CN1213135C - Detergent compositions - Google Patents

Abstract

A softening laundry detergent tablet comprises clay and laundry surfactant. The tablet is a compressed mass of particles including granules which consist largely of clay.

Description

Detergent composition

Invention field

The present invention relates to contain the soft detergent for washing clothes sheet of a large amount mild clay, it is particularly related to flaky this composition.

Background of invention

The known detergent compositions in tablet form that preparation is provided by the compacting granular detergent composition.Usually comprise in composition that a little binder is complete with retention tab.

Although require sheet should have good integrity before use, when contacting with washing water, also in use they should decompose fast in requirement.Knownly comprise a kind of decomposition agent, it can impel sheet to decompose.Known have various types of decomposition agents, comprises the type that is wherein caused decomposition by the swelling of decomposition agent.Propose various swelling decomposition agents in the literature, preferably mainly referred to starch, Mierocrystalline cellulose and water-soluble organic polymer.For example in EP-A-466484, also mentioned inorganic swelling decomposition agent such as wilkinite.

In it discloses, use same material as tackiness agent and decomposition agent.Wherein also mentioned decomposition agent can produce help wash, antiredeposition or fabric sofetening character.The amount of decomposition agent is 1%-5% preferably.Also mentioned sheet and can have uneven structure in EP-A-466484, it comprises a plurality of zone of dispersions, for example layer, insert or coating.

In WO98/40463, decomposition agent is such as starch or cellulosic material, and it only adds with the particulate form basically.

JP-A-9/87696 relates to the sheet that contains nonionic detergent composition and the main component of nonionogenic tenside conduct, particularly relate in the sheet storage process, suppressing nonionogenic tenside becomes silted up from sheet, it also relates to such situation, promptly when comprising mild clay, nonionogenic tenside causes the soft effect loss of expection.Its oil of having described the clay mineral that contains pulverizing and pulverizing absorbs the formation of the sheet of carrier and disintegrating agent.

Preferably provide and contain enough clays so that the softness laundry sheet of obvious soft effect to be provided.Although low amount clay can produce Decomposition, the clay amount that unfortunately produces useful soft effect can be inclined to the obstruction decomposition, rather than promotes it.This is because under a large amount clay that soft effect needs, when contacting with water, there is agglomerative trend in the clay of sheet, so that forms gel coat around sheet, and it hinders water and infiltrates in the sheet, therefore hinders sheet and disperses.

Therefore wish and can mix clay in such a way in sheet, promptly under the high density clay, gelation tendencies is reduced to minimum, and the Decomposition of clay gall increases to maximum.

Summary of the invention

According to one embodiment of the invention, a kind of soft detergent for washing clothes sheet that comprises clay and washing clothes form surface-active agent is provided, wherein this sheet is downtrodden particle object, the clay of at least 50% weight is to have its size at least 100 μ m as particle.This clay is the main component in this particle normally, and by particulate weight, content is at least 30% usually, and generally at least 50%, preferably at least 75%.This particle is preferably formed by the clay of 90% weight at least.

Preferably at least 60%, at least 75% and most preferably at least 90% clay is as at least 100 μ m usually, but the particle that is usually less than 1700 μ m exists.

By the weight of sheet, this sheet can contain at least 5%, and preferably at least 8%, the clay of at least 10% weight most preferably.By the weight of sheet, this amount can be lower than 25%, is usually less than 20%, preferably is no more than 15%.

Preferably at least 70%, the clay of preferred at least 90% weight is to exist as the particle with 150-850 μ m size.Preferably, all (for example at least 90% or 95% weight) particles basically that the preparation sheet is used have at least 100 μ m sizes, general 100-1700 μ m.

According to a second aspect of the invention, provide a kind of preparation to comprise the method for the soft detergent for washing clothes sheet of clay and washing clothes form surface-active agent, it comprises that the clay that at least 50% weight is provided is as the clay particle with at least 100 μ m sizes, this clay particle is mixed with other particulate state components of sheet, and with this mixture compacting in flakes.

Detailed Description Of The Invention

Preferably at least 50%, preferred 70%, most preferably at least 90% weight clay is to have 100-1700 μ m, preferred 100-1180 μ m, the most preferably particle form of 150-850 μ m size.Fine powder promptly has size and is lower than 20 μ m, preferably is lower than 10 μ m clay particles and preferably is lower than 10% of total clay weight, most preferably is lower than 5% of total clay weight, generally is lower than 1% weight.

Owing to add result's (replacement fine powder) of particulate, can increase the clay amount that can comprise, and not cause gelling.In addition, comprise that particulate replaces fine powder to increase the Decomposition of clay.

Available conventional clay agglomeration technique is made particle, and well as clay fines is by granulation, for example by agglomeration or extruding thus.In the presence of tackiness agent, carry out granulation, impelled particle formation usually.Preferred adhesive comprises, or is made up of water basically the most usually.Therefore, this particle can only be formed (for example being higher than 90% weight clay) by clay basically.

Yet, if need, can mix other materials as tackiness agent, for example water-soluble polyhydroxy compound (for example glycerine) or other conventional clay adhesives, preferably it is that water is diffluent.The total amount of tackiness agent is usually less than particulate 10% weight, generally is lower than 5% weight.If need, in particle, can comprise other materials, adopting easily, method adds this material in the sheet.Yet the amount of clay is generally at least 50% of particle weight, preferably at least 70% or 80%.

Clay particle can be evenly distributed in the sheet basically, and this thus high density has promoted soft effect, and this concentration and particle form will promote whole Decomposition.In addition, can be in one or more first areas of sheet than one or more second area middle particle concentration height of sheet.For example, in one embodiment, the clay particle amount that the first area can be contained is at least 1.5 times of second area clay amount, and 2-5 doubly usually.This means and to arrange the first area to disperse faster than second area.Clay amount in the first area is at least 5% usually, and normally at least 10% of first area weight.The clay amount of second area normally second area or each second area at least 0.1%, 1-5% for example.At least 60% weight of usually total clay amount, common 70% or 75% to 80% or 90% is in first area or each first area, what exist in second area or each second area is equal amount.

This sheet contains the detergent for washing clothes of at least 5% weight usually, generally includes nonionic and/or anion surfactant.If need, also can there be higher concentration (for example at least 1.5 times, 2-5 doubly usually) in tensio-active agent than other zones in some zones.Usually have the nonionic and/or the anion surfactant of at least 5% weight in any first area of sheet, its all the other zones than sheet have higher clay concentration.

In sheet, generally include the laundry enzyme.When there is higher concentration in clay in one or more first areas, preferably in these zones, there is more multienzyme than other zones, for example the amount in the first area should be at least 1.5 times that measure in other zones usually, usually at least 2 or at least 5 times, so that along with the first area is distributed in the washing water fast, enzyme disperses wherein as far as possible apace.

Sheet contains laundry bleach usually.If clay in one or more first areas than second area in concentration higher, then preferred SYNTHETIC OPTICAL WHITNER is at the concentration height of second area than the first area.Preferably the SYNTHETIC OPTICAL WHITNER concentration in second area or each second area is first area or each first area concentration 1.5 times at least, and preferably all SYNTHETIC OPTICAL WHITNER are in second area or each second area basically.

General preferred this washing sheet also should contain the clay flocculating agent, so that help clay deposition to fabric face.This is convenient to tructured sheets, so that clay disperses quickly than flocculation agent.For example, flocculation agent and clay can keep physical sepn each other, and on some degree, clay in discrete particle realizes by being enclosed in for this, even flocculation agent is at whole middle uniform distribution.Yet, when clay particle is concentrated in one or more first areas, general preferably in one or more second areas, comprising flocculation agent, laxity is divided than the first area in these zones.Preferably, all flocculation agents are in second area or each second area basically.

Unnecessary all second areas should have same composition, can have different the composition with other second areas by one or more second areas.

