CN101688158A - Manufacture of detergent granules by dry neutralisation - Google Patents

Abstract

A process for the manufacture of detergent granules comprising anionic non-soap surfactant the process comprising the dry neutralisation of surfactant acid with habit modified Sodium Carbonate, whichis a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer. A high active detergent granule comprising greater than 30 wt% anionic surfactant, the surfactant comprising a major part of non-soap anionic surfactant, habit modified Sodium Carbonate, and less than 10 wt% preferably zero, zeolite, is obtainable by the process.

Description

Make detergent particles by dry neutralization

The present invention relates to make detergent particles, relate to the method that comprises the detergent particles of the non-soap surfactant of anionic with yellow soda ash dry neutralization surfactant acid with formation especially by dry neutralization.

Background

Detergent particles is usually with coacervate (agglomerate) the form manufacturing than small-particle.Can realize this reunion by the combination of spraying drying, mixing or these technologies.Many detergent particles comprise non-soap anionic tensio-active agent, for example alkylbenzene sulfonate.This particle by with in solid alkali metal salt (the being generally yellow soda ash) original position and the acid precursor (hereinafter being called " surfactant acid ") of non-soap anionic tensio-active agent prepare.

GB 1369269 discloses by at the repacking mixing machine that has topping machanism (for example

The ploughshare mixing machine) will synthesize the acid of organic anion type washing composition in, mix this sour method that neutralizes with excessive powdery yellow soda ash as linear alkyl benzene sulphonic acid.Instructed with yellow soda ash and added synergistic agent (builder) and/or filling salt so that product is easier flows.In the process of adding acid, use chopper or cutting unit in the mixing machine.Embodiment 1 and 2 comprises tripoly phosphate sodium STPP in doing mixed thing.The powder of making is easily flow (free flowing).Embodiment 3 does not use tripoly phosphate sodium STPP, but the product needed pulverizing, and be not described to easily flow.A problem of the disclosure is, the preferably not phosphorous hydrochlorate of this particle nowadays, but the document not instruction remove phosphatic effective ways.

GB 2221695 has described the dry neutralization method of the detergent powder of preparation high-bulk-density in the high-speed mixing tablets press with stirring and cutting action.In most of embodiment, except that yellow soda ash, also use zeolite or tripoly phosphate sodium STPP.In embodiment 26 to 29, use the yellow soda ash of high content, and add special-purpose calcite glidant to help granulation with 4% amount.However, the non-constant of the flowing property of embodiment 26, and propose to add tripoly phosphate sodium STPP to remedy this problem.The problem of this method is that the use of glidant is great complex process factor, and the preferably not phosphorous hydrochlorate of this particle nowadays.

WO 2002/24854 has described the dry neutralization method of carrying out in the horizontal film evaportor.Instructed and used small grain size yellow soda ash to reduce the amount of unneutralized surfactant acid in the products obtained therefrom.Unneutralized material is known does not expect for this type of, because it continues with the yellow soda ash reaction and causes powder agglomates.In an embodiment, also add zeolite.This interpolation reduces the content of aniorfic surfactant in the detergent particles.In addition, if zeolite is not essential, nowadays preferably can in this detergent particles, not use zeolite in said preparation.

US 7053038 has described the dry neutralization method of using small grain size yellow soda ash and mineral acid (as sulfuric acid) to carry out in gas fluidisation granulator.All comprise zeolite and tripoly phosphate sodium STPP among all embodiment.

EP 1534812 discloses the dry neutralization of the premolding spray dried particle that comprises carbonate and polyacrylate.Under low shearing condition, carry out this method to avoid reunion.In all embodiments, this carbonate is the burkeite double salt that generates when yellow soda ash and sodium sulfate spraying drying together.These particles are too firm so that can not be with in the method for the invention.As further explaining subsequently, this method is not made crystal habit modification (habit modified) yellow soda ash.

EP 0221776 has described spraying drying yellow soda ash and crystal growth modifier to make the method for so-called crystal habit modification carbonate particle.This crystal growth modifier is the polymeric polycarboxylate preferably.This patent has been described the manufacturing of the burkeite of crystal habit modification in most of embodiment.The yellow soda ash itself that had only embodiment 1 crystal habit modification.

In WO 2006/081930 also with the habit modified spraying drying with as carrier granule.Use polyaspartic acid salts to replace the polycarboxylate of EP 0221776.

In this manual, habit modified is the term that is used to contain this type of prior art material.This term does not comprise the burkeite of crystal habit modification, can mix with required habit modified and incorporates into although can understand the burkeite of lower concentration, as long as the gained mixture keeps following characteristic.

Still need to make the method for detergent particles by dry neutralization, its do not require use as the additive of zeolite, tripoly phosphate sodium STPP or glidant and so on promoting gratifying granulation, and provide necessity conversion of surfactant acid simultaneously to tensio-active agent.

One object of the present invention is to provide the improving one's methods of detergent particles that comprises the non-soap anionic tensio-active agent by the dry neutralization manufacturing.Purpose also is to provide the detergent particles that comprises yellow soda ash and especially high-load non-soap anionic tensio-active agent, and it shows improved storage and use properties.

Summary of the invention

According to the present invention, the manufacture method of the detergent particles that comprises the non-soap surfactant of anionic is provided, this method comprises that described habit modified is the crystal growth modification yellow soda ash that comprises yellow soda ash and mixture of polymers with the step of habit modified dry neutralization surfactant acid.

The present invention also provides can be by the detergent particles of this method acquisition, it comprises aniorfic surfactant (it comprises the non-soap surfactant of anionic of major portion), the habit modified (it is the crystal growth modification yellow soda ash that comprises yellow soda ash and mixture of polymers) of at least 30 weight % and is lower than 10 weight %, is preferably 0 zeolite.

Detailed Description Of The Invention

Habit modified (HMC)

Habit modified is a crystal growth modification yellow soda ash, and it comprises yellow soda ash and mixture of polymers.Its manufacturing for example is described among the EP 0221776 and WO 2006/081930.The burkeite of itself and crystal habit modification is the double salt of yellow soda ash and sodium sulfate and inequality one by one.

When the crystallization of habit modified takes place, must there be polymkeric substance as crystal growth modifier, that is to say must be not later than yellow soda ash and be introduced into.

