CN1328599A - Detergent compositions in tablet form - Google Patents

Abstract

A detergent tablet of compressed particulate composition, and a process of making such a tablet, wherein the tablet or a region thereof comprises organic detergent and water-soluble detergency builder and the tablet or region thereof is compacted from a composition which contains: (i) particles which themselves contain at least 45 % of their own weight of nonionic detergent, and (ii) other ingredients.

Description

Detergent compositions in tablet form

The present invention relates to detergent compositions in tablet form (especially for the tablet of fabric washing).The advantage of this tablet is the volume that need not the user measures powder or liquid.That the substitute is that one or more tablets provide sufficient quantity is used for single load in the washing machine or the composition that can be used for hand-washing.Thereby for their easier processing and feeds of human consumer.

Detergent compositions in tablet form is existing in many documents to be described and sells on market.

Usually compress or compress by detergent composition and prepare this tablet a certain amount of particle form.We wish to have suitable physical strength in the tablet drying before use, but can decompose fast and dispersed/dissolved again when joining washings.Yet be difficult to obtain simultaneously this two kinds of performances.Because of when the density of using bigger pressure that tablet is compressed to make tablet and intensity are improved, its decomposition when tablet contacts with washings in use/dissolution rate reduction.Organic detergent plays tackiness agent, but this washing composition of typical amounts also can hinder the decomposition and the dissolving of tablet.Our EP-A-466485 has explained when tablet and has obtained when moistening that anionic detergent can form and hinder the viscous phase that water penetrates into described tablet inside.

This EP-A-466485 has described detergent tablet, and wherein first kind of particulate component at composition contains anionic detergent.This first kind of particulate component accounts for the 2-40% of total composition.In most of embodiment of present specification, nonionic detergent is mixed with the most particle that accounts for whole composition or appendix in these particles.

In the middle of some at present commercially available tablets, negatively charged ion and nonionic detergent are attached in the base materials powder jointly, this powder mixes the composition that is pressed into tablet with formation with other compositions.Described spray-dired base materials powder has constituted about 40% of composition.The nonionic detergent that it contains the anionic detergent that is about base materials powder 25% and is about described base materials powder 12%.

Adopt particle to prepare detergent tablet in the present invention in conjunction with the nonionic detergent of higher proportion.According to the present invention, a kind of tablet of compressing grains shape composition is provided, wherein said tablet or its district comprise organic detergent and water soluble detergency promoter, it is characterized in that described tablet or its district form by compressing in the composition that contains following material:

(i) comprise the nonionic detergent that accounts for himself weight at least 45% particle and

(ii) other compositions.

These tablets can be homogeneous phases, also can be heterogeneous.In this manual, term " homogeneous phase " is used to refer to by compressing the tablet that single particle shape composition is made, but is not to mean that all particles of said composition must be identical compositions.Term " heterogeneous " is used to refer to tablet and contains numerous discrete zones (as layer, insert or coating), and each zone of dispersion is compressing from granular composition all.In heterogeneous tablet, each zone of dispersion of described tablet will preferably constitute at least 10% of described tablet total weight amount.

We can prepare the tablet with good over-all properties by using these particles, and it has noticeable intensity before use, come and can decompose rapidly when use contacts it with water.

Described particle can comprise enough nonionic detergent to constituting at least 50% of himself weight.The composition in preferred described tablet or zone comprises the nonionic detergent of 1-40% (weight), and half exists with described particulate form at least for it.

Usually also there is anionic detergent, and provides with the particulate form of the non-soap anionic detergent that comprises himself weight at least 20%.

The tablet that the present invention is used for fabric washing will comprise (total) usually:

● at least 5% (weight), better at least 8% (weight), the paramount non-soap organic detergent (being preferably the combination of negatively charged ion and nonionic detergent) that is no more than 40% (weight), can be no more than 30% (weight);

● at least 15% (weight), better at least 20 or 25% (weight), paramount 80% (weight), can be no more than one or more washing assistants of 70 or 60% (weight), can be water soluble detergency promoter, water infusibility washing assistant or mixture water-soluble and water infusibility washing assistant;

● optional other compositions, its amount is at least 10% (weight) of described tablet.

The present invention also can comprise and is used for the tablet that machine is washed dish, it comprises on a small quantity, and (as the nonionic detergent of 1-8% (weight), condition is that tablet comprises described at least 45 nonionic detergent, the washing assistant of 20-99% and the particle that may not have anionic detergent of comprising.

Now the constitute of detergent tablet will be more gone through, and various optional and preferable feature will be mentioned.Nonionic detergent granules

The nonionic detergent granules that is used for the present invention comprises himself weight at least 45%, better at least 50% nonionic detergent (being one or more nonionics and the organic compound with detersive surfactant performance).Preferred its comprises synthetic (the being non-soap) anionic detergent that is less than 10% (weight), and preferably is substantially free of non-soap anionic detergent.

Nonionic organic detergent compound comprises and can react the product that obtains by alkylene oxide (particularly oxyethane) and the compound (as fatty alcohol, acid, acid amides or alkylphenol) with hydrophobic group and active hydrogen atom.

The nonionic detergent of non-ethoxylatedization comprises alkyl polyglycoside, glycerol monoethers and polyhydroxy amides (glucamide).

Concrete nonionic detergent compounds is alkyl (C _8-22) phenol-ethylene oxide condensate, linearity or branched aliphatic C _8-20The condensation product of primary alconol or secondary alcohol and oxyethane and the product that carries out the condensation gained by the reaction product that makes oxyethane and propylene oxide and quadrol.

