CN1364192A - Coated detergent tablet - Google Patents

Abstract

The present invention relates to a coated detergent tablet, the coating comprising a cation exchange resin.

Description

Coated detergent tablet

The present invention relates to coated detergent tablet, especially be applicable to those of washing machine, and relate to the method for preparing this coated detergent tablet.

Although proposed the cleaning compositions of tablet form usually, as yet (except being used for the soap bar of personal cleansing) do not obtain any substantive success, though the product of unit forms of distribution has some advantages.One of its reason may be that detergent tablet need be than complicated manufacturing process.Especially, need provide the tablet with coating usually, this has increased manufacture difficulty.

Although there is not the tablet of coating in full force and effect in use, they often lack required surface hardness, can not stand the wearing and tearing of making, packing and use a part as normal.The non-coated tablets of result is worn in these processes, causes the broken and active substance loss of tablet.

At last, the coating of tablet is often because aesthetic reasons, in order to the outward appearance of improving tablet or obtain some specific aesthetic effect.Proposed a lot of tablet coating methods, wherein manyly be that detergent tablet proposes.But all these methods have some defectives that for example are explained as follows.

The GB-A-0989683 that is published in April 22 nineteen sixty-five discloses and has a kind ofly prepared granulated detergent by tensio-active agent and inorganic salt, sprays water-soluble silicate, and detergent particles is pressed into the method for the tablet that can keep solid form.At last, a kind of easily water-soluble organic film-forming polymer (for example, polyvinyl alcohol) provides and has made the wear-resistant and accidental disruptive coating of detergent tablet.

The EP-A-0002293 that is published on June 13rd, 1979 discloses a kind of tablet coating that comprises salt hydrate such as acetate, metaborate, orthophosphoric acid salt, tartrate and vitriol.

The EP-A-0716144 that is published on June 12nd, 1996 also discloses a kind of detergent for washing clothes tablet with water-soluble coating, and this coating can be an organic polymer, comprises acrylic acid series/toxilic acid based copolymer, polyoxyethylene glycol, PVPVA and sugar.

The WO9518215 that is published in July 6 nineteen ninety-five provides a kind of water-insoluble coating that is used for the solid cast tablet.This tablet has the hydrophobic coat that comprises wax, lipid acid, fatty acid amide and polyoxyethylene glycol.

The EP-A-0846754 that is published on June 10th, 1998 provides a kind of tablet with the coating that comprises dicarboxylic acid, normally 40-200 ℃ of the fusing point of described coating material.

The EP-A-0846755 that is published on June 10th, 1998 provide a kind of have be included in 25 ℃ of water-fast materials down, as the tablet of the coating of C12-C22 lipid acid, hexanodioic acid or C8-C13 dicarboxylic acid.

The EP-A-0846756 that is published on June 10th, 1998 provides a kind of tablet with the coating that comprises disintegration material and preferred effervescent materials.

The invention provides a kind of method, coated tablets can have a coating thus, makes them can store harmlessly, transport and use, and described coating is broken when this tablet is in the washing machine easily, and release of active ingredients is to washing lotion.

The purpose of this invention is to provide a kind of tablet with coating, this coating enough is not subjected to mechanical force and is dispersed in the aqueous solution easily with protection tablet when storing, transporting and using firmly.

Summary of the invention

Purpose of the present invention realizes that by a kind of coated detergent tablet is provided described coating comprises a kind of Zeo-karb.

Detailed Description Of The Invention

Coating

The solidity of tablet can improve by preparing a kind of coated tablets, and described coating is covered with uncoated tablet, and the further like this mechanical characteristics that improves tablet keeps simultaneously or further improves solvability.This is applicable to multilayer tablet highly beneficially, and the mechanical characteristics that has more elastic layer like this can transfer to the rest part of tablet by this coating, thereby with the advantage and the advantages that has more elastic layer of coating.Really, mechanical constraint has improved the mechanical integrity of tablet like this by this coating transmission.Therefore in one embodiment of the invention, tablet can apply so that tablet can moisture absorption or only with very slow speed moisture absorption.This coating is also enough firm, and the medium mechanical shock that makes this tablet be stood in use, packing and transportation only is to cause very low-levelly breaking or wearing and tearing.At last, the preferably brittle so that tablet of this coating is broken rapidly when standing strong mechanical shock.Further advantageously, coating material dissolves under alkaline condition, or is easy to use tensio-active agent emulsification.Avoided like this in the wash(ing)cycle process, seeing resistates in the window at front-loading washing machine, and avoided the not dissolved particles or the deposition of agglomerate on the laundry load of coating material.

Water solubility is measured according to the test procedure that is entitled as " standard method of test of measuring water solubility " among the ASTM E1148-87.

The fusing point of this coating material is preferably 40-200 ℃.

Coating can be used in many ways.Two kinds of preferred coating methods are a) to apply and b with melting material) with the solution coating of this material.

In a), coating material applies being higher than under the temperature of its fusing point, solidifies on tablet then.At b) in, coating is used with solution, stays adherent coating after the described solvent seasoning.Basically insoluble material can for example be administered on the tablet by spraying or dipping.Usually when being sprayed to melting material on the tablet, it is frozen into adherent coating rapidly.If be impregnated into tablet in the melting material and taking-up subsequently, cooling causes the rapid solidification of coating material equally fast.In the solidification stages process, coating experiences some internal stress (for example cooling is shunk) and external stress (for example tablet is lax).This often causes some defective in structure, for example when the edge breaks that coating material is too crisp can not stand these mechanical stresses the time, as situation about only being made by the component of solidifying under 25 ℃ when coating.Really, this coating preferably comprises a kind of component of liquid that is under 25 ℃.It is believed that this liquid ingredient can make coating stand and absorb mechanical stress better by making coating structure have more flexibility.25 ℃ down for the component of liquid preferably to be lower than 10 weight % of coating, more preferably less than 5 weight %, most preferably be lower than the ratio adding coating material of 3 weight %.25 ℃ down for the component of liquid preferably to surpass 0.1 weight % of coating, more preferably surpass 0.3 weight %, most preferably surpass the ratio adding coating material of 0.5 weight %.Further preferably in coating, add fortifying fibre with this structure of further enhancing.

Preferably, this coating comprises a kind of crystalline texture.Should be appreciated that, by crystallization, this coating comprise a kind of in envrionment temperature (25 ℃) down for the solid material and have a kind of structure that shows some order.This can pass through conventional crystallography technology from one's body at material usually, detects as x-ray analysis.In a preferred embodiment, the material that forms crystalline texture can cocrystallization or only is the not essential component part cocrystallization of liquid with above-mentioned down at 25 ℃.Really, this not essential component preferably keeps liquid applying at this under 25 ℃ in crystalline texture, provides snappiness and to the patience of mechanical stress to this structure like this.In another embodiment, down can advantageously in the washing clothes process, have functionally, the silicone oil or the spice oil of foam inhibition effect for example are provided for the not essential component of liquid at 25 ℃.

Except being the not essential component of liquid down at 25 ℃, this coating comprises other material.Suitable coating material is a dicarboxylic acid for example.Specially suitable dicarboxylic acid be 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 composition thereof.Hexanodioic acid most preferably.

Obviously, fusing point is lower than 40 ℃ insoluble basically material and can not fully solidifies at ambient temperature, and has been found that fusing point surpasses about 200 ℃ material and can not actually use.Preferably use fusing point to surpass 90 ℃ acid such as nonane diacid, sebacic acid, dodecanedioic acid.In a preferred embodiment, have been found that it is specially suitable that fusing point surpasses 145 ℃ acid such as hexanodioic acid.

" fusing point " is meant the temperature when this material becomes clarified liq when for example slowly heating in kapillary.

According to the present invention, can use the coating of any desired thickness.In most of the cases, this coating is the 1-10% of tablet weight, preferred 1.5-5%.

The tablet coating is stone and provide to tablet and to add intensity.

At 25 ℃ of ester, monocarboxylic acid, paraffin, triactin, spices or basic solutions that comprise down polyoxyethylene glycol, thermal oil, silicone oil, dicarboxylic acid for the example of the not essential component of liquid.At 25 ℃ is down the approaching material that forms crystalline texture of structure optimization of the not essential component of liquid, and this structure can excessively not broken like this.In a most preferred embodiment, crystalline texture can name of an article Coasol by hexanodioic acid ^TMAvailable from making for the component of liquid (a kind of blend of the diisobutyl ester of pentanedioic acid, succsinic acid and hexanodioic acid) down of Chemoxy International at 25 ℃.Use this in hexanodioic acid the advantage of finely disseminated component provide snappiness.Coasol is passed through in the disintegration that should be noted that hexanodioic acid ^TMIn the adipic acid ester content and further improve.

