CN1127525A - Process for preparing washing or detergent extrudates - Google Patents
Process for preparing washing or detergent extrudates Download PDFInfo
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- CN1127525A CN1127525A CN 94192872 CN94192872A CN1127525A CN 1127525 A CN1127525 A CN 1127525A CN 94192872 CN94192872 CN 94192872 CN 94192872 A CN94192872 A CN 94192872A CN 1127525 A CN1127525 A CN 1127525A
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- weight
- premixture
- anion surfactant
- acid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
Abstract
The solubility of extruded washing or detergent agents depends to a large extent upon the form of the anionic surfactants when they are added to the premix to be extruded. In order to improve the solubility of the extrudates, the anionic surfactants are added to the premix only in a solid, powdery or granulated preparation form. Such preparation forms have at least partially an anionic surfactant content of at least 50 % by weight.
Description
The invention relates to the preparation method of solid detergent and sanitising agent or solid detergent or sanitising agent component, wherein use a kind of premixture, this premixture contains the anion surfactant of solid-state form, preferably highly enriched anion surfactant.Improve the rinsing and/or the solubility property of extrudate simultaneously.
Because its compactness shape also causes less surface thus, the solid detergent of high apparent specific gravity or sanitising agent, just on average greater than 500 grams per liters, with the suitable product material ratio of the comparability composition that 300 grams per liter apparent specific gravities are for example only arranged, has less dissolution rate, particularly under 15 ℃ to 60 ℃ low temperature.High apparent specific gravity washing composition similar problem will occur during rinsing in washing machine.
By a kind of preparation method of known high-density extrudate among International Patent Application WO-A-91/02047, under pressure, be extruded into rod solid pre-composition, the rod thing is extruded the back from porous mold and is cut into the pellet with predetermined size with cutter unit.Uniformly and the solid premixture contain softening agent and/or lubricant, under pressure or the input by particular energy make premixture soften and become extrudability.Preferred plasticizer and/or lubricant are tensio-active agent and/or polymkeric substance, and they are preferably with liquid, and pasty state or colloidal form add.Under processing temperature, be liquid nonionic type tensio-active agent and moisture aniorfic surfactant mashed prod for most preferably.This system no longer includes any shearing force after extruding from porous mold, and its viscosity change should make rod can be cut into predetermined size simultaneously.
For the dissolving properties that improves extrudate proposes in International Patent Application WO-A-93/02176, as nonionic surface active agent and softening agent and/or lubricant uses the ethoxylation alcohols and use to prevent that extrudate from hindering when being dissolved in the washing suspension with tight blended form with the structural breakdown agent in extrusion and form gel.By known among the German patent application DE-A-4203031, the solubility property that contains the basic vitriol extrudate of alkane (alkene) trends towards forming gel equally, by adding the alkyl-sulphate of short chain, as C
12-alkyl-sulphate is improved, in a preferred embodiment with short-chain alkyl vitriol with in the aqueous solution form introducing method.
Have now found that opposite with up to now prior art, the dissolving properties of extrudate depends on the form of the anion surfactant that is added greatly in pre-compound.
The objective of the invention is to prepare the extrudate of highdensity washing or cleaning action, under pressure, the solid premixture is squeezed into the rod thing, after rod is extruded from extrusion die, cut into the pellet of predetermined size with parting tool, it is characterized in that containing negatively charged ion and nonionic surface active agent in the premixture, and anion surfactant is introduced in the premixture with the form of solid, powdery or granular preparation individually.Anion surfactant to small part adds with dosage form, and its amount is that base calculates with the preparation, contains 50% (weight) anion surfactant at least.