Particularly preferably be the ethoxylate of primary alconol and secondary alcohol, particularly every mol of alcohol on average adopts the 3-20 moles of ethylene oxide to carry out the C of ethoxylation _9-11And C _12-15Primary alconol and secondary alcohol.

It is water-insoluble inorganic carrier material mostly that preferred nonionic detergent granules contains.Described insoluble carrier substance can comprise silicon-dioxide or silico-aluminate (as zeolite).Yet if there is silico-aluminate, preferred its amount is less than particulate 10% (weight).The amount of nonionic detergent can surpass particulate 50% (weight), as 52% or more than.

Contain the particle that is adsorbed on the nonionic detergent on the solid carrier material by in the mixing device of granulator or some other types, nonionic detergent being sprayed onto can prepare on the carrier substance.

Other materials that improve the effect of described practical physical performance also can have been comprised.Usually these materials are called " structural agent ".Its example be molecular-weight average 4,000-12, the polyethylene/polypropylene glycol in 000 scope, soda soap, molecular-weight average be 30,000-200, the polyvinyl alcohol in 000 scope.The amount of preferred structure agent is 0.5-20% (weight).Structural agent can add with other compositions, or adds during second step of granulation.

Preferred carrier is the silicon-dioxide that oil number is at least 1.0ml/g.Oil number is a parameter well known, and can measure by the technology described in the DIN ISO 787/5.Preferred oil number is 1.5ml/g at least, 2.0ml/g at least more preferably.

At least 10%, more preferably at least 15% this silicon-dioxide is preferably arranged in particle, and in the particle amount of silicon-dioxide greater than the amount (if present) of silico-aluminate.Described particle comprises the silico-aluminate that is lower than himself weight 10%.

By with various components at granulator (as Eirich RV02 granulator, or in following equipment: as from the Fukae mixing machine of the Fukae Powtech Co of Japan, by German Dierks﹠amp; The Diosna V-series that Sohne provides, available from the PharmaMatrix of Britain TH Fielder Ltd, from German Dais Werke GmbH, the Lodige CB of Mannheim series and Dais T160 series) in mix can single stage method or two-step approach production nonionic detergent granules.

The mean particle size range of preferred nonionic detergent granules is 200-2, and 000 μ m makes these particulate granularities of at least 80% at 180-2,000 μ m.Nonionic detergent granules can provide by 1%, more preferably 2% or 3% to 30% or the tablet that may be higher or the zone of tablet.More preferably these particles constitute the tablet of 8-20% or the zone of tablet.

The nonionic detergent that usually can comprise 1% (preferred 3%)-40% (weight) according to the zone of tablet of the present invention or tablet, its at least half particulate form with the nonionic detergent that contains at least himself weight 40% exist.Anionic detergent

Tablet comprises the anionic detergent of one or more the non-soap organic compound with detersive surfactant performance usually.

Anionic detergent can be all or is mainly comprised the linear alkyl benzene sulfonate of following formula:

In the formula, R is the linear alkyl of 8-15 carbon atom, M ⁺For adding dissolved cation, sodium especially.

Has formula

ROSO ₃ ^-M ⁺Primary alkyl sulphates industrial be important anionic detergent, and can be used among the present invention.R is the alkyl chain or the alkenylene chain of 8-18 carbon atom, a particularly 10-14 carbon atom in the formula, M ⁺For adding dissolved cation.

Common above-mentioned linear alkyl benzene sulfonate or primary alkyl sulphates or its mixture are required non-soap anionic detergents, and the negatively charged ion nonsoap detergent of 75-100% can be provided.

The example of other available non-soap anionic detergents comprises various alkene sulfonates, sulfonated alkane, dialkyl sulfosuccinate, and fatty sulfonate.

Anionic detergent particles can contain some nonionic detergent.Anionic detergent particles also can contain various submembers, as water, Xylo-Mucine, white dyes, dyestuff etc.

Preferably anionic detergent is mixed with the particulate form, these particles contain at least himself weight 20%, may be more at high proportion the anionic detergent of (for example at least 50% of himself weight).Can prepare the particle that comprises the 20-40% anionic detergent by spraying drying or granulation.

Being used for producing the method that contains the high concentration anionic washing composition sees and is set forth in WO 96/06916A and WO96/06917A (Unilever).In these methods, the moisture paste that will contain anionic detergent or acid detergent precursor and alkaline neutraliser is fed to drying zone, heat described paste therein to reduce its water content, the material behind the cooling drying forms detergent particles in the cooling zone subsequently.

Required drying zone is in the removal of micro-vacuum state with convenient moisture and volatile matter content.100 holder to atmospheric vacuum can provide sizable method handiness.But surpass the above extremely atmospheric vacuum of 500 holders and have the advantage that minimizing capital investment provides vacuum operating simultaneously again.

Described method can be carried out in any suitable device, but preferably uses flashing reactor.Suitable flashing reactor comprises as can be available from the FlashDrier system of VRV Spa Impianti Industriali.The heat transfer area of drying zone is at least 10m ²The heat transfer area that the cooling zone needs is at least 5m ²

As described in our WO97/32003A, can adopt cooling draught to handle material in the cooling zone.Perhaps, non-detergent solids material (as zeolite or silica dioxide granule) in small, broken bits can be incorporated in this district so that adhere on these particulate surfaces.This material can constitute the 3-25% of particle weight.

Above-mentioned processing route can provide at least 60% the anionic detergent that comprises particle weight and be no more than the detergent particles of flash drying of the water of particle 5% (weight).