Coating breaking when washing can promote by add a kind of disintegrating agent in coating.This disintegrating agent expands immediately when contact water and coating is broken into small pieces.This has improved the dissolving of coating in washing lotion.This disintegrating agent is with the highest by 30%, preferred 5-20%, and most preferably the amount of 5-10 weight % is suspended in the coating melt.Possible disintegrating agent is described in handbook of pharmaceutical excipients (Handbook of Pharmaceutical Excipient) (1986).The example of suitable disintegrants comprises starch; Natural, modification or pregelatinized starch, starch Sunmorl N 60S; Natural gum: agaropectin, guar gum, tracasol, POLY-karaya, pectin, tragacanth gum; Croscarmylose sodium, polyvinylpolypyrrolidone, Mierocrystalline cellulose, carboxymethyl cellulose, Lalgine and salt thereof, comprise polyacrylic ester, polymeric cationic amino acid such as poly-L-Lysine that sodium alginate, silicon-dioxide, clay, Polyvinylpyrolidone (PVP), soybean polysaccharide, ion exchange resin, the polymkeric substance that comprises positively charged ion (as quaternary ammonium) group, amine replace, PAH hydrogen chloride salt, and composition thereof.

According to the present invention, coating comprises a kind of Zeo-karb.Really find that this Zeo-karb is specially suitable disintegrating agent, and compare with anionite-exchange resin and to be more preferably.Really find, anionite-exchange resin usually since in coating procedure the thermolysis during use produce a kind of so-called " fish raw meat " smell.Use can prevent this " fish raw meat " smell according to Zeo-karb of the present invention, keeps disintegration properties simultaneously.

In a preferred embodiment, this coating comprises acid such as hexanodioic acid and a kind of clay such as the wilkinite that a kind of temperature of fusion is at least 145 ℃, this clay is used as disintegrating agent and makes the structure of hexanodioic acid more help the water infiltration like this, thereby has improved the dissemination of hexanodioic acid in water medium.Clay preferably has and is lower than 75 μ m, more preferably less than the particle diameter of 53 μ m, can obtain required effect like this on sour structure.Wilkinite preferably.Really, this sour fusing point makes the plain disintegrating agent of traditional fibre experience thermolysis in coating procedure, and the discovery of this clay is more thermally-stabilised.In addition, traditional Mierocrystalline cellulose disintegrating agent such as Nymcel ^TMDiscovery becomes brown under these temperature.

In another preferred embodiment, this coating also comprises fortifying fibre.Have been found that this fiber can further improve coating also reduces the defective of breaking as far as possible to the patience of mechanical stress appearance.For structure strengthens, this fiber preferred length is at least 100 μ m, more preferably is at least 200 μ m, most preferably is at least 250 μ m.The length of this fiber preferably is lower than 500 μ m, more preferably less than 400 μ m, most preferably is lower than 350 μ m, can not influence the dispersion of this coating in water medium like this.The material that can be used for these fibers comprises viscose rayon, natural nylon, synthetic nylon (polyamide 6 and 6,6 types), acrylic acid series material, polyester, cotton and derivatived cellulose such as CMC.Most preferably with trade(brand)name Solka-Floc ^TMAvailable from Fibers Sales ﹠amp; The cellulose materials of Development.Should be noted that these fibers do not need precompression usually when strengthening coating structure.These fibers are preferably to be lower than coating 5 weight %, more preferably less than the amount adding of 3 weight %.The add-on of these fibers is preferably more than the 0.5 weight % of coating, more preferably more than the 1 weight %.

A kind of preferred method that is used to prepare tablet of the present invention may further comprise the steps:

(a) form nuclear by the compression granulated material, described granulated material comprises tensio-active agent and detergent builders;

(b) coating material is administered on the nuclear, described coating material is a melt form;

(c) make the fusion coating material solidification;

Be characterised in that described coating comprises a kind of ion exchange resin.

Another preferred method that is used to prepare tablet of the present invention may further comprise the steps:

(a) form nuclear by the compression granulated material, described granulated material comprises tensio-active agent and detergent builders;

(b) coating material is administered on the nuclear, described coating material is dissolved in solvent or the water;

(c) make the evaporation of solvent or water;

Be characterised in that described coating comprises a kind of ion exchange resin.

This tablet can comprise the component of spices, tensio-active agent, enzyme, washing composition and so on.The typical tablet composition that is used for the preferred embodiment of the invention for example is disclosed in pending trial european patent application № 96203471.6,96203462.5,96203473.2 and 96203464.1.Below specifically provide the composition in the composition that enters detergent tablet or other washing composition form such as liquid or granula usually.

Zeo-karb

Preferable material is a Zeo-karb, for example is described in Kirk-Othmer encyclopedia of chemical technology (Encyclopedia of Chemical Technology) usually, the 4th edition, and 14 volumes, 738-740 page or leaf.The material of this paragraph is incorporated the present invention into as a reference at this:

Strong acid.Strong-acid cation-exchange resin has the sulfonic acid group-SO that is connected on the insoluble polymer matrix ₃H.Comprise other cationic liquid if functional group is hydrogen form and resin contact, hydrogen ion just leaves the solid phase and enters liquid phase, because their are substituted by the positively charged ion from liquid phase, for example

This liquid phase does not have the functional group of sodium ion and resin to change into sodium salt.Polyvalent cation is removed in a similar manner.Must all keep neutral charge in mutually at liquid phase and solid.

Always not requiring resin is hydrogen ion form with the absorption positively charged ion, in the time of especially will avoiding the pH value variation of liquid phase (in addition referring to hydrogen ion activity).For example, in family and industrial occasions, water softening is undertaken by the resin that uses the sodium ion form.

Sodium ion is replaced from resin by calcium ion, and for this reason, this resin has bigger selectivity.

In many industrial occasions, strong-acid cation-exchange resin uses the liquid that comprises low concentration of salt with processing with hydrogen form.

This so-called salt division reaction.Resin to the selectivity of sodium ion greater than to hydrionic selectivity.Negatively charged ion is removed with anionite-exchange resin in a similar manner.

Ion exchange reaction is a reversible.Regeneration step reverts back to ionic species before adsorption step with resin.The reversibility of reaction makes resin repeatedly use before considering replacing.Strong-acid cation-exchange resin is replied with dilute hydrochloric acid [7647-01-0] or sulfuric acid [8014-95-7] and is hydrogen, H ⁺Form.Sometimes use other mineral acid.But before using other acid, must take into full account safety, cost and treatment process.Acid concentration is generally 4%.The design of technology, system and the potentiality that form this sour insoluble salt are depended in use higher or low concentration.

Weak acid.Weakly acidic cationic exchanger resin has the hydroxy-acid group-COOH that is connected on the polymeric matrix.Although general not as strong resin in process application, these resins are included in many systems, wherein can advantageously use higher operational capability and bigger easy reproducibility.

Weakly acidic cationic exchanger resin can not divide neutral salt such as sodium-chlor [7647-14-5] basically.On the other hand, if ionogen is highly basic and faintly acid salt, exchange is favourable.

The na form of weak acid resin has the unusual highly selective to divalent cation in neutral, alkaline and weakly acidic solution.

Selectivity is so big, and the reaction that makes resin return back to the sodium ion form does not use the sodium chloride solution of any concentration to carry out.Preferred replacement scheme is with diluted acid regeneration, to use dilute sodium hydroxide [1310-73-2] that the gained hydrogen ion form is changed into the sodium ion form subsequently.

Commercially available Zeo-karb

Strong-acid cation-exchange resin

These resins are generally by forming with functionalized insoluble poly-(vinylbenzene-Vinylstyrene) multipolymer of sulfonic acid group.Sulfonic acid group can sour form or is existed with the salt with the metal counter ion.Many examples of these materials can be buied; By Rohm ﹠amp; The exemplary that Haas sells is: Amberlite  IR-120 (+), Amberlite  IR-120 (+) na form and Amberlite  IRP-169.Can be Dowex  50WX8-100, Dowex  HCR-W2 available from other example of Dow Chemical.The kind of several chemical aspect by changing resin such as sulfonation degree, degree of crosslinking, counter ion or be included in any other monomeric character in the polymerization procedure can be prepared other example to be given in the optimum performance in the application.

