CN114341325A

CN114341325A - Solid detergent composition

Info

Publication number: CN114341325A
Application number: CN202080058749.5A
Authority: CN
Inventors: L·E·戴维斯; A·F·布克斯德卡松; S·N·巴切洛尔
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2019-08-21
Filing date: 2020-08-20
Publication date: 2022-04-12
Also published as: WO2021032833A1; CN114286854A; EP4017956A1; EP4017955B1; WO2021032834A1; CN114258427A; EP4017954A1; EP4017957A1; ES2944450T3; EP4017952A1; CN114269889A; EP4017953A1; EP4017953B1; EP4017957B1; WO2021032818A1; ES2943558T3; EP4017956B1; ES2945459T3; ES2942916T3; EP4017954B1

Abstract

A solid composition comprising: a)25 to 88 weight percent of a non-crystalline chiral aminopolycarboxylate of free acid equivalent; and b)10 to 60% by weight of free acid equivalents of a non-crystalline organic acid other than aminopolycarboxylate; and c)0.00001 to 1.0 wt% of a colorant, wherein the colorant comprises a dye, a pigment, or a combination thereof, wherein the dye has an extinction coefficient greater than 1000L mol at a maximum absorption in the range of 400 to 700nm^‑1cm^‑1(ii) a And d)0.7 to 25% by weight of water; wherein the organic acid has an average molecular weight of up to 500 daltons, based on the free acid equivalent weight.

Description

Solid detergent composition

Technical Field

The present invention relates to solid compositions comprising an aminopolycarboxylate and an organic acid and water. The invention also relates to a method for manufacturing the solid composition.

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 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 negative impact of especially calcium and magnesium ions on stain/soil removal, so-called "builders" (complexing agents) are often applied in detergent products.

Phosphorus-based builders have been used in a wide variety of detergent products for many years. Some phosphorus-based builders, such as trisodium phosphate and Sodium Tripolyphosphate (STPP), have set benchmarks in the dishwasher detergent industry for superior performance. Thus, phosphorus containing builder components are generally considered "high performance" builders. The use of phosphorus-based builders in detergent products has led to environmental problems such as eutrophication. To reduce these problems, many jurisdictions have or are enacting 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 are equally effective and 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 are prone to moisture absorption. WO 2014/086662 discloses a solid GLDA (i.e. aminopolycarboxylate) material comprising a combination of GLDA, sulfuric acid and sodium sulfate crystals. Also described is a process for producing a solid GLDA composition comprising the following successive steps:

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

evaporating water from the phase to produce a precipitate.

It would be desirable to have available solid aminopolycarboxylate solids that have attractive properties such as light transmission and even transparency. This will open new possibilities for designing detergent products comprising such solids with additional visual appeal. Providing a detergent product with additional visual appeal is in fact very important to the commercial success of the detergent product. In the highly competitive market for detergent products, the detergent products need to be visually appealing and at least visually distinct from other such products.

It is an object of the present invention to provide stable aminopolycarboxylate solids in a novel attractive form which are suitable for use in detergent products, preferably also having improved dissolution/dispersion properties.

Disclosure of Invention

In a first aspect of the invention, one or more of the above objects are achieved by a solid composition comprising:

a)25 to 88 weight percent of a non-crystalline chiral aminopolycarboxylate of free acid equivalent; and

b)10 to 60% by weight of free acid equivalents of a non-crystalline organic acid other than aminopolycarboxylate; and

c)0.00001 to 1.0 wt% of a colorant, wherein the colorant comprises a dye, a pigment, or a combination thereof, wherein the dye has an extinction coefficient greater than 1000L mol at a maximum absorption in the range of 400 to 700nm^-1cm^-1(ii) a And

d)0.7 to 25 weight percent water; and is

Wherein the organic acid has an average molecular weight of up to 500 daltons, based on free acid equivalent weight.

The solid composition of the invention may be used as a detergent product per se or as part of a heterogeneous detergent product comprising other parts.

The solid composition of the present invention was found to be free of crystals of chiral polycarboxylic acid and crystals of organic acid as measured by WAXS using the method set forth in the examples. Of course, other ingredients may be incorporated into the solid composition as desired to provide a desired level of light transmission (e.g., to provide translucency/translucency). Thus, the solid compositions of the present invention have adjustable light transmittance, which is highly desirable in the preparation of detergent products. Surprisingly, such solid compositions can be prepared using only detergent actives. The composition also has low hygroscopicity (e.g. compared to the aminopolycarboxylate solid itself), which improves (storage) stability.

Without wishing to be bound by theory, it is believed that in the solid composition according to the invention, the organic acid is homogeneously mixed with the chiral aminopolycarboxylate and interacts with its molecules (although not covalently bound thereto). It is believed that this prevents (substantially) crystallization of any of these components. Thus, it was found that significant amounts of organic acids can be incorporated into solid compositions while maintaining light transmission (translucency). Another benefit of the solid composition of the present invention is that the composition may be free of further added crystal formation inhibitors.

The solid composition according to the invention can be prepared unexpectedly by a process which relates to the second aspect of the invention: process for manufacturing a solid composition according to the invention, comprising the following successive steps:

I. providing an aqueous solution comprising:

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

b) a non-crystalline organic acid different from a) in free acid equivalents; and

c) a colorant according to the present invention; and is

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

removing water from the aqueous solution by evaporation at a temperature of at least 50 ℃ to produce a liquid dried mixture having a water content of 0.7 to 25 wt%; and

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

The dried liquid formed by reducing the water content of the solution to 25% by weight or less is in a viscous (or rubbery) 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 (harder) solid can be obtained. This method offers the advantage that it allows the production of solid compositions in the form of (shaped) pieces. Further, the method can be used to coat a substrate with a solid composition by coating the solid substrate with a hot liquid via a dry mixture and allowing the hot mixture to cool while in contact with the substrate. It has been found that the solid compositions of the present invention have thermoplastic properties that can suitably be used to prepare detergent products and also make them more suitable for extrusion.

In view of the benefits provided by the solids of the present invention, the solids can be used to prepare detergent products with additional visual appeal. For example, it may form a detergent product itself or may be used as part of a detergent product comprising (visually distinct) other parts. Importantly, such detergent products with enhanced visual appeal can be prepared while using only (further) detergent actives.

Another aspect of the invention is the use of the solid composition of the invention for providing a partly or wholly semi-translucent detergent product.