These anionic detergent particles can comprise particle weight at least 66%, better at least 70% but be no more than 96% anionic detergent.The particulate porosity is the 0-25% of particle volume, and makes that at least 80% particulate granularity is the particle size distribution of 180-1500 micron.As mentioned above, can be by forming anionic detergent with original position in the free acid.Neutralizing agent can be sodium hydroxide solution or yellow soda ash.Yet, when anionic detergent is primary alkyl sulphates (PAS), make that owing to its acid form is unstable as if the original position neutralization be not the method that suits.

Anionic detergent particles can provide the tablet of 5%-at least 30% (weight) or the zone of tablet.Its amount can be at least 8% or 10%.Its amount can not surpass 20% of tablet or regional weight, and is all the more so when particle comprises the non-soap anionic detergent of himself weight at least 70% or 75%.

The organic detergent of other types such as ampholytic detergent can be included, but not preferred.Preferably at least 50% (weight), better all the non-soap organic detergents at least 90% (weight) tablet or the tablet zone are included in the particle that contains 40% nonionic detergent at least, or in other particles of the non-soap organic detergent that contains at least himself weight 20%.Strengthen and decompose particle

We find and disclosed and can improve the speed that tablet decomposes by some material before this.Thereby our EP-A-839906 points out and can improve the tablet decomposition rate by Tri sodium Phosphate (the I phase form that is rich in anhydrous Tri sodium Phosphate can also be carried out partially hydrated simultaneously).Our EP-A-711827 and EP-A-838519 point out to quicken to have by the material of high water soluble, particularly some salt the tablet decomposition rate of water-insoluble non-phosphorus Cleaning Aid Agent.

In a preferred form of the invention, the component in tablet or zone is to contain the particle that works the material that quickens the tablet Decomposition in water, and is the material of high-dissolvability or is the Tri sodium Phosphate of particular form, or is the two combination.This material can composition at least 15 or 20%, may at least 25% to 50 or 60% and tablet or its regional form that may be higher exist.

A kind of in two kinds of possible components is the high water soluble material, and it is for 20 ℃ of following solubleness being compound, the particularly salt of per 100 gram water at least 50 grams.

Solubleness at 20 ℃ of down per 100 gram water at least 50 grams are an especially high solubleness: manyly be classified as water miscible solubility of substances all less than this value.

Below enumerate the material of some available high water solubles, its solubleness is expressed the solid gram number that forms 100 gram water saturation solution down at 20 ℃:

Substance dissolves degree (gram/100 grams)

Two hydration Trisodium Citrates 72

Salt of wormwood 112

Urea＞100

Anhydrous sodium acetate 119

Sodium acetate trihydrate 76

Bitter salt 71

Potassium acetate＞200

And the solubleness of some other common materials under 20 ℃ is:

Substance dissolves degree (gram/100 grams)

Sodium-chlor 36

Disodium sulfate decahydrate 21.5

Anhydrous sodium carbonate 8.0

Anhydrous SPC-D 12

Anhydrous sodium perborate 3.7

Anhydrous Tri sodium Phosphate 15

The material of preferred this high water soluble mixes with the particle form (being that each such particle contains the material that surpasses 95% (weight)) of pure substantially material.But described particle can contain the material with this solubleness and the mixture of other materials, and condition is that the material of specific solubleness provides at least 50% (weight), these particles of better at least 80%.

Another kind of possibility is that the particle that described promotion is decomposed surpasses the particle that 50% (particulate weight) Tri sodium Phosphate is in anhydrous I phase form for containing.This particle can contain at least 80% (weight), may at least 95% (weight) triphosphate.

Tri sodium Phosphate is well-known as the chelating washing assistant in detergent composition.It exists with form and two kinds of anhydrous forms of crystalline state of hydration.The conventional crystalline state anhydrous form that has low temperature form is a known II steady I phase mutually and at high temperature.Be heated to transition temperature (being about 420 ℃) when above II at a good pace be converted into the I phase mutually, but reversed reaction is slower.Therefore at room temperature I phase Tri sodium Phosphate is metastable.

In US-A-4536377, provided the particulate method that contains a high proportion of Tri sodium Phosphate I phase under 420 ℃ the temperature by spraying drying production being lower than.

The particle that contains this I phase form will contain the Tri sodium Phosphate (triphosphate that has 55% (weight) in particle at least) of I phase form usually.The ratio that other forms of Tri sodium Phosphate exists usually is very low.Though not preferred, other salt also can be included in the particle.

This Tri sodium Phosphate is preferably partially hydrated.Hydration levels should be at least 1% of Tri sodium Phosphate weight in the particle.Its scope can be 2.5-4%, or higher, as height to 8%.

Suitable material is commercially available.Supplier comprises Rhone-Poulenc (France) and Albright ﹠amp; Wilson (Britain).

We find to be fit to especially from Rhone-Poulenc " Rhodiaphos HPA 3.5 ".A feature of the Tri sodium Phosphate of this grade is that its hydration in the Olten of standard experiment gets quite fast.We find that its hydration rate is the same with anhydrous Tri sodium Phosphate fast, but in use when described material contacts with water, in that to avoid hexahydrate that pre-hydration takes place aspect undesirable crystallization seemingly useful.Washing assistant

Washing assistant is contained in tablet or tablet zone usually.It can be the Tri sodium Phosphate of describing type just now.Comprise that II occupies the majority mutually or the Tri sodium Phosphate of hydration.The washing assistant that also can have some other types.

Water-soluble inorganic phosphor-contained washing assistant comprises alkali metal orthophosphate, metaphosphate, pyrophosphate salt and polyphosphate, and Tri sodium Phosphate and tri-potassium phosphate.