Weakly acidic cationic exchanger resin:

These resins are generally suitable alkenyl-carboxylic (as acrylic or methacrylic acid) and form with the multipolymer of Vinylstyrene.Hydroxy-acid group can sour form or is existed with the salt with the metal counter ion.Many examples of these materials can be buied; Exemplary is: Amberlite  IRP-64 (Rohm ﹠amp; Haas), Dowex  CCR-3 (+) (Dow Chemical).Other example can be prepared to be given in the optimum performance in the application as being included in the monomeric consumption in the polymerization procedure and the kind of kind, degree of crosslinking or counter ion in several chemical aspect by changing resin.

Mixed functionality:

Sometimes, Zeo-karb can comprise weak acid and strong acid functionality simultaneously.These resins are not easy to be referred to above resin, but within the scope of the invention.

The strong-acid cation-exchange resin of basic metal or alkaline-earth metal salt form finds it is to the most effective resin of tablet application.

The physical property of Zeo-karb:

Particle diameter:

For most of occasions, ion exchange resin adopts particle diameter to surpass 300 microns bead.But in some occasion, the preferred material that uses with low particle diameter.The particle diameter common use that descends for example is described in EP837110 (Rohm ﹠amp; Haas) suitable grinding plant carries out.For the present invention, the resin preferred powder is broken to and is lower than 200 microns median size.More preferably be crushed to and be lower than 100 microns particle diameter.In some occasion, resin can prepare the particle that need not to grind to obtain having preferable particle size under special conditions.

Moisture content:

The moisture content of resin can be determined by the step that is described in Kirk-Othmer encyclopedia of chemical technology (the 4th edition, 14 volumes, 755-756 page or leaf).For the present invention, resin uses the routine techniques drying, preferably is lower than 25% moisture content.More preferably, moisture content is lower than 12%.

The example that has the commercially available Zeo-karb of small particle size (being lower than 150 microns) and low moisture content (being lower than 12%) is simultaneously sold with title Purolite  C100NaMR (sodium salt of sulfonated polystyrene-divinyl benzene copolymer) and Purolite  C100CaMR (calcium salt of sulfonated polystyrene-divinyl benzene copolymer) by Purolite.Produce these materials and be used for pharmaceutical industries, apply disintegrating agent according to effective tablet of the present invention but also be used for preparation with the processing blood illness.

The highly soluble compound

Tablet can comprise the highly soluble compound.This compound can be by mixture or by single compound formation.The highly soluble compound is defined as follows:

Be prepared as follows the solution of the specific compound that comprises deionized water and 20 grams per liters:

1. 20 cuts being decided compound is placed in the Sotax beaker.This flask is placed in the thermostatic bath that is set at 10 ℃.Ship propeller formula agitator is placed in this beaker so that the bottom of agitator on the bottom of Sotax beaker 5 millimeters.The speed of rotation of mixing tank is set at 200 rev/mins.

2. 980 gram deionized waters are added the Sotax beaker.

3. after adding entry 10 seconds, use conductivity meter to measure the electric conductivity of this solution.

4. repeating step 3 when 20,30,40,50 seconds, 1 minute, 2 minutes, 5 minutes and 10 minutes after step 2.

5. use the observed value of in the time of 10 minutes, being got as plateau value or maximum value.

According to the present invention, it is peaked 80% if the electric conductivity of this solution reaches at (from finishing when this compound adds deionized water) within 10 seconds, and this specific compound is highly soluble so.Really, if monitor electric conductivity by this way, electric conductivity reaches a platform after certain hour, and this platform is considered to maximum value.This compound is preferably the flowable mass form of being made up of solid particulate under 10-80 easy to use ℃ temperature, but can use other form such as lotion or liquid.

The example of highly soluble compound comprises diisobutyl benzene sulfonic acid sodium salt (DIBS) or toluenesulfonic acid sodium salt.

Adhesive attraction

Tablet can comprise a kind of compound that the detergent based plasmid shape material that is used to form tablet is had adhesive attraction.This adhesive attraction to the detergent based plasmid shape material that is used to form tablet or tablet layer is characterised in that tablet or the layer required power of destruction based on the described washing composition matrix of suppressing under the controlled compression condition.For given power, high tablet or layer intensity represent that granula highly adheres to each other when being compressed, therefore strong adhesive attraction has taken place.The method of assessment tablet or layer intensity (being also referred to as the diameter rupture stress) is at pharmaceutical dosage forms: provide in the tablet (Pharmaceutical dosage forms:tablets) (volume 1, people such as H.A.Lieberman edits, publication in 1989).The tablet of the tablet of the former basic powder of the compound of adhesive attraction by will not having adhesive attraction or layer intensity and the powdered mixture that comprises this compound with adhesive attraction of 97 parts of former basic powder and 3 parts or layer intensity compare measures.This compound with adhesive attraction does not preferably have the form of water (water-content is lower than 10% (preferably being lower than 5%)) to add matrix with a kind of basically.Charge temperature is 10-80 ℃, more preferably 10-40 ℃.

Under 3000 newton's given force of compression, if have the tablet of 50 gram washing composition granulated material weight and 55 mm dias, compound by existence 3% in basic granulated material with adhesive attraction, improve its tablet tensile strength 30% (preferred 60%, more preferably 100%) more than, this compound is defined as the adhesive attraction that has granulated material in the present invention so.

An example with compound of adhesive attraction is two iso-alkyl benzene sulfonic acid sodium salts.

If integrate a kind of highly soluble compound that in addition granulated material that is used for tablet or layer is had adhesive attraction, wherein said tablet or layer form by the granulated material that compression comprises tensio-active agent, and tablet or the solvency action of layer in the aqueous solution obviously improve so.In a preferred embodiment, at least 1 weight % of tablet or layer is by the highly soluble compound formation, more preferably at least 2%, even more preferably at least 3%, most preferably the tablet of at least 5 weight % or layer are by this highly soluble compound formation that granulated material is had adhesive attraction.Should be noted that the composition that comprises highly soluble compound and tensio-active agent is disclosed in EP-A-0524075, described composition is a kind of liquid composition.

Compare with conventional tablet, the highly soluble compound that granulated material is had an adhesive attraction can access a kind ofly to has under the constant compression force than high tensile or the tablet that has equal tensile strength under low force of compression.Usually, the tensile strength of whole tablet surpasses 5kPa, preferably surpasses 10kPa, more preferably, in the laundry occasion, surpasses 15kPa, even more preferably surpasses 30kPa, most preferably surpasses 50kPa, especially washes the dishes or the automatic bowl occasion being used for; And tensile strength is lower than 300kPa, preferably is lower than 200kPa, more preferably less than 100kPa, even more preferably less than 80kPa, most preferably is lower than 60kPa.Really, in the laundry occasion, tablet should ratio as by compression less in the automatic bowl occasion, easier like this acquisition dissolving, therefore in the laundry occasion, tensile strength preferably is lower than 30kPa.

Can produce like this have can be suitable with the solidity of conventional tablet or mechanical endurance solidity and the tablet or the layer of mechanical endurance, thereby make tablet or the not too easier dissolving of compacting of layer simultaneously.In addition,, further promoted the dissolving of tablet or layer, caused a kind of synergy of being convenient to dissolve tablet of the present invention because this compound is a highly soluble.

Tablet is made

Which floor this tablet can comprise.With regard to the preparation individual layer, this layer can be thought tablet itself.

Detergent tablet can be simply by mixing solids component and making at conventional this mixture of tabletting machine compacting that for example is used for pharmaceutical industries.Preferably, basal component, especially the gelling tensio-active agent uses with granular form.Any liquid component, for example tensio-active agent or froth suppressor can add in the solid particulate composition in a usual manner.

Especially for laundry tablets, the composition of washing assistant and tensio-active agent and so on is spraying drying and compacting under suitable pressure subsequently in a usual manner.Preferably, be lower than 100000 newton,, even, most preferably be lower than 3000 newton's the system of defeating more preferably less than 5000 newton more preferably less than 50000 newton according to tablet use of the present invention.Really, the most preferred embodiment is the tablet that is applicable to laundry that a kind of use is lower than 2500 newton's the system of defeating, but also can for example consider to be used for the tablet of automatic bowl, be this automatic bowl tablet be more by compression than laundry tablets usually.

The granulated material that is used to prepare tablet can be made by any granulating or granulation process.An example of this technology be spraying drying (and stream or Countercurrent Spray Dryer in), obtain 600 grams per liters or lower low volume density usually.Granulated material with higher density can be by carrying out granulation or densification or making by a continuous granulation and densification technology (for example using Lodige  CB and/or Lodige  KM mixing tank) in high-shear batch mixer/tablets press.Any granulated material that other appropriate process comprises liquid bed technology, compaction process (as, roll-in), extrude and made by any chemical technology such as flocculation, crystallization, sintering etc.Also any other particle of individual particle, granula, ball or crystal grain.