Detailed Description

Definition of

Weight percentages (wt.%) are based on the total weight of the solid or detergent product indicated, unless otherwise indicated. It is understood that the total weight of the ingredients does not exceed 100 wt.%. The amounts expressed in parts by weight may in total exceed 100%. Unless otherwise indicated, whenever an amount or concentration of a component is quantified herein, the quantified amount or concentration refers to the component itself, even though it may be added as a solution or as a blend with one or more other ingredients as is common practice. Furthermore, it will be understood that the verb "to comprise" and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. Finally, reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one of the element is present, unless the context clearly requires that one and only one of the elements be present. Thus, the indefinite article "a" or "an" generally means "at least one". All measurements were performed under standard conditions, unless otherwise indicated. Whenever a parameter such as concentration or ratio is said 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 terms "distinctive" or "distinct" as used herein mean visually distinguishable by an untrained human eye.

The term "solid" according to the present invention is according to its ordinary usage. For example, a wine glass is considered to be a solid according to common usage, although in a strict physical sense it is a very viscous liquid. The solid is not in the form of a (fine) powder.

Unless otherwise indicated, the term "aminopolycarboxylate" includes partial or complete acids thereof. More preferred are salts of aminopolycarboxylates other than acids, and particularly preferred are alkali metal salts thereof. Unless otherwise indicated, the term "organic acid" includes partial or complete alkali metal salts thereof.

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

	Weight percent salt	Conversion factor	Weight% free acid equivalent
				GLDA (tetrasodium salt)	50	263.1/351.1	37.5
MGDA (trisodium salt)	50	205.1/271.1	37.8
				Citric acid (monosodium salt)	50	192.1/214.1	44.9
Sodium acetate	50	60.0/82.0	36.6

The term "light transmission" is used to indicate the ability of light in the visible spectrum to pass at least partially through a solid. For quantification, it is preferably evaluated by measuring the amount of light passing through based on a path length of 0.5cm through the solid. A solid is considered to be light-transmitting if it has a maximum transmission of at least 5% in the wavelength range of 400 to 700nm under the above measurement conditions. A solid is considered transparent if it has a maximum transmission of at least 20% in the above wavelength range. Herein, the light transmittance is defined as the ratio between the light intensity measured after the light has passed through a solid sample and the light intensity measured when the sample has been removed.

It is particularly desirable that the solid composition is capable of parallel light transmission, meaning that light is transmitted without significant 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 and small angle scattering. Wide angle scattering causes so-called haze or loss of contrast, while small/narrow angle scattering reduces the see-through quality or sharpness. Therefore, haze is preferably minimized and clarity is maximized by minimizing narrow angle scattering and wide angle scattering. Total light transmission, wide angle scattering and low angle scattering can be measured using a Haze-Gard I-Transmission Meter (SHBG4775) according to the supplier's instructions.

Amorphous chiral aminopolycarboxylates

Aminopolycarboxylates (chiral or achiral) are well known in the detergent industry and are sometimes referred to as aminocarboxylate chelants. They are generally considered to be strong builders. Chirality is a geometric property of a molecule caused by the molecule having at least one chiral center. The chiral molecules may not overlap on their mirror images. The chiral aminopolycarboxylate 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. In the case of GLDA, it is preferred that it is predominantly (i.e. greater than 80 mole%) present 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), hydroxyethylidene-diaminetetraacetic acid (HEDTA), hydroxyethylethylene-diaminetriacetic 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 (EDDMAL) and 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 solids of the present invention.

The solid of the invention comprises from 25 to 88% by weight of the chiral aminopolycarboxylate in free acid equivalents. Particularly preferred amounts of chiral aminopolycarboxylate are from 30 to 70 wt% and more preferably from 35 to 60 wt%. The weight of the chiral aminopolycarboxylate is measured on the basis of free acid equivalents.

Preferably, the solid of the invention contains at least 50 wt.%, more preferably at least 75 wt.% free acid equivalents of GLDA, MGDA, EDDS, IDS, IDM or mixtures thereof, based on the total weight of free acid equivalents of the chiral aminopolycarboxylate. More preferably, the solid contains at least 50 wt%, more preferably at least 75 wt% free acid equivalents of GLDA, MGDA, EDDS or mixtures thereof based on the total weight of free acid equivalents of the chiral aminopolycarboxylate. Even more preferably, the free acid equivalent aminopolycarboxylate consists essentially of free acid equivalent GLDA, MGDA, EDDS, or mixtures thereof. GLDA is generally most suitable because it can be made from bio-based materials (e.g., sodium glutamate, which itself can be made as a byproduct from corn fermentation). GLDA is also highly biodegradable.

Non-crystalline organic acids

The solid according to the invention comprises an organic acid, which is not an aminopolycarboxylate. The organic acid used in the solid according to the invention may additionally be any organic acid. Particularly good results are achieved using organic acids that are polyacids (i.e. acids having more than one carboxylic acid group) and more particularly using di-or tri-carboxylic acid organic acids.

The organic acids used in the present invention have an average molecular weight of at most 500 daltons, preferably at most 400 daltons, and more preferably at most 300 daltons, based on free acid equivalent weight. 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 view of consumer acceptance, the organic acids are preferably those which are also found to occur naturally (e.g. in plants). Thus, organic acids of note are acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, salts thereof, or mixtures thereof. Of particular interest are citric acid, aspartic acid, acetic acid, lactic acid, succinic acid, glutaric acid, adipic acid, gluconic acid, salts thereof, or mixtures thereof. Citric acid, lactic acid, acetic acid and aspartic acid are even more preferred. Citric acid and/or its salts are particularly advantageous because, in addition to being a builder, they are also highly biodegradable. Thus, advantageously the solid contains 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 citric acid.

The solids of the invention comprise 10 to 60% by weight of organic acid, the weight being based on equivalents of free acid. Preferred is a total amount of organic acids of 15 to 55 wt%, more preferably 25 to 50 wt%, based on the weight of free acid equivalents.

A) is defined: b) the weight ratio of (a) to (b) gives better results. Thus based on the weight of free acid equivalents, it is preferred that a): b) the weight ratio of (1): 2 to 1: 0.15, preferably 1: 1.5 to 1: 0.4, more preferably 1: 1.4 to 1: 0.5, and even more preferably 1: 1.2 to 1: 0.8.

coloring agent

The colorant comprises, and advantageously consists essentially of, a dye, a pigment, or a combination thereof. Thus, the colorant comprises at least one dye or at least one pigment, although there may be multiple dyes, multiple pigments, or mixtures of dyes and pigments. Preferably the colorant comprises at least one dye, and more preferably consists essentially of one or more dyes.