For our strong preferred as alkali silico-aluminate of fabric washing as environmentally acceptable water-insoluble washing assistant.Silico-aluminate can be crystalline state or amorphous to basic metal (preferred sodium), or its mixture, has following general formula:

0.8-1.5Na ₂O·Al ₂O ₃·0.8-6SiO ₂·xH ₂O

These materials contain some combination water and (are expressed as " xH ₂O "), and require to have the calcium ion-exchanged capacity that at least 50 milligrams of CaO/ restrain.Preferred sodium silicoaluminate contains 1.5-3.5 SiO ₂Unit (in the following formula).As described in detail in the literature, reaction is easy to prepare amorphous and the crystalline state material between water glass and the sodium aluminate by making.

Suitable crystalline sodium aluminosilicate ion-exchange washing assistant is seen and is set forth in for example GB1429143 (Procter ﹠amp; Gamble) in.Preferred such sodium silicoaluminate is well-known commercially available zeolite A and X zeolite, and described in EP 384070 (Unilever) and novel high alumina zeolite P required for protection.The zeolite P of this form also is referred to as zeolite MAP.Its a kind of commodity are called zeolite A24.Water-insoluble washing assistant can be the lamina sodium silicate described in the US4664839.

NaSKS-6 (being abbreviated as " SKS-6 " usually) is the trade mark by the crystalline layered silicate of Hoechst sale.NaSKS-6 has the δ-Na of layered silicate ₂SiO ₅Morphological form.Can be by as DE-A-3,417,649 and DE-A-3, the method described in 742,043 is prepared.Other this available layered silicates have general formula NaMSi _xO _2x+1YH ₂O, wherein M is sodium or hydrogen, x is the numeral (being preferably 2) of 1.9-4 and the numeral (being preferably 0) that y is 0-20.

The water soluble detergency promoter of non-phosphorus can be organic or inorganic.The inorganic builders that can exist comprises basic metal (being generally sodium) carbonate; And organic washing-assisting detergent comprises the polycarboxylic acid ester polymer, as polyacrylic ester and vinylformic acid/maleic acid, monomeric polycarboxylates such as citrate, gluconate, oxygen di-succinate (oxydisuccinates), glycerine one-, two-and three succinates, the carboxy methoxy-succinic acid ester, carboxymethoxyl malonic ester, pyridine dicarboxylate and hydroxyethyliminodiacetic acid ester.

The preferred tablet composition comprises polycarboxylic acid ester polymer, more preferably polyacrylic ester and vinylformic acid/maleic acid, and they can play washing assistant, can suppress again to take place simultaneously undesirablely to be deposited on the fabric from washings.

Washing assistant can particle form be sneaked into, and wherein contains the washing assistant of 40-80% (weight), and remainder is other materials (may not be washing composition).This particle can account for the 10-60% of composition in the zone of described tablet or tablet.Ratio

Generally speaking, tablet prepared in accordance with the present invention will contain the nonsoap detergent of 2 or 5% (weight) to 40 or 50% (weight) altogether, and 5 or 10% (weight) is to the washing assistant of 60 or 80% (weight).The individual areas of heterogeneous tablet can contain or can not contain the washing composition and the washing assistant of these ratios.Other compositions

Can contain bleaching system according to detergent tablet of the present invention.Preferably include one or more peroxy bleaching compounds, as inorganic persalt or organic peroxide acid, they can be mixed together use to improve the bleaching activity of cold washing with activator.If there is any peralcohol, then the scope of its amount is 10-25% (weight) tablet.

Preferred inorganic persalt is Sodium peroxoborate monohydrate and tetrahydrate, and SPC-D.People extensively disclosed various bleach activators in the art.Its preferred example comprises various peracetic acid precursors, as tetra acetyl ethylene diamine (TAED) and peroxybenzoic acid precursors.The quaternary ammonium that is disclosed in US 4751015 and US 4818426 (Lever Brothers Company) is with the Phosphonium bleach activator also enjoys people to pay close attention to.Another kind of available but be not the bleaching precursor the bleach activator type for as be disclosed in transition-metal catalyst among EP-A-458397, EP-A-458398 and the EP-A-549272.Bleaching system also can comprise bleaching stibilizer (heavy metal chelant), as ethylenediamine tetramethylene phosphonic acid ester and diethylenetriamine pentamethylenophosphonic acid(DTPP) ester.

Usually the amount of bleach activator is the 1-10% (weight) of tablet, may be lower in the situation of transition-metal catalyst, be 0.1% (weight) of tablet or higher.

Detergent tablet of the present invention also can contain a kind of at various dirts and the color spot thereby help the detergency enzymes of its removal of can degrading well known in the art.Suitable enzyme comprises various proteolytic enzyme, cellulase, lipase, amylase of removing from fabric various dirts and color spot and composition thereof of being used for.Detergency enzymes is used (choose wantonly and have supercoat) with the form of particle or marume usually, and its amount is about 3.0% (weight) of about 0.1%-of tablet.

Detergent tablet of the present invention also can contain white dyes, for example can be available from Tinopal (trade mark) DMS or the Tinopal CBS of Basel, SUI Ciba-Geigy AG.TinopalDMS is 4,4 '-two (2-morpholine also-4-anilino-inferior-triazine-6-base is amino) stilbene disulfonic acid disodium; And Tinopal CBS is 2,2 '-two (phenyl-styryl) disulfonic acid disodium.

