water;

wherein the organic acid has an average molecular mass of at most 500 Daltons, the molecular mass being based on the free acid equivalent.

The embossed detergent solid may form all or a portion of a unit dose detergent product.

The solid of the invention comprises chiral non-crystalline polycarboxylate and organic acid as can be measured through WAXS using the method exposed in the examples. By preferably having few or no crystals, the solid according to the invention can be highly light-transmitting. Of course, as desired, additional components may be mixed into the solid to provide a desired level of light transmittance (eg, provide semi-translucency/semi-transparency). As such, the solid of the invention has adjustable light transmittance, and/or adjustable light scattering, which is highly desirable in the manufacture of detergent products. Surprisingly, such a solid can be prepared using only detergent active ingredients. The solid may also have low hygroscopicity, which improves stability (in storage).

It was surprisingly found that the solid of the invention can be intricately surface-shaped and be a stable holding surface embossing. Furthermore, it was surprisingly found that the (local) light scattering of the inventive solid can be fine tuned providing embossing in some areas, but not others. In addition, the embossing allows the surface of the solid of the invention to provide adjustable tactile warning signals when detergent products are handled.

Without wishing to be bound by theory, it is believed that, in the solid according to the invention, the organic acid is homogeneously mixed with the chiral aminopolycarboxylate and molecularly interacts with it (although not covalently bound to it). This is believed to prevent any of these components from crystallizing (substantially) and forming a stable glass-like matrix that is highly light-transmissive and suitable for embossing. Another benefit of the solid of the invention is that the composition can be free of additionally added crystal formation inhibitors.

The solid according to the invention can be prepared with the following process, which refers to the second aspect of the invention: a process for manufacturing the solid according to the invention comprising the consecutive steps of:

I. provide an aqueous solution comprising:

a) non-crystalline chiral aminopolycarboxylate free acid equivalent; and

b) non-crystalline organic acid free acid equivalent different from a);

wherein the weight ratio of a):b) is from 1:2 to 8.8:1;

II. removing water from the aqueous solution by evaporation at a temperature of at least 50°C to produce a dried liquid mixture having a water content of from 0.7 to 25% by weight; and

III. reduce the temperature of the dried mixture to obtain a solid according to the invention

wherein the solid is surface embossed after step II.

The dried liquid that is formed by reducing the water content of the solution to 25% by weight or less is in a viscous (or gummy) state. By cooling the dried liquid, the viscosity increases to a level where the material becomes solid. Lower water content and/or cooling to lower temperatures provide increasingly harder solids. The process offers the advantage that it allows the production of embossed solids and preferably embossed and shaped solids. The solid of the present invention was found to have thermoplastic properties that can be suitably used in embossing. It also makes the solid suitable for extrusion. The dried viscous liquid obtained in step II is provided with a surface embossing, for example, by stamping and/or by solidifying in a mold having an embossing on one or more of the inner surfaces of the mold.

In view of the benefits provided by the solid of the invention, the solid can be used to prepare a detergent product having added visual and tactile appeal. For example, it can form a detergent product on its own or be used as part of a heterogeneous detergent product comprising additional parts. It is important to note that the solid according to the invention can be prepared using detergent actives and does not require the addition of additional non-detergent actives to provide the added visual appeal. The latter is especially beneficial, as consumers today desire component lists in which each component is present for a detergency benefit. In addition, consumers nowadays prefer to have short lists of components.

A further aspect of the invention is the use of the solid according to the invention to provide an embossed detergent product, which is preferably at least in part translucent, and more preferably has a non-uniform light scattering surface.

Detailed description

Figure 1: A black and white photograph of a solid with an overall orange shape according to the invention with surface embossing of regularly spaced dots, diagonally spaced bars and spaced triangular depressions.

Figure 2: A black and white photograph of a solid with an overall star shape according to the invention with three internal surface areas of star-shaped embossments and two internal surface areas of embossed circles. Part of the embossed area comprises regularly spaced dots and part of the embossed area shapes have an otherwise clear surface.

The latter provide low light scattering, the former provide greater light scattering due to the absence/presence of regularly spaced dots.

Definitions

Weight percentage (wt%) is based on the total weight of the solid composition or detergent product as indicated, unless otherwise indicated. It will be appreciated that the total weight amount of components will not exceed 100% by weight. The amounts expressed in parts in % by weight may exceed a total of 100%. Whenever an amount or concentration of a component is quantified herein, unless otherwise indicated, the quantified amount or concentration refers to that component per se, although it may be common practice to add such a component. in the form of a solution or a combination with one or more components. Furthermore, the verb "comprehend" and its conjugations are to be understood in their non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. Finally, the reference to an element by the indefinite article "a/uno" or "una" does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements. items. Therefore, the indefinite article "un/uno" or "una" normally means "at least one". Whenever a parameter, such as a concentration or a ratio, is said to be less than a certain upper limit, it should be understood that in the absence of a specified lower limit, the lower limit for that parameter is 0.

Unless otherwise specified, all measurements are taken under conventional conditions.

The term "distinctive" or "distinct" as used herein means that it is visually distinguishable by the untrained human eye.

The term "solid" according to the invention is according to its common usage. For example, a glass of wine is considered a solid in common usage, although in a strict physical sense it is an extremely viscous liquid. It will be appreciated that the solid according to the invention is embossed so that it is not a powdery composition or a granular composition of such small size that no embossing can be seen.

The term "aminopolycarboxylate" includes partial or total acids thereof unless otherwise specified. The salts, rather than the acids, of the aminopolycarboxylates are more preferred, and the alkaline salts thereof are particularly preferred. The term "organic acid" includes partial or total alkali salts thereof unless otherwise specified.

Concentrations expressed in "free acid equivalent" refer to the concentration of an aminopolycarboxylate or an acid, assuming that the aminopolycarboxylate acid is present exclusively in fully protonated form. The following table shows how free acid equivalent concentrations can be calculated for some aminopolycarboxylates (anhydrous) and acid salts (anhydrous).