The component of granulated material can mix by any usual manner.Batch of material is suitable in concrete mixer, Nauta mixing tank, ribbon blender or any other mixing tank for example.In addition, hybrid technique can by with every kind of component by weight to moving belt, and with they blend and carrying out in one or more rotating cylinders or mixing tank.Non-gelling binding agent is sprayable to the mixture of some or all granulated material components.Other liquid component is also sprayable to separately or on the mixture of premix of each composition.To segment flow promotor (separant such as zeolite, carbonate, silica) can preferably add in the granulated material so that this mixture is not too sticking when technology soon finishes after the spraying binding agent.

Tablet can use any compaction process, and as compressing tablet, briquetting or extrude, preferred pressed disc method is made.Suitable device comprises standard single cycle or rotary press (as Courtoy , Korch , Manesty  or Bonals ).The diameter of the tablet of making according to the present invention is preferably the 20-60 millimeter, and preferably at least 35 to the highest 55 millimeters, and weight is the 25-100 gram.The ratio of the height of tablet and diameter (or width) was preferably greater than 1: 3, more preferably greater than 1: 2.The compaction pressure that is used to prepare these tablets need be no more than 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 according to a preferred embodiment of the present invention, the density of tablet is at least 0.9 gram per centimeter ³, more preferably at least 1.0 gram per centimeters ³, and preferably be lower than 2.0 gram per centimeters ³, more preferably less than 1.5 gram per centimeters ³, even more preferably less than 1.25 gram per centimeters ³, most preferably be lower than 1.1 gram per centimeters ³

Multilayer tablet forms by every layer of matrix is placed in the matrix compulsory feeder in succession in rotary press usually.Along with the continuation of technology, hypothallus is therefore compressed together in precompressed and compression stage workshop section, forms multilayer tablet.Some rotary press has been arranged, also may before the whole tablet of compression, compression first add the bed of material.

The hydrotropic solvent compound

Highly soluble compound with adhesive attraction can be incorporated in the detergent tablet, and this compound also is a kind of hydrotropic solvent compound like this.This hydrotropic solvent compound generally can be used to promote surfactant dissolves by avoiding gelling.The following hydrotropic solvent that is defined as of specific compound is (referring to the dispersion Science and Technology (J.DispersionScience and Technology) of S.E.Friberg and M.Chiu, 9 (5﹠amp; 6), the 443-457 page or leaf, (1988-1989)):

1. prepare the solution that comprises 25 weight % specific compounds and 75 weight % water.

2. sad ratio according to 1.6 times of specific compound weight in the solution is added this solution subsequently, the temperature of described solution is 20 ℃.This solution is mixed with ship propeller formula agitator in the Sotax beaker, and described water screw is positioned at about 5 millimeters places on the beaker bottom, and the speed of rotation of described mixing tank is set at 200 rev/mins.

3. if sad dissolving fully, that is, if this solution comprises an only phase, described is liquid phase mutually, and this specific compound is a hydrotropic solvent so.

Should be noted that in a preferred embodiment of the invention described hydrotropic solvent compound is a kind of flowable mass of being made by solid particulate under 15-60 ℃ of operational condition.

The hydrotropic solvent compound comprises the following compound of enumerating:

Enumerating of commercially available hydrotropic solvent can be referring to McCutcheon emulsifying agent and the washing composition published by the McCutcheon branch of Manufacturing ConfectionersCompany.Valuable compounds therefrom also comprises:

1. the nonionic hydrotropic solvent that has following structural formula:

Wherein R is the C8-C10 alkyl chain, and x is 1-15, and y is 3-10.

2. anionic water soluble additive such as basic metal arylsulphonate.This comprises an alkali metal salt of phenylformic acid, Whitfield's ointment, Phenylsulfonic acid and many derivatives thereof, naphthoic acid and various hydrogenation aromatic acids.These examples of substances are derived from the sodium of toluenesulphonic acids, xylene monosulfonic acid, cumene sulfonic acid, naphthane sulfonic acid, naphthene sulfonic acid, methyl naphthalene sulfonic acid, dimethylnaphthalene sulfonic acid, trimethyl-naphthalene sulfonic acid, potassium and ammonium benzene sulfonate.

Other example comprises the salt of dialkyl benzene sulfonic acids, is the straight or branched alkylsulfonate that salt, the alkyl chain of the alkyl benzene sulphonate (ABS) of 3-10 (preferred 4-9) has 1-18 carbon atom as di-isopropyl Phenylsulfonic acid, ethyl-methyl Phenylsulfonic acid, alkyl chain length.

3. the ester of aqueous solvent soluble additive such as alkoxylate glycerine and alkoxylated glyceride, alkoxylate glycerine, alkoxylated fatty acid, the ester of glycerine, polyglycerol ester.Preferred alkoxylated glycerine has following structure:

Wherein 1, m and n be respectively the number of 0-about 20, and the about 2-of l+m+n=is about 60, preferably about 10-is about 45, and R represents H, CH ₃Or C ₂H ₅

Preferred alkoxylated glyceryl ester has following structure:

Wherein R1 and R2 respectively are C _nCOO or-(CH2CHR ₃-O) ₁-H, wherein R ₃=H, CH ₃Or C ₂H ₅And l is the number of 1-about 60, and n is the number of about 6-about 24.

4. for example be described in the polymer water soluble additive of EP636687:

Wherein E is a hydrophilic functional groups,

R is H or C ₁-C ₁₀Alkyl or hydrophilic functional groups;

R1 is H or low alkyl group or aromatic group,

R2 is H or cyclic alkyl or aromatic group.

The molecular weight of this polymkeric substance is generally about 1000-1000000.

5. the hydrotropic solvent that has anomalous structure is as 5-carboxyl-4-hexyl-2-tetrahydrobenzene-1-base sad (Diacid )

The use in the present invention of this compound can further increase the dissolution rate of tablet, because the hydrotropic solvent compound helps for example dissolving of tensio-active agent.This compound can be by mixture or by single compound formation.

Tensile strength

In order to measure the tensile strength of layer, this layer can be thought tablet itself.

According to the shape of the composition and the tablet of starting raw material, can regulate used compaction force and do not influence tensile strength and the disintegration time in washing machine.This technology can be used for preparing the even matter or the multilayer tablet of virtually any size or shape.

For cylindric tablet, tensile strength is corresponding to diameter rupture stress (DFS), and it is a kind of mode of the intensity of representing tablet or layer and is determined by following equation:

Tensile strength=2F/ π Dt

Wherein F is the maximum, force (newton) that causes fail in tension (breaking), and by by Van Kellindustries, the VK 200 tablet hardness testers that Inc. supplies with are measured.D is the diameter of tablet or layer, and t is the thickness of tablet or layer.For non-circular tablet, π D can be alternative by the girth of tablet simply.

(Method Pharmaceutical Dosage Forms:Tablets, the 2nd volume, 213-217 page or leaf).

The tablet that the diameter rupture stress is lower than 20kPa is considered to frangible and often causes some broken tablet to be delivered to the human consumer.Preferred diameter rupture stress is at least 25kPa.

This is equally applicable to tensile strength definition of non-cylindric tablet, is not circular to the vertical cross section of tablet height wherein, and power is along perpendicular to applying on tablet short transverse and the direction to the tablet lateral vertical, and described lateral vertical is in this non-circular cross sections.

Tablet distributes

The distribution speed of detergent tablet can be determined in such a way:

Two tablets of 50 grams of nominal are respectively weighed and put into the divider of Baucknecht  WA9850 washing machine subsequently.The water of supplying with washing machine is set to 20 ℃ of temperature and hardness 21 grains (grain)/gallon, and divider water inlet flow velocity is set at 8 liters/minute.Staying the content of the tablet resistates in the divider checks by connecting washing procedure and will being set at washing procedure 4 (white/colored, short period) wash(ing)cycle.Distribute the percentage resistates to determine as follows:

The former tablet weight in % distribution=remaining weight * 100/

Resistates content time is determined by repeating this step 10, and average residual excess content calculates based on 10 independent observed values.In this strenuous test, the resistates of 40% initial tablet weight is considered to acceptable.It is preferred being lower than 30% resistates, and to be lower than 25% be preferred.