Preferably include a kind of froth breaking material (all the more so when detergent tablet is mainly used in muzzle-loading rotary drum automatic washing machine).The froth breaking material of particle form is seen and is set forth among the EP 266863A (Unilever).This froth breaking particle generally includes as the froth breaking active substance, is adsorbed onto the mixture of the following various materials on the inorganic carrier material of water soluble carbonate alkali of porous absorption: silicone oil, vaseline, water drain silica and alkyl phosphate.

Also require detergent tablet of the present invention to comprise a certain amount of alkalimetal silicate, particularly sodium orthosilicate, water glass or disilicic acid sodium simultaneously.The existence of this alkalimetal silicate is preventing that aspect the corrosion of metal ingredient in washing machine also be useful except the effect that provides some decontaminations to help to wash.The particle that preferably is rich in washing composition contains the silicate of the 5-15% of particle weight.These basic metal persalts have improved particulate intensity and unrestricted flow before carrying out compressing tablet.

Other can be chosen the composition that is used for fabric washing detergent tablet of the present invention wantonly and comprise various anti redeposition agents (as Xylo-Mucine, straight linear polyethylene pyrrolidone) and various ether of cellulose (as methylcellulose gum and Type 3U), various fabric softeners; Various heavy metal chelants (as EDTA); Spices; With tinting material or lentigo decorations.Compressing tablet

Compressing tablet requires to comprise the particle that contains washing composition, the particle that promotes decomposition and the granular composition compacting of any other composition.Various tabletting machines are known and can be used.Usually a certain amount of granular composition that is enclosed in the mould being carried out hammering operates.

Compressing tablet can carry out under room temperature or the temperature more than the room temperature under the situation that does not apply heat.In order under the temperature more than the room temperature, to carry out compressing tablet, preferably with the feeding of pyritous granular composition to tabletting machine.Certainly this with heat transferred tabletting machine, but also can other mode come the heating tablet forming machine.

If heat is provided, then our imagination provides by conventional methods, as granular composition is not used micro-wave energy by baking oven.Tablet size and density

According to employed condition and whether its size represented the dosage or this dosage of part of the mean load of fabric washing or dishwasher, the magnitude range of tablet suits at the 10-160 gram, is preferably the 15-60 gram.Tablet can be an Any shape.But, be preferably the bulk that has even cross section basically, as right cylinder or cubes for the ease of packing.The total density range of tablet is preferably 1040 or 1050 grams per liters (can be 1100 grams per liters) to 1450 grams per liters or higher.The density range of tablet may be up to 1350 or 1400 grams per liters.

Embodiment 1

Adopt 1.2m ²The VRV flash dryer prepares the anionic detergent additive granules (LAS-A) that contains 70% (himself weight) linear alkyl benzene sulfonate in the mode described in the WO 97/32002.It has three equal casing profiles.The charging valve that is used for liquid and powder is close to before first hot section, in the end can obtain intermediate cross-section charging valve in two cross sections.Add zeolite by the valve in this last cross section.Electronic oil heater is one or two casing profile heat supply, and the oil temperature of using is 120-190 ℃.Use 15 ℃ room temperature process water to cool off sleeve pipe in the last cross section.The additional air flow quantity of controlling by reactor by the bypass of opening on the steam discharge exhaust fan is 10-50m ³/ hr.Motor turns round at full speed, and top speed is about 30m/s.

Proofread and correct the mono pump and come charging room temperature LAS acid, proofread and correct peristaltic pump and come the sodium hydroxide of charging 47%.Proofread and correct screw feeder and come charging yellow soda ash and zeolite A24.Yellow soda ash and liquid add before first hot section, and zeolite then joins chilled the 3rd cross section.

Product is the form of free flowing powder, contains:

LAS-A: composition	% (weight)
		Linear alkyl benzene sulfonate (LAS)	????70％
Yellow soda ash	????2％
		Zeolite	????25％
Non-washing composition impurity and moisture	????3％

By making the granulation preparation in Eirich RV02 granulator (may need the Loedige circulator) of nonionic detergent and silicon-dioxide and soap contain the nonionic detergent granules (ND1) of 56% nonionic detergent for more extensive.

Silicon-dioxide is by Britain Crosfield, the Sorbosil TC15 that Warrington provides.Nonionic detergent is heated, and mix, be sprayed onto then on the silicon-dioxide in the granulator, spray enough alkali simultaneously with the described lipid acid that neutralizes with lipid acid.Cooled product in fluidized-bed is also removed particulate simultaneously.Sieve removes the particle (＞1400 μ m) of super large.

Gained particle ND1 contains:

ND1: composition	% (weight)
		Nonionic detergent	????56％
Silicon-dioxide	????30％
		Soap and moisture	????14％

Produce as a comparison nonionic detergent granules (ND2) by making zeolite A24 (from the maximum aluminium zeolite P of Crosfields) and trisodium citrate granulation in L dige circulator.Nonionic detergent mixed with lipid acid and spray, also spray simultaneously 50% enough aqueous sodium hydroxide solution with in and lipid acid.Products therefrom contains:

ND2: composition	% (weight)
		Zeolite A24	????53.8
Trisodium Citrate	????7.9
		Nonionic detergent	????24.2
Soap	????4.1
		Moisture	????10.0

To L dige CB30 circulator, obtain zeolite builders particle ZB1 by 40% solution (Sokolan CP5 solution) continuously feeding with zeolite A24, particulate state trisodium citrate and acrylate/maleate copolymer.CB30 turns round under 1500rpm.To export powder and be incorporated into L dige KM300 ploughshare (120rpm), carry out densification therein.The gained powder is dry in fluidized-bed, and air themperature is 110 ℃.Gained lotion-aid particle composed as follows:

ZB1: composition	% (weight)
		Zeolite A24	????53.6
Trisodium citrate	????17.2
		?Sokolan?CP5	????19.0
Moisture	????10.2

Adopt detergent particles LAS-A and ND1 and lotion-aid particle ZB1 and other compositions to prepare the tablet of filling a prescription shown in the following table.Adopt ND2 to replace ND1 granules preparation contrast tablet.