Discrete first and second zones (when existing) can be some scopes or other sections in the sheet, for example forms the sheet generation by clay particle and other coarse particles materials, generally greater than 1mm, some of them or all big particles have a kind of capacity, remaining has another kind of capacity, forms first and second zones thus in the sheet of compacting.Yet preferably each zone is one deck, and this washing sheet is the multilayer tablet with at least two layers.Usually preferably should have three layers, this sheet generally is at the similar layer of each outside surface and the sandwich structure sheet between the different central core.Different layers pigmentable difference.

General first area is the 20-80% of sheet weight, about usually 40-60%, and common about 50%, the rest part of this sheet is a second area.

Of the present invention has the yardstick of being convenient to measure in washing machine.Preferred yardstick is 10-150g, and this yardstick can be selected according to the design of the washing machine of the washing loading of expection and use.

The preparation of sheet

Can simply solid constituent be mixed and suppress this mixture and prepare detergent tablet of the present invention with the conventional tabletting machine that uses in the medicine industry for example.Preferably, main component, particularly agglomerative tensio-active agent are to use with particle form.Any liquid components, for example tensio-active agent or suds suppressor can mix in the solid particulate component according to a conventional method.

Can use the ordinary method spraying drying such as washing assistant and tensio-active agent component, then with suitable pressure compacting.Preferably, sheet of the present invention is with being lower than 100000N, more preferably less than 50000N, even more preferably less than 5000N, most preferably is lower than the system of defeating of 3000N.In fact, the most preferred embodiment is with being lower than the sheet that 2500N defeats system.

The particulate material that is used to prepare sheet of the present invention can prepare by any granulating or prilling process.An example of this method is spraying drying (in following current or a Countercurrent Spray Dryer), and generally it obtains low bulk density 600g/l or lower.In high-shear batch mixer/tablets press by granulation and closely knit or (for example use Lodige by continuous granulation and densification process ^(R)CB and/or Lodige ^(R)The KM mixing machine) can prepare the particulate material of higher density.Other methods that are fit to comprise fluidized bed process, die mould method (die mould for example rolls), push and prepare any particulate matter with some chemical processes such as flocculence, crystallization (crystallisation sentering) etc.Each particle can also be any other particulate, particle, bead or particulate.

The component of particulate material can mix with any conventional equipment, and interrupter method is suitable for for example concrete mixer, Nauta mixing machine, ribbon blender or any other equipment.In addition, this blending means can be carried out continuously, by the weight of metering each component on moving belt, and mixes them in one or more cylinders or mixing machine.Can on the mixture of some or all particulate material components, spray non-agglomerative tackiness agent.Other liquid components also can be sprayed onto on the mixture of independent or premixed component.For example, can spray spices and white dyes slip.Preferably near the ending of technology the time, spray adhesive makes mixture that low viscosity be arranged, and afterwards the flow promotor of pulverizing (separant is zeolite, carbonate, silicon-dioxide for example) is added in the particulate material.

Available any die mould legal system is equipped with sheet, for example compressing tablet, briquetting or extruding, preferred compressing tablet.The equipment that is fit to comprises the single cycle of standard or rolling forming press (Courtoy for example ^(R), Korch ^(R), Manesty ^(R), or Bonals ^(R)).Prepared in accordance with the present invention preferably has diameter 20mm-60mm, and preferably at least 35 is also high to 55mm, and weight is between 25-100g.The ratio of the height of sheet and diameter (or width) was preferably greater than 1: 3, more preferably greater than 1: 2.The pressure for preparing these sheets uses surpasses 100000kN/m ², preferably be no more than 30000kN/m ², more preferably no more than 5000kN/m ², even more preferably no more than 3000kN/m ², be most preferably not exceeding 1000kN/m ²In the preferred embodiment of the invention, sheet has density and is at least 0.9g/cc, and more preferably 1.0g/cc at least preferably is lower than 2.0g/cc, more preferably less than 1.5g/cc, even more preferably less than 1.25g/cc, most preferably is lower than 1.1g/cc.

Available known technology prepares multilayer tablet.

Coating

By the sheet that preparation applies, can further improve the soundness of sheet of the present invention, coating has covered uncoated sheet of the present invention, has further improved the mechanical characteristics of sheet thus, keeps simultaneously or has further improved dispersion.

In one embodiment of this invention, sheet then can be coated, so that sheet does not absorb moisture content or only absorbs moisture content with very slow speed.This coating still is firm, so that sheet stands the damaged or wearing and tearing that the moderate mechanical impact causes no more than very low amount in use, packing and transportation.At last, coating is preferably frangible, so that the fragmentation when standing stronger mechanical impact of this sheet.In addition, if coated material disperses under alkaline condition or easily by tensio-active agent emulsification, this is favourable.This helps avoid at washing stage visible residue attached to the problem on the window of front-loading washing machine with also avoided particle or coated material group is deposited in the loading of washing.

With following ASTM E1148-87, exercise question is measured water-soluble for the experimental program of " measuring water miscible standard test method ".

The coated material that is fit to is a dicarboxylic acid.Particularly suitable dicarboxylic acid is selected from oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid and its mixture.This coated material has fusing point and is preferably 40 ℃-200 ℃.

This coating can be used with several different methods.Two kinds of preferred coating methods are a) to apply and b with melting material) with the solution coating of this material.

In a), coated material is to use and be solidificated on the sheet being higher than under the temperature of its fusing point.At b) in, coated material is to use as solution, solvent is dried, and stays adherent coating.Basically insoluble material can be administered on the sheet by for example spraying or flooding.Usually, when melting material was sprayed onto on the sheet, its meeting fast setting formed adherent coating.When sheet is dipped in the melting material, take out then, can cause the coated material fast setting when cooling off fast again.Obviously, have fusing point and be lower than 40 ℃ insoluble basically material and at room temperature be not enough to solidify, find to have fusing point and be higher than the use that do not gear to actual circumstances of about 200 ℃ material.Preferably, the fusing point of material is at 60 ℃-160 ℃, more preferably 70 ℃-120 ℃.

" fusing point " meaning is when material slowly heats in kapillary for example, the temperature when becoming transparent liquid.

Can use the coating of any desired thickness according to the present invention.For most of purposes, coating accounts for the 1%-10% of sheet weight, preferred 1.5%-5%.

The sheet coating is preferably adamantine and provide additional strength to sheet.

In the preferred embodiment of the invention, improve breaking that coating is in the suds by in coating, adding disintegrating agent.In a single day this disintegrating agent contacts the meeting swelling and coating is broken into small pieces with water.This will improve the dispersion of coating in washing soln.The amount height to 30% of the disintegrating agent that in the coating melts, suspends, preferred 5%-20%, most preferably 5%-10% weight.Possible disintegrating agent is described in the pharmaceutical excipient handbook (1986).The examples of disintegrants that is fit to comprises starch; The starch of natural, modification or pre-gelledization; Sodium starch gluconic acid; Natural gum; Agar gum; Guar gum; Viscogum BE; Kuteera gum; Pectin; Yellow work glue; Croscarmylosesodium, polyvinylpolypyrrolidone, Mierocrystalline cellulose, carboxymethyl cellulose, alginic acid and its salt comprise sodiun alginate, silicon-dioxide, clay, Polyvinylpyrolidone (PVP), soybean polysaccharide, ion exchange resin and its mixture.

Tensile strength

According to the shape of the composition and the sheet of raw material, can regulate the pressure of use, do not influence tensile strength and the resolving time in washing machine.Available this method prepares the homogeneous or the stratified pieces of virtually any size or shape.

For cylindrical, tensile strength is equivalent to radial crack stress (DFS), and it is a kind of method of expression sheet intensity, is determined by following equation:

Tensile strength=2F/ π Dt

With Van Kell industries, the VK200 sheet hardness tester of Inc. supply is measured, and wherein F is the maximum, force (newton) that causes tension force forfeiture (breaking).D is the diameter of sheet, and t is the thickness of sheet.

