CN108713056B

CN108713056B - Detergent composition in the form of a suspension

Info

Publication number: CN108713056B
Application number: CN201780014457.XA
Authority: CN
Inventors: E·M·G·巴布兹; M·P·J·范德尤曾; K·B·吉尔斯; R·J·默尔
Original assignee: Unilever NV
Current assignee: Unilever IP Holdings BV
Priority date: 2016-03-02
Filing date: 2017-03-01
Publication date: 2020-12-18
Anticipated expiration: 2037-03-01
Also published as: JP2019508539A; AR107754A1; PT3423558T; EP3423558A1; CN108713056A; TR201911188T4; WO2017148990A1; PL3423558T3; EP3423558B1

Abstract

The present invention provides a detergent suspension comprising 70-99.5 wt% of a fluid phase and 0.5-30 wt% of suspended particles having a diameter of at least 0.1mm, the detergent suspension comprising: 8-30 wt% water; 20-75% by weight of glycerol; 8-40 wt% of a builder; and 0.01 to 1 wt% of a structured biopolymer selected from the group consisting of xanthan gum, locust bean gum, guar gum, gum arabic, gellan gum, carrageenan, carboxymethyl cellulose, microcrystalline cellulose, microfibrillar cellulose and combinations thereof; wherein the combination of water and glycerol comprises at least 40 wt% of the detergent suspension, and wherein the water and glycerol are present in a weight ratio of water to glycerol of less than 2: 3. The detergent suspension according to the invention has a very low water activity, is very stable and easy to manufacture.

Description

Detergent composition in the form of a suspension

Technical Field

The present invention relates to detergent compositions in the form of suspensions. More particularly, the present invention relates to detergent compositions comprising a fluid phase and suspended particles, wherein the fluid phase comprises water, glycerol, builder and structured biopolymer, wherein the combination of water and glycerol comprises at least 40 wt% of the detergent suspension. Wherein the water and glycerol are present in a weight ratio of water to glycerol of less than 2: 3.

The detergent suspension of the present invention may be provided in the form of a pourable viscous product or a semi-solid gel.

Background

Detergent formulations typically contain a number of different active ingredients, including surfactants, builders, enzymes and bleaching agents.

Surfactants are used to release stains and soils and to disperse the released components into the cleaning solution. Surfactants are also used to provide glossy and dry dishware at the end of the wash. Enzymes help remove stubborn stains of proteins, starches and lipids by hydrolyzing these components. Bleaching agents are used in detergent compositions to remove bleachable stains, such as those associated with tea, coffee, red wine and various fruit and vegetable products, by oxidizing or reducing components that make up these stains. Typical oxidative bleaches for detergent formulations are chlorine and peroxygen based compounds, such as hypochlorite and percarbonate bleaches, respectively.

Builders are incorporated into detergent formulations to complex magnesium and calcium ions and maintain alkaline pH conditions. Phosphorus-based builders, such as phosphates, have been used in a variety of detergent compositions for many years. However, as part of the increasing trend towards environmentally friendly detergent compositions, alternative builders have been developed and these have found their way into commercial detergent products. Aminocarboxylate chelant L-glutamic-N, N-diacetate is an example of an environmentally friendly builder for commercial detergent products. Typically, the aminocarboxylate chelant is present in the detergent formulation in the form of its (fully deprotonated) sodium salt. The aqueous solution of the aminocarboxylate is basic.

Liquid detergent formulations have been developed because these products offer advantages over powder formulations in that they are easy to apply, can contain higher concentrations of active ingredients, are less subject to moisture damage during storage and/or are more easily dispersed into aqueous cleaning solutions. In order to provide liquid detergent compositions that deliver cleaning, spotting and film-forming properties similar to powder formulations, it is necessary to include components in the liquid product matrix that remain undissolved. These undissolved components, referred to herein as particles, need to be uniformly suspended throughout the product to ensure constant, optimal cleaning. Although this can be achieved by instructing the user to shake the product prior to use, it is clearly preferred to provide the liquid detergent formulation in the form of a suspension which remains stable during the life cycle of the product. However, this goal is very difficult to achieve, since the suspended particles undergo sedimentation and emulsification/flotation phenomena, causing the suspension to stratify over time.

Bleaching agents and enzymes are moisture sensitive detergent ingredients that lose their activity over time if the water activity of the detergent composition is too high.

EP-A1129160 describes liquid aqueous cleaning compositions containing water, glycerol, builder, enzymes and thickeners.

WO 2007/141527 describes a liquid dishwashing formulation containing water, GLDA, citric acid, a non-ionic surfactant and an enzyme.

DE 102014212643 a1 describes automatic dishwasher detergent suspensions comprising water, glycerol, builder and suspended enzyme particles.

WO 2013/092276 describes detergent formulations containing GLDA, water, citric acid, a non-ionic surfactant, a coated spray-dried percarbonate, an enzyme and other ingredients.

WO 2014/107578 describes detergent compositions containing water, glycerol, polyaminocarboxylic acids (chelating agents), nonionic surfactants, enzymes.