Further characterize habit modified by it by the specific surface area that nitrogen absorption records.According to based on J.Am.Chem.Soc.60, the ASTM D 3663-78 standard of the Brunauer described in 309 (1938), Emmett and Teller (BET) method is by the specific surface area (" SSA ") of this yellow soda ash of nitrogen absorption measurement.We use the Gemini Model 2360 surface-area analysers (can be available from Micromeritics Instrument Corp.of Norcross, Ga.).This habit modified is characterised in that to have 5 meters squared per gram or bigger, preferred 8 meters squared per gram or bigger, more preferably 10 meters squared per gram or bigger specific surface area (SSA).

Pore volume less than 2 microns holes can further characterize this habit modified.This measures by traditional mercury porosimetry.0.3 milliliter/gram or bigger pore volume are favourable.

The alternative characterization method that comprises the habit modified of polymkeric substance and yellow soda ash is it to be used in the method for claim 1 with sulfuric acid and to be determined at the non-soap surfactant content of the preceding accessible maximum sodium sulfonate anionic of excessive granulation (over-granulation) takes place.Excessively granulation is meant that discrete detergent particles begins to be agglomerated into viscosity agglomerate (sticky mess), and do not add glidant or as the situation of other solid material of zeolite or tripoly phosphate sodium STPP and so under can not it be discharged with the product form of easily mobile (free flowing).If the anionic sodium sulfonate surfactant content that reaches is preferably greater than 35 weight % greater than 30 weight %, more preferably greater than 45 weight %, then this yellow soda ash is crystal habit modification for the purpose of the present invention.

Habit modified is also referred to as HMC herein, can be by the spraying drying manufacturing described in EP 0221776 and WO2006/081930.Also can use the alternate dry method described in these patent applications: for example, dry air, baker (oven) drying, drum dried, ring type moisture eliminator drying (ring drying), lyophilize, solvent seasoning or microwave drying.

HMC also can followingly make: precipitation further comprises the polymer-modified saturated sodium carbonate solution of growth in vaporizer, is habit modified for example by the filtration method sediment separate out, and with this drying precipitate.Surplus solution replenishes and sends back to vaporizer with fresh sodium carbonate solution and polymers soln.The advantage that the precipitator method are better than relying on fully the exsiccant method is that energy consumption is lower.

Polymkeric substance

The basal component of habit modified is a polymkeric substance.Suitable crystal growth modification polymkeric substance can be selected from polycarboxylate.Because its biodegradability is advantageously used polyaspartic acid salts and poly aspartic acid.

Preferred polymer poly-carboxylate's crystal growth modifier of using among the present invention is with 0.1 to 20 weight % of yellow soda ash total amount, preferred 0.2 to 5 weight %, and most preferably the amount of 1 to 5 weight % is used.But; for the reason beyond the crystal growth modification; for example synergy (building), structurizing or antiredeposition; at detergent particles of the present invention or comprise in the close set compound of detergent particles of the present invention and may have more high-load polymkeric substance, for example yellow soda ash is up to 60 weight %.

This polycarboxylate crystal growth modifier preferably has at least 100, and advantageously 1000 to 300000,1000 to 250000 molecular weight especially.

Molecular weight is 3000 to 100000, is 3500 to 70000 especially, and it is preferred more in particular being 10000 to 70000 polycarboxylate crystal growth modifier.All molecular weight of mentioning herein are the molecular weight that provided by manufacturers.

Preferred crystal growth modifier is the homopolymer and the multipolymer of vinylformic acid or toxilic acid.What cherish a special interest is polyacrylate and vinylformic acid/maleic acid.

The suitable polymers of can be separately or uniting use comprises following:

Polyacrylic salt, as sodium polyacrylate, for example from Versicol (trade mark) E5, E7 and the E9 of Allied Colloids, molecular-weight average 3500,27000 and 70000; From Narlex (trade mark) LD 30 and 34 of NationalAdhesives and Resins Ltd., molecular-weight average is respectively 5000 and 25000; With Sokalan (trade mark) the PA series from BASF, molecular-weight average 250000; Ethene/maleic acid is for example from EMA (trade mark) series of Monsanto; Methylvinylether/maleic acid is for example from Gantez (trade mark) AN119 of GAF Corporation; Vinylformic acid/maleic acid is for example from Sokalan (trade mark) CP5 of BASF.

Second group of crystal group growth modifiers comprises poly aspartic acid and polyaspartic acid salts.

Preferred crystal group growth modifiers has at least 1000 in second group, and advantageously 3500 to 300000,4000 to 250000 molecular weight especially.Being 3500 to 100000 with molecular weight preferably, is 4000 to 70000 especially, more in particular is 5000 to 70000 polyaspartic acid salts crystal growth modifier and prepares HMC.All molecular weight of mentioning herein are the molecular weight that provided by manufacturers.

Polyaspartic acid salts is by L-aspartic acid (a kind of natural amino acid) synthetic biological polymer.Part is owing to hydroxy-acid group, and polyaspartic acid salts has and the similar character of polyacrylate.A kind of polyaspartic acid salts of preferred type is hot polymerization aspartate or TPA.This has following benefit: the environmentally friendly product of its biodegradable one-tenth, as carbonic acid gas and water, this is avoided removing TPA in sewage treatment process, and it can landfill disposal.

TPA can make to produce polysuccinimide by the temperature that at first aspartic acid is heated above 180 ℃.Make the polysuccinimide open loop form polyaspartic acid salts subsequently.Owing to can therefore observe two kinds of polymer bonds, [α]-key and [β]-key with two kinds of possible mode open loops.

0.1 to 20 weight % of yellow soda ash total amount, preferred 0.2 to 5 weight %, most preferably the crystal growth modifier of the amount of 1 to 5 weight % is enough to produce suitable habit modified usually.

If desired, the mixture of two or more polymerizable crystallizable growth modifiers can be used in method of the present invention and the detergent particles composition arbitrarily.

Yellow soda ash

The yellow soda ash that is used to make habit modified can be any kind.Have been found that synthetic light soda ash ash is especially preferred; Natural heavy soda ash is placed in the middle, and synthetic granular soda ash ash is least preferred starting material.

Surfactant acid

Surfactant acid is the acid precursor of the non-soap surfactant of anionic, and it will be neutralized the sodium salt that forms aniorfic surfactant when reacting with habit modified.But the surfactant acid of liquid pumping form is preferred.

A preferred anionoid type tensio-active agent is an alkylaryl sulphonate.Preferred surfactants acid is linear alkyl benzene sulphonic acid, is also referred to as LAS acid and HLAS.This surfactant acid in and the time produce corresponding linear alkylbenzene sulfonate (LAS).This LAS non-soap anionic tensio-active agent preferably has C8-18, more preferably C10-16, the most preferably alkyl chain length of C12-14.