At International Patent Application WO-A-91/02047, at length narrated the extrusion molding situation among WO-A-93/02176 and the early stage German patent application P 42 35 646.6.The preferred embodiment of the present invention is that premixture is fed to twin screw extruder equidirectional or that turn round continuously in the other direction, and its housing and forcing machine-granulation head can be heated to predetermined extrusion temperature.Premixture under the extrusion screw rod shear action preferably under at least 25 bar pressures (this is relevant with employed device), even can have under the lower pressure of extra high treatment capacity, be extruded into thin rod by extruder head and porous extrusion die, with the cutting knife that rotates extrudate is shredded at last, be preferably shaped to sphere or column type pellet.The length of the aperture of porous extrusion die and bar cutting will be by the size decision of selected pellet in advance.Can produce the pellet of predetermined homogeneous granules size in this embodiment, its granular size of determining is suitable for specific imagination and uses.Usually particle diameter preferably reaches as high as 0.8 centimetre.Important embodiment is to produce millimetre-sized even pellet, as in 0.5 to 5 millimeter scope, preferably is about in 0.8 to 3 millimeter.The length of raw pellets is about 1: 1 to about 3: 1 in an important embodiment.In another preferred version when raw pellets still be plasticity can carry out another time forming process step when moistening; The arm of angle that in this forming step thick extruded stock is existed falls the garden, thereby can obtain the particle of extruding of sphere or substantially spherical at last.In the time of if desired, can use a small amount of dry powder in this step, for example zeolite powder is such as zeolite NaA powder.This forming step can carry out in the habitual nodularization equipment in market.Importantly to guarantee, in this step, can only form a spot of fine particle.Extrudate preferably enters into drying process, as enters fluidized bed dryer.Containing superoxide-SYNTHETIC OPTICAL WHITNER, as the extrudate pellet of the boratory monohydrate of peroxide, can be dry and can not lose active oxygen between 80 ℃ to 150 ℃ entering air themperature.Drying process can be directly carry out behind the extrusion of thick extrudate in addition, promptly is included in balling machine and carries out carrying out before the optional step of moulding.
Only introduce in the premixture by the anion surfactant that the present invention added through the solid preparation.Solid preparation can be Powdered, and also spray-dired and/or granulation contains the more or less composition of high-content anion active agent in specified scheme.In the preferred version of the present invention, with the anion surfactant total, anion surfactant at least 30% (weight), preferably be at least 50%, be to introduce operation with solid, powdery or granular formulations form, wherein be base with the solid preparation, anionic surfactant concentration is at least 50% (weight), is preferably 60 to 100% (weight) and is preferably 70 to 95% (weight) especially.Anion surfactant can exist with single solid preparation form or can be distributed in a plurality of solid preparations fully.For example; the spraying drying pellet that contains one or more anion surfactants; its content be as can being up to 45% (weight), and can be by the pellet of granulation gained or the powder that preferably contains 75% (weight) anion surfactant at least can be used in the premixture.Contain at least 75% (weight) but only use in a kind of particularly preferred scheme of the present invention, and preferably contain the preparation of one or more anion surfactants of at least 80% (weight).The content of anion surfactant in premixture is preferably 5 to 30% (weight), perhaps also can be higher.The anion surfactant of considering lower aq from utilisation technology is relatively poor.
Can adopt sulfonate and sulfate type as anion surfactant.Preferred sulfonate surfactant has C
9-C
13-alkylbenzene sulfonate, alkene sulfonate, that is to say by the mixture of alkene sulfonate and hydroxyalkylated sulfonic acid salt and, for example by C with the two keys of terminal or internal stability
12-C
18The stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate of monoolefine by then making again with alkali or acid hydrolysis sulfonated product with the gaseous sulfur trioxide sulfonation.