DE-A102014212643 relates to liquid ADW detergent compositions comprising liquid and solid enzyme preparations. Example 1 describes a liquid ADW detergent containing glycerol, water, builder and solid enzyme.

Disclosure of Invention

The present inventors have developed a detergent suspension which, despite a high water content, has a very low water activity, is very stable and easy to manufacture.

The detergent suspension of the invention comprises from 70 to 99.5 wt% of a fluid phase and from 0.5 to 30 wt% of suspended particles having a diameter of at least 0.1mm, said detergent suspension comprising:

● 8-30 wt% water;

● 20-75% by weight of glycerol;

● 8-40 wt% of a builder; and

● 0.01.01-1% by weight of a structured biopolymer selected from the group consisting of xanthan gum, locust bean gum, guar gum, gum arabic, gellan gum, carrageenan, carboxymethyl cellulose, microcrystalline cellulose, microfibrillar cellulose and combinations thereof;

wherein the combination of water and glycerol comprises at least 40 wt% of the detergent suspension, and wherein the water and glycerol are present in a weight ratio of water to glycerol of less than 2: 3.

The inventors have found that the relative concentrations of the equilibrium components are important in order to obtain a stable suspension. The concentrations of, in particular, water, glycerol and builder should be chosen so as to achieve a water activity of not more than 0.7 at 20 ℃. Both glycerin and builders are hygroscopic components that can reduce the water activity of aqueous compositions. The present inventors have also found that phase separation and settling can be very effectively minimized in detergent compositions containing water, glycerin, builders, suspending particles and other detergent ingredients by incorporating a structured biopolymer in the formulation.

The detergent compositions of the present invention may be prepared in the form of a pourable (viscous) suspension or in the form of a semi-solid gel. In both cases stable suspensions can be prepared. The detergent suspensions of the invention also provide the advantage that a wide range of detergent ingredients can be incorporated therein in dispersed or dissolved form.

Detailed Description

A first aspect of the invention relates to a detergent suspension comprising 70-99.5 wt% of a fluid phase and 0.5-30 wt% of suspended particles having a diameter of at least 0.1mm, the detergent suspension comprising:

● 8-30 wt% water;

● 20-75% by weight of glycerol;

● 8-40 wt% of a builder; and

The term "builder" as used herein, unless otherwise specified, refers to a particulate material in liquid or solid form for softening water by removing calcium and magnesium ions from a wash liquor.

Whenever reference is made to water content, the water content includes unbound (free) as well as bound water, unless otherwise specified.

The terms "citrate", "carbonate", "phosphate" as used herein include both protonated acids and the corresponding salts of these acids. Thus, the term "citrate salt" includes both citric acid and its salts.

The term "pourable" as used herein refers to a composition that is capable of flowing under ambient conditions. Thixotropic compositions which can be made pourable by shear thinning are also considered pourable.

The term "thixotropic" as used herein means that the composition (e.g., gel or fluid) is viscous under static conditions and becomes less viscous when shaken, agitated, or otherwise stressed. In thixotropic compositions, this so-called "shear thinning effect" is reversible, i.e. the composition will return to a more viscous state once it is no longer subjected to shear stress.

Whenever a parameter such as concentration or ratio is said to be less than a certain upper limit, it is understood that the lower limit of the parameter is 0 without specifying the lower limit.

Whenever the amounts or concentrations of components are quantified herein, unless otherwise indicated, the quantified amounts or quantified concentrations refer to the components themselves, even though it is common practice to add such components in solution or as a mixture with one or more other ingredients.

The detergent suspension of the invention preferably comprises 75-99.2 wt.% of the fluid phase and 0.8-25 wt.% of suspended particles having a diameter of at least 0.1 mm. Most preferably, the detergent suspension comprises 80-99 wt% of the fluid phase and 1-20 wt% of suspended particles having a diameter of at least 0.1 mm.

The combination of glycerin, water and builder typically comprises at least 55 wt%, more preferably at least 60 wt%, most preferably from 65 to 92 wt% of the detergent suspension.

Detergent suspensions typically have a water activity of less than 0.7 at 20 ℃. More preferably, the suspension has a water activity in the range of 0.2 to 0.6 at 20 ℃. Even more preferably, the water activity of the detergent suspension at 20 ℃ is in the range of 0.3 to 0.5, most preferably 0.35 to 0.45.

Water activity is a thermodynamic property defined as the ratio of the vapor pressure of water to the vapor pressure of pure water in a particular material at the same temperature. If the water activity is 1, this means that the vapor pressure of water in the material is equal to the vapor pressure of water. In this case, all water molecules are free water molecules. If part of the water molecules are bound, the water activity will be below 1. Thus, water activity is a measure of the amount of water available for hydration of other chemicals.

Water and glycerin

The combination of glycerin and water typically constitutes at least 45 wt%, more preferably at least 48 wt%, most preferably 50-80 wt% of the detergent suspension.

According to a particularly preferred embodiment, the detergent suspension contains water and glycerol in a weight ratio of water to glycerol of less than 1:2, preferably less than 3: 10.

Preferably, the detergent suspension contains 10-25 wt%, more preferably 12-23 wt%, most preferably 13-22 wt% water.