The preferred second anionoid type tensio-active agent is alkyl and/or alkenyl sulfate hemiester (being the sulfating product of primary alconol), its in and the time produce alkyl and/or alkenyl sulfate.This type of non-soap anionic tensio-active agent comprises that primary alcohol sulfate, (PAS), especially chain length are C10-22, the PAS of preferred C12-14; Coco PAS expects especially.

Other suitable surfactant acid comprises alpha-olefin sulfonic acid, inner olefin sulfonic acid, fatty acid ester sulfonic acid and uncle's sulfonic acid.

Combination that also can the conspicuous surfactant acid of use technology personnel.

The soap that is formed by the dry neutralization of carboxylic acid or lipid acid can be used as auxiliary aniorfic surfactant and mixes use with this non-soap anionic tensio-active agent.Preferred carboxylic acid is the lipid acid with 12-18 carbon atom, for example the lipid acid of cocounut oil, plam oil, palm-kernel and butter.This lipid acid can be saturated or unsaturated, side chain or straight chain.Can use fatty acid mixt.Lipid acid can use with the content that is up to 30 weight % of this surfactant acid.

This surfactant acid (or mixture of surfactant acid) can use with part pre-neutralization form under the situation of not losing advantageous effects of the present invention.In fact, this surfactant acid is the mixture of surfactant acid and the non-soap surfactant of neutral anionic thereupon.

Optional other composition that exists in this procedure

This HMC dry neutralization method has all advantages and the handiness of the dry neutralization method of prior art.

This surfactant acid can mix adding with other liquid ingredient.Wherein, except that lipid acid of having discussed and neutral aniorfic surfactant, can be nonionic surface active agent with the most important annexing ingredient that this surfactant acid adds with liquid form.It adds in this surfactant acid usually reducing viscosity, thereby it can be added at a lower temperature.

The nonionic surface active agent that available is suitable comprises primary alcohol ethoxylate and secondary alcohol ethoxyl compound, especially use every mol of alcohol average 1 to 50, the C8-C20 fatty alcohol of preferred 1 to 20 moles of ethylene oxide ethoxylation is more particularly used the do-cis primary aliphatic alcohols and the secondary alcohol of average 1 to the 10 moles of ethylene oxide ethoxylation of every mol of alcohol.The nonionic surface active agent of non-ethoxylatedization comprises alkyl poly glucoside, glycerol monoethers and polyhydroxyamide (glucamide).As has been discus, the neutral aniorfic surfactant can mix with this surfactant acid.This can have the advantage of raising reaction vessel/mixing tank throughput.

Can comprise mineral acid with other fluid additive that this aniorfic surfactant acid adds or adds as independent liquid stream, as sulfuric acid, and hydrotropic solvent, as tosic acid.

Be enough to cause neutralization reaction but be not enough to cause the less water of remarkable reunion can be before surfactant acid is introduced mixing machine and its pre-mixing, but be not to add entry.Pigmented product if desired, in adding mixing machine to before, can be easily with dyestuff and surfactant acid and water pre-mixing.The addition of water mostly is about 2 weight % of particulate component total amount most.

Additional solid can be mixed with this habit modified.This can or carry out in the N-process before this surfactant acid neutralization.Unmodified yellow soda ash, promptly SODA ASH LIGHT 99.2 can be mixed use with this habit modified.Can add zeolite and/or other synergistic agent (builder) material, although do not need them just can obtain owing to the fine granularity energy that uses HMC.Except that may preferably avoiding using zeolite fully as finally brightening the coating.Complete detergent system still can be mixed with single simple dry neutralization particle, especially when using the lime-resistant surfactant adulterant.The lime-resistant surfactant adulterant is not require those single or blended tensio-active agents that exist synergistic agent to obtain effective detersive power in normal water hardness scope.We use the lime-resistance of following method test surfaces promoting agent adulterant.At first the surfactant blend of 0.7 grams per liter is dissolved in the water that contains the capacity calcium ion France (French) hardness (4 * 10 to obtain 40 ^-3Mole Ca ²⁺).Add other ionogen subsequently on demand, as sodium-chlor, sodium sulfate and sodium hydroxide to regulate ionic strength to 0.05M, pH to 10.After the specimen preparation 15 minutes, measure the light absorption ratio of 4 millimeters samples of light transmission of wavelength 540 nanometers.Carry out ten times and measure calculating mean value.The adulterant of anti-calcium is that mean value is lower than those of 0.08.

Lime-resistant surfactant adulterant that can dry neutralization comprises the mixture that LAS, SLES stick with paste and/or AOS sticks with paste with the high EO of non-ionic type.

Except that basic habit modified, also can in mixing machine, add the traditional synergistic agent and the yellow soda ash of non-crystal habit modification.The example of this class synergistic agent comprises alkali metal aluminosilicate, alkali metal phosphate of crystallization and amorphous and composition thereof.Total amount of habit modified and yellow soda ash should always surpass the required amount of neutralization, so that basicity is provided in product; About 10 to 15 weight % are excessive to be suitable.This represents molar excess 3: 1 or higher.

The solid that exists in the mixing machine can also comprise other solids component that need mix in this detergent particles, for example white dyes; Polycarboxylate polymer; Anti redeposition agent, for example Xylo-Mucine; Or filler, as sodium sulfate, diatomite, calcite, kaolin or wilkinite.

If desired, solia particle shape tensio-active agent, the for example alkylbenzene sulfonate of powder type and/or alkyl-sulphate, can constitute the part of this mixing machine feeding-in solid body, with the activity level of tensio-active agent in the further raising particle, but preferably make all aniorfic surfactant by dry neutralization.

Other aniorfic surfactant that can exist in the detergent particles of making by method of the present invention comprises secondary alkyl sulfate, sulfated alkyl ether and dialkyl sulfosuccinate succinate.That yes is known for aniorfic surfactant, and the reader who is familiar with technology can append this list.

The dry neutralization method

This surfactant acid preferably uses with liquid form, and advantageously reacts simultaneously at blended with the habit modified of molar excess, to form the sodium salt of this aniorfic surfactant simultaneously at blended.As the replacement scheme of the habit modified of using molar excess, can be with habit modified and more a spot of other traditional yellow soda ash, carry out this reaction as the mixture of light soda ash ash and/or burkeite, correspondingly reduce granulation benefit of the present invention., if use a large amount of yellow soda ash, this composite technology reduces the amount of required special crystal habit modification raw material.

In this dry neutralization reaction, can use the liquid-solid composition ratio wideer than normal range.Because this system is self-structureization (self structuring), need not zeolite or similar structurising agent (structurant), and this method is easy to control.