	Weight part
				Contrast	Embodiment 1
Anionic detergent particles LAS-A	????5.43	????5.43
			Nonionic zeolite particle ND2	????6.91	?????-
Nonionic silica dioxide granule ND1	?????-	????2.99
			Zeolite granular ZB1	????6.39	????13.33
Yellow soda ash	????1.26	????1.26
			Acrylate/maleate copolymer	????0.53	????0.53
Disilicic acid sodium	????1.44	????1.44
			The Xylo-Mucine particle	????0.17	????0.17
SPC-D	????5.92	????5.92
			The TAED particle	????2.09	????2.09
Sodium acetate trihydrate mixes with the zeolite that accounts for himself weight 1%	????10.38	????10.38
			The froth breaking particle	????0.74	????0.74
Sequestrant, white dyes, soil release polymer and painted sodium carbonate particle	????1.68	????1.68
			Amount to	????42.94	????45.96

Obtain containing the tablet of 43 gram Comparative composition, or contain the tablet of the composition of 46 gram embodiment 1.These tablets all contain 3.8 parts of alkylbenzene sulfonates, 1.67 parts of nonionic detergent, 8.5 parts of zeolites and 10.4 parts of sodium acetate trihydrates.Adopt the compelling force of 9.7kN to compress tablet.

Dissolution rate by the various soluble components of following measurement of test method tablet: tablet is put mesh size is 2mm, impregnated under 20 ℃ room temperature in 9 liters of plastics sieves in the tap water.The plastics sieve is fixed in the agitator that rotates with 200rpm.The monitoring electrical conductivity of water is until reaching steady state value.Electrical conductivity of water is changed to the time (T that reaches its final numerical value 90% ₉₀) as the dissolution time of tablet.

The intensity of test tablet by the following method: columned tablet is carried out radial compression till tablet rupture between the pressing plate of material-testing machine.Tablet generation explosion when breaking needs compelling force to keep the displacement that pressing plate falls.The compelling force of keeping described displacement when needs has fallen to it and has peakedly stopped measuring 25% the time.

Maximum, force is rupturing capacity (F _f).Adopt following equation can calculate the test parameter that is called the diameter rupture stress from the mensuration of this power: $\mathrm{\σ}=2\frac{F_f}{\mathrm{\πDt}}$ In the formula: σ is diameter rupture stress (handkerchief), F _fFor causing disruptive compelling force (newton), D is tablet diameters (rice), and t is a tablet thickness.

The diameter rupture stress that causes disruptive power and therefrom calculate is the direct evaluation of intensity, shows the resistance to breakage of tablet when the human consumer uses.Before breaking input energy (or mechanical work) be the tablet deformability tolerance and and the delivery period between the resistance to breakage of tablet closely related.We are called " energy to fracture " at this energy or the merit before will breaking, for the graphic representation of compelling force and displacement with upper and lower area to rupture point.Provide by following equation: $E_b=\underset{0}{\overset{X_f}{\∫}}F\left(X\right)\mathrm{dX}$ In the formula: E _bBe energy to fracture (Jiao) that x is displacement (rice), F is the compelling force (newton) at displacement x place, and X _fDisplacement when breaking.

Dissolution time, rupture stress and energy to fracture are shown in following table:

	Contrast	Embodiment 1
			?DFS(kPa)	????18.9	????21.5
?T 90(second)	????123	????120
			?E b(mJ)	????9.2	????17.3

As can be seen, the energy to fracture of embodiment 1 tablet contrasts the energy to fracture of tablet and will get well, and other performances are then similar.

Embodiment 2 and 3

As preparation anionic detergent additive granules (LAS-B) as described in the embodiment 1, but detergent content is higher.They contain:

LAS-B: composition	% (weight)
		Linear alkyl benzene sulfonate	82％
Yellow soda ash	4％
		Zeolite	10％
Non-washing composition impurity and moisture	4％

The non-ionic particle ND1 of above particle LAS-B and previous embodiment is mixed two kinds of detergent composition listing with the preparation following table mutually with other materials.The particle (can available from the Rhodia-Phos HPA 3.5 of Rhone-Poulenc) that comprises the Tri sodium Phosphate that contains 70%I phase form and 3.5% combination water.

	Weight part
				Embodiment 2	Embodiment 3
Anionic detergent particles (LAS-B)	????13.5	????13.5
			Nonionic detergent granules (ND1)	????8.9	????8.9
Rhodiaphos HPA 3.5 triphosphates	????46.65	????30.2
			Acrylate/maleate copolymer	????1.5	????1.5
Water glass	????4.0	????4.0
			Xylo-Mucine particle (SCMC)	????0.3	????0.3
White dyes on the inert support	????0.15	????0.15
			SPC-D	????15.1	????15.1
The TAED particle	????3.4	????3.4
			The froth breaking particle	????3.2	????3.2

Sequestrant, soil release polymer and painted sodium carbonate particle	????2.7	????2.7
			Amount to	????99.4	????82.95

Powder (BP1) preparation contrast detergent composition by the following spraying drying base of forming:

BP1: composition	Weight part
		LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium	????11.0
?C 13-15Fatty Alcohol(C12-C14 and C12-C18) 7EO	????2.6
		?C 13-15Fatty Alcohol(C12-C14 and C12-C18) 3EO	????2.4
Soap	????0.2
		Tri sodium Phosphate *	????16.9
Acrylate/maleate copolymer	????1.5
		Water glass	????4.0
The Xylo-Mucine particle	????0.3
		White dyes on the inert support	????0.15
Moisture and impurity	????5.95
		Amount to	????45

^*The form of the anhydrous Tri sodium Phosphate of 70%II phase joins in the slurry to contain at least.