In another preferred embodiment, the detergent suspension contains 25-65 wt.%, more preferably 30-60 wt.%, most preferably 32-55 wt.% of glycerol.

Builder

In a preferred embodiment, the detergent suspension contains 10 to 35 wt% of builder. Even more preferably, the detergent suspension contains 11-30 wt%, most preferably 12-25 wt% of builder.

Traditional phosphorus-based builders, such as phosphates, have been used as builders, but due to environmental pressures, alternative builders have been developed. These include organic builders such as citrate and aminocarboxylate chelants as well as inorganic builders such as carbonates, especially sodium carbonate.

In a preferred embodiment, the detergent suspension comprises a builder, wherein the builder is selected from the group consisting of aminocarboxylate chelants, citrates, carbonates, phosphates, and combinations thereof. More preferably, the builder comprises an aminocarboxylate chelant. Aminocarboxylate chelants are very hygroscopic and, in combination with glycerin, aminocarboxylate chelants are very effective at reducing the water activity of the aqueous detergent suspension of the present invention. In another preferred embodiment, the detergent suspension comprises a builder, wherein the builder is selected from the group consisting of citrate, carbonate, and combinations thereof.

The aminocarboxylate chelant is preferably selected from the group consisting of glutamic acid N, N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), iminodisuccinic acid (IDS), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA), nitrilotriacetic acid (NTA), aspartic acid diethoxysuccinic Acid (AES), aspartic acid-N, -diacetic acid (ASDA), hydroxyethylenediaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), iminodifumaric acid (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), iminodimalic acid (IDM), ethylenediamine difumaric acid (EDDF), ethylenediamine dimalic acid (EDDM), ethylenediamine ditartaric acid (EDDT), ethylenediamine disuccinic acid (EDDS), ethylenediamine dimaleic acid (EDDMAL), and dipicolinic acid (dipicolinic acid), and salts thereof.

In a preferred embodiment, the detergent suspension contains a builder, wherein the builder is an aminocarboxylate chelant selected from the group consisting of GLDA, MGDA, IDS and combinations thereof, with GLDA being particularly preferred.

According to a particularly preferred embodiment, the detergent suspension contains citrate in a concentration of at least 0.1 wt.%, more preferably 0.2-20 wt.%, most preferably 0.25-5 wt.% citric acid equivalents.

Structured biopolymer

The detergent suspension of the invention contains 0.01 to 1 wt% of the structured biopolymer. The inventors have found that the use of biopolymers capable of structuring water (e.g. by gelation) makes it possible to prepare highly stable suspensions. Preferably, the suspension contains at least 0.05 wt.%, more preferably at least 0.08 wt.%, most preferably at least 0.1 wt.% of the structured biopolymer

In other words, the suspension preferably contains at least 0.15% structured biopolymer by weight of water. Even more preferably, the product contains 0.2-3%, most preferably 0.3-2% by weight of water of the structured biopolymer.

Preferably, the structured biopolymer used according to the present invention is selected from xanthan gum, guar gum, carboxymethyl cellulose, microfibril cellulose and combinations thereof. Most preferably, the structuring biopolymer is xanthan gum.

According to a particularly advantageous embodiment, the detergent suspension of the invention contains 0.03 to 0.5 wt.%, more preferably 0.05 to 0.3 wt.% of xanthan gum.

In other words, the detergent suspension typically contains 0.2-5% xanthan gum by weight of water. Even more preferably, the detergent suspension contains 0.3-3%, most preferably 0.4-2% xanthan gum by weight of water.

Fluid phase

The fluid phase of the detergent suspension of the invention consists essentially of glycerol, water and builder. The structured biopolymer is also contained in the fluid phase of the suspension.

The fluid phase may additionally contain liquid and non-liquid components in dissolved or non-dissolved form. Only the dissolved components and the undissolved components present as particles/droplets with a diameter of less than 100 μm are considered to be part of the fluid phase.

In addition to the liquid component aminocarboxylate chelant, the fluid phase may suitably contain other detergent ingredients. Examples of such ingredients include surfactants, scale inhibitors, glass corrosion inhibitors, rust inhibitors, fragrances, dyes, and combinations thereof.

Granules

The particles suspended in the detergent suspension of the present invention preferably contain detergent ingredients selected from the group consisting of bleaching agents, bleach activators, water-soluble salts, carbohydrates, enzymes and combinations thereof. The particles in the detergent suspension preferably contain at least 50 wt% of a solid component selected from the group consisting of bleach, bleach activator, water-soluble salt, carbohydrate, enzyme and combinations thereof.

According to a preferred embodiment, the granules contain a bleaching agent. According to another preferred embodiment, the granule contains an active enzyme.

The suspension contains particles that do not dissolve in the continuous fluid phase during the service life of the product.

In a preferred embodiment, the suspension contains at least 0.5% by weight of suspended particles having a diameter of at least 0.2 mm.

Rheology of

According to a particularly preferred embodiment of the invention, the detergent suspension is a thixotropic composition.