The observed value that should be noted that the water hardness provides with traditional " grain/gallon " unit, and therefore 0.001 mol=7.0 grain/gallons are represented the concentration of calcium ion in solution.

Effervescent

Detergent tablet also can comprise effervescent.

The effervescent effect of this paper definition is meant, because chemical reaction produces carbon dioxide and discharges bubble from liquid between solubility acid source and the alkaline carbonate:

Promptly

Other example in acid plus carbonate source and other effervescent system can be referring to (pharmaceutical dosage forms: tablet, the 1st volume, 287-291 page or leaf).

Except detergent ingredients, effervescent can add in the tablet mixture.In detergent tablet, add the disintegration time that this effervescent can be improved tablet.Its amount is preferably the 5-20% of tablet, most preferably 10-20 weight %.Preferably, effervescent should be with the aggregate of variable grain or with compact, rather than adds with separating particles.

Owing to produce gas by effervesce in tablet, this tablet can have higher D.F.S. and still have the disintegration time identical with the tablet that does not have effervescent effect.Keep identical with the tablet that does not have this effect if having the D.F.S. of the tablet of effervescent effect, the disintegration of tablet with effervescent effect is faster.

Can further help dissolving by the compound that uses sodium acetate or urea and so on.Enumerating also of suitable dissolution aids can be referring to pharmaceutical dosage forms: tablet, roll up 1, the 2 edition, and edit ISBN 0-8247-8044-2 by people such as H.A.Lieberman.

Detersive surfactant

Tensio-active agent is generally comprised within the detergent composition.The dissolving of tensio-active agent promotes by adding the highly soluble compound.

Amount that can about 1-55 weight % is used for the indefiniteness example of this tensio-active agent, comprises conventional C ₁₁-C ₁₈Alkylbenzene sulfonate (" LAS ") and primary, side chain and random C ₁₀-C ₂₀Alkyl-sulphate (" AS "), has structural 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 wherein at least about 7, preferably at least about 9 integer, and M is water solubilising positively charged ion, especially sodium, unsaturated vitriol such as oleyl sulfate, C ₁₀-C ₁₈Alkyl alkoxy sulfate (" AE _xS "; Especially C EO 1-7 ethoxy sulfate), ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (especially EO 1-5 ethoxy carboxylate), C ₁₀-C ₁₈Glyceryl ether, C ₁₀-C ₁₈Alkylpolyglycosides and poly-glycosides of corresponding sulphating and C ₁₂-C ₁₈α-sulfonated fatty acid ester.If desired, also can comprise conventional nonionic and amphoterics such as C in the total composition ₁₂-C ₁₈Alkylethoxylate (" AE ") comprises so-called narrow peak alkylethoxylate and C ₆-C ₁₂Alkyl phenolic alkoxy thing (especially ethoxylate and mixing oxyethyl group/propoxy-), C ₁₂-C ₁₈Trimethyl-glycine and sultaine (" sultaine "), C ₁₀-C ₁₈Amine oxide and analogue.Also can use C ₁₀-C ₁₈N-alkyl polyhydroxy fatty acid amide.Exemplary comprises C ₁₂-C ₁₈The N-methyl glucose amide.Referring to WO9206154.Other sugared deriving surface promoting agent comprises N-alkoxyl group polyhydroxy fatty acid amide, as C ₁₀-C ₁₈N-(3-methoxy-propyl) glucamide.For low foam, can use the N-propyl group to N-hexyl C ₁₂-C ₁₈Glucamide.Also can use C ₁₀-C ₂₀Conventional soap.High if desired foam can use side chain C ₁₀-C ₁₆Soap.The mixture of negatively charged ion and nonionogenic tenside is particularly useful.Other conventional surfactant is enumerated in standard textbook.In a preferred embodiment, tablet comprises the tensio-active agent of at least 5 weight %, more preferably at least 15 weight %, even more preferably at least 25 weight %, the most preferably tensio-active agent of 35-45 weight %.

Non-gelling binding agent

Non-gelling binding agent can be incorporated in the detergent composition with further promotion dissolving.

If use non-gelling binding agent, suitable non-gelling binding agent comprises synthetic organic polymer such as polyoxyethylene glycol, Polyvinylpyrolidone (PVP), polyacrylic ester and water-soluble acrylic ester multipolymer.Handbook of pharmaceutical excipients (the 2nd edition) has following binding agent classification: gum arabic, Lalgine, Carbomer Xylo-Mucine, dextrin, ethyl cellulose, gelatin, guar gum, hydrogenated vegetable oil 1 type, Natvosol, Vltra tears, Liquid Glucose, magnesium aluminum silicate, Star Dri 5, methylcellulose gum, polymethacrylate, polyvidone (povidone), sodiun alginate, starch and zein.Most preferred binding agent also has active cleaning function in the laundry washing lotion, cationic polymers for example, i.e. ethoxylation hexamethylene-diamine quaternary ammonium compound, two (hexa-methylene) triamine or other is as five amine, the poly-ethyleneamines of ethoxylation, Malaysia acrylic acid polymer.

Non-gelling binder material preferably sprays and therefore has and is lower than 90 ℃, preferably is lower than 70 ℃, even preferably is lower than 50 ℃ suitable melting temperature, can not damage or decompose other activeconstituents in the matrix like this.Most preferably can the fusion form non-aqueous liquid binding agent (that is, not being aqueous solution form) of spraying.But they are also by the dried solid binder that enters matrix but have adhesive property in tablet that adds.

The consumption of non-gelling binder material is preferably the 0.1-15% of composition, more preferably less than 5%, especially is lower than 2 weight % of tablet when it is non-laundry active substance.

Gelling binding agent such as nonionogenic tenside preferably avoid being liquid or fusion form.Nonionogenic tenside and other gelling binding agent also are not precluded within outside the composition, but they are preferably as the granulated material component and on-liquid is worked in the detergent tablet.

Washing assistant

Detergent builders can randomly be included in the composition of this paper to help the control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant is usually used in the fabric laundry composition to help to remove particulate soil.

The content of washing assistant changes broad according to the end-use of composition.

Inorganic or contain polyphosphate (tri-polyphosphate, pyrophosphate salt and vitreous state polymer metaphosphate are specifically arranged), phosphonate, phytic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and the silico-aluminate that P detergent use washing assistant includes, but is not limited to basic metal, ammonium and alkanol ammonium.But nonphosphate builders needs in some occasion.Importantly, even the composition of this paper is good as performance astoundingly in the presence of the Citrate trianion or in what is called " inferior helping washed (the underbuilt) " occasion may come across zeolite or layered silicate washing assistant the time at so-called " weak " washing assistant (comparing with phosphoric acid salt).

The example of silicate-like builder is an alkalimetal silicate, particularly its SiO ₂: Na ₂The O ratio is 1.6: 1-3.2: those in 1 scope and layered silicate licensed to the lamina sodium silicate described in the United States Patent (USP) 4664839 of H.P.Rieck as on May 12nd, 1987.NaSKS-6 is the trade mark (abbreviating " SKS-6 " in this article as) by the crystalline layered silicate of Hoechst company supply.Be different from zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has the δ-Na of layered silicate ₂SiO ₅Form.It can prepare by the method that for example is described in German patent DE-A-3417649 and DE-A-3742043.SKS-6 is the layered silicate that highly is preferred for herein, but other this class layered silicate, as have general formula NaMSi _xO _2x+1YH ₂Those layered silicates of O can be used for the present invention, and wherein M is sodium or hydrogen, and x is 1.9-4, preferred 2 number, and y is 0-20, is preferably 0 number.From various other layered silicates of Hoechst company be included as α-, β-and NaSKS-5, NaSKS-7 and the NaSKS-11 of γ-form.As mentioned above, δ-Na ₂SiO ₅(NaSKS-6 form) most preferably is used for this.Other silicate, for example Magnesium Silicate q-agent also can use, and it can be used as crisp dose in granular recipe, as the stablizer of oxygen bleaching agent with as the component in the foaming hierarchy of control.

The example of carbonate builders is alkaline earth and alkaline carbonate, and for example the German patent application № 2321001 on November 15th, 1973 is disclosed.