(medicinal metering form method: sheet (Tabelets), the 2nd volume, 213-217 page or leaf).Have the sheet that radial crack stress is lower than 20kPa and be considered to frangible, and may cause supplying with some damaged sheets of human consumer.Preferred radial crack stress is at least 25kPa.

This is equally applicable to the non-cylindrical sheet and determines tensile strength, is not circular perpendicular to the cross section of sheet height wherein and is wherein prolonging perpendicular to the sheet height with perpendicular to the lateral direction of sheet and apply power, and the cross section of this side right and wrong circle is vertical.

Pore forming material

In another embodiment preferred of the present invention, this detergent tablet also can comprise pore forming material.

The foaming meaning of this paper definition is because the acid source of solubility and the chemical reaction between the alkaline carbonate produce carbon dioxide, and the result sends gas foam from liquid,

That is:

The other example of acid plus carbonate source and other pore forming material systems can be referring to (medicinal metering form (Pharmaceutical Dosage Forms): sheet, the 1st volume, 287-291 page or leaf).

Except detergent components, pore forming material can be added in the sheet mixture.In detergent tablet, add the resolving time that pore forming material has improved sheet.Its amount is preferably the 5%-20% of sheet weight, most preferably 10%-20%.Preferably, pore forming material should be as the agglomerate of variable grain or as fine and close thing, rather than adds as independent particle.

Produce gas owing to bubble in the sheet,, but still have the identical resolving time with bubble-tight so sheet can have higher D.F.S..When blistered D.F.S. was identical with bubble-tight maintenance, blistered decomposition was faster.

Other dispersing auxiliary can provide by using the compound such as sodium acetate or urea.The catalogue of the dispersing auxiliary that is fit to also can be referring to medicinal metering form: sheet, and the 1st volume, the 2nd edition, by volumes such as H.A.Lieberman, ISBN 0-8247-8044-2.

Tackiness agent

Disperse in order further to promote, non-agglomerative tackiness agent can be attached in the particle, forms sheet.

If use non-agglomerative tackiness agent, suitable non-cementitious adhesive comprises for example polyoxyethylene glycol of synthetic organic polymer, Polyvinylpyrolidone (PVP), polyacrylate and water-soluble polyacrylate multipolymer. pharmaceutical excipient handbook second edition has been listed the tackiness agent of following type: Sudan Gum-arabic, alginic acid, Carbomer, Xylo-Mucine, dextrin, ethyl cellulose, gel, guar gum, the hydrogenated vegetable oil Class1, Natvosol, Vltra tears, Liquid Glucose, neusilin, Star Dri 5, methylcellulose gum, the polyisobutene hydrochlorate, polyvinylpyrrolidone, sodium alginate, starch and zein.Most preferred tackiness agent also has active cleanup action in laundry, cationic polymers for example, i.e. for example five amine, the poly-ethyleneamines of ethoxylation, toxilic acid acrylate copolymer of ethoxylation hexamethylene-diamine quaternary ammonium compound, two or six ethylidene triamines or other materials.

Preferably spray non-agglomerative adhesive material, it has and is lower than 90 ℃ thus, preferably is lower than 70 ℃, even more preferably less than 50 ℃ suitable fusing point, so as not destroy or the matrix of degrading in other active constituents.Most preferred is the liquid adhesive (promptly not in the aqueous solution) of non-water, and it can the fusion form spray.But they can also be to add the solid binder that mixes in the matrix by doing, but it has bond property in sheet.

The preferred usage quantity of non-agglomerative adhesive material is the 0.1%-15% of composition, more preferably less than 5%, particularly if it is non-laundry active substance, then is lower than 2% of sheet weight.

Preferably avoid using the cementitious adhesive of liquid or fusion form, for example nonionogenic tenside.Nonionogenic tenside and other cementitious adhesives are not precluded within outside the composition, but preferably they are components as particulate material, rather than are worked in the detergent tablet as liquid.

Clay

Provide the employed clay mineral of soft character to can be described as expandable three layers of clay to the present composition, i.e. aluminium-silicate and Magnesium Silicate q-agent, its ion-exchange capacity is at least 50meq/100g.Describe the employed term of clay " expandable " and refer to when clay contacting water, bedded clay structure is by swelling or expansible ability.Three layers of swelling clay used herein are those materials that are categorized as terre verte on geology.

Two kinds of dissimilar smectite-type clay are arranged; First kind, aluminum oxide is present in the lattice silicate; Second type terre verte, magnesium oxide is present in the lattice silicate.The general formula of these terre vertes for aluminum oxide and magnesium oxide type clay, is respectively Al ₂(Si ₂O ₅) ₂(OH) ₂And Mg ₃(Si ₂O ₅) (OH) ₂People recognize that the water of hydration scope in the following formula can change with the processing that clay stands.This use to terre verte among the present invention is inessential, and this inflatable character that is hydrated clay is by the lattice silicate structures shape.In addition, replace by the atom of iron and magnesium and can occur in the lattice of terre verte, and metallic cation is such as Na ⁺, Ca ⁺⁺And H ⁺Can coexist with water of hydration, electric neutrality is provided.Except hereinafter described, this positively charged ion replaces inessential for the use of clay of the present invention, because required clay physical properties does not change basically.

The feature of three layers of expanded aluminum silicate that the present invention is useful also is the dioctahedron lattice, and three layers of Magnesium Silicate q-agent of expansible have the trioctahedron lattice.

Above-mentioned as this paper, the clay that uses in the present composition contains cation balance ion such as proton, sodium ion, potassium ion, calcium ion, magnesium ion etc.Get used to according to main or unique a kind of positively charged ion difference clay that is adsorbed.For example, the sodium clay is that the positively charged ion that wherein is adsorbed mainly is a kind of clay of sodium.This positively charged ion that is adsorbed can be included in the aqueous solution in the cationic permutoid reaction that exists.The general permutoid reaction that contains terre verte is represented by following equation:

Because in above-mentioned balanced reaction, the ammonium ion of 1 equivalent weight replaces the sodium of 1 equivalent weight, people get used to measuring cation exchange capacity (CEC) (being sometimes referred to as " basic exchange capacity ") by milligramequivalent/100g clay (meq/100g).The cation exchange capacity (CEC) of clay is to measure with several method, comprise electrodialysis, with ammonium ion exchange, titration then, or by the Yamamoto Methylene Blue ZF method, it is listed in Grimshaw's " chemistry of clay and physics " (The Chemistryand Physics of Clays), 264-265 page or leaf, interdisciplinary science (Interscience) (1971) fully.The cation exchange capacity (CEC) of clay mineral relates to the inflatable character of this factor such as clay, the electric charge of clay, and it is determined by crystalline network etc. again at least.The cation exchange capacity (CEC) of clay from for the about 2meq/100g of kaolin to for changing in about 150meq/100g of some smectites clay and the bigger scope.Illite clay have ion-exchange capacity sometimes this scope than lower part, promptly for average illite clay, about 26meq/100g.

Illite and kaolin, they have low relatively ion-exchange capacity, the preferred clay that is not used as the present composition.In fact, this illite and kaolin have constituted the main ingredient of clay dirt, and they are to remove from fabric face by the present composition as mentioned above.Yet terre verte has the about 70meq/100g of ion-exchange capacity such as nontronite, and montmorillonite, it has ion-exchange capacity greater than 70meq/100g, finds that it can be used in the present composition, this is that they deposit on the fabric, provide required soft effect.Therefore, the useful clay mineral of the present invention can be characterized by and have the expandable three layer smectite-type clay of ion-exchange capacity at least about 50meq/100g.

Although do not plan bound by theory, obviously can obtain favourable softness (with possible removing dyestuff etc.) effect and its physical properties and ion-exchange character of the present composition owing to use therein clay.In other words, the unexpansive clay of description of test is such as kaolin and illite, and it is that two classes have the clay that ion-exchange capacity is lower than 50meq/100g, and it does not provide the favourable aspect of the clay that uses in the present composition.