The term "thixotropic" is that the product is viscous under static conditions and becomes less viscous when shaken, stirred or otherwise stressed. In thixotropic compositions, this so-called "shear thinning effect" is reversible, i.e. the composition will return to a more viscous state once it is no longer subjected to shear stress. This thixotropic behaviour of the detergent suspension of the invention can be demonstrated by measuring the storage modulus (G ') and the loss modulus (G') of the product as a function of the angular frequency (ω) on a rheometer in oscillatory mode. Both G 'and G "of the detergent suspension increase as a function of angular frequency (ω), since G" increases at a faster rate than G'. At very low angular frequencies (ω), G "of the detergent suspension is lower than G ', but at ω in the range of 0.05-50rad/s G" exceeds G'.

Using plate-plate geometry, spindle PP50/S (grit blast) and 3mm gap size, using Anton

The MCR 302 rheometer measures both the storage modulus (G') and the loss modulus (G ") of detergent suspensions at 20 ℃. The program settings of the application are as follows:

● the strain gamma was chosen in the linear visco-elastic range of the product (LVER determined from amplitude sweep). The strain was kept constant at 0.1%.

● starting at 0.01rad/s, the log of the increasing slope of the angular frequency ω is set on the sample from low to high frequency. The end ω is 100rad/s unless the sample is very hard.

● the setting for collecting the measurement points is a "no time setting". In this mode, the device waits for a steady state condition before it acquires its measurement point.

● take six measurement points every ten.

Using oscillatory rheology, both viscous-like and elastic-like properties of a material can be quantified on different time scales. The basic principle of an oscillatory rheometer is to induce sinusoidal shear deformation in a sample and measure the resultant stress response; the time scale of the detection is determined by the oscillation frequency ω of the shear deformation. The sample was placed between the two plates. While the top plate is held stationary, the motor rotates the bottom plate, thereby applying a time-dependent strain γ (t) γ · sin (ω t) on the sample. At the same time, the time-dependent stress σ (t) was quantified by measuring the torque exerted by the sample on the top plate.

Measuring this time-dependent stress response at a single frequency immediately reveals the critical differences between the materials. If the material is an ideal elastic solid, the sample stress is proportional to the strain deformation and the proportionality constant is the shear modulus of the material. The stress is always exactly in phase with the applied sinusoidal strain deformation.

Conversely, if the material is a purely viscous fluid, the stress in the sample is proportional to the strain deformation rate, where the proportionality constant is the viscosity of the fluid. The applied strain and the measured stress are out of phase, with a phase angle of pi/2.

Viscoelastic materials exhibit responses that contain both in-phase and out-of-phase contributions. These contributions reveal the extent of solid-like and liquid-like behavior. As a result, the overall stress response shows a phase shift relative to the applied strain deformation, which is between solid and liquid, 0< < π/2. The viscoelastic behavior of the system at ω is characterized by a storage modulus G' (ω) and a loss modulus G "(ω), which characterize the solid-like and fluid-like contributions to the measured stress response, respectively. For sinusoidal strain deformation γ (T) ═ γ 0sin (ω T), the stress response of the viscoelastic material is given by σ (T) ═ G' (ω) γ 0sin (ω T) + G "(ω) γ 0cos (ω T).

Whether the product behaves more like a solid or more like a liquid depends on the time scale when it is deformed. At the lowest achievable frequency, the detergent suspensions of the invention have a loss modulus below the storage modulus, indicating solid-like behavior, while at the highest achievable frequency the loss modulus dominates the response, indicating viscous-like behavior.

According to a particularly advantageous embodiment of the invention, the detergent suspension is a thixotropic composition having a storage modulus (G' (ω)) at 20 ℃ and a loss modulus (G "(ω)) at 20 ℃, both moduli being measured as a function of the angular frequency (ω) on a rheometer of the oscillation mode operating at 0.1% strain, wherein:

● at an angular frequency (ω) in the range of 50 to 100rad/s, G "(ω) > G' (ω), and

● G '(omega) < G' (omega) at an angular frequency (omega) in the range of 0.01 to 0.05 rad/s.

The storage modulus (G') of the detergent suspension is generally in the range of 1-100Pa, more preferably 8-30Pa, most preferably 10-20Pa at 0.2 rad/s. The loss modulus (G') of the detergent suspension is preferably in the range of 1-100Pa, more preferably 3-60Pa, most preferably 8-30Pa at 0.2 rad/s.

According to another advantageous embodiment of the invention, the detergent suspension is a non-pourable semi-solid gel suspension.

Surface active agent

The present detergent suspension preferably contains one or more surfactants. The surfactants in the present invention are, for example, "Surfactant Science Series", Vol.82, Handbook of detergents, Part A: properties, chapters 2(Surfactants, classification), g.brown (editorial). Typically, the detergent composition contains from 0.5 to 30 wt%, preferably from 1 to 20 wt%, more preferably from 1.3 to 10 wt% of one or more surfactants. In a preferred embodiment, the surfactant is selected from one or more nonionic surfactants.