The silico-aluminate washing assistant can be used for the present invention.The silico-aluminate washing assistant is particularly important in the heavy duty detergent granular detergent composition of supply at present, and can be the important washing assistant composition in the liquid detergent formula.The silico-aluminate washing assistant comprises those with following experience structural formula:

M _z(zAlO ₂) _y]·xH ₂O

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

Useful aluminosilicate ion exchange material can be buied.These silico-aluminates can be crystalline or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.A kind of method for preparing aluminosilicate ion exchange material is disclosed in the United States Patent (USP) 3985669 of authorizing people such as Krummel on October 12nd, 1976.The preferred synthetic crystallization aluminosilicate ion exchange material that can be used for this can name of an article Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X obtain.In an especially preferred embodiment, the crystal aluminosilicate ion-exchange material has following structural formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] _xH ₂O

Wherein x is about 20-about 30, especially about 27.This material is called Zeolite A.Dehydration zeolite (x=0-10) also can be used for this paper.The particle diameter of preferred silico-aluminate is about 0.1-10 micron.

Be applicable to that organic detergent washing assistant of the present invention includes, but is not limited to various multi-carboxylate's compounds." multi-carboxylate " used herein is meant to have a plurality of carboxylate groups, the compound of preferred at least 3 carboxylate groups.The multi-carboxy acid salt washing agent generally can sour form add composition, but also can the neutralized salt form add.If use with salt form, basic metal such as sodium, potassium and lithium or alkanol ammonium salt are preferred.

The multi-carboxy acid salt washing agent comprises various useful materials.The important multi-carboxy acid salt washing agent of one class comprises the ether multi-carboxylate, comprises oxygen di-succinate, for example is disclosed in the United States Patent (USP) 3128287 of authorizing Berg on April 7th, 1964 and authorizes people's such as Lamberti United States Patent (USP) 3635830 on January 18th, 1972.Authorize " TMS/TDS " washing assistant in people's such as Bush the United States Patent (USP) 4663071 in addition referring on May 5th, 1987.Suitable ether carboxylate also comprises ring compound, and alicyclic compound especially is as described in United States Patent (USP) 3923679,3835163,4158635,4120874 and 4102903 those.

Other useful detergent use washing assistant comprises the multipolymer, 1 of ether hydroxypolycarboxylic acid salt, maleic anhydride and ethene or vinyl methyl ether, 3,5-trihydroxybenzene-2,4, various basic metal, ammonium and the substituted ammonium salt of 6-trisulfonic acid and carboxymethyl oxygen base succsinic acid, polyacetic acid such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and multi-carboxylate such as mellitic acid, succsinic acid, oxygen di-succsinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyl oxygen base succsinic acid and soluble salt thereof.

Citrate trianion washing assistant such as citric acid and soluble salt thereof (particularly sodium salt) are because of it can derive from the multi-carboxy acid salt washing agent that renewable resources and biodegradable become the particularly important in the efficient liquid washing composition.Citrate trianion also can be used in the granular composition, particularly mixes use with zeolite and/or layered silicate washing assistant.Oxygen di-succinate also is useful especially in this composition and mixture.

What also be applicable to detergent composition of the present invention is 3,3-dicarboxyl-4-oxa--1, and 6-adipate and related compound thereof are disclosed in and authorized in the United States Patent (USP) 4566984 of Bush on January 28th, 1986.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and salt thereof.Particularly preferred this compounds is a laurylene base succsinic acid.The specific examples of succinate washing assistant comprises: lauryl succinate, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinate and analogues.The lauryl succinate is a preferred washing assistant wherein, and is described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.

Other suitable multi-carboxylate is disclosed in the United States Patent (USP) 4144226 of authorizing people such as Crutchfield on March 13rd, 1979 and the United States Patent (USP) 3308067 of authorizing Diehl on March 7th, 1967.In addition referring to the United States Patent (USP) 3723322 of Diehl.

Lipid acid such as C ₁₂-C ₁₈Monocarboxylic acid also can add composition so that additional washing assistant activity to be provided separately or with aforementioned washing assistant, especially Citrate trianion and/or succinate washing assistant together.The use of lipid acid generally can reduce foam, and this is that formulator will be considered.

In the time can using phosphorus base washing assistant, especially when preparation is used for the soap bar of hand clothes washing operation, can use various alkali metal phosphates tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate as the well-known.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonate (referring to for example United States Patent (USP) 3159581,3213030,3422021,3400148 and 3422137).

SYNTHETIC OPTICAL WHITNER

The detergent composition of this paper can optionally comprise SYNTHETIC OPTICAL WHITNER or comprise SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more activator of bleaching agent.If exist, it is about 30% that the content of SYNTHETIC OPTICAL WHITNER is generally the about 1-of detergent composition, and it is about 20% to be more typically about 5-, especially for fabric washing.If exist, it is about 60% that the content of activator of bleaching agent is generally about 0.1-of the bleaching composition that comprises SYNTHETIC OPTICAL WHITNER+activator of bleaching agent, is more typically about 0.5-about 40%.

The SYNTHETIC OPTICAL WHITNER that is used for this paper can be textiles cleaning, hard-surface cleaning known at present or become known other cleaning purpose be used for any SYNTHETIC OPTICAL WHITNER of detergent composition.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Perborate bleach such as Sodium peroxoborate (as, one-or tetrahydrate) can be used for this.

The another kind of SYNTHETIC OPTICAL WHITNER that can use ad lib comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this SYNTHETIC OPTICAL WHITNER comprises magnesium salts, 4-nonyl amino-4-oxa-perbutyric acid and the diperoxy dodecanedioic acid of six hydration Magnesium monoperoxyphthalates, inclined to one side chlorine peroxybenzoic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in United States Patent (USP) 4483781 (Hartman, authorized on November 20th, 1984), U.S. Patent application 740446 people such as (submit) Burns, european patent application 0133354 (people such as Banks on June 3rd, 1985, on February 20th, 1985 is open) and United States Patent (USP) 4412934 people such as (, mandate on November 1 nineteen eighty-three) Chung.Highly preferred SYNTHETIC OPTICAL WHITNER comprises that also 6-nonyl amino-6-oxa-crosses caproic acid, for example is described in United States Patent (USP) 4634551 people such as (, on January 6th, 1987 authorized) Burns.

Also can use peroxygen bleach.Suitable peroxy bleaching compound comprises peroxide hydrated sodium carbonate and suitable " percarbonate " SYNTHETIC OPTICAL WHITNER, peroxide hydration trisodium phosphate, peroxide hydration urea and sodium peroxide.Also can use the persulphate SYNTHETIC OPTICAL WHITNER (as, by the commercial OXONE that makes of DuPont).

Preferred percarbonate bleach comprises that median size is the about 1000 microns dried particle of about 500-, the described particle that is no more than about 10 weight % less than about 200 microns and the described particle that is no more than about 10 weight % greater than about 1250 microns.Optionally, percarbonate can scribble silicate, borate or water soluble surfactant active.Percarbonate can be available from various commercial source such as FMC, Solvay and Tokai Denka.

Also can use the SYNTHETIC OPTICAL WHITNER mixture.

Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with activator of bleaching agent, like this (that is, in the washing process process) on-the-spot peroxy acid that forms corresponding to activator of bleaching agent in the aqueous solution.Authorize people's such as Mao United States Patent (USP) 4915854 April 10 nineteen ninety, and the various indefiniteness examples of activator are disclosed United States Patent (USP) 4412934.Nonanoly acyloxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activator are used always, also can use its mixture.Other the typical SYNTHETIC OPTICAL WHITNER and the activator that can be used for this can be in addition referring to United States Patent (USP)s 4634551.

The bleach-activating agent of deriving of amido very preferably has structural formula:

R ¹N (R ⁵) C (O) R ²C (O) L or R ¹C (O) N (R ⁵) R ²C (O) L,

R wherein ¹For containing the alkyl group of about 12 carbon atoms of the 6-that has an appointment, R ²For containing the alkylidene group of about 6 carbon atoms of 1-, R ⁵For H or contain alkyl, aryl or the alkaryl of about 10 carbon atoms of the 1-that has an appointment, and L is any suitable leavings group.Leavings group is meant any group that can cement out from bleach-activating agent the nucleophilic attack of bleach-activating agent because of the all-hydrolytic negatively charged ion.Preferred leavings group is a phenylbenzimidazole sulfonic acid salt.

Preferred example with bleach-activating agent of above structural formula comprises (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate described in the United States Patent (USP) 4634551, (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and composition thereof, incorporates it into the present invention as a reference.

Another kind of bleach-activating agent comprises the United States Patent (USP) 4966723 disclosed benzoxazine type activators of authorizing people such as Hodge October 30 nineteen ninety, incorporates it into the present invention as a reference.Benzoxazine type activator very preferably is:

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

R wherein ⁶For H or contain alkyl, aryl, alkoxy aryl or the alkylaryl group of about 12 carbon atoms of 1-.Lactan activator very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, hendecene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, hendecene acyl group Valerolactim nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and composition thereof.Authorize the United States Patent (USP) 4545784 of Sanderson in addition referring on October 8th, 1985, it discloses acyl caprolactam, comprising the benzoyl caprolactam that is absorbed in the Sodium peroxoborate, incorporates it into the present invention as a reference.