Permissible free-water total amount preferably amounts to the 8 weight % that should not surpass total composition in this method, preferably is no more than 4 weight %.

When using habit modified in the dry neutralization method, the gained particle comprises neutral aniorfic surfactant and any excessive habit modified.This habit modified is the excellent carrier (substrate) of additional liquid component, and it also serves as buffer reagent in the detergent composition in the mode identical with yellow soda ash.Therefore the present invention can be advantageously used in the preparing washing powder, if wherein use yellow soda ash and do not have any other synergistic agent--especially use lime-resistant surfactant adulterant or mixture.For guaranteeing to exist in this particle the yellow soda ash of significant quantity, can exist far more than in and the habit modified of aequum.

The known technology characteristics of dry neutralization those skilled in the art is, surfactant acid should enough gently add in this mixing machine so that it is consumed at once, and can not accumulate in the mixing machine with unreacted form.We have found that this is equally applicable to use the technology of habit modified.Add surfactant acid required and the preferred time depend on the amount that will add certainly, but add usually preferably through at least 1 minute, more preferably through 2 to 12 minutes, most preferably carried out in 3 to 10 minutes.

Mixing machine

The common not type of fastidious used mixing machine of this method is as long as provide violent mixing.We have found that in order to obtain whole advantage of the present invention, it is favourable using the mixing machine with chopping effect.The HMC starting material have relatively low crushing strength, should select mixing machine so that its smash and the material that provides fine rapidly and have big total surface area thereupon to be used for reaction and to be used for granulation again.Therefore, traditional fluidized bed pelletizer is not preferred for the dry neutralization method of using crystal habit modification carbonate.

This mixing preferably has and uses in the mixing machine of stirring action and cutting action and carry out, and these effects most preferably can as described belowly separate use.Cutting action is preferred chopping effect.This can advantageously realize as mixing machine by high-speed mixer/tablets press of selecting to have stirring action and cutting action.This high-speed mixer/tablets press preferably has rotatable stirrer and cutting element, their speed operations can separately changing independently of one another.This type of mixing machine can stir high-energy input and combine with cutting action, but also is used in the stir mode that other milder is provided under the situation that cutting unit moves or do not move.Cutting unit is shut down in solid pre-mixing process.

Mixing machine is preferred, and for high anionic charging, horizontal or vertical axle cutting unit is expected.Fukae Powteh Co Ltd. equally preferably, the FukaeFS-G type mixing machine that Japan makes; This equipment is can be via the bowl shaped container form of open top charging basically, is furnished with the agitator with basic Z-axis and is positioned at cutting unit on the sidewall near its bottom.

The speed operation can separately changing independently of one another of this agitator and cutting unit.This container can be cooled.

Other mixing machine that is considered to be suitable in the method for the invention comprises the SangyoCo. from Fuji, the Fuji of Japan (trade mark) VG-C series; With from Zanchetta﹠amp; Co srl, the Roto of Italy (trade mark).

Another mixing machine that is considered to be suitable in the method for the invention is from MortonMachine Co.Ltd., Scotland's

(trade mark) FM series batch blender.The difference of this and mixing machine mentioned above is that its agitator has transverse axis.Sigma mixer and sigma mixing machine (Winkworth machinery limited) are the suitable mixing machines with chopping effect.

The temperature of powder material remains on 55 ℃ or lower throughout in the mixing machine, preferably is lower than 50 ℃, more preferably less than 47 ℃, desirably is lower than 40 ℃.If temperature rises so high, can take place to reunite and caking.

Detergent particles

The particulate product of this method is that tap density is the granular solids of 450 to 720 grams per liters.Size-grade distribution usually makes at least 50 weight %, preferred at least 70 weight %, and more preferably the particle of at least 85 weight % is less than 1700 microns, and fine particle content is low.Usually need not further to handle to remove excessive particle or particulate.

This product has excellent flowability energy, low compressibility and minimum caking tendency usually.Directly the granulated detergent particle from this dry neutralization method can have 25 weight % to 45 weight % or even higher aniorfic surfactant content.The convenience that need not granulation aid (as zeolite) and drive reaction causes realizing aniorfic surfactant content especially high in this particle.For example, be higher than about 30 weight %, preferably be higher than 35 weight %, even the aniorfic surfactant that is higher than 40 weight % or surpasses 45 weight % can mix in this detergent particles.Aniorfic surfactant preferably comprises the soap that is lower than 10 weight % of aniorfic surfactant total amount in the detergent particles.

This detergent particles can also comprise the water of the amount that accounts for particulate 0 to 8 weight %, preferred 0 to 4 weight %.

Detergent particles stable storing under high humidity level by this method acquisition.Therefore, they can be used in widely in the Betengent product.

Desirably, this detergent particles has and is no more than 2 length-to-diameter ratio, more preferably roughly spherical with reduce with the powder detergent composition that is mixed with in other particle segregation and improve the outward appearance of powder.

Further processing

If desired, can make the back to wherein sneaking into other composition at detergent particles.This detergent particles can mix with commonly used any composition in the detergent formulation.They can be done with solid material and mix, and can be advantageously to wherein further adding liquid, to utilize their unnecessary carrier fluid ability.Especially advantageously add traditional content thus or even be higher than the spices of traditional content.

If desired, also can use the non-soap surfactant of other type, for example cationic, amphoteric ion type, amphoteric or semi-polarity tensio-active agent with this particle.Many suitable detergent active compounds are that can get and abundant descriptions in the literature, and for example at Schwartz, " the Surface-Active Agents and Detergents " of Perry and Berch work is in I and the II volume.

Also can there be soap, so that foam control and extra detersive power and mechanical-power-producing (builderpower) to be provided.Fully-formulated compositions can comprise the soap of maximum 8 weight %.

Comprise that the detergent composition of the detergent particles of making by method of the present invention can contain other detergent ingredients of convention amount, for example, SYNTHETIC OPTICAL WHITNER, enzyme, profoamer as required or Foam Control, anti redeposition agent are as cellulose polymer compound; Anti-scaling, spices, dyestuff, dope dye (shading dyes), white dyes, water glass; Inhibiter comprises silicate; Inorganic salt, as sodium sulfate, enzyme; Colour particles; Foam Control; With the fabric softening compound.If desired, this detergent particles can mix with other organic or inorganic synergistic agent, and described synergistic agent provides with the particle form of pure synergistic agent or synergistic agent and other mixture of ingredients usually.Especially preferred organic synergistic agent is an acrylate copolymer, vinylformic acid/maleic acid more particularly, and suitably with 0.5 to 15 weight %, the amount of preferred 1 to 10 weight % is used.This base polymer also plays the effect of crystal habit modification polymkeric substance.