According to a particularly preferred embodiment, the composition contains 0.1 to 15 wt.%, more preferably 0.5 to 10 wt.%, most preferably 1 to 5 wt.% of a nonionic surfactant or a mixture of two or more nonionic surfactants. Examples of nonionic surfactants useful in the compositions of the present invention include condensation products of hydrophobic alkyl, alkenyl or alkylaromatic compounds bearing functional groups having free reactive hydrogens useful for condensation with hydrophilic alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, polyethylene oxide or polyethylene glycol, to form nonionic surfactants. Examples of such functional groups include hydroxyl, carboxyl, mercapto, amino or amide groups.

Examples of useful hydrophobes for commercial nonionic surfactants include C8-C18 alkyl fatty alcohols, C8-C14 alkylphenols, C8-C18 alkyl fatty acids, C8-C18 alkyl mercaptans, C8-C18 alkyl fatty amines, C8-C18 alkyl amides and C8-C18 alkyl fatty alkanolamides. Thus, suitable ethoxylated fatty alcohols may be selected from ethoxylated cetyl alcohol, ethoxylated ketostearyl alcohol, ethoxylated isotridecyl alcohol, ethoxylated lauryl alcohol, ethoxylated oleyl alcohol and mixtures thereof. Examples of suitable nonionic surfactants for use in the present invention can be found in Plurafac, supplied by BASF^TMLF series and Synperonic supplied by Croda^TMLow to non-foaming ethoxylated/propoxylated linear alcohols of the NCA series. Also of interest are the capped ethoxylated alcohols available as the SLF 18 series from BASF, and from Lutensol supplied by BASF^TMAlkyl polyglycol ethers prepared from linear saturated C16-C18 fatty alcohols of the AT series. Is suitable for the inventionOther nonionic agents of the composition are available from BASF/Cognis as Dehypon^TM3697 GRA or Dehypon^TMModified fatty alcohol polyglycol ether available from Wet. Also suitable for use in the present invention are Lutensol from BASF^TMThe TO series of nonionic agents are alkyl polyglycol ethers prepared from saturated iso C13 alcohols. Amine oxide surfactants may also be used as anti-redeposition surfactants in the present invention. Examples of suitable amine oxide surfactants are C10-C15 alkyl dimethyl amine oxides and C10-C15 amidoalkyl dimethyl amine oxides. The present inventors have found that detergent compositions which are not only chemically but also physically very stable can be produced if the nonionic surfactant used is a solid at ambient temperature. Thus, advantageously, the composition of the invention contains from 0.1 to 30 wt%, more preferably from 0.5 to 20 wt%, even more preferably from 1 to 10 wt%, most preferably from 1 to 5 wt% of a nonionic surfactant which is solid at 25 ℃.

If anionic surfactants are used, the total amount present is preferably less than 5 wt%, more preferably no more than 2 wt%. Further, if an anionic surfactant is present, it is preferable that a defoaming agent that suppresses foaming be present. Examples of suitable anionic surfactants are methyl ester sulfonate (methyl sulfonate) or sodium lauryl sulfate. Preferably no anionic surfactant is present in the composition of the present invention.

Silicates of acid or alkali

Silicates may be added to the formulation. Silicates may be used as builders, buffers or article care agents. Preferred silicates are sodium silicates such as sodium disilicate, sodium metasilicate and crystalline phyllosilicates and mixtures thereof. The silicate is preferably used in the detergent suspension at a concentration of 0.5 to 8 wt%, more preferably 0.8 to 6 wt% of the composition.

Enzyme

Examples of enzymes suitable for use in the cleaning compositions of the present invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleaning situations, thereby making it easier to remove soils or stains from objects being washed, so that the soils or stains are more easily removed in subsequent cleaning steps. Both degradation and alteration can improve soil removal.

Preferably, the one or more active enzymes comprised in the composition of the invention are selected from the group consisting of proteases, amylases, cellulases, peroxidases, mannanases, pectate lyases and lipases. Most preferably, the active enzyme is selected from the group consisting of proteases, amylases, and combinations thereof.

The composition of the invention generally contains at least 10mg/kg, more preferably at least 20mg/kg, even more preferably at least 50mg/kg, most preferably at least 100mg/kg of active enzyme. The concentration of active enzyme is preferably not more than 50g/kg, more preferably not more than 40g/kg, most preferably not more than 30 g/kg.

According to a particularly preferred embodiment, the composition contains at least 10mg/kg, more preferably at least 20mg/kg, most preferably at least 50mg/kg of active amylase.

According to another particularly preferred embodiment, the composition contains at least 100mg/kg, more preferably at least 200mg/kg, most preferably at least 400mg/kg of active protease.

The enzyme may be added in liquid or encapsulated form. Examples of encapsulated enzymes are enzyme granules of the D, E and HS types of Genencor and T, GT, TXT and Evity of Novozymes^TMAnd (4) forming granules.