Suitable dyes and pigments are listed in the International color index of the Society of dyeing and printing workers and the American Association of Textile chemistry and printing workers 2002(Society of Dyers and Colourists and American Association of Textile Chemists and Colourists 2002). Dyes are colored organic compounds that are soluble in the medium of application, preferably an aqueous medium, and do not retain a crystalline or particulate structure when dissolved. In contrast, pigments are colored, black, white or fluorescent particulate organic or inorganic solids that retain a crystalline or particulate structure in the application (preferably aqueous media). Pigments change color by selective absorption of light and/or (selective) scattering of light. Dyes change color by selectively absorbing light.

The colorants are present in a total amount of 0.00001 to 1.0 wt.%, preferably 0.00001 to 0.1 wt.%, more preferably 0.00005 to 0.01 wt.%, and even more preferably 0.0001 to 0.01 wt.%.

Dye material

Dyes are described in Industrial Dyes, edited by K.Hunger, 2003Wiley-VCH ISBN 3-527-30426-6.

The extinction coefficient of the dye at the maximum absorption in the visible range (400 to 700nm) is greater than 1000L mol^-1cm^-1Preferably greater than 2000L mol^-1cm^-1More preferably greater than 3000L mol^-1cm^-1Even more preferably more than 4000L mol^-1cm^-1And even more preferably still greater than 5000L mol^-1cm^-1And still even more preferably greater than 10000L mol^-1cm^-1。

The dyes used in the present invention are selected from cationic, anionic and nonionic dyes. Anionic dyes are negatively charged in aqueous media at pH 7. Examples of anionic dyes can be found in the category of acid dyes and direct dyes in the color index (association of dyeing and printing workers and association of textile chemistry and printing workers in the united states). The anionic dye preferably contains at least one sulfonic acid or carboxylic acid group. Nonionic dyes are uncharged in aqueous media at pH 7, examples being found in the class of disperse and solvent dyes in the color index.

The cationic dye is positively charged in an aqueous medium at pH 7, preferably on a side chain quaternary amine.

The dye may be alkoxylated. The alkoxylated dye preferably has the following general form: the dye-NR 1R 2. the-NR 1R2 group is attached to the aromatic ring of the dye. R1 and R2 are independently selected from polyoxyalkylene chains having 2 or more repeating units and preferably having 2 to 20 repeating units. Examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidyl oxide, butylene oxide, and mixtures thereof, with ethylene oxide being most preferred.

Preferably the dye is selected from acid dyes and alkoxylated dyes, and more preferably from acid dyes.

Preferably the dye is selected from the group comprising anthraquinones; monoazo; a bisazo; a xanthene; phthalocyanine or phenazine chromophores, and preferably selected from those containing anthraquinone or monoazo chromophores.

The dye may be of any colour, preferably the dye is blue, violet, green or red. Most preferably the dye is blue or violet.

Preferably the dye is selected from: acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid yellow 3, acid red 94, acid red 51, acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, acid violet 9, acid red 52, food black 1, food black 2, acid red 163, acid black 1, acid orange 24, acid yellow 23, acid yellow 40, acid yellow 11, acid red 180, acid red 155, acid red 1, acid red 33, acid red 41, acid red 19, acid orange 10, acid red 27, acid red 26, acid orange 20, acid orange 6, solvent violet 13, solvent green 3, solvent blue 63, solvent yellow 33, or mixtures thereof.

Pigment (I)

The pigment may be selected from inorganic and organic pigments, most preferably the pigment is an organic pigment. Inorganic Pigments are described in Industrial Inorganic Pigments, G.Buxbaum and G.Pfaff editions (3rd edition Wiley-VCH 2005). Suitable organics are described in Industrial Organic Pigments, W.Herbst and K.Hunger eds (3rd edition Wiley-VCH 2004)

Pigments are hardly soluble colored particles, preferably they have a primary particle size of 0.02 to 10 microns, where the length represents the longest dimension of the primary particle. The primary particle size was measured by scanning electron microscopy. Most preferably the organic pigment has a primary particle size of 0.02 to 0.2 microns.

By "practically insoluble" is meant having a water solubility of less than 500 parts per trillion (ppt), preferably 10ppt, at 20 degrees celsius using a 10 weight percent surfactant solution.

The organic pigments are preferably selected from monoazo pigments, β -naphthol pigments, naphthol AS pigments, benzimidazolone pigments, metal complex pigments, isoindolinone and isoindoline pigments, phthalocyanine pigments, quinacridone pigments, perylene and perinone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, anthraquinone pigments, anthrapyrimidine (anthrypirtine) pigments, flavanthrone pigments, anthanthrone pigments (anthanthanthrone), dioxazine pigments and quinophthalone pigments.

Azo and phthalocyanine pigments are the most preferred pigment classes.

Preferred pigments are pigment green 8, pigment blue 28, pigment yellow 1, pigment yellow 3, pigment orange 1, pigment red 4, pigment red 3, pigment red 22, pigment red 112, pigment red 7, pigment brown 1, pigment red 5, pigment red 68, pigment red 51, pigment 53, pigment red 53: 1. pigment red 49, pigment red 49: 1. pigment Red 49: 2. pigment Red 49: 3. pigment red 64: 1. pigment red 57, pigment red 57: 1. pigment red 48, pigment red 63: 1. pigment yellow 16, pigment yellow 12, pigment yellow 13, pigment yellow 83, pigment orange 13, pigment violet 23, pigment red 83, pigment blue 60, pigment blue 64, pigment orange 43, pigment blue 66, pigment blue 63, pigment violet 36, pigment violet 19, pigment red 122, pigment blue 16, pigment blue 15: 1. pigment blue 15: 2. pigment blue 15: 3. pigment blue 15: 4. pigment blue 15: 6. pigment green 7, pigment green 36, pigment blue 29, pigment green 24, pigment red 101: 1. pigment green 17, pigment green 18, pigment green 14, pigment brown 6, pigment blue 27, and pigment violet 16.

The pigment may be of any color, preferably the pigment is blue, violet, green or red. Most preferably, the pigment is blue or violet.

Depending on the aminopolycarboxylate and the acid used, the solids of the invention may be colored and, for example, have a yellowish hue. The light transmission of such solids can be further improved by adding a relatively coloring agent of the color wheel, preferably a dye. For example, yellow is opposite to blue on the color wheel, and purple is opposite to green. This will make the solid more colorless in nature, which may be preferred. It should be noted that typical dyes need to be added in relatively small amounts to be effective. It is therefore recommended that their content be not higher than 0.5% by weight, and preferably at most 0.2% by weight.