Except oxygen bleaching agent, other SYNTHETIC OPTICAL WHITNER also is known in the art and can be used for the present invention.The non-oxygen bleaching agent that one class has special value comprises the photoactivation SYNTHETIC OPTICAL WHITNER, as sulfonated zinc and/or aluminium phthalocyanine.License to people's such as Holcombe United States Patent (USP) 4033718 referring on July 5th, 1977.If use, detergent composition generally comprises this SYNTHETIC OPTICAL WHITNER of the about 1.25 weight % of about 0.025-, particularly sulfonate zinc phthalocyanine.

If desired, bleaching compounds can utilize manganic compound to come catalysis.This compound be in the art know and comprise for example United States Patent (USP) 5,246,621, United States Patent (USP) 5,244,594, United States Patent (USP) 5,194,416, United States Patent (USP) 5,114,606 and European patent application publication No. 549,271A1,549272A1,544,440A2 and 544, disclosed manganese-based catalyst among the 490A1.The preferred example 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 composition thereof.Other metal matrix bleaching catalyst comprises United States Patent (USP) 4,430,243 and United States Patent (USP) 5,114,611 in disclosed those.In following United States Patent (USP), also reported manganese with various complex compound parts in the application that strengthens on the bleaching effect: 4,728,455,5,284,944,5,246,612,5,256,779,5,280,117,5,274,147,5,153,161 and 5,227,084.

In fact and non-exclusively, can adjust the compositions and methods of the invention, be equivalent to the active bleaching catalyst material of 0.1ppm at least in containing water lotion, to provide, and preferably in washing liquid, provide about 0.1-about 700ppm, the catalyst substance of the about 500ppm of more preferably about 1-.

Enzyme

Enzyme can be included in the present invention prescription, is used for various fabric washing, comprising: remove for example protein-based, carbohydrate-based or triglycerin ester group spot; The dyestuff (refugee dye) that prevents to come off shifts; And be used for fabric and reform.The enzyme that adds comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and composition thereof.The enzyme that also can comprise other kind.They can have any suitable source, as plant, animal, bacterium, fungi and yeast source.But Several Factors is depended in its selection, as pH-activity and/or optimal stability state, thermostability with to the stability of activated detergent, washing assistant etc.In this respect, bacterium or fungal enzyme are preferred, as bacterial amylase and proteolytic enzyme and fungal cellulase.

The add-on of enzyme is enough to provide the highest about 5 milligrams of weight usually, more common about 0.01-3 milligram organized enzyme/gram composition.Unless refer else, it is about 5% that the present composition generally comprises about 0.001-, the commercial enzyme preparation of preferred 0.01-1 weight %.Proteolytic enzyme amount in this commodity preparation is enough to provide the activity of 0.005-0.1 Anson unit (AU)/gram composition usually.

The suitable example of proteolytic enzyme is a subtilysin, and it is the specific bacterial strain generation by subtilis (B.subtilis) and Bacillus licheniformis (B.Licheniforms).Another suitable proteolytic enzyme is produced by bacillus (Bacillus) bacterial strain, and its activity in whole pH is the 8-12 scope is the highest, and is developed and sell with trade(brand)name ESPERASE by Novo Industries A/S.The preparation of this kind of enzyme and similar enzyme has description in the English Patent 1243784 of Novo.Be applicable to that the commercially available proteolytic enzyme of removing protein-based spot comprises by Novo IndustriesA/S (Denmark) with trade(brand)name ALCALASE and SAVINASE with by International Bio-Synthetics, those that Inc (Holland) sells with trade(brand)name MAXATASE.Other proteolytic enzyme comprises protease A (open on January 9th, 130756,1985 referring to european patent application) and proteolytic enzyme B (being disclosed in the european patent application 130756 on January 9th, 1985 referring to people such as european patent application of submitting on April 28th, 1,987 87303761.8 and Bott).

Amylase comprises that for example English Patent 1,296, the α-Dian Fenmei, the International Bio-Synthetics that describe among 839 (Novo), the TERMAMYL of the RAPIDASE of Inc. and Novo Industries.

The cellulase that can be used among the present invention comprises bacterium or fungal cellulase.Preferably, their optimal ph is 5-9.5.Suitable cellulase is disclosed in the United States Patent (USP) 4 of authorizing people such as Barbesgoard on March 6th, 1984,435,307, wherein disclose and derived from Humicolainsolens and rotten fungal cellulase of planting trichoderma strain DSM1800 or Aeromonas cellulase 212-position replacement fungi, and the cellulase that from the hepatopancreas of extra large mollush (Dolabella AuriculaSolander), extracts.Suitable cellulase also is disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2.247.832 in.CAREZYME (Novo) is useful especially.

The lipase that is applicable to washing composition comprises by those of Rhodopseudomonas microorganisms, as disclosed Situ Ci Shi Rhodopseudomonas ATCC 19.154 among the GB1372034.In addition referring to the lipase on February 24th, the 1978 disclosed Japanese patent application 5320487.This lipase can derive from the Amano Pharmaceutical Co.Ltd. that is positioned at Japanese Nagoya, and commodity are called Lipase P " Amano ", are designated hereinafter simply as " Amano-P ".Other commercially available lipase comprises the Amano-CES lipase from thickness look bacillus, as derives from the lipolyticum thickness look bacillus varient NRRLB 3673 of the Toyo JozoCo. of Japanese Tagata; Derive from the thickness look bacillus lipase of U.S. U.S.Biochemical Corp. and Dutch Disoynth Co.; And from the lipase of high calamus Rhodopseudomonas.Plant by the lanuginosa corruption that to belong to the LIPOLASE enzyme (in addition referring to EP341947) derive and can derive from Novo be to be used for a kind of preferred fat enzyme of the present invention.

Peroxidase and oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching ", prevent that promptly dyestuff or pigment other matrix to washing lotion of breaking away from from matrix in washing operation from shifting.Peroxidase is known in the art and comprises for example horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro-and bromine peroxide enzyme.The cleaning composition that contains peroxidase is disclosed in for example the pct international patent application WO 89/099813 of O.Kirk (on October 19th, 1989 is open, transfers Novo Industries A/S).

The United States Patent (USP) 3553139 of authorizing people such as McCarty on January 5th, 1971 also discloses the mode in various enzyme materials and the adding synthesis of detergent composition thereof.Authorizing people's such as Place United States Patent (USP) 4101457 and the United States Patent (USP) 4507219 of authorizing Hughes on March 26th, 1985 on July 18th, 1978 also discloses enzyme.The United States Patent (USP) 4261868 of authorizing people such as Hora on April 14th, 1981 discloses enzyme material and the adding in this prescription thereof that can be used for liquid detergent formula.The enzyme that is used for washing composition can adopt the whole bag of tricks to be stablized.The European patent (application publication number 0 199 405, application number 86200586.5) of the Venegas that authorized people's such as Gedge United States Patent (USP) 3600319 on August 17th, 1971 and published on October 29th, 1986 is open and exemplified various enzyme stabilization techniques.The enzyme stabilising system also has description, for example in United States Patent (USP) 3519570.

Other component that is usually used in detergent composition and can adds in the detergent tablet comprises sequestrant, stain remover, anti-soil dirt deposition agent, dispersion agent, froth suppressor, fabric softener, dye transfer inhibitor and spices again.

Below the compound that openly is used for product is advantageously packed at packaging system.

Packaging system can be formed by the flexible materials sheet material.The material that is suitable as flexible sheet material comprises individual layer, co-extrusion or laminated film.These films can comprise various components such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate.Preferably, packaging system is lower than 5 gram/skies/rice by MVTR ²Polyethylene and Bioriented polypropylene co-extrusion film form.The MVTR of packaging system preferably is lower than 10 gram/skies/rice ², more preferably less than 5 gram/skies/rice ²Film (2) can have all thickness.Thickness should be 10-150 μ m usually, preferred 15-120 μ m, more preferably 20-100 μ m, even more preferably 25-80 μ m, most preferably 30-40 μ m.