This powder is mixed with following other compositions:

Composition	Weight part
		Base materials powder (BP1)	????45
Rhodiaphos HPA3.5 triphosphate	????30.2
		SPC-D	????15.1
The TAED particle	????3.4
		The froth breaking particle	????3.2
Sequestrant, soil release polymer and painted sodium carbonate particle	????2.7
		Amount to	????99.6

With these compositions each other abreast shown in the following table:

	Weight part
				Composition	Embodiment 2	Embodiment 3	The comparative example
LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium	????11.0	????11.0	????11.0
				Nonionic detergent	????5.0	????5.0	????5.0
Silico-aluminate	????1.35	????1.35	????0
				Silicon-dioxide	????2.65	????2.65	????0
Rhodiaphos HPA 3.5 triphosphates	????46.65	????30.2	????30.2
				Other triphosphates	????0	????0	????16.9
Acrylate/maleate copolymer	????1.5	????1.5	????1.5
				Water glass	????4.0	????4.0	????4.0
SPC-D	????15.1	????15.1	????15.1
				The TAED particle	????3.4	????3.4	????3.4
The froth breaking particle	????3.2	????3.2	????3.2
				SCMC on the carrier and white dyes	????0.45	????0.45	????0.45
Sequestrant, soil release polymer and painted sodium carbonate particle	????2.7	????2.7	????2.7
				Soap, yellow soda ash, moisture and other impurity	????2.35	????2.35	????6.15
Amount to	????99.35	????82.9	????99.6

Every kind of composition 40 grams are pressed into the right cylinder tablet of 44 mm dias.Use the compaction force of different amounts.The composition of embodiment 2 also is pressed into 32 gram tablets so that make the tablet of this composition contain the washing composition that contrasts the tablet equal amtss with 40 grams.

Test as 1 pair of each tablet of embodiment.The results are shown in following table, this table is set shows that the tablet with similar diameter rupture stress (DFS) compares.

Compaction force (kN)	Embodiment 2 (40 gram tablet)			Comparative example's (40 gram tablet)
								??DFS(kP ????a)	????T 90(second)	????E b????(mJ)	??DFS(kPa ????)	????T 90(second)	????E b????(mJ)
?30	????55.8	????180	????20.5
							?9.7				????54.2	????400	????15
?15	????27.4	????140	????13.9
							?9.7	????18.6	????105	????6.7
?5.0				????20.9	????220	????6.4
							?5.0	????7.4	????115	????2.8
?2.5				????6.5	????190	????2.25

Compaction force (kN)	Embodiment 3 (40 gram tablet)			Embodiment 3 (32 gram tablet)			Comparative example's (40 gram tablet)
											???DFS(k ????Pa)	???T 90(second)	????E b???(mJ)	???DFS(k ????Pa)	???T 90(second)	????E b????(mJ)	??DFS(k ????Pa)	????T 90(second)	????E b????(mJ)
?9.7							????54.2	????400	????15
										?15	????39.1	????250	????20.3	????36.1	????275	????22.9
?7.5							????36.8	????310	????10.5
										?9.7	????29.9	????200	????15.2	????23.4	????240	????14.1
?5.0							????20.9	????220	????6.4
										?5.0	????10.8	????145	????6.1	????9.8	????140	????5.7
?2.5							????6.5	????190	????2.25

Obviously the invention enables and to improve energy to fracture, reduce dissolution time and/or reduce tablet weight (and this transports the identical weight washing composition just required).

Embodiment 4

The various tablets that use as additive granules LAS-B in the aforementioned embodiment and ND1 are prepared as follows prescription:

	Weight part
		Anionic detergent particles (LAS-B)	16.0
Nonionic detergent granules (ND1)	10.0
		Rhodiaphos HPA3.5 triphosphate	48.0
Acrylate/maleate copolymer	2.0
		Water glass	4.0
The Xylo-Mucine particle	0.5
		Polyvinylpyrolidone (PVP)	1.0
Yellow soda ash	7.0
		Sodium sulfate	5.0
The froth breaking particle	3.5
		Sequestrant, soil release polymer and painted sodium carbonate particle	3.0
Amount to	100

Embodiment 5

Various additive granules described in the previous embodiment (LAS-B and ND1) 40 restrain tablets with what other compositions used that preparation has two-layer (10 grams and 30 restrain) that weight do not wait.Total prescription is similar to embodiment 2, but contains many slightly alkylbenzene sulfonate and few slightly triphosphate.Use with embodiment 2 and 3 in used have same composition but prepare from the base materials powder (BP1A) of different batches of taking-ups have the contrast tablet that does not wait weight two-layer.Total prescription is identical with the prescription of aforementioned contrast tablet.

When these two-layer tablets of preparation, the composition that will be used for one deck places mould and carries out slight compacting, and the composition that will be used for another layer then adds mould, applies compaction force to mould.