Shading dye

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

Water (W)

The solids according to the invention comprise from 0.7 to 25% by weight of water. It has surprisingly been found that the use of such a water content provides a solid having a good balance of hardness and plasticity. Depending on the water content, the solids may be harder solids having a water content in the lower range of 0.7 to 25 wt.%. The overall plastic and thermoplastic properties provide a significant practical advantage in that the solid can be (mechanically) processed with a low probability of breaking or crack formation. Also, it is also important that it can provide an improved sensory experience when handled by the consumer.

Use a composition having a lower limit of the range of preferably at least 1.0 wt.%, 1.2 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 2.0 wt.%, 2.5 wt.%, and even more preferably 3.0 wt.%; the amount of water combined with the upper limit of the range of up to 20 wt.%, 18 wt.%, 17 wt.%, 15 wt.%, 13 wt.%, 11 wt.%, 10 wt.% and even more preferably 8 wt.% achieves better results. The lower limit and the upper limit may be arbitrarily combined, e.g., preferably 1.0 to 20% by weight, more preferablyAn amount of water of 1.4 to 15 wt.%, even more preferably 1.5 to 8 wt.%, is selected. The latter range provides further optimization between suitable hardness, reduced brittleness, particularly when including sulfonated polymers and/or polycarboxylate polymers (as described below). Water Activity a of the solid according to the invention_wAnd may be 0.7 or less. Preferred is water activity a_wIs at most 0.6, and further preferably at most 0.5. Water Activity a_wA preferred lower limit of (d) may be 0.15.

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

A highly preferred solid composition according to the invention therefore comprises:

a)30 to 70% by weight of a non-crystalline chiral aminopolycarboxylate of free acid equivalent; and

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

c)0.00001 to 0.1% by weight of a colorant according to the present invention; and

d)0.7 to 15 wt% water;

wherein a), b), c) and d) form 70 to 100 wt% of the total weight of the solid composition.

Based on the above, an even more preferred solid composition according to the invention comprises:

a)35 to 60% by weight of a non-crystalline chiral aminopolycarboxylate of free acid equivalent; and

b)25 to 50 weight percent free acid equivalent of a non-crystalline organic acid other than an aminopolycarboxylate; and

c)0.00005 to 0.01 weight percent of a colorant, wherein the colorant consists essentially of a colorant comprising anthraquinone; monoazo; a bisazo; a xanthene; a phthalocyanine or phenazine chromophore; and

d)1.0 to 10 wt% water;

wherein a), b), c) and d) form 80 to 100 wt% of the total weight of the solid composition.

Of course in view of the above, an even more preferred solid composition according to the invention comprises:

c)0.0001 to 0.01 weight percent of a colorant, wherein the colorant consists essentially of: acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid yellow 3, acid red 94, acid red 51, acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, acid violet 9, acid red 52, food black 1, food black 2, acid red 163, acid black 1, acid orange 24, acid yellow 23, acid yellow 40, acid yellow 11, acid red 180, acid red 155, acid red 1, acid red 33, acid red 41, acid red 19, acid orange 10, acid red 27, acid red 26, acid orange 20, acid orange 6, solvent violet 13, solvent green 3, solvent blue 63, solvent yellow 33, or mixtures thereof; and

d)2.0 to 8 wt% water;

wherein a), b), c) and d) form 90 to 100 wt% of the total weight of the solid composition.

pH profile

Highly advantageously, the solid of the invention preferably has the following pH profile: by mixing the solid in a ratio of 1: a solution of a solid prepared in water at a weight ratio of 1 has a pH of at most 10.0 as measured at 25 degrees celsius. This pH profile improves the stability of the solid. Particularly good results are achieved 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 a solution prepared by dissolving 1 wt% of the solid in water, as measured at 25 degrees celsius, is at least 5.0, and more preferably at least 6.0, and more preferably at least 6.5.

Other ingredients

The solids of the invention may comprise other ingredients such as further detergent active ingredients.

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

It was found that the inclusion of such polymers reduces hygroscopicity, increases hardness, plasticity and increases the glass transition temperature. Improved plasticity is beneficial because it makes the solids easier to (mechanically) process (i.e., at elevated temperatures) and makes it easier to manufacture detergent products comprising the solids. A higher glass transition temperature is beneficial because it contributes to the stability of the solid during storage and handling, especially in view of temperature stress. That is, not too high a glass transition temperature will aid in the rapid dissolution of the product in warm water, as the solid is aided in liquefaction by increased surface area during use. Preferably, the glass transition temperature (T) of the solid_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. The reduction in hygroscopicity is more pronounced if the polymer used (in particular the carboxylate polymer) has a lower maximum of the average molecular weight.

Sulfonated polymers

The sulfonated polymers used according to the present invention may be copolymers or homopolymers. Preferably, the sulfonated polymer is a copolymer.

Suitable sulfonated polymers preferably have a mass average molecular weight of 3000 to 50000, more preferably 4500 to 35000.

In a preferred embodiment, the solid composition comprises a sulfonated polymer comprising polymerized units of one or more unsaturated sulfonated monomers selected from the group consisting of 2-acrylamidomethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic 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, styrene-co-polymers of the formula, Sulfomethacrylamide, sulfomethylmethacrylamide.

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

CH₂＝CR¹-CR²R³-O-C₄H₃R⁴-SO₃X

wherein

R¹、R²、R³、R⁴Independently represent C₁-C₆Alkyl or hydrogen;

x represents hydrogen or an alkali metal (alkali).

According to a particularly preferred embodiment, the sulfonated polymer is a sulfonated polymer comprising monoethylenically unsaturated C₃-C₆Copolymers of polymerized units of monocarboxylic acids. More preferably, the sulfonated copolymer comprises the following monomers in polymerized form:

from 50 to 90% by weight of one or more monoethylenically unsaturated C₃-C₆A monocarboxylic acid;

10-50% by weight of an unsaturated sulphonate monomer as defined herein before.

According to another preferred embodiment, the monoethylenically unsaturated C in the sulfonated copolymer₃-C₆The monocarboxylic acid is selected from the group consisting of acrylic acid, meth (acrylic) acid, and combinations thereof.

Thus, highly preferred for use in the solids of the present invention are sulfonated copolymers having the following combination of properties:

present in an amount of from 10 to 35% by weight, based on free acid equivalents; and is

It is partially or fully neutralized; and is

It has an average molar mass (Mw) of 3000 to 50000;

it comprises in polymerized form the following monomers: 50-90% by weight of one or more monoethylenically unsaturated C₃-C₆A monocarboxylic acid; and 10-50 wt% of an unsaturated sulfonate monomer selected from the group consisting of 2-acrylamidomethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid.