By C
12-C
18For example hydrolysis or neutralization and the alkylsulfonate that makes also suit-alkane then through sulfochlorination or sulfoxidation.The ester of alpha-sulfo-fatty acid (sulfonated ester) also suits, hydrogenant Oleum Cocois for example, two salt of the α of palm kernel oil or tallow fatty acids-sulfonated methyl ester and corresponding alpha-sulfo-fatty acid.Other suitable anion surfactant is a sulfonated fatty acid glycerine fat.So-called fatty acid glycerine fat can be regarded as list, two and three fat and composition thereof, and they are with 1 to 3 mole fatty acid esterification or with 0.3 to 2 mole of glycerin triglyceride level is carried out fat group-transfer effect and make by single glycerine for example.Sulfonated products is a kind of mixture of complexity, and it contains monoglyceride, and the sulfonate of glycerine dibasic acid esters and triglyceride level, its sulfonic group are in the α position and/or be interior sulfonic group.Sulfonated soap, sulphate of glyceryl ester, glycerine vitriol, glycerine and soap class are to form with by product.If with saturated fatty acid or the hydrogenant fatty glyceride mixt raw material as method of sulfonating, the control that then depends on method is easy to make the percentage composition of α-alpha-sulfonated fatty acid disalt to bring up to about 60% (weight) component very much.
Suitable sulfated surfactant is a sulfuric acid monoester natural and primary alconol synthetic source, and the preferred basic vitriol of alkane (alkene) is C
12-C
18The sulfate hemiester of Fatty Alcohol(C12-C14 and C12-C18), as the coconut Fatty Alcohol(C12-C14 and C12-C18), tallow Fatty Alcohol(C12-C14 and C12-C18), lauryl alcohol, tetradecyl alcohol, hexadecanol or stearyl alcohol or C
10-C
20-hydroxyl synthol and those secondary alcohol with identical chain length scope.Other preferred alkane (alkene) sulfovinate contains above-mentioned chain length, contain synthetic petroleum chemistry base the straight chained alkyl group those and, their degradation property is similar to the suitable compounds that oiling is learned based raw material.With regard to washing process, C
10-C
18The basic vitriol of alkane (alkene) is preferred especially, and is particularly particularly favourable with washing composition to machine, C
16-C
18Basic vitriol of-alkane (alkene) and low melting point anion surfactant, particularly have lower Kraft point (Krafft point) and in low wash temperature, combining to use as the anion surfactant that presents minimum crystallization trend under the room temperature to 40 ℃ has advantage.Therefore in the preferred embodiment of the invention, washing composition contains the mixture of long-chain and short-chain fat alkyl-sulphate, preferably C
12-C
14Fatty alkyl vitriol or C
12-C
18-fatty alkyl vitriol and C
16-C
18The mixture of fatty alkyl vitriol is C particularly
12-C
16Fatty alkyl vitriol and C
16-C
18The mixture of fatty alkyl vitriol.Be used for the basic vitriol of alkane (alkene) that washing process gives mixture in the preferred version of the present invention, its short-chain alkyl vitriol such as C
12-the alkyl-sulphate or the content of the alkyl-sulphate of short chain more, the total amount in whole used alkane (alkene) hydrocarbon vitriol is 30% (weight) to the maximum.Its feature is not only used saturated alkyl vitriol in another preferred version of the present invention, and use contains the best C of thiazolinyl chain length
16To C
22Unsaturated thiazolinyl vitriol.In this scheme, particularly preferably be and mainly contain C
16Saturated sulfonated Fatty Alcohol(C12-C14 and C12-C18) and mainly contain C
18The mixture of undersaturated sulfonated Fatty Alcohol(C12-C14 and C12-C18), as HD-Ocenol
RThe solid of type (a kind of Henkelk GaA product) or the fatty alcohol mixture of liquid.Wherein the weight ratio of alkyl-sulphate and alkenyl sulfate is 10: 1 to 1: 2, and is particularly about 5: 1 to 1: 1st, preferred.
C straight chain or side chain with 1 to 6 moles of ethylene oxide ethoxylation
7-C
12The sulfuric acid monoester of alcohol, as, the C of the 2-methyl-side chain of 3.5 moles of ethylene oxide (EO) contained
9-C
11Alcohol or contain the C of 2 to 4 EO
12-C
18-Fatty Alcohol(C12-C14 and C12-C18) all suits.Because its high foaming power, the use that is in the suds can only be a minute quantity, for example 1 to 5% (weight).