The terre verte that uses in the present composition is commercially available fully.This clay comprises for example polynite, volchonskoite, nontronite, hectorite, talcum powder, sauconite and vermiculite.The clay here can be buied by the extensive stock name, for example from Georgia Kaolin company, and Elizabeth, Thixogel#1 that the New Jersey is buied and Gelwhite GP; From AmericanColloid company, Skokie, Volclay BC and Volclay#325 that the Illinois is buied; Black HillsBentonite BH450 that buys from International Minerals and Chemicals and Veegum Pro and the Veegum F that buys from R.T.Vanderbilt.People recognize that this smectite type mineral substance that obtains by above-mentioned trade(brand)name can comprise the mixture of various discrete mineral plastids.The mixture of this smectite minerals matter is applicable to the present invention.

Be applicable to the present invention although have cation exchange capacity (CEC) at least about the smectite-type clay of 50meq/100g, preferably some clay.For example, Gelwhite GP is the terre verte of extremely white form, and therefore when preparation white particulate detergent composition, it is preferred.Volclay BC contains at least 3% iron (to be expressed as Fe in lattice ₂O ₃) the smectite-type clay mineral, it has very high ion-exchange capacity, it is to be used for one of the most effective clay of laundry composition, considers that from the angle of product performance it is preferred.

Being used for clay mineral that the present invention is fit to can show 14 real X-ray diffraction figures according to terre verte and select.This feature pattern is measured with the exchange capacity that aforesaid method carries out and is combined, and provides selection to be used for the basis of the specific smectite type mineral substance of granular detergent composition disclosed by the invention.

Clay preferably mainly is a particulate state, and at least 50% (preferably at least 75% or at least 90%) was to have size 100-1800 μ m at least, preferably to 1180 μ m, and the particle form of preferred 150-850 μ m.Clay amount in the preferred particulates is at least 50% of a particle weight, usually at least 70% or 90%.

Detersive surfactant

The unrestricted example that is applicable to tensio-active agent of the present invention generally is that content is anion surfactant such as sulfonate, vitriol and the ether sulfate of about 1%-about 55% (weight).These comprise conventional C ₁₁-C ₁₈The uncle and the random C of alkylbenzene sulfonate (" LAS ") and side chain ₁₀-C ₂₀Alkyl-sulphate (" AS "), formula CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃And CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃C ₁₀-C ₁₈Secondary (2,3) alkyl-sulphate, x and (y+1) be integer wherein at least about 7, preferably at least about 9, M is water miscible positively charged ion, particularly sodium, unsaturated vitriol is oleyl sulfate for example, C ₁₀-C ₁₈Alkyl alkoxy sulfate (" AE _xS "; EO 1-7 ethoxy sulfate particularly), C ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (particularly EO1-5 ethoxy carboxylate), C ₁₀-C ₁₈Glyceryl ether, C ₁₀-C ₁₈Alkyl polyglycoside and the many glycosides of they corresponding sulfations, and C ₁₂-C ₁₈α-sulfonated fatty acid ester.If necessary, in total composition of the present invention, also can comprise for example C of conventional nonionic and amphoterics ₁₂-C ₁₈Alkylethoxylate (" AE ") comprises alkylethoxylate and C that so-called narrow peak distributes ₆-C ₁₂Alkyl phenolic alkoxy thing (particularly ethoxylate and blended oxyethyl group/propoxylated glycerine), C ₁₂-C ₁₈Trimethyl-glycine and sultaine, C ₁₀-C ₁₈Amine oxide etc.Also can use C ₁₀-C ₁₈N-alkyl polyhydroxy fatty acid amide, typical example comprises C ₁₂-C ₁₈The N-methyl glucose amide.Referring to WO 92/06154.Other sugared deutero-tensio-active agents comprise N-alkoxyl group polyhydroxy fatty acid amide, for example C ₁₀-C ₁₈N-(3-methoxy-propyl) glucamide.When the low foaming of needs, can use the N-propyl group to N-hexyl C ₁₂-C ₁₈Glucamide.Also can use C ₁₀-C ₂₀Conventional soap.High if desired foaming effect can use side chain C ₁₀-C ₁₆Soap.The mixture of negatively charged ion and nonionogenic tenside is useful especially.Other conventional useful negatively charged ion, both sexes, nonionic or cats products are listed in the standard textbook.

In preferred embodiments, described comprises at least 5% weight tensio-active agent, more preferably at least 15% weight, even more preferably at least 25% weight, most preferably 35%-55% weight tensio-active agent.The amount of anion surfactant is at least 1.5 times of other tensio-active agent total amounts preferably, generally at least 2 or 3 times.

Washing assistant

Detergent builders optionally is included in the present composition to help control mineral substance hardness.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for the composition of laundering of textile fabrics, to help removing particulate fouling.

The content of washing assistant can change in wide region according to the end-use of composition.

Inorganic or phosphorous washing assistant comprises, but be not limited to: following basic metal, ammonium and alkanol ammonium salt: poly-phosphate (is exemplified as tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.But, need non-phosphorus Cleaning Aid Agent in certain areas.Importantly, in addition so-called " weak " washing assistant (with phosphate ratio) as Citrate trianion down, or under generable what is called " hanged down " situation composite when use zeolite or layered silicate washing assistant, the effect of the present composition was good unexpectedly.

The example of silicate-like builder is an alkalimetal silicate, and particularly those have SiO ₂: Na ₂Silicate and the layered silicate of the ratio of O in 1.6: 1 to 3.2: 1 scopes, the lamina sodium silicate of describing in the U.S. Pat 4664839 as the H.P.Rieck that authorizes on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " in this article usually) by the crystalline layered silicate of Hoechst sale.Do not resemble zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na ₂SiO ₅The layered silicate of morphological form.It can be by the method preparation as describing in DE-A-3417649 and DE-A-3742043.SKS-6 is a layered silicate very preferably used herein, but the present invention can use other layered silicate, has general formula NaMSi as those _xO _2x+1YH ₂The layered silicate of O, wherein M is sodium or hydrogen, and x is 1.9 to 4 numerical value, is preferably 2, and y is 0 to 20 numerical value, is preferably 0.Various other layered silicates of buying from Hoechst comprise NaSKS-5, NaSKS-7, and NaSKS-11, and they are with α, β and γ form.As mentioned above, δ-Na ₂SiO ₅(NaSKS-6 form) most preferably used herein.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as crisp dose of granular recipe, as the stablizer of oxygen bleaching agent with as the component of control foam system.

The example of carbonate builders is alkaline-earth metal and the alkaline carbonate on November 15th, 1973 disclosed German patent application 2321001.

The silico-aluminate washing assistant is useful in the present invention.The silico-aluminate washing assistant is most important in the most common commercially available heavy duty type granular detergent composition, and also can be builder component important in the liquid detergent formula.The silico-aluminate washing assistant comprises the washing assistant with following empirical formula:

Mz(zAlO ₂)y].xH ₂O

Wherein z and y are at least 6 integer, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about 15 to about 264 integer.

Useful aluminosilicate ion exchange material is commercial the purchase.These silico-aluminates can be crystallization or amorphous structure, and can be the silico-aluminate or synthetic the obtaining of natural generation.The method for preparing aluminosilicate ion exchange material is disclosed in the people's such as Krummel that authorized on October 12nd, 1976 the U.S. Pat 3985669.The preferred synthetic crystallization aluminosilicate ion exchange material that is used for this paper can buy by zeolite A, zeolite P (B), zeolite MAP and the X zeolite of registration.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂].xH ₂O

Wherein x is about 20 to about 30, especially about 27.This material is called zeolite A.Dehydration zeolite (x=0-10) also can use in this article.Silico-aluminate preferably has the granularity of diameter for about 0.1-10 micron.

The organic detergent washing assistant that is fit to the object of the invention includes, but are not limited to: various multi-carboxylate's compounds." multi-carboxylate " used herein refers to has a plurality of carboxylic acid groups, preferred at least 3 carboxylic acid groups' compound.The multi-carboxy acid salt washing agent generally can add in the composition with sour form, but also can add with the form of neutralized salt.When using with the form of salt, basic metal is preferred as sodium, potassium and lithium or alkanol ammonium salt.