Polycarboxylate polymers

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

Is suitably aPoly(s) are polymerizedThe carboxylate polymer has an average molar mass Mw of 500 to 500000. They may be modified or unmodified, but are preferably unmodified. They may also be copolymers or homopolymers, although homopolymers are considered more beneficial.

Polycarboxylate polymers having an average molar mass (Mw) of 900 to 100000, more preferably 1100 to 10000, give better results in further improving the described benefits of adding polymer.

Preferably the solid comprises a polycarboxylate polymer selected from the group consisting of polyacrylates, copolymers of polyacrylates, polymaleates, copolymers of polymaleates, polymethacrylates, copolymers of polymethacrylates, polymethyl-methyl acrylates, copolymers of polymethyl-methyl acrylates, polyaspartates, copolymers of polyaspartates, polylactates, copolymers of polyitaconates, and combinations thereof.

A highly preferred polycarboxylate polymer is polyacrylate. Suitable polyacrylates are commercially available, e.g., from BASF under the 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 solids of the invention are polyacrylates having the following combination of properties:

It is partially or fully neutralized; and is

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

It is a homopolymer.

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

The solid composition preferably contains no more than 30% by weight of ingredients other than aminopolycarboxylate, organic acid, polyacrylate, dye and water, more preferably no more than 20% by weight, still even more preferably no more than 10% by weight, still even more preferably no more than 5% by weight, still even more preferably no more than 2% by weight, and still even more preferably substantially no further ingredients are present. If further ingredients are present in the solid composition, these are preferably water-soluble, non-crystalline ingredients.

In the form of a solid

The solid compositions of the present invention may have any suitable shape and size. The solid composition may be in any form, but is not a (fine) powder. The latter is because, when being a (fine) powder, it will be difficult to perceive the improved light transmittance of the solid composition due to the inherent light scattering property of the (fine) powder.

When used as part of a detergent product or other product, it is preferably in the range of 0.2 to 15cm³And even more preferably 0.4 to 10cm³Most preferably 0.5 to 5cm³Is present in at least one continuous volume. The preferred volume allows the solid of the present invention to be readily visible to the naked eye, thereby allowing its visual appeal to be better perceived. The solid may be present in any suitable shape.

When used as part of a detergent product or other product, it preferably has at least oneContinuous, preferably flat overall, 0.5 to 25cm²And even more preferably 1.0 to 10cm²Most preferably 1.5 to 5cm²Surface area of (a). The preferred dimensions allow the untrained human eye to better perceive its visual appeal.

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

Detergent product

The solid composition may form a detergent product per se or form part of a detergent product. If part of a detergent product, the detergent product comprises solids according to the first aspect of the invention in an amount of from 1 to 90 wt%, preferably from 2 to 85 wt%, more preferably from 5 to 70 wt%.

In the case of dishwasher detergent products, particularly preferred amounts of solids of the invention are 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 toilet seat cleaner products, particularly preferred amounts of solids 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.%.

In the case of laundry detergent products, particularly preferred amounts of solids of the invention are from 1 to 60 wt%, more preferably from 2 to 50 wt%, and even more preferably from 5 to 35 wt%.

At least a portion of the solids is visually distinct from the remainder of the detergent product portion. The visual distinctiveness of the solid according to the invention is preferably based on a solid having a (higher) light transmission compared to the solid part of the other detergent product. The distinctiveness of the solid may be further enhanced by suitable distinctive coloring. This may be achieved by making it more or less colored (e.g., colorless). It is of course preferred that the light transmission is maintained to an appreciable extent when coloring 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 solids of the present invention are particularly envisaged for use in providing a detergent product with enhanced visual appeal.

The solid may be present in any suitable shape or shapes, such as in one or more layers, wires (e.g., rods, beams), spherical or rectangular shapes, or combinations thereof. Preferred shapes are as follows: cuboids, cylinders, spheres, rods, X-shaped rods, pyramids, prisms, cones, domes and (circular) tubes. More preferred shapes among these are rods, X-shaped rods, cylinders, cuboids, (round) tubes and spheres.

Regardless of the geometric arrangement of the solids of the invention (within the overall detergent product), it is preferred that at least part of the solids form 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 solids. Preferably at most 95%, 90% and more preferably at most 85% of the surface area of the detergent product is formed by the solids.

The solids of the invention may act as a matrix in a detergent product and retain part or all of the further ingredients in the detergent product. In this sense, the solid body of the invention can be used to form a (partial) skin (skin). Advantageously, the solid body acts as a light-transmitting matrix housing one or more distinct bodies, which are visible in the matrix. The body is preferably spherical or cubic in shape. The body is preferably coloured.

Generally, those skilled in the art have the ability to use the solids of the present invention to achieve their advantages in the preparation of more attractive detergent products. As mentioned above, the manner in which solids (where the solids remain visibly apparent) are used in detergent products is understandable, as their light-transmitting and/or glossy nature is highly preferred.

The detergent product according to the invention comprises a solid according to the invention. Thus, the detergent product (as a whole) will thus comprise the chiral aminopolycarboxylate, the organic acid, the colorant and water. The detergent product further preferably comprises, but preferably in other parts than the solid part of the invention, at least one other detergent active, and preferably one or more of enzymes, enzyme stabilizers, bleaches, bleach activators, bleach catalysts, bleach scavengers, drying aids, silicates, metal conditioners, colorants, perfumes, lime soap dispersants, antifoams, anti-tarnish agents, anti-corrosion agents, surfactants and other builders.

Other builders

Other builder materials may be selected from 1) calcium sequestrant materials, 2) precipitation materials, 3) calcium ion exchange materials and 4) mixtures thereof.

Examples of calcium sequestrant builders include alkali metal polyphosphates, such as sodium tripolyphosphate, and organic sequestrants, such as ethylenediaminetetraacetic acid. Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate. Preferably, the detergent product comprises from 5 to 50 wt%, most preferably from 10 to 35 wt% sodium carbonate.

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, for example zeolite ｃA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and zeolite P type, as described in EP- ｃA-0384070.