Proteolytic enzymes in the context of the present invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisin (EC 3.4.21.62). The proteolytic enzymes used in the present invention may be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. Preferred proteolytic enzymes are those derived from: bacillus, such as Bacillus lentus, Bacillus gibsonii, Bacillus subtilis, Bacillus licheniformis, Bacillus alkalophilus, Bacillus amyloliquefaciens and Bacillus pumilus, with Bacillus lentus and Bacillus gibsonii being most preferred. An example of such a proteolytic enzyme is excelase from Genencor^TM，Properase^TM，Purafect^TM，Purafect^TMPrime，Purafect^TMOx；And Novozymes under the trade name Blaze^TM，Ovozyme^TM，Savinase^TM，Alcalase^TM，Everlase^TM，Esperase^TM，Relase^TM，Polarzyme^TM，Liquinase^TMAnd Coronase^TMThose that are sold.

The starch hydrolyzing enzymes used in the present invention may be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. Preferred starch hydrolyzing enzymes are alpha-amylases derived from a strain of Bacillus, such as Bacillus subtilis, Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus. An example of such a starch hydrolyzing enzyme is the Stainzyme from Novozymes under the trade name Stainzyme^TM，Stainzyme^TMPlus，Termamyl^TM，Natalase^TMAnd Duramyl^TMProduction and distribution; and Powerase of Genencor^TM，Purastar^TM，Purastar^TMOxam。Stainzyme^TM，Stainzyme^TMPlus and Powerase^TMIs a preferred amylase.

According to a particularly preferred embodiment of the invention, the composition contains an active protease and the protease activity of the freshly prepared composition does not decrease more than 70%, more preferably not more than 50%, most preferably not more than 20% when stored in a closed container at 20 ℃ for 8 weeks. Well known enzyme stabilizers such as polyol/borax, calcium, formate or protease inhibitors such as 4-formylphenylboronic acid may also be present in the composition.

Bleaching agent

The present detergent suspension preferably contains at least 0.3 wt%, more preferably 1-15 wt%, most preferably 2-12 wt% of a bleaching agent.

The bleaching agent may suitably comprise 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.

Examples of peroxides are monopersulfates, perborate monohydrate, perborate tetrahydrate and the acids and corresponding salts of percarbonates. Organic peracids useful herein include alkyl and aryl peroxyacids such as peroxybenzoic acid and cyclo-substituted peroxybenzoic acids (e.g., peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g., peroxylauric acid and peroxystearic acid), and phthaloyl amido Peroxycaproic Acid (PAP). Typical diperoxy acids useful in the present invention include alkyl diperoxy acids and aryl diperoxy acids, such as 1, 2-diperoxydodecanedioic acid (DPDA), 1, 9-diperoxyazelaic acid, diperoxycarbazelaic acid, diperoxydecanedioic acid and diperoxyiisophthalic acid, and 2-decyldiperoxybutane-1, 4-diacid.

The detergent suspension of the invention preferably contains a bleaching agent in particulate form. More preferably, the composition contains 0.3 to 15 wt%, more preferably 0.5 to 10 wt% of bleach particles.

According to a preferred embodiment, the bleach particle is a coated particle comprising one or more core particles comprising bleach, said one or more core particles being surrounded by a water-soluble coating. The water-soluble coating advantageously comprises a coating agent selected from the group consisting of alkali sulfates, alkali carbonates or alkali chlorides, and combinations thereof.

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

If desired, bleach catalysts may be added, such as manganese complexes as described in EP-A-0458397, for example Mn-Me TACN, or sulfonimides (sulfonimines) of US-A-5,041,232 and US-A-5,047,163. Cobalt or iron catalysts may also be used.

Dispersion polymers

The detergent suspension may suitably contain one or more dispersing polymers. The dispersion polymers mentioned in the present invention are selected from the group consisting of antiplaque agents and/or antifouling agents.

Of suitable antiplaque polymeric agentsExamples include hydrophobically modified polycarboxylic acids, such as Acusol^TM460 ND (from Dow) and Alcosperse from Akzo Nobel^TM747, and synthetic clays, preferably those having a high surface area, are very useful for preventing spotting, particularly those formed when dirt and dispersed residues are present where water accumulates on the glass, and spots formed when water is subsequently evaporated.

Examples of suitable anti-fouling agents include organic phosphonates, amino carboxylates, polyfunctional substituted compounds, and mixtures thereof.

Particularly preferred anti-scaling agents are organic phosphonates such as alpha-hydroxy-2 phenylethyl bisphosphonate, ethylene diphosphonate, hydroxy 1, 1-hexylene (hydroxy 1,1-hexylidene), vinylidene-1, 1-diphosphonate, 1, 2-dihydroxyethane 1, 1-diphosphonate and hydroxy-ethylene 1, 1-diphosphonate. Most preferred are hydroxy-ethylene 1, 1-diphosphonate (EDHP) and 2-phosphonobutane, 1,2, 4-tricarboxylic acid (Baysiit, from Bayer). Suitable anti-fouling agents are water-soluble dispersion polymers prepared from allyloxybenzenesulfonic acid monomers, methallylsulfonic acid monomers, copolymerizable nonionic monomers, and copolymerizable ethylenically unsaturated carboxylic acid monomers, as described in US 5547612, or as acrylic acid sulfonated polymers, as described in EP 851022. Polymers of this type comprise polyacrylates with methyl methacrylate, sodium methallylsulfonate and sulfophenol methallyl ether, for example Alcosperse supplied^TM240(akzo nobel). Also suitable are terpolymers containing polyacrylate and 2-acrylamido-2-methylpropanesulfonic acid, such as Acumer 3100 available from Dow. Alternatively, polymers and copolymers of acrylic acid having a molecular weight between 500 and 20,000, such as homopolycarboxylic acid compounds having acrylic acid as monomer units, may also be used. The average weight of such homopolymers in the acid form is preferably from 1,000 to 100,000, in particular from 3,000 to 10,000, for example Sokolan from BASF^TMPA 25 or Acusol from Dow^TM425。