In the multi-carboxy acid salt washing agent, comprise multiple useful material.A kind of multi-carboxy acid salt washing agent of important kind comprises the ether multi-carboxylate, comprise the oxygen disuccinate, as those disclosed in the U.S. Pat 3128287 of the Berg that authorizes on April 7th, 1964 and the people's such as Lamberti that authorized on January 8th, 1972 the U.S. Pat 3635830.Also referring to " TMS/TDS " washing assistant in the people's such as Bush that authorized on May 5th, 1987 the U.S. Pat 4663071.The ether multi-carboxylate who is fit to also comprises ring compound, particularly alicyclic compound, as in U.S. Pat 3923679; US3835163; US4158635; Described in US4120874 and the US4102903 those.

Other useful washing assistant comprises ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxyl methoxyl group succsinic acid, various polyacetic acids, as basic metal, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and poly carboxylic acid such as mellitic acid, succsinic acid, the oxygen disuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and their water-soluble salt.

The Citrate trianion washing assistant, for example, citric acid and its water-soluble salt (particularly sodium salt) they are the multi-carboxy acid salt washing agents of particularly important in the heavy duty liquid laundry detergent prescription, reason is that they can obtain having biodegradability with them by renewable resource.Citrate trianion also can be used in the particulate composition, particularly is used in combination with zeolite and/or layered silicate washing assistant.The oxygen disuccinate is also particularly useful in this composition and mixture.

Be suitable in the U.S. Pat 4566984 that also has the Bush that authorizes on January 28th, 1986 of detergent composition of the present invention disclosed 3,3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and their salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The specific examples of succinate washing assistant comprises: lauryl succinate, nutmeg base succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in this group, and is described in the disclosed european patent application 86200690.5/0,200,263 on November 5th, 1986.

Other multi-carboxylates that are fit to be disclosed in the people's such as Crutchfield that authorized on March 13rd, 1979 U.S. Pat 4144226 and the U.S. Pat 3308067 of the Diehl that authorized on March 7th, 1967 in.Also referring to U.S. Pat 3723322.

Lipid acid, for example C ₁₂-C ₁₈Monocarboxylic acid also can mix in the composition individually, or mixes in the composition with aforesaid washing assistant, especially Citrate trianion and/or the combination of succinate washing assistant, so that extra washing assistant activity to be provided.Use lipid acid generally can weaken foaming, this prescription teacher should consider.

Under the situation that can use phosphorous washing assistant, especially, can use various alkali metal phosphates tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate as is well known at the stick prescription that is used for hand-washing operation.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonate (referring to, for example, U.S. Pat 3159581; 3213030; 3422021; 3400148 and 3422137).

SYNTHETIC OPTICAL WHITNER

Detergent composition of the present invention can contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When existing, the content of SYNTHETIC OPTICAL WHITNER is generally detergent composition, in particular for the detergent composition of laundering of textile fabrics about 1% to about 30%, more typically be about 5% to about 20%.If contain bleach-activating agent, its content be generally comprise SYNTHETIC OPTICAL WHITNER add bleach-activating agent bleaching composition about 0.1% to about 60%, more preferably about 0.5% to about 40%.

SYNTHETIC OPTICAL WHITNER used herein can be to be applicable to cleaning fabric, cleans crust, or other is known now or with any SYNTHETIC OPTICAL WHITNER in the detergent composition of known cleaning use.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example monohydrate or tetrahydrate).

Unrestricted operable another kind of SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-nonyl amino-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the U.S. Pat 4483781 of the Hartman that authorized on November 20th, 1984, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740446, February in 1985 people such as disclosed Banks on the 20th european patent application 0133354 and the people's such as Chung that authorize November 1 nineteen eighty-three U.S. Pat 4412934 in.Highly preferred SYNTHETIC OPTICAL WHITNER also comprises 6-nonyl amino-6-oxo-mistake oxy hexanoic acid of describing as in the U.S. Pat 4634551 that licenses to people such as Burns on January 6th, 1987.

The present invention also can use peroxygen bleach.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate and its equivalent " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is by the DuPont commercial production).

Preferred percarbonate bleach comprises having average particle size at about 500 dried particles to about 1000 micrometer ranges, be no more than about 10% (weight) less than about 200 microns described particle, be no more than about 10% (weight) greater than about 1250 microns described particle.Percarbonate can optionally use silicate, borate or water soluble surfactant active to apply.Percarbonate can be from various suppliers such as FMC, and Solvay and Tokai Denka obtain.

Also can use the mixture of SYNTHETIC OPTICAL WHITNER.

Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly at washing process).The various non-limiting examples of activator are disclosed in and license in people's such as Mao the U.S. Pat 4915854 and U.S. Pat 4412934 April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are typical activators, also can use their mixture.Typical SYNTHETIC OPTICAL WHITNER of useful herein other and activator are in addition referring to U.S. Pat 4634551.

Amido deutero-bleach-activating agent very preferably has formula:

R1N (R5) C (O) R2C (O) L or R1C (O) N (R5) R2C (O) L

R wherein ¹Be to contain 6 the alkyl of having an appointment, R to about 12 carbon atoms ²Be to contain 1 alkylidene group, R to about 6 carbon atoms ⁵Be that have an appointment 1 alkyl to about 10 carbon atoms, aryl or alkaryl and L of H or contain is any suitable leavings group.Leavings group is owing to cross hydrolysis negatively charged ion nucleophilic attack bleach-activating agent, result's substituted any group from the bleach-activating agent.Preferred leavings group is a benzene sulfonate.

The preferred embodiment of following formula bleach-activating agent comprises (6-decoyl amino-caproyl) oxygen base benzene sulfonate of describing as in U.S. Pat 4634551 (document is quoted for referencial use by this paper); (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate; (6-caprinoyl amino-caproyl) oxygen base benzene sulfonate and their mixture.

Another kind of bleach-activating agent is included in disclosed benzo oxazinyl activator in the people's such as Hodge that authorize October 30 nineteen ninety the U.S. Pat 4966723 (this patent is quoted for referencial use by this paper).The activator very preferably of benzo oxazinyl is:

Another kind of preferred bleach-activating agent comprises the acyl lactam activator, especially the acyl caprolactam of following formula and acyl group Valerolactim:

R wherein ⁶Be H or have 1 alkyl, aryl, alkoxy aryl, or alkaryl to about 12 carbon atoms.Lactan activator very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5,5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam; the decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim; the capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim; the nonanoyl Valerolactim; 3,5,5-trimethyl acetyl base Valerolactim and their mixture.Also referring to the U.S. Pat 4545784 of the Sanderson that authorized on October 8th, 1985, this patent is quoted for referencial use by this paper, wherein disclose acyl caprolactam, comprises benzoyl caprolactam, and they are adsorbed in the Sodium peroxoborate.

Those SYNTHETIC OPTICAL WHITNER of non-oxygen bleaching agent also are well known in the art, and can be used for the present invention.The non-oxygen bleaching agent that one class is good especially comprises photoactivated SYNTHETIC OPTICAL WHITNER such as sulfonated Phthalocyanine Zinc and/or aluminium.License to people's such as Holcombe U.S. Pat 4033718 referring on July 5th, 1977.If necessary, detergent composition generally contains have an appointment 0.025% such SYNTHETIC OPTICAL WHITNER to about 1.25% (weight), especially phthalocyanine sulfonic acid zinc.

If necessary, bleaching compounds can come catalysis with manganic compound.This compounds is a compound well known in the art, comprises, for example at U.S. Pat-A-5246621, US-A-5244594, US-A-5194416, US-A-5114606 and EP-A-549271, EP-A-549272, disclosed manganese among EP-A-544440 and the EP-A-544490-catalyst based; The preferred embodiment of these catalyzer comprises Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₃, Mn ^IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃(PF ₆) and their mixture.Other metallic bleaching catalysts are included in those disclosed among U.S. Pat 4430243 and the US5114611.The manganese that use has various complex ligands is used for improving bleaching power and also is reported in following United States Patent (USP): 4728455,5284944,5246612,5256779,5280117,5274147,5153161 and 5227084.