The detergent product may also contain 0-65% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkylsuccinic acid or alkenylsuccinic acid, nitrilotriacetic acid or other builders mentioned below. Many builders are also bleach stabilizers due to 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 well described in the literature. The ratio of surfactant to aluminosilicate (when present) is preferably greater than 5: 2, more preferably greater than 3: 1.

as an alternative 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 at most 5 wt%, more preferably at most 1 wt%, and in particular are substantially free of phosphorus-based builders. Examples of phosphorus-based builders are 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP), ethylenediamine tetramethylene phosphate (EDTMP), tripolyphosphate, pyrophosphate.

Alkali metal carbonates are suitable and are preferably present in detergent products in view of their dual function as builders and buffers. 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%. This alkali carbonate level provides good Ca for most types of water hardness levels²⁺And Mg²⁺Ion scavenging, and other builder effects, such as providing good buffering capacity. Preferred alkali metal carbonates are sodium carbonate and/or potassium carbonate, with sodium carbonate being particularly preferred. Detergents present in the inventionThe alkali metal carbonate in the product may be present as such or as part of a more complex ingredient (e.g. sodium carbonate in sodium percarbonate).

Surface active agent

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

In the case of dishwasher 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 cleaner products, particularly preferred amounts of surfactant are from 0.5 to 55% by weight, preferably from 10 to 40% by weight. 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 the group of surfactants described in "Surface Active Agents" Vol.1, Schwartz & Perry, Interscience 1949, Vol.2Schwartz, Perry & Berch, Interscience 1958, the current version of "McCutcheon's Emulsifiers and Detergents", published by the Manufacturing conditioners Company or "Tenside-Taschenbuch", H.Stache,2nd Edn., Carl Hauser Verlag, 1981.

Nonionic surfactant

Suitable nonionic surfactants which may 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, in particular ethylene oxide, alone or together with propylene oxide.

Preferably, low-foaming nonionic surfactants are used, in particular selected from alkoxylated alcohols. Alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18C atoms and an average of from 1 to 12mol of Ethylene Oxide (EO) per mole of alcohol, in which the alcohol residue may be linear or methyl-branched, preferably in the 2-position, or may contain mixed linear and methyl branches, are preferably used as nonionic surfactantsEsterified residues, as are commonly present in oxo alcohol (oxo alcohol) residues. In particular, however, alcohol ethoxylates with linear residues are preferred, which are prepared from alcohols of natural origin having from 12 to 18C atoms, for example from coconut, palm, tallow or oleyl alcohol, and have an average of from 2 to 8 mol EO per mol alcohol. Preferred ethoxylated alcohols include, for example, C with 3 EO to 4 EO_12-14Alcohol, C with 7 EO_9-12Alcohols, C with 3 EO, 5 EO, 7 EO or 8 EO_13-15Alcohols, C with 3 EO, 5 EO or 7 EO_12-18Alcohols and mixtures of these, e.g. C with 3 EO_12-14Alcohol and C with 5 EO_12-19A mixture of alcohols. Preferred tallow fatty alcohols with more than 12 EO have 60 to 100 EO, and more preferably 70 to 90 EO. A particularly preferred tallow fatty alcohol having more than 12 EO is a tallow fatty alcohol having 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, and in particular from the group of EO-AO-EO nonionic surfactants. The nonionic 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). Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.

The most preferred nonionic surfactants are according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, and even more preferably wherein n is 0 and m is 18 to 25. Surfactants according to this formula are particularly useful for reducing spotting of dishware 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 detergent product preferably comprises from 0.5 to 15 wt% of a nonionic surfactant. More preferred total nonionic surfactants are in an amount of 2.0 to 8 wt%, and even more preferably 2.5 to 5.0 wt%. The nonionic surfactant used in the detergent product 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 ranging from 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 sulphates, especially those obtained by sulphating higher C8 to C18 alcohols (produced for example from tallow or coconut oil), sodium and potassium alkyl C9 to C20 benzene sulphonates, especially sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulfates, particularly those 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 benzene sulfonates and sodium C12 to C18 alkyl sulfates. Also applicable are surfactants such as those described in EP-A-328177(Unilever) which exhibit resistance to salting out, alkylpolyglycoside surfactants as described in EP-A-070074, and alkylmonoglycosides.

Bleaching system

It is preferred that the 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 detergent products of the 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' -Tetraacetylethylenediamine (TAED), Sodium Nonanoyloxybenzenesulfonate (SNOBS), sodium benzoyloxybenzenesulfonate (SBOBS) and cationic peroxyacid precursors (SPCC), as described in US-A-4751015.

Preferably, the detergent product comprises a bleach catalyst. Especially preferred are bleach catalysts as manganese complexes, for example Mn-Me TACN as described in EP-A-0458397, and/or the sulfonimides of US-A-5041232 and US-A-5047163. 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 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 are proteases, amylases, or combinations thereof. If present, each enzyme is present in an amount of 0.0001 to 1.0 wt%, more preferably 0.001 to 0.8 wt%.

Silicates of acid or alkali

Silicates are known detergent ingredients and are often included to provide dishwashing care benefits and reduce the corrosion of dishware. 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% of the weight of the detergent product.

Perfume

Preferably the detergent product of the invention comprises one or more colourants, 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 (Cosmetic, Toiletry and Fragrance association)1992International layers Guide, published by CFTA Publications, and the OPD1993Chemicals layers Directory 80 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 top notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

Detergent product forms

The detergent product of the invention may be in any suitable form. Due to the presence of the solid according to the invention, it contains at least a solid fraction. The remainder of the detergent product may also be non-solid, e.g. in liquid form, but preferably contains at least one other non-powder non-liquid solid portion, e.g. and preferably a compacted powder (which is no longer considered to be a powder per se).

The detergent product is preferably provided in a water-soluble or water-dispersible unit dose. Particularly preferred unit doses are in the form of sachets containing at least one other non-shape stable ingredient, such as a liquid and/or a powder; or in the form of a tablet. As is known in the art, for ease of use, a unit dose is sized and shaped to fit into a detergent cup of a conventional household dishwasher, washing machine or toilet seat holder. In a preferred embodiment, the unit dose detergent product has a unit weight of from 5 to 50 grams, more preferably from 10 to 30 grams, even more preferably from 12 to 25 grams.

Advantageous unit dose pouches preferably have more than one compartment.

Advantageous unit dose tablets are those having more than one visually distinct tablet region. Such regions may be formed, for example, by two distinct (colored) layers or tablets having a body and distinct inserts, such as to form nested eggs (nested-eggs). However, 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 through physical isolation.

Especially in case the detergent product is a dishwasher detergent product, a more preferred unit dose is a tablet.