Other suitable anion surfactant is an alkyl sulfo succinate, its sulfosuccinate or sulfosuccinic ester are also known, and be by sulfo-succinic acid and alcohol, monoesters and/or dibasic acid esters that preferred Fatty Alcohol(C12-C14 and C12-C18) and preferred ethoxylized fatty alcohol are constituted, preferred sulfosuccinic ester contains C
8To C
18-Fatty Alcohol(C12-C14 and C12-C18) group or its mixture.Particularly preferred sulfosuccinic ester contains the Fatty Alcohol(C12-C14 and C12-C18) deutero-Fatty Alcohol(C12-C14 and C12-C18) group by ethoxylation, and considers that by separating Fatty Alcohol(C12-C14 and C12-C18) is nonionic surface active agent (chats face to face as follows and state).Fatty Alcohol(C12-C14 and C12-C18) group wherein is that the Fatty Alcohol(C12-C14 and C12-C18) deutero-sulfosuccinic ester by narrow scope ethoxylation is particularly preferred.The preferred basic succsinic acid of alkane (alkene), in the basic chain of alkane (alkene), contain 8 to 18 carbon atoms or its salt also operable.
The preferred anionic surfactants tensio-active agent is alkylbenzene sulfonate and/or alkane (alkene) basic vitriol, particularly fatty alkyl vitriol.In another preferred version of the present invention, it is characterized in that in premixture, using the benzene sulfonamide acid esters and/or the basic vitriol of alkane (alkene) of 8 to 25% (weight).If sodium alkyl benzene sulfonate is with high density powder form, as have the powder that activity substance content is higher than 85% (weight), for example 90% (weight) is used as independent anion surfactant, then will be particularly advantageous.In another program of the present invention, the basic vitriol of alkylbenzene sulfonate and alkane (alkene), particularly fatty alkyl vitriol was preferably 1.2: 1 with 0.5: 1 to 1.5: 1, especially preferably was used as anion surfactant with 1: 1 weight ratio in premixture.The premixture that does not have alkylbenzene sulfonate also is preferred.In all cases; the basic vitriol of alkane (alkene) is added in the premixture as unique anion surfactant or as one in a plurality of anion surfactants; have the basic sulphate content of alkane (alkene) and be at least 75% (weight); the solid preparation of particularly preferred at least 80% (weight); can be by International Patent Application WO-A-93/04162 or early stage German patent application DE 42 32874 described methods; pass through granulation; randomly simultaneously dry, particularly in fluidized-bed and produce.
Anion surfactant can be with its sodium salt, and the form of sylvite or ammonium salt exists and as organic bases, as single-, two-or the form of the soluble salt of trolamine exist.The preferred anionic surfactants tensio-active agent is with its sodium salt or sylvite, particularly exists with its sodium-salt form.
Except anion surfactant, other composition of premixture is the soap class, and 0.5 to 4% (weight) content is preferably arranged.Suitable soap class is saturated fatty acid soaps class, as lauroleate, and myristate, palmitate or stearate and especially by natural acid, as Oleum Cocois, palm kernel oil or tallow fatty acids, deutero-soap class mixture.Particularly preferably be saturated C in the soap class mixture by 50 to 100% (weight)
12-C
24-fatty acid soaps and 0 to 50% (weight) oleate soap are formed.