Which composition skilled detergent formulation Designers can determine be adapted at mixing in the mixing machine, and which composition is not suitable for.

This detergent particles can with available from any conventional washing agent manufacturing process another kind of powder mixes of (comprising spraying drying or non-spray-drying process).For simplicity, this type of other powder is known as basic powder hereinafter.Since the detergent particles of making by the present invention can with this type of other powder mixes, obtain significant formulation flexibility, and the content of active material can be very high in the fully-formulated compositions, can improve synergistic agent content necessarily simultaneously.

The total amount of the tensio-active agent that exists in this detergent composition is 5 to 40 weight % suitably, although can use the amount outside this scope on demand.

This detergent particles accounts for 30 to 100 weight % of final full formula detergent composition usually.Usually, the full formula detergent composition that comprises the detergent particles of making by method of the present invention can comprise 5 to 45 weight %, the granular product that the aniorfic surfactant of preferred 10 to 35 weight %, this anion surfactant react from dry neutralization wholly or in part.Method of the present invention especially can be used for making detergent powder or the component that contains high-load relatively aniorfic surfactant (for example 15 to 30 weight %, more specifically 20 to 30 weight %).In addition, this full formula detergent composition can comprise the nonionic surface active agent of 0 to 10 weight % and the fatty acid soaps of 0 to 5 weight %.

Full formula detergent composition--detergent particles that comprises other composition and make by the dry neutralization of habit modified--preferably has at least 400 grams per liters, more preferably the tap density of at least 450 grams per liters.

Further describe the present invention referring now to following non-limiting examples.In an embodiment, except that above-mentioned SSA, pore volume and load test, measure detergent particles character according to following known test program.

Dynamic flow rate (DFR)

This is also referred to as flow velocity.Can utilize what record by follow procedure is that the dynamic flow rate (DFR) of unit quantizes flow of powder with the milliliters/second.Equipment therefor is made of 35 millimeters cylindrical glass tube with 600 millimeters of length of internal diameter.This pipe is clipped in certain position securely so that its longitudinal axis is vertical.Its lower end is that 15 ° and lower part outlet bore dia are that 22.5 millimeters smooth pvc awl comes to an end with interior angle.Above outlet, locate to place first beam sensor for 150 millimeters, above first sensor, locate to place second beam sensor for 250 millimeters.

In order to measure the dynamic flow rate of powdered sample, for example, temporarily seal outlet opening by covering with a slice card, powder is poured this cylinder top into via funnel, and is higher about 10 centimetres than upper sensor until the powder position; It is uniform that dividing plate between funnel and the pipe is guaranteed to fill.Open outlet subsequently, the time t (second) that lower sensor spends is reduced to from upper sensor in electronic measurement powder position.Measure usually and repeat twice or three times, and average.If V is the pipe volume (milliliter) between the transmitter of upper and lower, provide this dynamic flow rate DFR (milliliters/second) by following equation:

$\mathrm{DFR}=\frac{V}{t}\mathrm{ml}/s$

Unconfined compression test (UCT)

In this test, the powder that has just made is pressed into compacts, measures the required power of this compacts of destroying.With the powder cylinder of packing into, and make its surfacing.On powder, place 50 gram vinyl discs, on dish, slowly place the plunger of 10 kilogram weights, make it stay original position 2 minutes.Remove weight and plunger subsequently, remove this cylinder lentamente from powder, stay the powder cylinder of self-support, its top has this 50 gram vinyl disc.If this compacts does not break, on first vinyl disc, place second 50 gram vinyl disc, and stopped about 10 seconds.If this compacts does not break yet subsequently, on vinyl disc, increase the dish of one 100 gram, and stopped 10 seconds.Gain in weight at interval with 10 seconds with 0.25 kilogram increment subsequently, cave in up to compacts.Required gross weight realized caving in record.

The cohesion of powder (w) classification by weight is as follows:

W＜1.0 kilogram good flow.

1.0 kilogram＜w＜2.0 kilogram medium flowing.

2.0 kilogram＜w＜5.0 kilogram cohesive.

5.0 kilogram＜w is cohesive very.

Dissolution time (T90)

In 1 liter of beaker, pack into 500 milliliters 20-25 ℃ deionized water, and stir with being adjusted to the magnetic stirrer that produces about 4cm.Powdered sample is added in the entry.Measure dissolving according to electrical conductivity of solution." T90 " value is 90% time that is spent that reaches final conductivity value.

Tap density (BD)

Get 1 liter of container filling detergent particles and the weight increased value during jolt ramming gently, measure tap density.

Embodiment

Acquisition is used for the yellow soda ash material of dry neutralization.Dense granule shape yellow soda ash (reference carbonate A) and light soda ash ash (reference carbonate B) are directly from Brunner Mond.Manufacturing reference carbonate C as described below and HMC1 to 6.

The spray-dired HMC of HMC1-(low humidity)

Prepare HMC according to WO 2006/081930A1 by in steel basin, 29.8 kilograms of Sokalan CP5 solution (40% active material) and 1373.8 kg water being mixed.Subsequently 596.4 kilograms of light sodium carbonates (from Brunner Mond) are dissolved in this solution.Gained solution is the finished product water capacity of spraying drying to 1.8% (by IR Balance) in the spray-drying tower of 2.5 rice diameters subsequently.

The spray-dired HMC of HMC2-(high humidity)

The preparation method is as HMC1, and just this HMC is by the finished product water capacity of spraying drying to 12.9% (by IR Balance).

The HMC of HMC3-oven drying

0.06 kilogram of Sokalan CP5 solution (40% active material) is mixed in steel basin with 2.74 kg water.Subsequently 1.2 kilograms of light sodium carbonates (from Brunner Mond) are dissolved in this solution.Gained solution is (about 0.5 centimetre of solution deep) drying in 85 ℃ baker in tray subsequently.

The HMC of HMC4-drum dried

Use the bitubular moisture eliminator drying of 0.391 rice diameter to consist of the solution (25.6 seconds time of drying, 148 ℃ of rotary drum temperature) of 69.58% water, 0.6%Sokalan CP5 (100% active material) and 29.82% light sodium carbonate (from BrunnerMond) by weight.