Preferably, the unit dose detergent product is packaged to improve hygiene and consumer safety. The packaging material is advantageously based on a water-soluble film, preferably a polyvinyl alcohol (PVA) -based film. Such packaging prevents the detergent product from coming into direct contact with the skin of the consumer when a unit dose is placed in a detergent cup/holder of, for example, a dishwasher. Of course, a further benefit is that the consumer does not need to remove the water soluble packaging before use.

Detergent products according to the invention may be prepared using methods and apparatus known in the art of detergent product manufacture. Detergent products according to the invention may be prepared by combining the solids of the invention with the remainder of the detergent ingredients. A particularly preferred combination for preparing a tablet is by compressing a solid onto (or into) the remainder of the tablet ingredients and/or by adding a solid in heated (liquid) form.

Preferred detergent product formulations

Highly preferred general detergent product formulations are as follows:

composition (I)	Amount (wt.%)
		The solid according to the invention	1 to 80
Surface active agent	0.5 to 70
		Phosphate salts	At most 1.0
Preferably the total amount of perfume and colorant	0.0001 to 8.0

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

composition (I)	Amount (wt.%)
		The solid according to the invention	15 to 40
Other builders, preferably alkali metal carbonates	5 to 20
		Nonionic surfactant	0.5 to 15
Enzyme	0.001 to 0.8
		Silicates of acid or alkali	1 to 10
Bleaching agent + bleaching activator + bleaching catalyst	2 to 20
		Phosphate salts	At most 1.0
Preferably the total amount of perfume and colorant	0.001 to 1.5

In the case of a toilet seat cleaner product, the product is preferably a solid block composition, e.g. not comprising a liquid part and/or a powder/granular part and even more preferably having the following composition:

composition (I)	Amount (wt.%)
		The solid according to the invention	40 to 70
Anionic surfactants	10 to 40
		Nonionic surfactant	0.5 to 15
BleachingAgent + bleach activator	2 to 20
		Total amount of phosphate	At most 1.0
Preferably the total amount of perfume and colorant	0.001 to 8

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

composition (I)	Amount (wt.%)
		The solid according to the invention	5 to 35
Surface active agent	10 to 35
		Enzyme	0.001 to 0.8
Phosphate salts	At most 1.0
		Preferably the total amount of perfume and colourant is	0.001 to 4

Method for producing solid

The process for manufacturing the solid composition according to the invention has the advantage of being simple and economical and does not require the addition of further crystal formation inhibitors.

Step i. of the process according to the invention is the provision of an aqueous solution comprising:

c) a colorant according to the invention, and

wherein a): b) the weight ratio of (1): 2 to 8.8: 1.

the combination of the ingredients in step I may be performed in any order. The amount of water used to provide the aqueous solution is advantageously sufficient to completely dissolve components a), b) at the boiling temperature to simplify the process. The colorant is uniformly distributed in the aqueous solution (e.g., the pigment is not readily soluble). Both the chiral aminopolycarboxylate and the organic acid may be added as separate preformed aqueous solutions, which is preferred for further process simplification.

It should be noted that in the case where the colorant contains a pigment, since the pigment has low solubility in water, a complete aqueous solution is not formed. However, since the pigments are present in relatively low amounts (up to 0.1% by weight based on the total weight of the final solid), it is sufficient to disperse them in the aqueous solution, preferably homogeneously.

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

The aqueous solution of step I should be homogeneous at least with respect to the chiral aminopolycarboxylate, the organic acid, the colorant and the water. Therefore, it is particularly preferred to physically mix the aqueous solution in step I. The aqueous solution provided in step I may be viscous. Preferably, the aqueous solution provided in step I comprises from 40 to 95 wt%, preferably from 45 to 85 wt% of water.

The final solid is preferably characterized by a ratio based on 1: 1 weight ratio of solution, a highly preferred pH profile of up to 10.0 measured at 25 degrees celsius. This can be achieved by suitably adjusting the pH of the aqueous solution of step I accordingly, for example and preferably, using conventional means. For example, the balanced use of the acid or (partially) neutralized salt forms of the components a) and b) and c) can be applied.

In step II of the process, water is removed from the aqueous solution provided in step I by evaporation at a temperature of at least 50 degrees celsius to provide a water content of 0.7 to 25% 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.

The 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 rapid removal of water, which is advantageous for obtaining the benefits of the solid according to the invention. Thus, the removal of water may be performed by any suitable means, but preferably such that the removal of water is comparable to, or faster than, boiling under otherwise standard ambient conditions.

Preferably step II does not involve spray drying. In particular, spray drying may promote crystal formation and thus reduce the light transmission of the resulting solid. Furthermore, if spray dried to a powder, the powder needs to be further reconstituted to a substantially non-powder solid. This can be done, for example, by reheating the powder, melting and cooling to form a non-powdered solid, but this requires substantial reprocessing of the product, which requires a significant amount of time and energy.

In step III, the temperature of the dried mixture is preferably reduced to less than 45 ℃ to obtain a solid. More preferably, the temperature is reduced to less than 40, 35, 30 degrees celsius, even more preferably to 15 to 25 degrees celsius, and still even more preferably to 20 to 25 degrees celsius to obtain a solid. Step III may be performed using passive or active cooling. Active cooling may be performed using any conventional means, such as by refrigeration.

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

Preferably, the solid according to the invention is obtained by the process according to the invention. In view of the aforementioned properties, the solids prepared according to the process of the invention prove to be very advantageous.

Unless otherwise stated, a preferred aspect in the context of one aspect of the invention (e.g. the solid) may also be applied mutatis mutandis (e.g. the use of the solid) as a preferred aspect in the context of one of the other aspects of the invention.

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 solids using wide angle X-ray scattering technique (WAXS). XRD was performed using a D8 Discover X-ray diffractometer (activa # 114175) from Bruker AXS. XRD measurements were performed using the following settings:

	2θ(7-55°)
		θ1	7.0
θ2	10.0/25.0/40.0
		x-ray generator (kV/. mu.A)	50/1000
Time (seconds)	300
		Collimator (mm)	1
Detector distance (cm)	32.5
		Tube anode	Cu

Differential scanning calorimetry

Differential Scanning Calorimetry (DSC) was used to measure the glass transition temperature (Tg) of the solid. The apparatus used for DSC analysis was a Perkin Elmer power compensated DSC8000 equipped with Intracololer III as cooling device. A stainless steel sample pan was used, supplied with the equipment from the supplier, 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 will be used when running the measurements:

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

Examples 1 and 2

The solid compositions according to the invention were prepared starting from aqueous solutions having the composition shown in table a below.

Table a. composition of aqueous solution, amounts are given in parts by weight.