The term "translucency" is used in the sense of the ability of light in the visible spectrum to pass through the solid, at least in part. For quantification, it is preferably evaluated based on a path length of 0.5 cm through the solid, measuring the amount of light passing through it. The solid is considered to be translucent if, under the aforementioned measurement conditions within the wavelength range 400 to 700 nm, it has a maximum transmittance of at least 5%. The solid is considered to be transparent if, within the range of wavelengths mentioned above, it has a transmittance maximum of at least 20%. In this case, the transmittance is defined as the ratio between the light intensity measured after the light has passed through the solid sample and the light intensity measured when the sample has been withdrawn.

It is particularly desirable that the solid composition be capable of parallel light transmittance, which means light transmission without appreciable light scattering. Preferably, the degree of light scattering is less than 40%, 30%, 20%, 10%, 5%, 3%, 1%. "Scatter", as used herein, preferably refers to both wide angle scatter and small angle scatter. Wide-angle scatter causes what is known as haze or loss of contrast, while small-angle scatter reduces clarity or see-through quality. Therefore, it is preferable to minimize haze and maximize clarity through minimal narrow and wide angle scattering. Total light transmittance, wide angle scattering, and small angle scattering can be measured using a Haze-Gard I Clear Gauge (SHBG4775) and according to the supplier's instructions. Solid embossed detergent

The solid comprises at least one embossing area. By embossing is meant an area comprising raised portions that rise above the local surface plane and/or comprising depressed portions that are below the local surface plane. The embossing may be present over the entire surface area of the detergent solid, but is preferably present over a portion of the surface area to allow local adjustable surface-based light scattering. Preferably the embossed area covers from 1 to 90% of the total surface area, more preferably from 5 to 70% and even more preferably from 10 to 60%.

The embossing area comprises bumps and/or depressions. Preferably the embossing comprises

• protrusions having a height from the local surface plane of at least 2 microns, preferably from 10 to 500 microns, more preferably from 15 to 250 microns and even more preferably from 20 to 100 microns;

• depressions having a depth from the local surface plane of at least 2 microns, preferably from 10 to 500 microns, more preferably from 15 to 250 microns and even more preferably from 20 to 100 microns;

or a combination thereof. Combinations of bumps and depressions are preferred. Even more preferably the indicated height and depth of the bumps and depressions respectively apply to the average of the bumps and/or depressions.

Preferred embossments provide at least one letter, number, symbol, image, or pattern on the surface of the solid of the invention.

By the term symbol as used in this case is meant the indication of an idea or relationship, generally in an abstract way, which does not imply the use of at least one letter or number. An example of the latter is a hazardous material symbol (for example, to tell parents to keep the solid out of the reach of small children and/or pets). By the term image as used in this case is meant any decorative embossing which does not involve the use of at least one letter, number or symbol. Examples of the latter are flowers. Preferably the images represent real objects. By the term pattern is meant a repeating surface embossing of embossing units. The embossing units are preferably dots, squares or bars of which dots are preferred. Preferably the pattern is regularly spaced and/or provides a geometric pattern. Preferably the patterned area provides a shape recognizable by the presence of the patterned area (or by the absence of the patterned area in other areas). Reference is made to Figure 2, in which dot-patterned regions are visible. The dotted regions provide two star-shaped areas by virtue of the dot pattern that is present and one star-shaped area that is visible by virtue of being free of the surrounding dot pattern. The presence or absence of the pattern on the surface can be used to advantage to control light spread and can provide areas of low light spread and areas of high (higher) light spread.

More preferably the embossing provides a word (for example, a brand name), information about the use of the detergent (for example, an image of a glass of wine for an intended use to clean glassware), information on sustainability (for example, a picture of a leaf), a smiley, a warning sign, a geometric pattern, or a combination thereof.

Non-crystalline chiral aminopolycarboxylate

Aminopolycarboxylates (chiral or non-chiral) are well known in the detergent industry and often Sometimes referred to as aminocarboxylate chelators. They are generally appreciated for being strong adjuvants. Chirality is a geometric property of molecules induced by molecules that have at least one chiral center. A chiral molecule is not superimposable on its mirror image. The chiral aminopolycarboxylate as used in the invention may comprise all of its molecular mirror images.

Chiral and preferred aminopolycarboxylates are glutamic acid-N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodymalic acid (IDM) or a mixture thereof, plus preferred are GLDA, MGDA, EDDS or a mixture thereof and even more preferred are GLDA and MGDA or a mixture thereof. In the case of GLDA, preferably, it is present predominantly (ie, more than 80 mol%) in one of its chiral forms. Examples of non-chiral 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), hydroxyethylenediaminetetraacetic acid (HEDTA), hydroxyethylenediaminetriacetic acid (HEEDTA), iminodifumaric acid (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid (EDDM) , ethylenediamineditartaric acid (EDDT), ethylenediaminodimaleic acid and (EDDMAL), dipicolinic acid. Non-chiral aminopolycarboxylates are preferably present in an amount of at most 10% by weight, more preferably at most 5% by weight, and even more preferably essentially absent from the solid of the invention.

The solid of the invention comprises from 25 to 88% by weight of free acid equivalent of chiral aminopolycarboxylates. A particularly preferred amount of chiral aminopolycarboxylate is from 30 to 70% by weight and more preferably from 35 to 60% by weight. The weight of chiral aminopolycarboxylates is measured on a free acid equivalent basis.

Preferably, the solid of the invention contains at least 50% by weight, more preferably at least 75% by weight of free acid equivalent of GLDA, MGDA, EDDS, IDS, IDM or a mixture thereof, based on the total weight of chiral aminopolycarboxylate free acid equivalent. More preferably, the solid contains at least 50% by weight, more preferably at least 75% by weight of free acid equivalent of GLDA, MGDA, EDDS or mixtures thereof, based on total free acid equivalent weight. of chiral aminopolycarboxylate. Even more preferably, the free acid equivalent of aminopolycarboxylate consists essentially of one free acid equivalent of GLDA, MGDA, EDDS or a mixture thereof. GLDA is generally more appreciated as it can be made from biobased materials (for example, monosodium glutamate, which itself can be made as a by-product of corn fermentation). Furthermore, GLDA is highly biodegradable.

Non-crystalline organic acid

The solid according to the invention comprises organic acid, said acid not being an aminopolycarboxylate. The organic acid used in the solid according to the invention can otherwise be any organic acid. Particularly good results were achieved with organic acids that are polyacids (ie, acids having more than one carboxylic acid group), and more particularly with di- or tricarboxylic organic acids.