The HMC of HMC5-microwave drying

1.5 gram Sokalan CP5 solution (40% active material) are mixed in beaker with 68.5 gram water.Subsequently 30 gram light sodium carbonates (from Brunner Mond) are dissolved in this solution.Gained solution is (about 0.5 centimetre of solution deep) drying in microwave oven (SamsungMX35 1000W) in tray subsequently.

The sedimentary HMC of HMC6-

In glass beaker, 29.8 gram Sokalan CP5 solution are dissolved in the 1400 gram deionized waters.590 gram light sodium carbonates (from Brunner Mond) are added in this solution.Gained solution is heated to 70 ℃ subsequently under constant agitation, and keeps opening wide so that evaporation to atmosphere.Continue to heat and stir and reduce to the only about half of of its original volume until liquor capacity.With the gained slurries filtration to remove sedimentary crystal in the evaporative process.These crystal subsequently 85 ℃ of following oven dryings to make the finished product.

The spray-dired modification burkeite of reference carbonate C-

425.2 kg water are added in 1 cubic metre the mixing vessel with paddle wheel.One after the other, in this water, add 25.3 kg polypropylene acid sodium solutions (from the SokalanPA40 of BASF), then add 330 kilo sulfuric acid sodium.Make mixture temperature rise to 60 ℃ and stirred 8 minutes subsequently.When keeping stirring, add 123.7 kilograms of yellow soda ash (from the light soda ash ash of BrunnerMond) subsequently to form slurry.The temperature of gained mixture rose to 82 ℃ and restir 12 minutes subsequently.Add 54.9 kilograms of alkaline silicate solutions (from the Crystal 112 of Ineos Silicas) subsequently.The similar burkeite solid support material of making among the embodiment of slurry spraying drying with gained 53 weight % with formation and EP 1534812 (Kao).

Use the BET method of having described to measure the specific surface area (SSA) of the sample of as above making and the porosity of fine porosity (＜2 micron diameter).In addition, by dry neutralization experiment, the maximum of LAS acid (HLAS) surfactant acid that mensuration can be used with dissimilar yellow soda ash.

In table 1, summarized SSA, porosity and the HLAS capacity of used carbonate material.As can be seen, between the amount of SSA and surfactant acid, there is dependency.

Table 1

Carbonate	Embodiment	Pore volume milliliter/gram (diameter＜2 micron)	SSA (meters squared per gram)	LAS capacity (gram HLAS/100 gram carriers)
					Fine and close SODA ASH LIGHT 99.2	Reference A	??0.07	??0.46	??9.4
The light soda ash ash	Reference B	??0.21	??1.00	??22.5*
					Burkeite	Reference C	??0.48	??3.08	??10.0
Spray-dired HMC	??HMC1	??0.64	??8.17	??98.3
					The HMC of drum dried	??HMC4	??0.78	??8.69	??807
Microwave HMC	??HMC5	??0.72	??8.88	??122.0
					The HMC of oven drying	??HMC3	??0.78	??10.86	??157.5
Precipitation HMC	??HMC6	??0.77	??12.36	??135.0

* can not granulation.This product is viscosity agglomerate (sticky mess), therefore the amount of the surfactant acid of herein putting down in writing and fict particulate load capacity.

In all embodiments, used surfactant acid is LAS acid: C9 to C11 linear alkyl benzene sulphonic acid, molecular-weight average are 320, and purity 97% contains 0.8% water.

Embodiment 1-in the Fukae mixing machine in and LAS acid

4.0 kilograms of HMC1 are packed in Fukae FS30 high shear granulator/mixing machine, use the agitator speed of 200rpm and the chopper speed of 1300rpm to mix.In mixed powder, added 1.8 kilograms of LAS acid through 4 minutes with constant rate of speed with peristaltic pump.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 130), and tap density is that 705 kilograms per cubic meter and dissolution time (T90) are 34 seconds.

Embodiment 2-in the ploughshare mixing machine in and LAS acid

12 kilograms of HMC1 are packed in Morton (130 liters) ploughshare tablets press/mixing machine, use the agitator speed of 100rpm and the chopper speed of 1000rpm to mix.In mixed powder, added 5.09 kilograms of LAS acid through 4.5 minutes with constant rate of speed with peristaltic pump.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 135), and tap density is that 532 kilograms per cubic meter and dissolution time (T90) are 30 seconds.

Embodiment 3-in sigma mixer (Z blade mixture) in and LAS acid

0.3 kilogram of HMC1 is packed in Winkworth (2Z type) sigma mixer.In mixed powder, poured 0.135 kilogram of LAS acid into through 4 minutes with constant rate of speed.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 108), and tap density is that 496 kilograms per cubic meter and dissolution time (T90) are 25 seconds.

Embodiment 4-in high shear mixer in and LAS acid

1.0 kilograms of HMC1 are packed in Zanchetta RotoJunior (10 liters) high shear granulator/mixing machine, use the agitator speed of 350rpm and the chopper speed of 1350rpm to mix.In mixed powder, added 0.45 kilogram of LAS acid through 4 minutes with constant rate of speed with peristaltic pump.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 142), and tap density is that 549 kilograms per cubic meter and dissolution time (T90) are 32 seconds.

Embodiment 5-passes through among the high humidity HMC and LAS acid

This is the repetition of embodiment 1 basically, but uses 4.0 kilograms of more HMC2 replacement HMC1 of high humidity.This HMC is packed in Fukae FS30 high shear granulator/mixing machine, use the agitator speed of 200rpm and the chopper speed of 1300rpm to mix.In mixed powder, added 1.54 kilograms of LAS acid through 4 minutes with constant rate of speed with peristaltic pump.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 144), and tap density is that 570 kilograms per cubic meter and dissolution time (T90) are 34 seconds.

Embodiment 6-is with in LAS acid/NI adulterant and HMC

400 gram LAS acid are restrained ethoxylated alcohol nonionic surface active agent (from the Neodol 25-7 of Shell Chemicals) thorough mixing to form the liquid adulterant with 100.

1.0 kilograms of HMC1 are packed in Zanchetta RotoJunior (10 liters) high shear granulator/mixing machine, use the agitator speed of 350rpm and the chopper speed of 1350rpm to mix.In mixed powder, added 0.453 kilogram of LAS acid/nonionic surface active agent liquid adulterant through 4 minutes with constant rate of speed with peristaltic pump.After the interpolation of liquid adulterant is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 129), and tap density is that 655 kilograms per cubic meter and dissolution time (T90) are 40 seconds.

Embodiment 7-is with in LAS acid/lipid acid adulterant and HMC

400 gram LAS acid are restrained lipid acid (Pristerine 4916) thorough mixing to form the liquid adulterant with 100.