In actual applications, be not subjected to limitation, the present composition and method can be conditioned so that provide in wash water solution at least about per active bleaching catalyst of 1/10000000th, preferably provide about 0.1ppm to about 700ppm in washing soln, more preferably from about 1ppm is to the catalyst substance of about 500ppm.

Enzyme

Can comprise in the present invention prescription that enzyme for example removes the spot that contains protein, carbohydrate or triglyceride level to reach the multiple purpose of laundering of textile fabrics, to comprise, and restore for the dye migration that suppresses to come off with for fabric.The enzyme that is impregnated in comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, and their mixture.The enzyme that also can comprise other type.They can be from any suitable source, for example plant, animal, bacterium, mould and yeast source.Yet their selection is subjected to the control of several factors, as pH-activity and/or optimum stabilization, thermostability with to stability of activated detergent, washing assistant or the like.Aspect this, bacterium or fungous enzyme are preferred, as bacterial amylase and proteolytic enzyme and mould cellulase.

Usually the enzyme that mixes q.s to be providing every gram detergent composition up to about 5 milligrams of weight, more typical be about 0.01 milligram to about 3 milligrams of organized enzymes.In other words, the present composition generally comprises about 0.001% to about 5%, preferred 0.01%-1% (weight) commercial enzyme preparation.Proteolytic enzyme is usually to be enough to provide 0.005 to be present in this commodity preparation to the active content of 0.1Anson unit (AU) in every gram composition.

Suitable examples of proteases is a subtilisin, and it is that special bacterial strain by Bacillus subtillis and bacillus licheniformis obtains.Another kind of suitable proteolytic enzyme is to be obtained by bacillus strain, and it has maximum activity in the pH8-12 scope, and it is by exploitation of Novo Industries A/S company and sale, and the commodity of registration are called ESPERASE.The preparation of this kind of enzyme and similar enzyme is described among the british patent specification GB1243784 of Novo company.The commercially available proteolytic ferment that is fit to remove based on the albumen dirt comprises by Novo Industries A/S (Denmark) with trade(brand)name ALCALASE and SAVINASE with by International Bio-Synthetics, those that Inc. (Holland) sells with MAXATASE.Other proteolytic enzyme comprises protease A (referring to the EP-A-130756 that announced on January 9th, 1985); Proteolytic enzyme B (referring to the EP-A-130756 of the european patent application 87303761.8 of application on April 28th, 1987 and the Bott that announced on January 9th, 1985 etc.).

Amylase comprises, for example in GB-A-1296839 (Novo), describe-amylase, International Bio-Synthetics, the RAPIDASE of Inc. and the TERMAMYL of NovoIndustries.

The cellulase that can be used among the present invention comprises bacterium and mould cellulase.Preferably their best pH is 5-9.5.The cellulase that is fit to is disclosed in the U.S. Pat 4435307 of authorizing in 6 days March in 1984 of people such as Barbesgoard, it discloses by Humicolainsolens and the rotten cellulase that extracts in the mould cellulase that trichoderma strain DSM1800 produces or cellulase 212 that produces the mould that belongs to Aeromonas and the hepatopancreas by extra large mollush (DolabellaAuricula Solander) of planting.Suitable cellulase also is disclosed in GB-A-2075028; Among 6B-A-2095275 and the DE-OS-2247832.CAREZYME (Novo) is useful especially.

The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, as those lipase of Situ Ci Shi pseudomonas (Pseudomonas stutzeri) ATCC 19.154 generations, as is disclosed in the English Patent 1372034.Also referring to the lipase in the Japanese patent application of openly examining in special permission on February 24th, 1,978 5320487 for the public.This lipase can be available from Amano Pharmaceutical Co.Ltd. Japan Nagoya, and commodity are called lipase P " Amano ", hereinafter referred to as " Amano-P ".Other merchant sells lipase and comprises Amano-CES, the lipase that obtains by thickness look bacillus, for example, and the lipolyticum NRRLB 3673 of thickness look bacillus variation, they are available from Toyo Jozo Co., Tagata, Japan; Derive from U.S.Biochemical Corp. in addition, the thickness look bacillus lipase of the Disoynth company of the U.S. and Holland and the lipase that obtains by gladiolus pseudomonas (Pseudomonas gladioli).Planting bacterium (Humicola lanuginosa) by the fetal hair corruption derives and obtains and be the preferred herein lipase that uses at the LIPOLASE enzyme (also referring to EP0341947) that can be purchased by Novo.

Peroxidase is and oxygen source, for example, percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination, and they are used for " solution bleaching ", promptly avoid in washing operation on the dyestuff that comes off from substrate or pigment migration other substrate to the washing soln.Peroxidase is that prior art is known, comprises for example horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed in the PCT International Application No. WO 89/099813 of the O.Kirk that for example announced on October 19th, 1989, and it transfers Novo Industries A/S.

Various enzyme materials and the method that they are mixed in the synthetic detergent composition also are disclosed in the people's such as McCarty that authorized on January 5th, 1971 the U.S. Pat 3553139.Enzyme also be disclosed in the people's such as Place that authorized on July 18th, 1978 U.S. Pat 4101457 and the U.S. Pat 4507219 of the Hughes that authorized on March 26th, 1985 in.The enzyme material that is used for liquid detergent formula is disclosed in the people's such as Hora that authorized on April 14th, 1981 the U.S. Pat 4261868 with methods that they are incorporated into these prescriptions.The enzyme that is used for washing composition can make it stable with various technology.The technology of stabilized enzyme discloses and illustrates the European patent application publication No. 0199405 at the Venegas of the people's such as Gedge of mandate on August 17th, 1971 U.S. Pat 3600319 and announcement on October 29th, 1986, in the application number 86200586.5.The enzyme stabilising system for example also is described in the U.S. Pat 3519570.

Flocculation agent

Most of clay flocculating polymers are polymkeric substance and the multipolymers by this monomer such as oxyethane, acrylamide, vinylformic acid, dimethyl aminoethyl methacrylic acid ester, vinyl alcohol, vinyl pyrrolidone and piperazine (ethylene imine) the suitable long-chain of deutero-.Natural gum also is fit to as guar gum.

Preferably oxyethane, acrylamide or polymerizing acrylic acid thing.If their molecular weight is at 100000-10 1,000,000, then these polymkeric substance have strengthened the deposition of fabric sofetening clay greatly.It is 150000-5 1,000,000 that preferred this polymkeric substance has molecular-weight average.

Most preferred polymkeric substance is poly-(oxyethane).Molecular weight distribution can easily use poly-(oxyethane) standard of the relative narrow molecular weight distributions of gel permeation chromatography to measure.

The amount of flocculation agent is the 0.5-10% of sheet weight preferably, most preferably from about 2-6%.

Flocculation agent preferably mainly is a particulate state, and at least 50% weight (preferably at least 75%, most preferably at least 90%) is to have size 100-1800 μ m at least, preferably to 1180 μ m, the most preferably particle form of 150-850 μ m.Preferably, the amount of flocculation agent is at least 50% of a particle weight in the particle, generally at least 70% or 90%.

Other components normally used and that can mix in the detergent tablet of the present invention comprise sequestrant, dirt release agent, dirt anti redeposition agent, dispersion agent, whitening agent, suds suppressor, fabric softener, dye transfer inhibitor and spices in detergent composition.

Will be appreciated that working as clay material was pressed before mixing sheet or cleaning compositions, can improved decomposition or dispersiveness.For example, be included in the sheet of downtrodden clay before mixing in the sheet, its than be included in mix in the sheet before the sheet of downtrodden same clay material decompose fast.Especially, the amount of pressure that is used to suppress clay is important to obtaining clay particle, and it helps to decompose or disperse.