Preferably have oxyalkylated as nonionic surface active agent, preferably liquid ethoxylation, particularly contain the primary alconol that average 1 to 30 mole oxyethane (EO) is arranged in 8 to 18 carbon atoms and the every mol of alcohol, therein alcohol groups can be straight chain or on 2, methyl branch is arranged, perhaps can contain just like the straight chain that usually in the oxo process alcohol groups, exists and the form of mixtures of methyl branch group.Particularly with the alcohol of straight chain group ethoxylation of the natural source alcohol that contains 12 to 18 carbon atoms, Oleum Cocois for example, palm kernel oil, 2 to 8 EO of tallow Fatty Alcohol(C12-C14 and C12-C18) or oleyl alcohol and every mol of alcohol average out to are preferred.Preferred ethoxylated alcohol has the C that contains 3EO or 4EO
12-C
14Alcohol contains the C of 7EO
9-C
11Alcohol contains 3EO, 5EO, the C of 7EO or 8EO
13-C
15Alcohol contains 3EO, 5EO, the C of 7EO
12-C
18Alcohol and composition thereof for example contains the C of 3EO
12-C
14The pure and mild C that contains 5EO
12-C
18The mixture of alcohol.The mean value of above-mentioned ethoxylation degree representative statistics can be an integer or mark to specific product.Preferred alcohol ethoxylate have narrow homologue distribute (ethoxylate of close limit, NRE).Other preferred nonionic surfactants particularly contains 11EO, the tallow Fatty Alcohol(C12-C14 and C12-C18) of 14EO or 25EO.Find, these nonionic surface active agent even also can be with anion surfactant granulation or spraying drying, thus improve the use properties of made extrudate.Also can the alcohol alcoxylates of 80EO at the most will be contained by International Patent Application WO-A-93/02176 is described except described alcohol alcoxylates, preferably 30 or the tallow Fatty Alcohol(C12-C14 and C12-C18) of 40EO or preferably to have relative molecular weight be 200 to 600 polyoxyethylene glycol with other nonionic surface active agent except above-mentioned alcohol alcoxylates is mixed together and uses.The objective of the invention is according to early stage German patent application P 43 19 666.7 disclosedly, the alcohol alcoxylates that contains 40EO at most joins in the premixture with the solid preparation form and is preferred and particularly preferably is the granular preparation that contains high-content alkane (alkene) sulfovinate in premixture.
Other suitable nonionic surface active agent is that general formula is RO (G)
xAlkylglycoside, wherein R represent uncle's straight chain or methyl branch, especially 2-methyl branch, contain 8 to 22, preferably contain the aliphatic group of 12 to 18 carbon atoms, and G represents to contain the sugared unit of 5 or 6 carbon atoms, be preferably glucose.Its low polymerization degree x represents the distribution of single glycoside and oligomeric glycoside, is a numerical value, preferably 1.2 to 1.4 value in 1 to 10.The glycosidic amount of alkyl in premixture for example is 1 to 5% (weight).
The nonionic surface active agent class that other is suitable, it both can use separately or can be used in combination with other nonionogenic tenside, particularly use with oxyalkylated Fatty Alcohol(C12-C14 and C12-C18), be oxyalkylated, be preferably ethoxylation or ethoxylation and propenoxylated fatty acid alkyl ester, preferably contain 1 to 4 carbon atom at alkyl, fatty acid methyl ester particularly, described in Japanese patent application JP-A-58/217598 or by the preparation of the method described in International Patent Application WO-A-90/13533.The nonionic surface active agent of amine oxide type, as N-coconut alkyl-N, N-dimethyl amine oxide compound and N-tallow gastral cavity base-N, N-dihydroxyl amine oxides and fatty acid chain alkanol acyl ammonium also suit.The preferable amount of these nonionic surface active agent is not higher than wherein used ethoxylized fatty alcohol, particularly is not higher than its half amount.Other is suitable can be used for replacing alkyl glucoside or the tensio-active agent that is used in combination with alkyl glucoside is the poly-hydroxy fatty acid acid amides of general formula (I),
(I) R in the formula
2-CO represents to contain the aliphatic acyl radical group of 6 to 22 carbon atoms, R
3Represent hydrogen, contain the groups or the hydroxyalkyl group of 1 to 4 carbon atom, [Z] is the poly-hydroxyalkyl group that contains 3 to 10 carbon atoms and 3 to 10 oh groups of straight or branched.The poly-hydroxy fatty acid acid amides is a known substances, and it normally by with ammonia, alkylamine or alkanolamine reduction amination reducing sugar, carries out acidylate with lipid acid, fatty acid alkyl ester or lipid acid chlorination thing then and make.
The consumption of non-ionic surface active is preferably 0.5 to 25% (weight) in premixture.Favourable amount is 2 to 20% (weight), 5 to 15% (weight) more preferably, and the nonionogenic tenside of 50 to 100% (weight) is made up of the alcohol of ethoxylation.