Also suitable are polycarboxylate copolymers of monomers derived from acrylic acid and maleic acid, such as CP5 from BASF. In the acid formThe average molecular weight of these polymers is preferably 4,000 to 70,000. Modified polycarboxylates such as Sokalan from BASF may also be used^TMCP42，Sokalan^TMCP50, or Alcoguard from Akzo Nobel^TM4160。

Mixtures of anti-fouling agents may also be used. Particularly useful are mixtures of organic phosphonates and acrylic polymers. Preferably, the content of the dispersion polymer is 0.2 to 10% by weight, preferably 0.5 to 8% by weight, and further preferably 1 to 6% by weight of the total composition.

Other ingredients

The glass corrosion inhibitor can prevent irreversible corrosion and iridescence of glass surfaces in machine dishwashing detergents. The claimed compositions may suitably contain a glass corrosion inhibitor. Suitable glass etchants can be selected from the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof, and precursors thereof. Most preferred are salts of bismuth, magnesium or zinc or combinations thereof. The preferred amount of glass corrosion inhibitor in the present composition is 0.01 to 2 wt.%, more preferably 0.01 to 0.5 wt.%.

Rust inhibitors can prevent or reduce the staining, corrosion or oxidation of metals such as silver, copper, aluminum and stainless steel. Rust inhibitors such as benzotriazole or bis-benzotriazole and substituted or substituted derivatives thereof and those described in EP 723577 (Unilever) may also be included in the composition. Other rust inhibitors which may be included in the detergent suspension are mentioned in WO 94/26860 and WO 94/26859. Suitable redox activators are, for example, complexes selected from cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, zinc or zirconium, wherein the metal is in the oxidation state II, IV, V or VI.

Optionally, other components may be added to the formulation, such as perfumes, colorants or preservatives. The desired viscosity properties (profile) of the detergent suspension depend on the end use of the product. Depending on the application, it may be a liquid, gel or paste. Another aspect of the invention relates to a water-soluble pouch (sachet) filled with a composition as defined hereinbefore.

Package (I)

The detergent suspension is particularly suitable for packaging in a container (e.g. a bottle) comprising a container wall and an outlet for adapting the detergent dosage to the amount of soil on the dishes. Such containers or bottles are suitable for a variety of uses. In a preferred embodiment, the container has at least one translucent outer wall.

In another embodiment, the pourable detergent composition may be packaged in a container suitable for single use.

According to this embodiment, the container contains one unit of detergent formulation and is at least partially made of a water-soluble material. Examples of containers that can be used according to this embodiment are sachets (pouches) and sachets.

Suitably, the disposable container is not only water insoluble, but also water permeable. More specifically, it is preferred that the container is made of a water permeable and water soluble polymer selected from the group consisting of polyvinyl alcohol, cellulose ethers, polyethylene oxide, starch, polyvinyl pyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene maleic anhydride, hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, carboxymethyl cellulose, polyacrylates, alginates, acrylamide copolymers, guar gum, casein, ethylene-maleic anhydride resin series, polyethyleneimine, ethyl hydroxyethyl cellulose, ethyl methyl cellulose, hydroxyethyl methyl cellulose and combinations thereof. Even more preferably, the disposable container is made of polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, and combinations thereof.

In another preferred embodiment, the disposable container is made of a water permeable and water insoluble polymer selected from the group consisting of butyral resins, polyvinyl acetals, poly (vinyl butyral-co-vinyl alcohol-co-vinyl acetate), polyvinyl butyrals, polyvinyl acetates, and combinations and comonomers thereof.

Most preferably, the disposable container is made of polyvinyl alcohol, copolymers of polyvinyl alcohol, and combinations thereof. Preferred polyvinyl alcohols have a weight average molecular weight of 1,000 to 300,000, more preferably 2,000 to 150,000, and most preferably 3,000 to 100,000.

According to a preferred embodiment, the container contains 5-40ml, more preferably 8-30ml, most preferably 10-20ml of detergent suspension.

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

Examples

Example 1

Pourable thixotropic machine dishwashing products were prepared based on the formulations shown in table 1.