Wrapping material preferably comprise and have the hypoxemia transmitance, are usually less than 300 centimetres ³/ rice ²/ day, preferably be lower than 150 centimetres ³/ rice ²/ day, more preferably less than 100 centimetres ³/ rice ²/ day, even more preferably less than 50 centimetres ³/ rice ²/ day, most preferably be lower than 10 centimetres ³/ rice ²The isolation layer that is common in wrapping material in/sky.Typical material with this isolation performance comprises Bioriented polypropylene, polyethylene terephthalate, nylon, polyethylene/vinyl alcohol or comprises the laminating material and the SiO of one of these materials _X(Si oxide) or tinsel such as aluminium foil.These wrapping material can produce useful influence to the stability of product when for example storing.

In Packaging Method, use the Packaging Method that is disclosed in WO92/20593 usually, comprise and flow packing or walk around packing (over wrapping).If use these technology, providing can be the longitudinal sealing of fin seal or lap seal, seals first end of this packaging system then with the first end package, seals second end with the second end package subsequently.Packaging system can comprise the instrument of sealing again that for example is described in WO92/20593.Especially, be particularly suitable for using twist thread, cold sealing or tackiness agent.Really, can on the position of contiguous packaging system second end, cold seal strip or adhesive tape be administered on the surface of packaging system, like this this band initial sealing simultaneously and seal this packaging system again.In this case, tackiness agent or cold seal strip can promptly only adhere to the surface on another adhesive surface corresponding to the zone with adhesive surface.This instrument of sealing again also can comprise in order to prevent non-required adherent pad.This pad is described in the WO95/13225 that publishes May 18 nineteen ninety-five.A plurality of pads and a plurality of adhesion material bar also can be arranged.Major requirement is, between the outside of this packing and the inside contact minimum, even after opening this packaging system for the first time.Can use cold sealing, especially cold sealing lattice (grid), cold like this sealing can help to open this packaging system.

Embodiment

Following composition is made by mixing the dried spices and binding agent of adding on material and the subsequent spray.

	% forms
		The dried thing anion surfactant aggregation A anion surfactant aggregation B non-ionic surface active agent aggregation cationic surfactant aggregation activator of bleaching agent aggregation ZnPc sulfonate capsule foam in hibitors phyllosilicate fluorescer sodium carbonate citric acid SODIUM PERCARBONATE chelating agent particle HEDP soil release polymer protease ball cellulase ball lipase ball amylase ball soap spraying thing spices spraying thing binding agent spraying thing that adds amounts to	9.79 22.3 9.13 4.67 6.09 0.027 2.80 9.75 0.115 8.06 4.67 12.3 0.494 0.820 0.363 0.967 0.210 0.350 1.134 1.40 0.561 4.00 100％

Anion surfactant aggregate A comprises 40% anion surfactant, 29% zeolite and 20% yellow soda ash.

Anion surfactant aggregate B comprises 40% anion surfactant, 27% zeolite and 11% yellow soda ash.

The nonionogenic tenside aggregate comprises 25% nonionogenic tenside, the hexamethylene-diamine of ethoxylation more than 7% (quaternary ammonium salt), 36% anhydrous sodium acetate, 20% yellow soda ash and 12% zeolite.

The cats product aggregate comprises 20% cats product and 56% zeolite.

The activator of bleaching agent aggregate comprises 81%TAED, 17% acrylic acid series/toxilic acid based copolymer and 2% water.

Zinc phthalocyanine sulfonate capsule is 10% active.

Froth suppressor comprises 11.5% silicone oil and 88.5% starch.

Layered silicate comprises 95%SKS-6,2.5% water glass-2.0R and 2.5% water.

Fluorescent agent comprises white dyes 47 (70% activity) and white dyes 49 (13% activity).

The sequestrant particle comprises ethylenediamine disuccinate and is 58% activity.

Binding agent is many ethoxylations hexamethylene-diamine (quaternary ammonium salt)

Prepare a series of tablets according to following examples:

45 gram said compositions are added in the cylindric tablet mould of 54 millimeters of diameters, use Lloyd Instruments LR50 test set to compress then with the speed of 10 mm/min.Take out the gained tablet and use following equation to calculate the diameter rupture stress from mould, wherein F causes disruptive institute afterburning (newton), and D is that tablet diameters (rice) and h are tablet height (rice).Use VANKEL VK-200 tablet hardness tester to measure rupturing capacity.Optimize compression load, make that the diameter rupture stress that uses following equation to calculate is 11 (± 1) kPa: $s\left(\mathrm{Pa}\right)=\frac{2F}{\mathrm{\πDh}}$

Prepare a series of similar 11 (± 1) the kPa tablet that is used for following examples according to this mode.

Tablet applies

Hexanodioic acid (du Pont LGA level) is heated to 163 ℃ under gentle agitation, until fusion in thermostatic bath.Under continuously stirring, add disintegrating agent subsequently, obtain the even matter suspension in hexanodioic acid like this.The tablet of as above preparation is immersed in this liquid subsequently, and cooling obtains final coated tablets.

Embodiment

With the wet Zeo-karb Amberlite  IRP-69 that sells of particle size range 100-500 order (that is, being lower than 150 microns) (from Rohm ﹠amp; Haas) in 130 ℃ of baking ovens dry 6 hours.Its amount with 3% in above-mentioned steps is used as disintegrating agent in coating compound, obtaining gross weight is that 48 grams and diameter rupture stress are the tablet of 26kPa.This tablet is immersed in the deionized water under 20 ℃, and it is 5 seconds that coating begins the required timing of disintegration, judges by beginning effervesce from tablet matrix.The tablet smell is joyful, is similar to the spices of preparation.

The comparative example A

To be used as disintegrating agent in coating compound available from Mierocrystalline cellulose disintegrating agent Nymcel  zsb16 amount with 10% in above-mentioned steps of Metsa, obtaining gross weight is that 48 grams and diameter rupture stress are the tablet of 28kPa.The tablet smell is joyful, is similar to the spices of preparation.But when this tablet was immersed in the deionized water under 20 ℃, it was 25 seconds that coating begins the required timing of disintegration, judged by beginning effervesce from tablet matrix.

Comparative Examples B

With the wet anionite-exchange resin Dowex  1X4-400 that sells of particle size range 200-400 order (that is, being lower than 75 microns) (from Rohm ﹠amp; Haas) in 130 ℃ of baking ovens dry 6 hours.Its amount with 3% in above-mentioned steps is used as disintegrating agent in coating compound, obtaining gross weight is that 48 grams and diameter rupture stress are the tablet of 28kPa.This tablet is immersed in the deionized water under 20 ℃, and it is 7 seconds that coating begins the required timing of disintegration, judges by beginning effervesce from tablet matrix.Tablet has fishy smell flavor beastly, may be because resin decomposes the formation that causes amine.

From embodiment as can be seen, small particle size (＜200 microns) Zeo-karb is than the more effective disintegrating agent of the plain disintegrating agent of conventional fibre when producing the rapid disintegration tablet coating under low levels.In addition, they do not have the smell relevant with amine-functionalized anionite-exchange resin, and than more effective on the anionite-exchange resin cost, and more effective than the plain disintegrating agent of conventional fibre under obviously lower content.

Claims (10)

1. coated detergent tablet, described coating comprises a kind of Zeo-karb.

2. according to the coated detergent tablet of claim 1, wherein said coating comprises a kind of component of liquid that is under 25 ℃.

3. according to the tablet of claim 1, wherein said coating also comprises a kind of crystalline texture.

4. according to the tablet of claim 3, the material that wherein forms described crystalline texture is a dicarboxylic acid.

5. according to the tablet of any claim 1 or 4, wherein said coating is made up of hexanodioic acid basically.

6. according to the tablet of claim 1, wherein said coating also comprises fortifying fibre.

7. according to the tablet of claim 1, wherein said Zeo-karb is that particle diameter is lower than 200 microns particle.

8. method for preparing according to the tablet of any above claim, it may further comprise the steps:

(a) form nuclear by the compression granulated material, described granulated material comprises tensio-active agent and detergent builders;

(b) coating material is administered on the nuclear, described coating material is the form of melt;

(c) make the fusion coating material solidification;

It is characterized in that described coating comprises a kind of Zeo-karb.

9. method for preparing according to the tablet of any claim 1-7, it may further comprise the steps:

(a) form nuclear by the compression granulated material, described granulated material comprises tensio-active agent and detergent builders;

(b) coating material is administered on the nuclear, described coating material is dissolved in solvent or the water;

(c) make the evaporation of solvent or water;

It is characterized in that described coating comprises a kind of Zeo-karb.

10. method for preparing tablet according to any claim 8 or 9, wherein said coating comprises the acid that a kind of temperature of fusion is at least 145 ℃.