The organic acids used in the invention have an average molecular mass of at most 500 Daltons, preferably at most 400 Daltons and more preferably at most 300 Daltons, the molecular mass being based on free acid equivalent. The organic acid used according to the invention preferably comprises 3 to 25 carbon atoms, more preferably 4 to 15 carbon atoms. In view of consumer acceptance, organic acids are preferably those that also occur naturally, such as in plants. As such, the organic acids of interest 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, their salts or mixtures of the same. Of these, citric acid, aspartic acid, acetic acid, lactic acid, succinic acid, glutaric acid, adipic acid, gluconic acid, their salts or mixtures thereof are of particular interest. Citric acid, lactic acid, acetic acid and aspartic acid are even more preferred. Citric acid and/or its salt are especially beneficial since, in addition to acting as an adjuvant, they are also highly biodegradable. As such, it is advantageous if the solid contains at least 10, more preferably at least 15, even more preferably at least 20, most preferably at least 25% by weight free acid equivalent of citric acid.

The solid of the invention comprises from 10 to 60% by weight of the organic acid, the weight being based on the equivalent free acid. A total amount of organic acid of from 15 to 55% by weight is preferred, more preferably from 25 to 50% by weight, based on the weight of free acid equivalents.

Better results were achieved with certain weight ratios of a):b). Therefore, it is preferred that the reason by weight of a):b) 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 and even more preferably from 1:1.2 to 1:0.8, based on the weight of free acid equivalents.

Water

The embossed solid according to the invention comprises from 0.7 to 25% by weight of water. It was surprisingly found that the use of such a water content gave a solid with a good balance of hardness and plasticity and stability of the embossing structure. Depending on the water level, the solid can be a harder solid with water levels in the lower range of from 0.7 to 25% by weight water. The general plasticity and thermoplastic properties offer the significant practical advantage that the solid can be (machined) with a low probability of breakage or cracking and that it has improved stability of the embossed structure. Also, not unimportantly, it can provide an enhanced sensory experience when handled by the consumer.

Best results were achieved with amounts of water that have a lower end of the range of at least 1.0, 1.2, 1.4, 1.5, 1.6, 2.0, 2 0.5 and even more preferably 3.0% by weight; combined with an upper range limit of at most 20, 18, 17, 15, 13, 11, 10 and even more preferably 8% by weight. The lower ends and the upper ends can be easily combined, such that an amount of water of preferably from 1.8 to 20% by weight, more preferably from 1.4 to 15% by weight, even more preferably from 1.5 to 8% by weight. These latter ranges provide a further optimum balance between adequate hardness, reduced brittleness especially when sulfonated polymer and/or polycarboxylate polymer (as described below) is included. The water activity aw of the solid according to the invention may be 0.7 or less. A water activity aw of at most 0.6 is preferred, and further preferred is at most 0.5. The preferred lower limit of water activity aw may be 0.15.

Advantageously, the total amount of non-crystalline chiral aminopolycarboxylate, non-crystalline organic acid and water is from 60 to 100% by weight based on the total weight of the solid according to the invention, preferably from 70 to 100% by weight, more preferably from 80 to 100% by weight, even more preferably from 90 to 100% by weight and even more preferably from 95 to 100% by weight of the total weight of the solid according to the invention.

As such, a highly preferred embossed detergent solid according to the invention comprises:

a) from 30 to 70% by weight of non-crystalline chiral aminopolycarboxylate free acid equivalent; and b) from 15 to 55% by weight of free acid equivalent of non-crystalline organic acid other than aminopolycarboxylate; and

c) from 0.7 to 15% by weight of water;

wherein a), b) and c) form from 70 to 100% by weight of the total weight of the embossed detergent solid. Given the above, an even more preferred embossed detergent solid according to the invention comprises:

a) from 35 to 60% by weight of non-crystalline chiral aminopolycarboxylate free acid equivalent; and b) from 25 to 50% by weight of free acid equivalent of non-crystalline organic acid other than aminopolycarboxylate; and

c) from 1 to 10% by weight of water;

wherein a), b) and c) form from 80 to 100% by weight of the total weight of the embossed detergent solid. Clearly, given the foregoing, the even more preferred embossed solid detergent according to the invention comprises:

a) from 35 to 60% by weight of non-crystalline chiral aminopolycarboxylate free acid equivalent; and b) from 25 to 50% by weight of free acid equivalent of non-crystalline organic acid other than aminopolycarboxylate; and

c) from 2.0 to 8% by weight of water;

wherein a), b) and c) form from 90 to 100% by weight of the total weight of the embossed detergent solid.

pH profile

Very advantageously, the solid of the invention preferably has the following pH profile: the pH of a solution of the solid prepared by dissolving the solid in water in a 1:1 weight ratio is at most 10.0, as measured at 25°C. Such a pH profile improves the stability of the solid. Particularly good results were achieved for said pH profile which is at most 9.0, more preferably at most 8.0. Many detergent products are generally alkaline. As such, for practical reasons and to increase formulation freedom, preferably the pH of a solution prepared by dissolving 1% by weight of the solid in water is at least 5.0 and more preferably at least 6.0 and most preferably at minus 6.5 as measured at 25°C.

additional components

The solid of the invention may comprise additional components, such as additional detergent active components.

The solid of the invention preferably comprises sulfonated polymer, polycarboxylate polymer or a combination thereof in a total amount of from 0.3 to 50% by weight, more preferably from 5 to 40% by weight, even more. preferably from 10 to 35% by weight and still even more preferably from 15 to 25% by weight, based on the free acid equivalent of the polymer.

The inclusion of such polymers was found to reduce hygroscopicity, increase hardness, plasticity and improve glass transition temperature. The improved plasticity is beneficial in that it facilitates the (mechanical) working of the solids (ie at elevated temperatures) and facilitates the manufacture of the detergent product comprising the solid. A higher glass transition temperature is beneficial in that it aids in the stability of the solid during storage and handling, particularly in view of thermal stresses. That being said, a glass transition temperature that is not too high will aid rapid dissolution of the product in warm water as it helps liquefy the solid during use by increasing the surface area. Preferably, the glass transition temperature (T ^g ) of the solid is less than 80°C, more preferably from 10 to 60°C, even more preferably from 15 to 50°C and most preferably from 20 to 40°C. The reduction in hygroscopicity was more pronounced if the polymer (particularly the carboxylate polymer) used has a lower peak average molecular weight.