TABLE 1

Composition (I)	By weight%
		Glycerol	47.50
Citric acid (50%)	1.43
		Dissolvine^TMGL 47-S¹	9.40
Dissolvine^TMPD-S 2²	18.40
		Demineralized water	7.99
Xanthan gum	0.21
		Light carbonate ash (carbonate ash light)	12.10
Percarbonate salts³	1.10
		Lutensol^TMAT80 (nonionic surfactant)	1.87

1 contains approximately 48% by weight of GLDA and 45% by weight of water

2 contains approximately 85% by weight GLDA and 9% by weight water

3 coating of percarbonate, 98% by weight, 0.2mm to 1.4 mm

The product was prepared as follows: the liquid premix was prepared by mixing glycerol and xanthan gum into a homogeneous suspension. Next, demineralized water was added under constant stirring. Thereafter, Dissolvine is administered at ambient temperature^TMGL 47-S and citric acid. Next, Dissolvine^TMPD-S is mixed in. Finally, the remaining ingredients were added to the mixture with stirring. All ingredients were mixed under vacuum to minimize bubble formation.

The detergent product thus obtained is a stable suspension which does not phase separate or settle when stored at ambient conditions. The product was very viscous but could be poured out of the bottle without problems.

Example 2

Thixotropic machine dishwashing compositions were prepared based on the formulations shown in table 2.

TABLE 2

A and B are comparative examples.

The composition was prepared in 3kg batches in a Unimix (from Haagen & Rinau) mixer, which was operated under vacuum at 70rpm while maintaining the temperature of the mixer contents at 20 ℃. The mixing procedure used was as follows:

● introducing glycerin and xanthan gum, and mixing for 20 min;

● adding demineralized water, and stirring for 20 min;

● citric acid solution and Dissolvine are added^TMGL 47-S, continue mixing for 5 minutes;

● Dissolvine is added^TMPD-S2, continue mixing for 40 minutes;

● adding Lutensol^TMAT80 and carbonate, and stirring for 30 minutes;

● percarbonate was added and mixing continued for 35 minutes.

These compositions were analyzed for water activity and stability. The results are shown in Table 3.

TABLE 3

	Composition 1	Composition A.	Composition B.
				Water activity	0.38	0.39	0.56
Stability of	Is very stable	Phase separation shortly after preparation	Sedimentation during storage

Claims

1. A detergent suspension comprising 70-99.5 wt% of a fluid phase and 0.5-30 wt% of suspended particles having a diameter of at least 0.1mm, wherein the fluid phase comprises water, glycerol, builder and a structured biopolymer,

wherein said suspended particles comprise detergent ingredients selected from the group consisting of bleaching agents, bleach activators, bleach catalysts, enzymes, surfactants, builders, dispersing polymers and combinations thereof,

the detergent suspension comprises:

8-30% by weight of water;

20-75% by weight of glycerol;

8-40 wt% of a builder; and

0.01-1 wt% of a structured biopolymer selected from the group consisting of xanthan gum, locust bean gum, guar gum, gum arabic, gellan gum, carrageenan, carboxymethyl cellulose, microcrystalline cellulose, microfibrillar cellulose and combinations thereof;

2. The detergent suspension according to claim 1, wherein the water and glycerol are present in the suspension at a weight ratio of water to glycerol of less than 1: 2.

3. The detergent suspension according to claim 1, wherein the water and glycerol are present in the suspension at a weight ratio of water to glycerol of less than 3: 10.

4. The detergent suspension according to any one of claims 1-3, wherein said builder is selected from the group consisting of aminocarboxylate chelants, citrates, carbonates, phosphates, and combinations thereof.

5. The detergent suspension according to claim 4, wherein said builder is an aminocarboxylate chelant selected from glutamic acid N, N-diacetic acid, methylglycine diacetic acid, iminodisuccinic acid, and combinations thereof.

6. The detergent suspension according to any one of claims 1-3, wherein the structured biopolymer is xanthan gum.

7. The detergent suspension according to any one of claims 1-3, wherein the suspension has a water activity of no greater than 0.70 at 20 ℃.

8. A detergent suspension according to any of claims 1-3, wherein the suspension contains 25-65 wt% glycerol.

9. The detergent suspension according to any one of claims 1-3, wherein the suspension contains 10-30 wt% builder.

10. The detergent suspension according to any of claims 1-3, wherein the suspension contains 0.2-5% structured biopolymer by weight of water.

11. A detergent suspension according to any of claims 1-3, wherein the suspension contains 0.5-30 wt% of a surfactant.

12. The detergent suspension according to any one of claims 1-3, wherein the suspension contains citrate in a concentration of at least 0.1% citric acid equivalents by weight.

13. The detergent suspension according to any one of claims 1-3, wherein the suspension is a pourable thixotropic suspension having a storage modulus (G' (ω)) at 20 ℃ and a loss modulus (G "(ω)) at 20 ℃, both moduli being measured as a function of angular frequency (ω) on a rheometer of oscillatory mode operating at 0.1% strain, wherein:

at an angular frequency (ω) in the range of 50 to 100rad/s, G "(ω) > G' (ω), and

g "(ω) < G' (ω) at an angular frequency (ω) in the range of 0.01 to 0.05 rad/s.

14. The detergent suspension according to any one of claims 1-3, wherein the suspension is a pourable suspension having a storage modulus (G') in the range of 1-100Pa at 0.2rad/s and 20 ℃.

15. The detergent suspension according to any one of claims 1-3, wherein the suspension is a pourable suspension having a loss modulus (G ") in the range of 1-100Pa at 0.2rad/s and 20 ℃.