Various prescriptions are shown in following table:

	Weight part
								The comparative example			Embodiment 5
	Thin layer	Thick-layer	Amount to	Thin layer	Thick-layer	Amount to
							Base materials powder (BP1A)	4.57	13.6	?18.17	??-	??-	??-
Anionic detergent particles (LAS-B)	?-	???-	???-	?1.59	?4.73	?6.32
							Nonionic detergent granules (ND1)	???-	????-	???-	?0.90	?2.67	?3.57
Rhodiaphos HPA3.5 triphosphate	3.05	9.07	?12.12	?4.51	?13.42	?17.93
							Acrylate/maleate copolymer	??-	????-	????-	?0.15	?0.45	?0.6
Water glass	??-	????-	????-	?0.40	?1.20	?1.6
							SCMC particle, white dyes and soil release polymer	??-	????-	????-	?0.07	?0.20	?0.27
SPC-D	0	6.05	?6.05	?0	?6.05	?6.05
							The TAED particle	1.36	0	?1.36	?1.36	?0	?1.36
The froth breaking particle	0	1.28	?1.28	?0	?1.28	?1.28
							Sequestrant and painted sodium carbonate particle	1.02	?0	?1.02	?1.02	?0	?1.02
Amount to	10	?30	?40	?10	?30	?40

In the foregoing description 1 identical mode each tablet and contrast tablet are tested, are obtained following result:

Compaction force (kN)	Embodiment 5			Comparative example's (two-layer tablet)
								??DFS(kP ????a)	????T 90(second)	????E b???(mJ)	?DFS(kPa ????)	????T 90(second)	????E b???(mJ)
?30	????55.8	????120	????41.7
							?20	????43.1	????115	????28.0
?9.7	????21.4	????105	????10.6	????52.1	????275	????15.7
							?5.0	????8.2	????105	????2.7	????21.8	????210	????7.1
?2.5				????7.0	????135	????2.6

Claims (17)

1. the detergent tablet of compressing grains shape composition, wherein said tablet or its zone comprise organic detergent and water soluble detergency promoter, it is characterized in that described tablet or its zone are formed by the composition compacting that comprises following material:

(i) contain the nonionic detergent that accounts for himself weight at least 45% (weight) particle and

(ii) other compositions.

2. according to the tablet of claim 1, wherein said composition contains the particle of the nonionic detergent of at least 50% (weight).

3. according to the tablet of claim 1 or claim 2, the composition in wherein said tablet or zone contains the nonionic detergent of 3-40% (weight), and half exists with described particulate form at least for it.

4. according to the tablet of any one aforementioned claim, the composition in wherein said tablet or zone also comprises the particle of the non-soap anionic detergent that contains himself weight at least 20%.

5. according to the tablet of claim 4, the composition in wherein said tablet or zone contains the nonsoap detergent of 5-50% (weight), and half exists with the particulate form of the nonionic detergent that contains 45% (weight) or with the particulate form of other nonsoap detergents of containing himself weight 20% at least at least at least for it.

6. according to the tablet of any one aforementioned claim, wherein the non-soap organic detergent at least 90% in tablet or its zone is included in the particle of the nonionic detergent that contains himself weight 45% (weight) at least, or is included in the particle of other nonsoap detergent that contains himself weight at least 20% (weight).

7. according to the tablet of any one aforementioned claim, the composition in wherein said tablet or zone comprises that one or more that contain himself weight at least 80% are selected from the particle of following water-soluble substances: the water solubilities of 20 ℃ of per down 100 gram water surpass the compounds of 50 grams, contain the Tri sodium Phosphate of the I phase anhydrous form of himself weight at least 50%, and composition thereof.

8. according to the tablet of claim 7, the composition in wherein said tablet or zone contains the described particle of 15-60% (weight), and this particle contains one or more water-soluble substances of himself weight at least 80%.

9. according to the tablet of claim 7, the composition in wherein said tablet or zone contains the described particle of 25-50% (weight), and this particle contains one or more water-soluble substances of himself weight at least 80%.

10. according to each tablet among the claim 7-9, the composition in wherein said tablet or zone contains the described triphosphate of 20-60% (weight), this triphosphate by partially hydrated be at least 1% (weight) of described Tri sodium Phosphate so that make the amount of the combination water that contains.

11. according to each tablet among the claim 7-9, the composition in wherein said tablet or zone contains the particle of 25-55% (weight), this particle contain himself weight at least 95%, by partially hydrated so that make that the content of combination water is the triphosphate of at least 1% (weight) of described Tri sodium Phosphate.

12. according to each tablet among the claim 7-9, the composition in wherein said tablet or zone contains the described particle of at least 20% (weight), described particle contain account for himself weight at least 80% one or more, the salt that surpass 50 grams at the water solubilities of 20 ℃ of per down 100 gram water.

13. according to the tablet of claim 12, wherein said compound is the Trisodium Citrate of one or more part or all of hydration, the sodium acetate and the potassium acetate of partly or entirely hydration.

14. according to the tablet of any one aforementioned claim, wherein described in general tablet contains the non-soap organic detergent of 5-40% and the washing assistant of 15-80%.

15., amount to the Tri sodium Phosphate that contains in anhydrous form 30-60% (weight) according to the tablet of claim 14.

16. according to the tablet of any one aforementioned claim, wherein said tablet or its regional composition contain the particle of 10-60%, this particle contains the washing assistant of himself weight 40-80% and other non-washing composition materials of himself weight 20-60%.

17. be used for preparation method as at the defined tablet of each aforementioned claim, this method comprises makes the described particle of the nonionic detergent that contains himself weight at least 45% itself mix with other detergent ingredients, then resulting composition is pressed into tablet.