Sulfonated polymer

The sulfonated polymer used according to the present invention may be a copolymer or a homopolymer. Preferably the sulfonated polymer is a copolymer.

Suitable sulfonated polymers preferably have a mass average molecular weight of from 3,000 to 50,000, more preferably from 4,500 to 35,000.

In a preferred embodiment, the solid composition comprises sulfonated polymer comprising polymerized units of one or more unsaturated sulfonate monomers selected from 2-acrylamidomethyl-1-propanesulfonic acid, 2-methacrylicamido-2-methyl-1-propanesulfonic acid, 3- methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid , 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide.

According to another preferred embodiment, the solid composition comprises sulfonated polymer comprising polymerized units of one or more unsaturated sulfonate monomers represented by the following formula:

CH ² =CR1-CR2R3-OC ⁴ H ^to R4-SO ^to X

In which

R1, R2, R3, R4 independently represent C1-C6 alkyl or hydrogen;

X represents hydrogen or alkali.

According to a particularly preferred embodiment, the sulfonated polymer is a copolymer comprising polymerized units of monoethylenically unsaturated C3-C6 monocarboxylic acid. More preferably, the sulfonated copolymer comprises the following monomers in polymerized form:

• 50-90% by weight of one or more C3-C6 monoethylenically unsaturated monocarboxylic acids;

• 10-50% by weight of unsaturated sulfonate monomers as defined herein above.

According to another preferred embodiment, the C3-C6 monoethylenically unsaturated monocarboxylic acids in the sulfonated copolymer are selected from acrylic acid, meth(acrylic) acid, and combinations thereof. As such, highly preferred for use in the solid of the invention are sulfonated copolymers having the following combined properties:

• which are present in an amount of from 10 to 35% by weight, based on the free acid equivalent; and

• that are partially or completely neutralized; and

• having an average molar mass (Mw) of from 3,000 to 50,000

• comprising the following monomers in polymerized form: 50-90% by weight of one or more C3-C6 monoethylenically unsaturated monocarboxylic acids; and 10-50% by weight of unsaturated sulfonate monomers selected from 2-acrylamidomethyl-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid.

Polycarboxylate polymer

The term "polycarboxylate polymer" is used herein to also encompass the acid form and is different from the acid that is present in the solid.

Suitable polycarboxylate polymers have an average molar mass Mw of from 500 to 500,000. They may be modified or unmodified, but are preferably unmodified. They can also be copolymers or homopolymers, although homopolymers are considered more beneficial.

Polycarboxylate polymers having an average molar mass (Mw) of from 900 to 100,000, more preferably 1100 to 10,000, fared best in terms of further enhancing the described benefits of adding polymer.

Preferably, the solid comprises polycarboxylate polymer selected from polyacrylate, polyacrylate copolymers, polymaleate, polymaleate copolymers, polymethacrylate, polymethacrylate copolymers, polymethyl methacrylate, polymethyl methacrylate copolymers, polyaspartate, polyaspartate copolymers, polylactate, polylactate copolymers, polyitaconates, polyitaconate copolymers, and combinations thereof.

Highly preferred polycarboxylate polymers are polyacrylates. Suitable polyacrylates are commercially available, such as BASF under the trade name Sokalan PA 13 PN, Sokalan 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 80 S and Sokalan PA 110 S.

Polyacrylates that are partially or completely neutralized are preferred.

As such, highly preferred for use in the solid of the invention are polyacrylates having the following combined properties:

• which are present in an amount of from 10 to 35% by weight, based on the free acid equivalent; and

• that are partially or completely neutralized; and

• having an average molar mass (Mw) of from 900 to 100,000; and

• that are homopolymers.

Of the polycarboxylate polymers and sulfonated polymers, the polycarboxylate polymers are most preferred.

Dyes in the solid

The solid of the invention may, depending on the aminopolycarboxylate and acid used, be colored and, for example, have a yellowish tinge. The translucency of such a solid can be further improved by adding a colorant opposite the color wheel, which is preferably a dye. For example, yellow opposes blue on the color wheel, and violet opposes green. This will render the solid essentially more colorless, which may be preferred. It is noted that it is necessary to add typical dyes in relatively small amounts to be effective. Therefore, it is suggested that its level is not more than 0.5% by weight and is preferably at most 0.2% by weight.

The embossed detergent solid preferably contains no more than 30% by weight of components other than aminopolycarboxylate, acid, polyacrylate and/or sulfonated polymer, dyes and water, more preferably no more than 20% by weight, still even more preferably no more than 10 % by weight, still even more preferably not more than 5% by weight, still even more preferably not more than 2% by weight and still even more preferably essentially no additional components are present. If additional components are present in the solid composition, these are preferably water-soluble non-crystalline components.

solid shape

The solid of the invention can be of any suitable shape and size.

When used, as part of a detergent product or otherwise, it is preferably present in at least a continuous volume of from 0.2 to 15 cm3, even more preferably from 0.4 to 10 cm3, most preferably from 0, 5 to 5 cm3. Said preferred volumes allow the solid of the invention to be easily visible to the naked eye, allowing it to be better appreciated for its visual appeal. The solid may be present in any suitable form.

When used, as part of a detergent product or otherwise, it preferably has at least a continuous, preferably generally flat, surface area of from 0.5 to 25 cm2, even more preferably from 1.0 to 10 cm2, most preferably from 2.0 to 5 cm2. Said preferred sizes allow the embossing to be easily visible to the naked eye, allowing its visual appearance to be better appreciated by the untrained human eye.

The solid preferably has a maximum transmittance within the wavelength range 400 to 700 nm 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%. According to another preference, the solid has an average transmittance in the wavelength range from 400 to 700 nm of at least 5%, more preferably at least 10%, even more preferably at least 20% and most preferably preferably at least 25%.

detergent product

The embossed detergent solid can form a detergent product (unit dose) by itself or be part of a detergent product (unit dose). If it forms part of a unit dose detergent product, the detergent product comprises the solid according to the first aspect of the invention in an amount of from 1 to 90% by weight, preferably in an amount of from 5 to 85% by weight, more preferably in an amount of from 10 to 70% by weight, and even more preferably in an amount of from 20 to 50% by weight.