1.0 kilograms of HMC1 are packed in Zanchetta RotoJunior (10 liters) high shear granulator/mixing machine, use the agitator speed of 350rpm and the chopper speed of 1350rpm to mix.In mixed powder, added 0.45 kilogram of LAS acid/lipid acid liquid adulterant through 4 minutes with constant rate of speed with peristaltic pump.After the interpolation of liquid adulterant is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 148), and tap density is that 582 kilograms per cubic meter and dissolution time (T90) are 40 seconds.

Embodiment 8-in sigma mixer in and LAS acid

This is the repetition of embodiment 3 basically, uses the material HMC3 of oven drying to replace spray-dired HMC1.The HMC3 of 0.3 kilogram of oven drying is packed in Winkworth (model 2Z) sigma mixer.In mixed powder, poured 0.135 kilogram of LAS acid into through 4 minutes with constant rate of speed.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 111), and tap density is that 482 kilograms per cubic meter and dissolution time (T90) are 27 seconds.

Embodiment 9-in sigma mixer in and LAS acid

This is the repetition of embodiment 8, uses more LAS acid.0.3 kilogram of HMC3 is packed in Winkworth (model 2Z) sigma mixer.In mixed powder, poured 0.215 kilogram of LAS acid into through 4 minutes with constant rate of speed.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 120), and tap density is that 526 kilograms per cubic meter and dissolution time (T90) are 34 seconds.

Embodiment 10-in high shear mixer in and LAS acid

This is the modification of embodiment 9, uses more LAS acid and different mixing machines.1.0 kilograms of HMC3 are packed in Zanchetta RotoJunior (10 liters) high shear granulator/mixing machine, use the agitator speed of 350rpm and the chopper speed of 1350rpm to mix.In mixed powder, added 0.45 kilogram of LAS acid through 4 minutes with constant rate of speed with peristaltic pump.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 110), and tap density is that 557 kilograms per cubic meter and dissolution time (T90) are 33 seconds.

Embodiment 11-in high shear mixer in and LAS acid

This is the repetition of embodiment 10, uses even more LAS acid.1.0 kilograms of HMC3 are packed in Zanchetta RotoJunior (10 liters) high shear granulator/mixing machine, use the agitator speed of 350rpm and the chopper speed of 1350rpm to mix.In mixed powder, added 0.721 kilogram of LAS acid through 4 minutes with constant rate of speed with peristaltic pump.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 142), and tap density is that 655 kilograms per cubic meter and dissolution time (T90) are 42 seconds.

Comparative example A-in Fukae, use in the yellow soda ash and LAS acid

This is a Comparative Examples, and it replaces the HMC neutralisation of embodiment 1 with the similar approach of using unmodified yellow soda ash.With 4.0 kilograms of mean particle sizes is that 110 microns commercial light soda ash ash (from Brunner Mond) (reference carbonate B) is packed in Fukae FS30 high shear granulator/mixing machine, uses the agitator speed of 200rpm and the chopper speed of 1300rpm to mix.In mixed powder, added 1.032 kilograms of LAS acid through 4 minutes with constant rate of speed with peristaltic pump.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

The product of this excessive granulation has the extreme difference flowing property, has damp sand shape outward appearance, and is not suitable for use in detergent particles.Make in this way, even use the surfactant acid of low amount can not produce gratifying particle.

Embodiment 12 to 16 and B-use various carbonate material dry neutralization LAS acid

Embodiment 12

With 30 gram HMC1 place laboratory scale tablets press (Braun MR 500CA) and with the LAS acid-respons, this LAS acid begins until granulation by manual this tablets press that adds of the vertical small bore of tablets press lid through syringe.The LAS acid weight that add this moment is 18 grams.Further add LAS acid subsequently, begin image planes until particle and roll into a ball equally stick together (excessively granulation).For forming detergent particles, the maximum of the LAS acid that can add is 29.5 grams.

Embodiment 13

With 20 gram HMC3 place laboratory scale tablets press (Braun MR 500CA) and with the LAS acid-respons, this LAS acid begins until granulation by manual this tablets press that adds of the vertical small bore of tablets press lid through syringe.The LAS acid weight that add this moment is 15 grams.Further add LAS acid subsequently, begin image planes group until particle and equally stick together.For forming detergent particles (before excessive granulation), the maximum of the LAS acid that can add is 31.5 grams.

Embodiment 14

With 30 gram HMC4 place laboratory scale tablets press (Braun MR 500CA) and with the LAS acid-respons, this LAS acid begins until granulation by manual this tablets press that adds of the vertical small bore of tablets press lid through syringe.The LAS acid weight that add this moment is 13 grams.Further add LAS acid subsequently, begin image planes group until particle and equally stick together.For forming detergent particles (before excessive granulation), the maximum of the LAS acid that can add is 24.2 grams.

Embodiment 15

With 20 gram HMC5 place laboratory scale tablets press (Braun MR 500CA) and with the LAS acid-respons, this LAS acid begins until granulation by manual this tablets press that adds of the vertical small bore of tablets press lid through syringe.The LAS acid weight that add this moment is 13 grams.Further add LAS acid subsequently, begin image planes group until particle and equally stick together.For forming detergent particles (before excessive granulation), the maximum of the LAS acid that can add is 24.4 grams.

Embodiment 16

This embodiment is the repetition of embodiment 12, replaces 30 gram HMC1 with 30 gram HMC6.

The amount of the LAS acid that adds during to " maximum granulation " (that is: the LAS acid maximum before excessively granulation takes place) is determined as 37.0 grams.

Comparative Examples B

With 40 gram commercial anhydrous sodium carbonates (from the light soda ash ash of Brunner Mond) (reference carbonate B) place laboratory scale tablets press (Braun MR 500CA) and with the LAS acid-respons, this LAS acid begins until granulation by manual this tablets press that adds of the vertical small bore of tablets press lid through syringe.The LAS acid weight that add this moment is 9 grams.Even under low like this LAS acid addition, the quality of this particle aspect mobile and viscosity is still very poor.Further adding LAS acid causes particle to begin to form even more tacky agglomerate.

Embodiment 17-22 has shown the granulation under a series of LAS/ carbonate ratios

One of advantage of method of the present invention is the ability of successful granulation in the HLAS of wide region carbonate ratio.Prepare these a series of embodiment to prove this benefit.Method is identical with embodiment 4 with material.

The amount of the LAS acid that adds, and the key physical properties of gained detergent particles (BD-tap density, DFR-dynamic flow rate, d-mean particle size and T90-dissolution rate) is presented in the table 2.All samples all has good sreen analysis (granulometry), flow velocity and dissolving properties.