In addition, when mild clay is pressed, when mixing in cleaning compositions or the sheet then, decomposition that not only is improved or dispersion, and fabric had good flexibility.

Preferably, clay composition obtains by the compacting clay material.Preferable methods comprises makes clay material bear 10MPa pressure at least, or even 20MPa or even the step of 40Mpa pressure at least.This can be for example by with the clay material tablet forming or roll and carry out, randomly in conjunction with one or more other components, form clay gall or thin slice, preferably carry out size then and reduce, for example grind the clay gall of compacting, form the clay particle of compacting.This particle can mix in sheet or the cleaning combination then.

Pressed disc method and rolled-on method are that prior art is known.For example, can or use the Chilsonator rolling apparatus of buying by Fitzpatrick company to carry out the clay compacting in Lloyd 50K tabletting machine.

In an embodiment, by the washing composition original washing powder that is prepared as follows composition in the table 1.All particulate materials of this basic composition are to be mixed together in mixing drum, form the single-size mixture.In this mixes, tackiness agent in the sprinkling.

In mixing drum, mix 95 parts of original washing powders, and dilute with 5 parts of montmorillonitic clays.

Prepare sheet then by the following method.The adding of 42.8g mixture is had in the circular mould of diameter 5.4cm, and compacting generation sheet tensile strength (or radial crack stress) is 15kPa.

By " The sheet dispersion experiment" amount of residue in the evaluation washing machine feeder compartment: two kinds of laundry sheets are put into Baucknecht WA9850 feeder compartment.The water design temperature that provides to washing machine is 8 ℃, and hardness is 21 grain/grams, and the water inlet flow velocity of feeder compartment was set in 4L/ minute, and flowing time is 78 seconds.Connect the washing machine power supply, be set in washing procedure 4 (white/colored, short period) wash(ing)cycle, check remaining residue amount in the feeder compartment.Press following mensuration residual value:

Table 1

			(％)
Negatively charged ion agglomerate 1	21.45
		Negatively charged ion agglomerate 2	12
The positively charged ion agglomerate	5.45
		Layered silicate	10.8
SPC-D	11.19
		The bleach-activating agent agglomerate	5.49
Yellow soda ash	10.64
		The EDDS/ sulphate particle	0.47
Hydroxyl ethane di 2 ethylhexyl phosphonic acid tetra-na salt	0.73
		The dirt release agent polymkeric substance	0.33
Fluorescent agent	0.18
		Phthalocyanine sulfonic acid zinc capsule	0.025
The soap powder end	1.4
		Suds suppressor	1.87
Citric acid	7.1
		Proteolytic enzyme	0.79
Lipase	0.28

Cellulase	0.22
		Amylase	1.08
The di-isopropyl benzene sulfonate	0.75
		Tackiness agent
Cationic polymers	0.42
		PEG 4000	0.725
PEG 1000	0.365

Negatively charged ion agglomerate 1 is by 40% anion surfactant, and 27% zeolite and 33% carbonate are formed.

Negatively charged ion agglomerate 2 is by 40% anion surfactant, and 28% zeolite and 32% carbonate are formed.

The positively charged ion agglomerate is by 20% cats product, and 56% zeolite and 24% vitriol are formed.

Layered silicate is made up of 95%SKS 6 and 5% silicate.

The bleach-activating agent agglomerate is by 81%TAED, and 17% vinylformic acid/maleic acid (sour form) and 2% water are formed.

Quadrol N, N-disuccinic acid sodium salt/sulphate particle be by 58% quadrol N, N-disuccinic acid sodium salt, and 23% vitriol and 19% water are formed.

Phthalocyanine sulfonic acid zinc capsule is 10% active.

Suds suppressor is by 11.5% silicone oil, and 59% zeolite and 29.5% water are formed.

Table 2 has been summarized ten kinds of different embodiment.

Table 2

	1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10
											Original washing powder	95	95	95	95	95	95	95	95	95	95
											Clay A powder	5
The clay A agglomerate of combination water (150-1700 μ m)		5
											The clay A agglomerate of combination water/glycerine/paraffin (100-1700 μ m)			5
											Clay B powder				5
The clay B agglomerate 150-850 μ m of combination water					5
											Clay B extrudate (150-1700 μ m)						5
Clay B extrudate (850-1400 μ m)							5

Clay B extrudate (425-850 μ m)								5
											Clay B extrudate (150-425 μ m)									5
Clay B extrudate (100-150 μ m)										5

In embodiment 1-3, use one-level montmorillonitic clay (the clay A of mark).In embodiment 4-10a, use the montmorillonitic clay (the clay B of mark) of different stage.

In embodiment 2, prepare particle by the following method.

450g clay A is added in the Braun mixing tank, model 4262, blade is set in 3000rpm.In the blade mixed clay, 84g distilled water was sneaked in the clay in 15 seconds gradually.After adding after water injection, water and clay mixture were mixed 2 minutes in addition.Then with the agglomerate of preparation in being set in 90 ℃ Sherwood Scientific fluidized bed dryer dry 30 minutes.Sieve this exsiccant agglomerate, from mixture, remove oversize particle (greater than the particle of 1700 μ m) and less than the particle of 150 μ m.

In embodiment 5, make to use the same method, just remove particle less than 100 μ m.

In embodiment 3, use same procedure with embodiment 1, only be to use 23g paraffin solution, 15g glycerine and the 32g water of 84g to replace 84g distilled water, from mixture, remove particle less than 100 μ m.

In each embodiment 6-10, use following method to prepare extrudate.

500g clay B is mixed with 250g distilled water.The mixture that obtains is delivered in the Dome extrusion machine that screw rod is set in 80rpm.The mixture that uses the screening of ASTM screening plant to obtain then.The extrudate of dry preparation in being set in 90 ℃ Sherwood Scientific fluidized bed dryer is 30 minutes then.With the screening of exsiccant extrudate, obtain defined size-grade distribution, from mixture, remove oversize particle and fine powder.

When using clay A powder and clay B powder (embodiment 1 or 4), the agglomerate of clay A and B and extrudate have provided quite low % residue (therefore disperseing preferably).In embodiment 5,8 and 9, obtain minimum residue (therefore disperseing best).The advantageous effects that this explanation clay adds as the particle at size 150-850 mu m range, particularly all particles have mean sizes ± 300 μ m basically.

Other embodiment comprise the sheet by following composition powder preparation:

Embodiment A and B

Table A: detergent based powder composition

	ExA	ExB
				(％)	(％)
The clay extrudate	14.00	14.00
			The flocculation agent agglomerate	3.8	3.8
Negatively charged ion agglomerate 1	32	38
			Anion particle 2	2.27	2.27
The positively charged ion agglomerate	4.0
			SPC-D	8.0	10.0
The bleach-activating agent agglomerate	2.31	2.8
			Yellow soda ash	21.066	16.57
The EDDS/ sulphate particle	0.19	0.19
			Hydroxyl ethane di 2 ethylhexyl phosphonic acid tetra-na salt	0.34	0.34

Fluorescent agent	0.15	0.15
			Phthalocyanine sulfonic acid zinc capsule	0.027	0.027
Soap powder	1.40	1.40
			Suds suppressor	2.6	2.6
Citric acid	4.0	4.0
			Proteolytic enzyme	0.45	0.45
Cellulase	0.20	0.20
			Amylase	0.20	0.20
Spices	1.00	1.00
			Tackiness agent
Pluriol 1000	2.0	2.0

The clay extrudate comprises 97%CSM Quest 5A clay and 3% water.

The flocculation agent starting material are polyethylene oxides of molecular-weight average 300000.

Negatively charged ion agglomerate 1 comprises 40% anion surfactant, 27% zeolite and 33% carbonate.

Negatively charged ion agglomerate 2 comprises 40% anion surfactant, 28% zeolite and 32% carbonate.

The positively charged ion agglomerate comprises 20% cats product, 56% zeolite and 24% vitriol.