In the case of dishwashing detergent products, the particularly preferred amount of the solid of the invention is from 5 to 60% by weight, more preferably from 10 to 50% by weight and even more preferably from 15 to 40% by weight. .

In the case of detergent products for the rim of the toilet bowl, the particularly preferred amount of the solid of the invention is from 10 to 85% by weight, more preferably from 20 to 80% by weight and even more preferably from 40 to 70% by weight.

In the case of laundry detergent products, the particularly preferred amount of the solid of the invention is from 1 to 60, more preferably 2 to 50% by weight, and even more preferably 5 to 35% by weight.

At least part of the solid according to the invention is visually distinct from the rest of the part(s) of the detergent product. The visual distinctiveness of the solid is preferably based on the solid having a (higher) translucency compared to the other solid part(s) of the detergent product and/or the present embossing. The distinctive character of the solid can be further enhanced by a suitable distinctive colouring. This can be by making it a more intense or less intense color (for example, colorless). Preferably, by Of course, when staining is applied, translucency is maintained to an appreciable degree. Colorants, such as dyes and/or pigments, are generally effective in low amounts and, as such, this is usually not problematic. In any case, it is particularly envisaged that the solid composition of the invention will be used to provide a detergent product with improved visual appeal.

The solid may be present in any suitable shape or shapes, such as one or more layers, linear structures (eg, rods, beams), spherical or cuboid shapes, or combinations thereof. Preferred shapes are: cuboid, cylinder, sphere, rod, X-bar, pyramid, prism, cone, dome, and tube (circular). Of these most preferred shapes are bar, X-bar, cylinder, cuboid, tube (circular) and sphere.

Whatever the geometric arrangement of the solid of the invention (within the detergent product in general), it is preferred that at least part of the solid 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 made up of the solid. Preferably at most 95%, 90% and more preferably at most 85% of the surface area of the detergent product is made up of the solid.

The solid of the invention in the detergent product can itself act as a matrix and contain part, or all, of the additional components in the detergent product. In this sense, the solid of the invention can be used to form a (partial) embossed skin. Advantageously, the solid acts as a translucent matrix containing one or more distinct bodies, which may be visible in the matrix. The bodies preferably having the shape of spheres or cubes. The bodies being preferably colored.

In general, one skilled in the art is endowed with the ability to use the embossed solid of the invention to their advantage when preparing more attractive detergent products. As described above, highly preferred ways of using the solid in a detergent product are in which the solid remains clearly visible, which can be appreciated by its translucent and/or shiny nature and, of course, by its embossing.

The detergent product according to the invention comprises the embossed solid according to the invention. As such, the detergent product (as a whole) will comprise chiral aminopolycarboxylate, organic acid and water by virtue of this. The detergent product preferably further comprises, but preferably in the other part(s) than the solid of the invention, at least one additional detergent active ingredient, and preferably one or more of enzymes, enzyme stabilizers, detergents, bleach, bleach activator, bleach catalyst, bleach removers, drying aids, silicates, metal care agents, colorants, perfumes, lime soap dispersants, antifoam, antitarnish, anticorrosion agents, surfactants and other adjuvants.

additional adjuvants

Additional builder materials may be selected from 1) calcium sequestering materials, 2) precipitating 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 ethylenediaminetetraacetic acid. Examples of precipitation builder materials include sodium orthophosphate and sodium carbonate. Preferably the detergent product comprises sodium carbonate in the range from 5 to 50% by weight, most preferably 10 to 35% by weight. Examples of calcium ion exchange builder materials include the various types of water-insoluble amorphous or crystalline aluminosilicates, of which zeolites are the best known representatives, for example, zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also zeolite type P as described in EP-A-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 alkenylsuccinic acid, nitrilotriacetic acid or other builders mentioned below. Many builders are also bleach stabilizing agents by virtue of their ability to complex with metal ions. Zeolite and carbonate (including bicarbonate and sesquicarbonate) are additional preferred builders. The builder may be crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is normally present at a level of less than 15 % by weight Aluminosilicates are materials having the general formula: 0.8-1.5 M2O.AhO3.0.8-6 SiO2, where M is a monovalent cation, preferably sodium.

These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units in the above formula. They can be easily prepared by reaction between sodium silicate and sodium aluminate, as widely described in the literature. The ratio of surfactants 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 can be used. In this invention, the term "phosphate" encompasses diphosphate, triphosphate and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (eg SKS-6 from Hoechst). However, preferably the detergent is a phosphate-free detergent, ie it contains less than 1% by weight of phosphate and preferably is essentially phosphate-free.

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 product according to the invention comprises at most 5% by weight, more preferably at most 1% by weight. and particularly essentially does not contain phosphorus-based builders. Examples of phosphorous-based builders are 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepenta(methylenephosphonic) acid (DTPMP), ethylenediaminetetramethylenephosphonate (EDTMP), tripolyphosphate, pyrophosphate.

Alkali carbonate is appreciated in view of its dual function as builder and buffer and is preferably present in the detergent product. If present, the preferred amount of alkali carbonate in the detergent product is from 2 to 75% by weight, more preferably from 3 to 50% by weight and even more preferably from 5 to 20% by weight. . Such an alkali carbonate level provides good removal of Ca2+ and Mg2+ ions for most types of water hardness levels, as well as other adjunctive effects, such as providing good buffering capacity. Preferred alkali carbonates are sodium and/or potassium carbonate, of which sodium carbonate is particularly preferred. The alkali carbonate present in the detergent product of the invention may be present as such or as part of a more complex component (eg sodium carbonate in sodium percarbonate).

surfactant

It is preferred that the detergent product of the invention comprises 0.5 to 70% by weight of surfactant, more preferably 2 to 50% by weight. The surfactant can be nonionic or anionic.

In the case of dishwashing detergent products, the particularly preferred amount of surfactant is from 0.5 to 25% by weight, preferably 2 to 15% by weight. In the case of toilet bowl rim detergent products, the particularly preferred amount of surfactant is from 0.5 to 55, preferably 10 to 40% by weight. In the case of laundry detergent products, the particularly preferred amount of surfactant is from 2 to 70, preferably from 10 to 35% by weight.

The nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described in "Surface Active Agents" vol. 1, by Schwartz and Perry, Interscience 1949, vol. 2 from Schwartz, Perry and Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by the Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd ed., Carl Hauser Verlag, 1981. Preferably , the surfactants used are saturated.