	Example 1	Example 2
			¹GLDA	46	46
²Citric acid	46	46
			³Polyacrylic acid salt	8	8
Pigment blue 15: 1	0.005	-
			⁴Liquidant blue	-	0.005
Water (W)	128	128

¹GLDA: dissolvine GL-47-S (supplier: Akzo Nobel) is a 47% GLDA solution containing 50% water. The amounts given in table a are the amounts of GLDA.

²Citric acid: the solution was used as a 50% solution. The amounts given in table a are the amounts of citric acid.

³Polyacrylate salt: sokalan PA 25CL (supplier BASF) was supplied as granules containing 80% polyacrylate. The average molar mass Mw was 4000. The amounts in table a are the amounts of polyacrylate.

⁴Liquitant blue (acid blue dye; supplier Milliken)

The aqueous solution was heated to boiling in a jacketed vessel. The pourable material was then poured onto a plate and allowed to cool and solidify. The solid compositions according to examples 1 and 2 were subsequently analyzed. Both were found to exhibit clear, glossy, thermoplastic, with a distinct uniform blue coloration.

Claims

1. A solid composition comprising:

d)0.7 to 25 weight percent water;

wherein the organic acid has an average molecular weight of up to 500 daltons, based on the free acid equivalent weight.

2. The solid composition of claim 1, wherein the dye has an extinction coefficient greater than 3000L mol at the absorption maximum in the range of 400 to 700nm^-1cm^-1Preferably greater than 5000L mol^-1cm^-1And more preferably greater than 10000L mol^- ¹cm^-1。

3. A solid composition according to claim 1 or claim 2, wherein the dye is selected from those comprising anthraquinone, monoazo, disazo, xanthene, phthalocyanine or phenazine chromophores, and preferably from those comprising anthraquinone or monoazo chromophores.

4. The solid composition of any one of the preceding claims, wherein the dye is selected from acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid yellow 3, acid red 94, acid red 51, acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, acid violet 9, acid red 52, food black 1, food black 2, acid red 163, acid black 1, acid orange 24, acid yellow 23, acid yellow 40, acid yellow 11, acid red 180, acid red 155, acid red 1, acid red 33, acid red 41, acid red 19, acid orange 10, acid red 27, acid red 26, acid orange 20, acid orange 6, solvent violet 13, solvent green 3, solvent blue 63, solvent yellow 33, or mixtures thereof.

5. A solid composition according to any preceding claim, wherein the pigment is an organic pigment, preferably wherein the organic pigment is selected from monoazo pigments, β -naphthol pigments, naphthol AS pigments, benzimidazolone pigments, metal complex pigments, isoindolinone and isoindoline pigments, phthalocyanine pigments, quinacridone pigments, perylene and perinone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, anthraquinone pigments, anthrapyrimidine pigments, flavanthrone pigments, anthanthrone pigments, dioxazine pigments and quinophthalone pigments or mixtures thereof, and more preferably from azo pigments, phthalocyanine pigments or mixtures thereof.

6. The solid composition of any one of the preceding claims, wherein the pigment is selected from pigment green 8, pigment blue 28, pigment yellow 1, pigment yellow 3, pigment orange 1, pigment red 4, pigment red 3, pigment red 22, pigment red 112, pigment red 7, pigment brown 1, pigment red 5, pigment red 68, pigment red 51, pigment 53, pigment red 53: 1. pigment red 49, pigment red 49: 1. pigment Red 49: 2. pigment Red 49: 3. pigment red 64: 1. pigment red 57, pigment red 57: 1. pigment red 48, pigment red 63: 1. pigment yellow 16, pigment yellow 12, pigment yellow 13, pigment yellow 83, pigment orange 13, pigment violet 23, pigment red 83, pigment blue 60, pigment blue 64, pigment orange 43, pigment blue 66, pigment blue 63, pigment violet 36, pigment violet 19, pigment red 122, pigment blue 16, pigment blue 15: 1. pigment blue 15: 2. pigment blue 15: 3. pigment blue 15: 4. pigment blue 15: 6. pigment green 7, pigment green 36, pigment blue 29, pigment green 24, pigment red 101: 1. pigment green 17, pigment green 18, pigment green 14, pigment brown 6, pigment blue 27 and pigment violet 16 or mixtures thereof.

7. The solid composition of any one of the preceding claims, wherein a): b) the weight ratio of (1): 2 to 1: 0.15, preferably 1: 1.5 to 1: 0.4, more preferably 1: 1.4 to 1: 0.5.

8. the solid as claimed in any of the preceding claims, wherein the amount of the chiral aminopolycarboxylate is from 30 to 70% by weight and more preferably from 35 to 60% by weight, said weight being based on free acid equivalents.

9. The solid according to any of the preceding claims, wherein the amount of the organic acid is from 15 to 55 wt. -%, preferably from 25 to 50 wt. -%, the weights being based on free acid equivalents.

10. The solid as claimed in any one of the preceding claims, wherein the chiral aminopolycarboxylate comprises glutamic acid N, N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediamine disuccinic acid (EDDS) or mixtures thereof, and preferably wherein the chiral aminopolycarboxylate is glutamic acid N, N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA) or mixtures thereof.

11. The solid of any one of the preceding claims, wherein the organic acid comprises acetic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, salts thereof, or mixtures 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.

12. The solid as claimed in any one of the preceding claims, wherein the amount of water is from 1.0 to 20 wt%, preferably from 1.4 to 15 wt%, more preferably from 1.5 to 8 wt%.

13. The solid of any preceding claim, wherein a), b), c) and d) form 60 to 100 wt%, preferably 70 to 100 wt%, more preferably 80 to 100 wt%, even more preferably 90 to 100 wt%, and still even more preferably 95 to 100 wt% of the total weight of the solid composition.

14. The solid of any one of the preceding claims, wherein the solid comprises a sulfonated polymer, a polycarboxylate polymer, or a combination thereof, the total amount of the sulfonated polymer, polycarboxylate polymer, or combination thereof being from 0.3 to 50 wt.%, preferably from 5 to 40 wt.%, more preferably from 10 to 35 wt.%, and even more preferably from 15 to 25 wt.%, based on the free acid equivalent of the polymer.

15. A unit dose detergent product comprising a solid composition as claimed in any preceding claim in an amount of from 1 wt% to 90 wt%, preferably in an amount of from 2 wt% to 85 wt% and more preferably in an amount of from 5 wt% to 70 wt%, preferably a dishwasher detergent product comprising from 5 wt% to 60 wt% surfactant.