Layered silicate comprises 95%SKS 6 and 5% silicate.

The bleach-activating agent agglomerate comprises 81%TAED, 17% vinylformic acid/maleic acid (sour form) and 2% water.

Quadrol N, N-disuccinic acid sodium salt/sulphate particle comprises 58% quadrol N, N-disuccinic acid sodium salt, 23% vitriol and 19% water.

Phthalocyanine sulfonic acid zinc capsule is 10% active.

Suds suppressor comprises 11.5% silicone oil (available from Dow Corning), 59% zeolite and 29.5% water.

Embodiment C (citric acid of corpusculed)

In the composition of Embodiment B, with the used citric acid of citric acid replacement of corpusculed.Before use, grind used citric acid to following psd with coffee grinder.

	Particulate maximum greater than 1.4mm	Particulate maximum less than 150 μ m
			Embodiment B	8％	12％

	Particulate minimum less than 150 μ m
		Embodiment C	80％

Embodiment D-F (composition of phosphorylation)

	Embodiment D	Embodiment E	Embodiment F
					(％)	(％)	(％)
The clay extrudate	13.00	13.00	13.00
				The flocculation agent agglomerate	3.5	3.5	3.5
Anion particle	38.2	38.2	38.2
				SPC-D	8.0

The Sodium peroxoborate monohydrate		8.0
				Sodium perborate tetrahydrate			8.0
The bleach-activating agent agglomerate	2.3	2.3	2.3
				The HPA tripoly phosphate sodium STPP	15.4	15.4	15.4
Yellow soda ash	10.043	10.043	10.043
				The EDDS/ sulphate particle	0.19	0.19	0.19
Hydroxyl ethane di 2 ethylhexyl phosphonic acid tetra-na salt	0.34	0.34	0.34
				Fluorescent agent	0.15	0.15	0.15
Phthalocyanine sulfonic acid zinc capsule	0.027	0.027	0.027
				Soap powder	1.40	1.40	1.40
Suds suppressor	2.6	2.6	2.6
				Citric acid	1.0	1.0	1.0
Proteolytic enzyme	0.45	0.45	0.45
				Cellulase	0.20	0.20	0.20
Amylase	0.20	0.20	0.20
				Spices	1.00	1.00	1.00
Tackiness agent
				Pluriol 1000	2.0	2.0	2.0

The clay extrudate comprises 97%CSM Quest 5A clay and 3% water.

The flocculation agent starting material are polyethylene oxides of molecular-weight average 300000.

Layered silicate comprises 95%SKS 6 and 5% silicate.

The bleach-activating agent agglomerate comprises 81%TAED, 17% vinylformic acid/maleic acid (sour form) and 2% water.

Quadrol N, N-disuccinic acid sodium salt/sulphate particle comprises 58% quadrol N, N-disuccinic acid sodium salt, 23% vitriol and 19% water.

Phthalocyanine sulfonic acid zinc capsule is 10% active.

Suds suppressor comprises 11.5% silicone oil (available from Dow Corning), 59% zeolite and 29.5% water.

This anion particle is the blowing powder with following composition:

(％)

Linear alkylbenzene sulphonic acid 17.7

Nonionic C35 7EO 2.0

Nonionic C35 3EO 5.9

Soap 0.5

Tripoly phosphate sodium STPP is (available from 47.8

Rhone Poulenc's

Rhodia-Phos HPA3.5)

Water glass 10.8

Xylo-Mucine 0.4

Vinylformic acid/maleic acid 2.1

Salt, moisture content 12.9

Embodiment G and H

		ExG	ExH
						(％)	( ％ )
The clay extrudate		14.00	1 4. 0 0
				The flocculation agent agglomerate		3.8	3. 8
Negatively charged ion agglomerate 1		32	3 2
				Anion particle 2		2.27	2. 2 7
The positively charged ion agglomerate		4.0	4. 0
				SPC-D		8.0	8. 0
The bleach-activating agent agglomerate		2.31	2. 3 1
				Yellow soda ash		18.066	1 8. 0 6 6
The EDDS/ sulphate particle		0.19	0.

			1 9
				Hydroxyl ethane di 2 ethylhexyl phosphonic acid tetra-na salt		0.34	0. 3 4
Fluorescent agent		0.15	0. 1 5
				Phthalocyanine sulfonic acid zinc capsule		0.027	0. 0 2 7
Soap powder		1.40	1. 4 0
				Suds suppressor		2.6	2. 6
Arbocel TF-30-HG		5.0
				Vivapur G22			5. 0
Citric acid		2.0	2. 0
				Proteolytic enzyme		0.45	0. 4 5
Cellulase		0.20	0. 2 0
				Amylase		0.20	0. 2 0

Spices		1.00	1. 0 0
				Tackiness agent
Pluriol 1000		2.0	2. 0

The clay extrudate comprises 97%CSM Quest 5A clay and 3% water.

The flocculation agent starting material are polyethylene oxides of molecular-weight average 300000.

Negatively charged ion agglomerate 1 comprises 40% anion surfactant, 27% zeolite and 33% carbonate.

Negatively charged ion agglomerate 2 comprises 40% anion surfactant, 28% zeolite and 32% carbonate.

The positively charged ion agglomerate comprises 20% cats product, 56% zeolite and 24% vitriol.

Layered silicate comprises 95%SKS 6 and 5% silicate.

The bleach-activating agent agglomerate comprises 81%TAED (tetra acetyl ethylene diamine), 17% vinylformic acid/maleic acid (sour form) and 2% water.

Quadrol N, N-disuccinic acid sodium salt/sulphate particle comprises 58% quadrol N, N-disuccinic acid sodium salt, 23% vitriol and 19% water.

Phthalocyanine sulfonic acid zinc capsule is 10% active.

Suds suppressor comprises 11.5% silicone oil (available from Dow Corning), 59% zeolite and 29.5% water.

Arbocel TF-30-HG and Vivapur G22 are the Mierocrystalline celluloses that contains available from the decomposition agent of Rettenmaier company.

Example I-N

Repeat embodiment A-G, will by shown in the sheet of preparation of compositions immerse and comprise 80 parts of hexanodioic acids and mix in the body lotion with 18.5 parts of CSM Quest 9 clays and 1.5 parts of Coasol (Coasol is a diisobutyl adipate).

This sheet also can comprise high-molecular-weight poly (oxyethane), Mierocrystalline cellulose decomposition agent and/or acetate.It should also comprise high dissolubility salt.

Claims (12)

1. soft detergent for washing clothes sheet that comprises clay and washing clothes form surface-active agent, wherein this sheet is downtrodden particle object, the clay of at least 75% weight is that the particle as size 100-1180 μ m exists.

2. according to the sheet of claim 1, wherein the clay content of sheet is at least 5% of a sheet weight.

3. according to the sheet of claim 1, wherein the clay content of sheet is at least 8% of a sheet weight.

4. according to the sheet of claim 3, wherein the clay content of sheet is at least 10% of a sheet weight.

5. according to the sheet of claim 1, wherein the clay of 75% weight is the particle existence as size 150-850 μ m.

6. according to each sheet among the claim 1-5, wherein clay particle contains the clay of at least 50% weight.

7. according to the sheet of claim 6, wherein clay particle contains the clay of at least 70% weight.

8. according to the sheet of claim 7, wherein clay particle contains the clay of at least 90% weight.

9. according to each sheet among the claim 1-5, wherein clay particle only is made up of the tackiness agent of clay or clay and as many as 10% weight clay particle basically.

10. require among the 1-5 each sheet according to aforesaid right, wherein this sheet also comprises the clay flocculating agent.

11. according to each sheet among the claim 1-5, wherein particle is all particles that have size at least 100 μ m basically.

12. method for preparing the soft detergent for washing clothes sheet that comprises clay and washing clothes form surface-active agent, it comprises that the clay that at least 50% weight is provided is as the particle with at least 100 μ m sizes, this clay particle is mixed with other particulate state components of sheet, and with this mixture compacting in flakes.