Nonionic surfactants

Suitable nonionic surfactants that can be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially oxides of ethylene, either alone or with propylene oxide.

Preferably, low foaming nonionic surfactants are used, particularly from the group of alkoxylated alcohols. In particular, alkoxylated primary alcohols, advantageously ethoxylated, with preferably 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcoholic residue can be linear or preferably branched with methyl in the 2-position or may contain linear and methyl-branched residues in the mixture, as are normally present in oxoalcohol residues, are preferably used as nonionic surfactants. In particular, however, alcohol ethoxylates with linear residues prepared from naturally occurring alcohols with 12 to 18 carbon atoms, e.g. coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol. Preferred alcohol ethoxylates include, for example, C ^12-14 alcohols with 3 EO to 4 ^EO, C ^9-12 alcohol with 7 EO, C ^13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 ^{EO ,} C ^12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ^12-14 alcohol with 3 EO and C ^12-19 alcohol with 5 EO. Preferred tallow fatty alcohols with more than 12 EO have from 60 to 100 EO, and more preferably from 70 to 90 EO. Particularly preferred tallow fatty alcohols with more than 12 EO are tallow fatty alcohols with 80 EO.

Nonionic surfactants from the group of alkoxylated alcohols are also particularly preferably used, particularly preferably from the group of mixed alcohol alkoxylates and in particular from the group of nonionic surfactants E0-AO-EO. The nonionic surfactants used preferably come from from the groups 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). Such nonionic surfactants (PO/EO/PO) are additionally distinguished by good foam control.

The most preferred nonionic surfactants are according to the formula:

where n is from 0 to 5 and m is from 10 to 50, more preferably where n is from 0 to 3 and m is from 15 to 40, and even more preferably where n is 0 and m is from 18 up to 25. Surfactants according to this formula were particularly useful in reducing stains on dishware treated in a dishwasher. Preferably at least 50% by weight of the nonionic surfactant comprised by the detergent product of the invention is nonionic surfactant according to this formula. Such nonionic surfactants are commercially available, for example under the trade name Dehypon WET (supplier: BASF) and Genapol EC50 (supplier Clariant).

The detergent product preferably comprises from 0.5 to 15% by weight of nonionic surfactant. The most preferred total amount of nonionic surfactants is from 2.0 to 8% by weight and even more preferred is an amount of from 2.5 to 5.0% by weight. The nonionic surfactant used in the detergent product can be a single nonionic surfactant or a mixture of two or more nonionic surfactants.

The nonionic surfactant is preferably present in amounts of 25 to 90% by weight based on the total weight of the surfactant system. Anionic surfactants may be present, for example, in amounts in the range of from 5 to 40% by weight of the surfactant system.

anionic surfactants

Suitable anionic surfactants that can be used are preferably water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. . Examples of suitable synthetic anionic surfactants are sodium and potassium alkyl sulphates, especially those obtained by sulphating C8 to C18 higher alcohols, produced, for example, from tallow or coconut oil, sodium and potassium C9 to C20 alkyl benzene sulphonates, particularly sodium C10 to C15 linear secondary alkyl benzenesulfonates; and sodium alkyl glyceryl ether sulfates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. Preferred anionic surfactants are sodium C11 to C15 alkyl benzenesulfonates and sodium C12 to C18 alkyl sulfates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salinization, the alkylpolyglycoside surfactants described in EP-A-070074 and alkylmonoglycosides.

bleaching system

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

The detergent product of the invention may contain one or more bleach activators such as peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples, N,N,N',N'-tetraacetylethylenediamine (TAED), sodium nonanoyloxybenzenesulfonate (SNOBS), sodium benzoyloxybenzenesulfonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in the document can be named US-A-4,751,015.

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

enzymes

The detergent product of the invention preferably comprises one or more enzymes selected from proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases. Particularly preferred is protease, amylase, or a combination thereof. If present, the level of each enzyme is from 0.0001 to 1.0% by weight, more preferably 0.001 to 0.8% by weight.

silicates

Silicates are known detergent components and are often included to provide dishwashing care benefits and reduce dishware corrosion. Particularly preferred silicates are sodium disilicate, sodium metasilicate, and crystalline phyllosilicates or mixtures thereof. If present, the total amount of silicates is preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight and even more preferably from 2.5 to 5.0% by weight. of the detergent product.

Fragrance

Preferably, the detergent product of the invention comprises one or more dyes, perfumes or a mixture thereof in an amount of from 0.0001 to 8% by weight, more preferably from 0.001 to 4% by weight and even more preferably from 0.001 to 1.5% by weight.

The perfume is preferably present in the range from 0.1 to 1% by weight. Many suitable examples of perfumes are given in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. In perfume mixtures, preferably from 15 to 25% by weight are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80). Preferred top notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide, and cis-3-hexanol.

matting dyes

In particular, for laundry detergent products according to the invention, it is preferred that they comprise a matting dye. For example, tinting dyes are added to laundry detergent formulations to improve the whiteness of fabrics. The shading dyes are preferably blue or violet dyes that are substantive to fabrics. A mixture of shading dyes can be used and are indeed preferred for treating mixed fiber textiles. The preferred amount of shading dyes is from 0.00001 to 1.0% by weight, preferably 0.0001 to 0.1% by weight and an amount of 0.001 to 0.01% by weight is particularly preferred. Shading dyes are discussed in WO2005/003274, WO2006/032327, WO2006/032397, WO2006/045275, WO2006/027086, W002008/017570, WO 2008/141880, WO2009/132 870, WO2009/141173, WO2010/099997, WO 2010/102861, WO2010/148624, WO2008/087497 and WO2011/011799. Detergent product form

The detergent product of the invention may be in any suitable form. Due to the presence of the solid of the invention, it contains at least one solid part. The remainder of the detergent product may also be non-solid, such as in liquid form, but preferably contains at least one additional non-powdery, non-liquid, solid part, such as and preferably a compacted powder (which is no longer considered a dust as such). 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, comprising at least one additional non-shaped stable component, such as a liquid and/or powder; or in pill form. For ease of use, the unit dose is sized and shaped to fit in the detergent drawer of a conventional household dishwashing machine, washing machine or toilet rim holder, as is known in the art. In a preferred embodiment, the unit dose detergent product has a unit weight of 5 to 50 grams, more preferably a unit weight of 10 to 30 grams, even more preferably a unit weight of 12 to 25 grams.