Table 2

Embodiment	??17	??18	??19	??20	??21	??22
							LAS acid/HMC w/w	356 gram/kilograms	406 gram/kilograms	449 gram/kilograms	502 gram/kilograms	544 gram/kilograms	624 gram/kilograms
BD (kilograms per cubic meter)	??594.45	??592.425	??619.65	??635.625	??663.75	??743.625
							DFR (milliliters/second)	??98	??118	??120	??125	??87	??85
D (micron)	??365	??331	??362	??392	??311	??460
							T90 (second)	??41.7	??37.7	??42	??44	??48.5	??57.5

Comparative Examples C: use burkeite (reference carbonate C) preparing washing agent particle

1.5 kilograms of spray-dired reference carbonate C are packed in Zanchetta RotoJunior (10 liters) high shear granulator/mixing machine, use the agitator speed of 350rpm and the chopper speed of 1350rpm to mix.In mixed powder, added 0.15 kilogram of LAS acid through 2.5 minutes with constant rate of speed.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.This granular disintegration is runny powder (flow velocity 115), and tap density is 715 kilograms per cubic meter.

Comparative Examples D: use ground SODA ASH LIGHT 99.2 preparing washing agent particle

In 1.5 kilograms of yellow soda ash (from the light soda ash ash of BrunnerMond) (reference carbonate D) the Zanchetta RotoJunior that packs into (10 liters) high shear granulator/mixing machines that are ground to 50 microns mean particle sizes in advance, use the agitator speed of 350rpm and the chopper speed of 1350rpm to mix.In mixed powder, added 0.364 kilogram of LAS acid through 5.75 minutes with constant rate of speed.The amount that adds just is enough to prevent excessive granulation.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.This granular disintegration is runny powder (flow velocity 90), and tap density is 705 kilograms per cubic meter.

The spices of embodiment 23 and 24-detergent particles loads

Embodiment 23

In laboratory scale rotating disk, spray the detergent particles of 200 grams from embodiment 2 with 6.0 gram spice oils.The flow velocity of gained powder is measured as 137 gram/minute.

Embodiment 24

In laboratory scale rotating disk, spray the detergent particles of 200 grams from embodiment 2 with 10.0 gram spice oils.The flow velocity of gained powder is measured as 140 gram/minute.

Embodiment 25-LAS acid neutralizes in high shear mixer (no chopping effect)

1.0 kilograms of HMC1 are packed in Zanchetta RotoJunior (10 liters) high shear granulator/mixing machine, use the agitator speed of 350rpm but close cutting unit and mix.In mixed powder, use peristaltic pump to add 0.353 kilogram of LAS acid through 4 minutes with constant rate of speed.After LAS acid interpolation is finished, continue again to mix 30 seconds, after this, from mixing machine, discharge solid product.

This granular disintegration is easy dissolving, runny powder (flow velocity 146), and tap density is 549 kilograms per cubic meter, and the UCT value is 2.5 kilograms--this means its easy caking, when for example in the storehouse, storing.Therefore, because the lower and agglomeration problems shown in high UCT result of carrying capacity of attainable aniorfic surfactant, this modification of this method is so not preferred.

Point out that this embodiment is the repetition (chopper/cutting unit of embodiment 4 all moves) of embodiment 4 basically and realizes higher surfactant content, similar DFR and identical tap density, is the zero agglomeration problems that also therefore do not have but recorded UCT.

Embodiment 26 and Comparative Examples E-stability in storage

The detergent particles of 380 gram embodiment 2 was being stored for 6 weeks in the common cardboard box (be of a size of 15.4 centimetres wide, 7.5 centimetres dark, and 13.0 centimetres high) that opens wide under the relative humidity of 28 ℃ temperature and 70%RH.When store finishing, these detergent particles are caking not, and remains runny (flow velocity-133).

For relatively, the 388 products storages under the same conditions in the cardboard box of same type that restrain comparative example As were less than for 6 weeks.Store when finishing the back taking-up, this powder is seriously formed bulk, can not freely flow out from carton.

Compare with the particle that uses traditional yellow soda ash to make in the dry neutralization method, the particle of the present invention that uses habit modified to make in the dry neutralization method does not lump under higher surfactant content.

Claims (13)

1. be used to prepare the method for the detergent particles that comprises the non-soap surfactant of anionic, it comprises that described habit modified is the crystal growth modification yellow soda ash that comprises yellow soda ash and mixture of polymers with habit modified dry neutralization surfactant acid.

2. use described surfactant acid according to the process of claim 1 wherein with liquid form.

3. according to each method of aforementioned claim, the habit modified of wherein said surfactant acid and molar excess is reacted simultaneously at blended, to form the sodium salt of described aniorfic surfactant simultaneously at blended.

4. according to the method for claim 3, wherein in mixing machine, mix, and in the dry neutralization reaction process, use described chopping effect with chopping effect.

5. according to the method for claim 4, wherein in mixing machine, mix, and in the dry neutralization reaction process, use described stirring action and cutting action with stirring action and cutting action.

6. according to each method of aforementioned claim, wherein neutralizing agent comprises the mixture of crystal habit modification carbonate and more a spot of yellow soda ash and/or burkeite.

7. according to each method of aforementioned claim, wherein said habit modified is characterised in that specific surface area is 5 meters squared per gram or bigger, preferred 8 meters squared per gram or bigger, even more preferably 10 meters squared per gram or bigger.

8. according to the method for claim 7, wherein said habit modified is characterised in that aspect the hole of 2 micron diameters pore volume is 0.3 a milliliter/gram or bigger.

9. can be by the high active detergent granules that obtains according to each method of aforementioned claim, it comprises:

A) greater than the aniorfic surfactant of 30 weight %, described tensio-active agent comprises the non-soap anionic tensio-active agent of major portion,

B) habit modified, its be comprise yellow soda ash and mixture of polymers crystal growth modification yellow soda ash and

C) be lower than 10 weight %, be preferably 0 zeolite.

10. according to the detergent particles of claim 9, the content that it is characterized in that non-soap anionic tensio-active agent in the particle is preferably greater than 35 weight % greater than 30 weight %, even greater than 40 weight %, and preferred even greater than 45 weight %.

11. according to the detergent particles of claim 9 or claim 10, it further comprises spices.

12. according to each detergent particles of claim 9 to 11, it further comprises nonionic surface active agent.

13. according to each detergent particles of claim 9 to 12, it further comprises soap.