Advantageous unit dose bags preferably have more than one compartment.

Advantageous unit dose tablets are those having more than one visually distinct tablet region. For example, such regions may be formed by two distinct (colored) layers or a tablet having a main body and a distinct insert, such as forming a nested egg. Regardless of their orientation, a benefit of the use of multi-compartment bags/multi-region tablets is that they can be used to reduce/prevent unwanted chemical reactions between two or more components during storage through physical segregation.

Especially in the event that the detergent product is a dishwashing detergent product, the most preferred unit dose is one tablet.

Preferably, the unit dose detergent product is wrapped to improve hygiene and consumer safety. Advantageously, the wrapper is based on a water soluble film which is preferably a polyvinyl alcohol (PVA) based film. Such wrapping prevents direct contact of the detergent product with the consumer's skin when the unit dose is placed in the detergent tray/holder of, for example, a dishwasher. Of course, an added benefit is that the consumer also does not need to remove a water soluble wrapper prior to use. Packaging of the detergent product further improves the stability of the detergent product.

Detergent products according to the invention can be prepared using methods and equipment known in the field of detergent product manufacturing. The detergent product according to the invention can be prepared by combining the solid of the invention together with the other detergent components. In view of tablet preparation, a particularly preferred way of combining is by compressing the solid onto (or into) the rest of the tablet components and/or by adding the solid in heated (liquid) form onto the rest of the components, preferably preformed.

Preferred detergent product formulations

A highly preferred general detergent product formulation is as follows:

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

In the case of a toilet rim detergent product, the product is preferably a solid block composition, for example not comprising liquid parts and/or powder/granular parts and even more preferably having the following composition:

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

Procedure for manufacturing the solid

The process for making the embossed detergent solid according to the invention has the benefit of being both simple and inexpensive and omits the need to add additional crystal formation inhibitors. The simplicity and ease of the process also makes it a process that can provide the embossed solid with a reduced amount of energy, and makes for more modifiable factory-scale production with a reduced amount of waste (for example, less complexity). reduces the amount of product that needs to be discarded due to product imperfections).

Step I of the process according to the invention is to provide an aqueous solution comprising: a) non-crystalline chiral aminopolycarboxylate free acid equivalent; and

b) free acid equivalent of non-crystalline organic acid other than aminopolycarboxylate,

wherein the ratio of a):b) is from 1:2 to 8.8:1.

The combination of the components in step I. can be carried out in any order. The amount of water to be used to beneficially provide the aqueous solution is sufficient to completely dissolve components a) and b) at boiling temperature to simplify processing. Both the chiral aminopolycarboxylate and the organic acid can be added as separate pre-made aqueous solutions, which is preferred to further simplify processing.

Heat can be applied to (more quickly) dissolve components a) and b). Applying heat in stage I is preferred as it not only reduces the time to dissolve (if necessary) components a) and b), but can also reduce the amount of water needed to provide dissolution, saving costs. Also, having less water in the solution provided in stage I. can save time to complete stage II. of the procedure. Preferably, in step I. an aqueous solution is provided 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°C.

The aqueous solution in stage I. must be homogeneous at least with respect to the chiral aminopolycarboxylate, the organic acid and the water. As such, it is particularly preferred that the aqueous solution from Step I. be subjected to physical mixing. The aqueous solution provided in stage I. may be viscous. Preferably, the aqueous solution provided in step I comprises from 40 to 95% by weight of water, preferably from 45 to 85% by weight.

The final solid is preferably characterized by a highly preferred pH profile of at most 10.0, based on a 1:1 weight ratio solution of the solid in water, as measured at 25°C. This can easily be achieved by suitably adjusting the pH of the aqueous solution accordingly, such as and preferably in Step I, using conventional means. For example, a balanced use of acid or (partially) neutralized salt forms of components a) and b) can be applied.

In stage II. From the process, water is removed from the aqueous solution provided in stage I. by evaporation at a temperature of at least 50°C, to provide a water content of from 0.7 to 25% by weight. Preferably, water is removed from the aqueous solution by evaporation at a temperature of at least 70°C, more preferably at least 90°C and most preferably at least 100°C. The preferred way to remove water in stage II. is by applying sufficient heat to bring the aqueous solution provided in step I to a boil. This allows rapid removal of the water, which is advantageous to obtain the benefits of the solid according to the invention. As such, the removal of water can be accomplished by any suitable means, but is preferably such that the removal of water is on par with, or faster than, boiling at otherwise conventional ambient conditions.

Stage II. preferably it does not involve spray drying. In particular, spray drying can encourage crystal formation and thus reduce the translucency of the resulting solid.

Furthermore, if spray-dried to a powder, the powder requires further recombination into a substantial non-powdery solid of appreciable size to be embossed. This could be done, for example, by reheating the powder, melting it and cooling it to form a solid of substantial size, but this requires substantial reworking of the product, which requires a lot of time and energy.

In stage III. the temperature of the dried mixture is preferably reduced to less than 45°C to obtain a solid. More preferably, the temperature is reduced to less than 40, 35, 30°C, even more preferably to 15 to 25°C and still even more preferably to 20 to 25°C to obtain a solid. Stage III. It can be done using passive or active cooling. Active cooling can be done using any conventional means such as by refrigeration.

In a stage III. Particularly preferred, cooling of the dried mixture is achieved by heat exchange with the rest of the (cooler) parts of the detergent product. In this regard, it is particularly preferred that the "solid" is applied in a liquid/viscous form having an elevated temperature, on top of the remainder of the detergent product and allowed to solidify in situ.

Embossing of the solid can take place at any suitable point after stage II, which means a point where the material is sufficiently viscous/solid to be stably embossed. A preferred way of providing the embossing is by embossing the solid by means of a stamp or roller.

Another way of providing the embossing is by casting the sufficiently liquid/viscous dried mixture into a suitable mould, which carries a suitable embossing template inside the mould. In general, given the information provided that the solid is hard when cooled, but may be more elastic at elevated temperature, the person skilled in the art can use this to his or her own advantage to perform proper embossing.

Preferably, the solid according to the invention can be obtained by the process according to the invention. Solids prepared according to the process of the invention were shown to be highly beneficial in view of the attributes noted above.

Unless otherwise stated, preferred aspects in the context of one aspect of the invention (for example, the solid) are also applicable as preferred aspects in the context of one of the other aspects of the invention by making the necessary changes ( for example, use of the solid).

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

examples

Analytical methods

X-ray diffraction ( XRD)

XRD is used to detect the presence of crystalline material in the solid using the Wide Angle X-ray Scattering (WAXS) technique. XRD is carried out using a Bruker AXS D8 Discover X-ray diffractometer (activation number: 114175). XRD measurements are made using the following settings:

Differential scanning calorimetry

Differential scanning calorimetry (DSC) is used to measure the glass transition temperature (Tg) of the solid. The equipment used for DSC analysis was a Perkin Elmer power balanced DSC8000 device equipped with an Intracooler III as cooling medium. The stainless steel sample tray supplied by the supplier with the kit is used and filled according to the supplier's instructions with the material to be tested. The amount of material added to the sample tray (sample weight) is from 10 to 40 mg. The following settings must be used to run the measurement:

The Tg of the samples is measured with the second heating (ie, the last heating step in the DSC temperature regime).

Examples 1 and 2

Solid compositions according to the invention were prepared starting from an aqueous solution having a composition as set forth in Table A below.

Table A. Composition of the aqueous solutions, the amounts are given in parts in % by weight.

After dissolution, the aqueous solutions were heated to boiling in a pan. Boiling was then continued to allow evaporation of the water. The liquid was poured into silicon-based molds in the general shape of either an orange-like shape, a shell shape, or a star shape, which molds have small embossments on the inside surface. The liquid was allowed to passively cool to room temperature in the molds to solidify. After cooling to room temperature, the silicon molds were removed and the solids were photographed. Figure 1 is a photograph of an orange-like shape and Figure 2 is a photograph of the star shape. Small surface embossing can be easily appreciated from the photographs. Embossing not only provides an enhanced visual experience, but also an enhanced tactile experience.

Claims (15)

1. Solid embossed detergent comprising: a) from 25 to 88% by weight of non-crystalline chiral aminopolycarboxylate free acid equivalent; and b) from 10 to 60% by weight of free acid equivalent of non-crystalline organic acid other than aminopolycarboxylate; and c) from 0.7 to 25% by weight of water; wherein the organic acid has an average molecular mass of at most 500 Daltons, the molecular mass being based on the free acid equivalent. Solid according to claim 1, in which the embossed area covers from 1 to 90% of the total surface area, preferably from 5 to 70% and more preferably from 10 to 60%. The solid according to claim 1 or claim 2, wherein the embossing comprises • protrusions having a height from the local surface plane of at least 2 microns, preferably from 10 to 500 microns, more preferably from 15 to 250 microns and even more preferably from 20 to 100 microns; • depressions having a depth from the local surface plane of at least 2 microns, preferably from 10 to 500 microns, more preferably from 15 to 250 microns and even more preferably from 20 to 100 microns; • or a combination thereof. The solid according to any preceding claim, wherein the embossing provides at least one letter, number, symbol, image or pattern, more preferably at least one word, cup image, leaf image, emoticon, warning sign or pattern of points. A solid according to any preceding claim, wherein the amount of the chiral aminopolycarboxylate is from 30 to 70% by weight and more preferably from 35 to 60% by weight, the weight being based on free acid equivalent. . The solid according to any preceding claim, wherein the amount of the organic acid is from 15 to 55% by weight, preferably from 25 to 50% by weight, the weight being based on free acid equivalents. 7. Solid according to any preceding claim, wherein the chiral aminopolycarboxylate comprises glutamic acid-N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS) or a mixture thereof and preferably wherein the chiral aminopolycarboxylate is glutamic acid-N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA) or a mixture thereof. 8. Solid according to any preceding claim, wherein the organic acid comprises acetic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acid, its salt, or a mixture thereof, preferably wherein the organic acid comprises citric acid, lactic acid, acetic acid or mixtures thereof, and more preferably wherein the organic acid comprises citric acid. 9. Solid according to any preceding claim, wherein the amount of water is from 1.0 to 20% by weight, preferably from 1.4 to 15% by weight and more preferably from 1.5 to 8% by weight. Solid according to any preceding claim, wherein a), b) and c) form from 60 to 100% by weight, preferably from 70 to 100% by weight, more preferably from 80 to 100% by weight. weight, even more preferably from 90 to 100% by weight and still even more preferably from 95 to 100% by weight of the total weight of the embossed detergent solid. Solid according to any preceding claim, comprising sulfonated polymer, polycarboxylate polymer or a combination thereof in a total amount of from 0.3 to 50% by weight, preferably from 5 to 40% by weight, more preferably from 10 to 35% by weight and even more preferably from 15 to 25% by weight, based on the free acid equivalent of the polymer. A solid according to any preceding claim, wherein the solid has a maximum transmittance within the wavelength range 400 to 700 nm of at least 5%, preferably at least 10%, more preferably at least 10%. 20%, even more preferably at least 25% and even more preferably at least 30%, wherein the transmittance is evaluated based on a 0.5 cm path length through the solid composition, measuring the amount of light that passes through it. 13. Process for manufacturing the solid comprising at least one embossed surface according to any preceding claim comprising the consecutive steps of: I. provide an aqueous solution comprising: a) non-crystalline chiral aminopolycarboxylate free acid equivalent; and b) non-crystalline organic acid free acid equivalent different from a) wherein the weight ratio of a):b) is from 1:2 to 8.8:1; II. removing water from the aqueous solution by evaporation at a temperature of at least 50°C to produce a dried liquid mixture having a water content of from 0.7 to 25% by weight; and III. reduce the temperature of the dried mixture to obtain a solid wherein the solid is provided with a surface embossing after stage II. The method of claim 13, wherein at least part of the embossing is achieved by embossing, molding or a combination thereof and preferably by embossing. Use of the solid according to any one of claims 1 to 12, to provide an embossed detergent product which is at least in part translucent and more preferably which has a non-uniform light scattering surface, wherein the light scattering it can be measured using a Haze-Gard I Transparency Gauge type SHBG4774, which is operated according to the supplier's instructions.