The alkylbenzene sulfonate that it is characterized in that containing in the used premixture 15 to 25% (weight) in the preferred version of the present invention is as unique anion surfactant, preferably use with the form of 85 to 95% (weight) powder and 0.5 to 5% (weight) nonionogenic tenside, preferably ethoxylized fatty alcohol and/or alkyl are joined sugar, particularly the Fatty Alcohol(C12-C14 and C12-C18) of the ester fat alcohol of ethoxylation or ethoxylation and the glycosidic mixture of alkyl.
It is characterized in that containing in the employed premixture 10 to 20% (weight) anion surfactant in another preferred version of the present invention, preferably by the alkylbenzene sulfonate of 0.8: 1 to 1.2: 1 weight ratio and the above-mentioned nonionogenic tenside of basic vitriol of alkane (alkene) and 0.5 to 5% (weight).
Particularly preferred scheme of the present invention, it is characterized in that in the employed premixture, contain 5 to 15% (weight) anion surfactant, preferably by the alkylbenzene sulfonate of 0.5: 1.2 weight ratio and the mixture of the basic vitriol of alkane (alkene), particularly preferred is alkylbenzene sulfonate and the mixture of the basic vitriol of alkane (alkene) and the nonionogenic tenside of 10 to 20% (weight) of 0.5: 1 to maximum 1: 1 weight ratio, ethoxylized fatty alcohol or preferably by the mixture of the nonionic surface active agent of ethoxylized fatty alcohol and other, wherein the Fatty Alcohol(C12-C14 and C12-C18) content with its ethoxylation of nonionic surface active agent total is at least 50% (weight), particularly preferred at least 60% (weight), in the perhaps used premixture, as unique tensio-active agent, the amount that contains 5 to 15% (weight), preferably basic vitriol of the alkane of at least 8% (weight) (alkene) and 5 to 15% (weight), the preferably above-mentioned nonionogenic tenside of at least 8% (weight).The basic vitriol of alkane (alkene) often uses the highly enriched pellet that contains the basic vitriol of 80 to 95% (weight) alkane (alkene), if alkylbenzene sulfonate is not can introduce in present method with the form of spraying drying pellet as the next alkylbenzene sulfonate of situation of unique anion surfactant, calculate with the spraying drying pellet in this pellet, its alkyl benzene sulphonate (ABS) salts contg is under 45% (weight).
The for example inorganic and organic washing assistant of other compositions of premixture, alkaline carbonate and alkalimetal silicate, white dyes, SYNTHETIC OPTICAL WHITNER, burnt hair inhibitor and optional froth suppressor, bleach boosters, enzyme, the yarn fabric softening agent, the vitriol of pigment and spices and neutral salt such as sodium and potassium and muriate.
Suitable inorganic builders is for example zeolite, phosphoric acid salt and layer silicate.
At the synthetic zeolite of the employed fine crystalline that contains combination water of washing composition level NaA type zeolite preferably.But the mixed type zeolite of zeolite NaX and NaA and NaX also suits.Zeolite can the spray-dried powders form use, even by also using with undried still moist steady suspension in its production.When zeolite uses with form of suspension, can contain a small amount of nonionogenic tenside as stablizer, as the C that contains 2 to 5 ethylene oxide groups based on 1 to 3% (weight) of zeolite
12-C
18Different three decyl alcohol of Fatty Alcohol(C12-C14 and C12-C18) or ethoxylation.Suitable zeolite average particle size is less than 10 μ m (volume distributed median; Measure with Coulter Counter method).Preferably contain 18 to 22% (weight), the preferred combination water that contains 20 to 22% (weight).
Suitable substituent or the part substituent that is used for zeolite is natural source or synthetic layer silicate.By patent application DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 known corresponding layer silicates.Its applicability is not limited to specific composition or structural formula.But be applicable to the preferably terre verte, particularly wilkinite of the object of the invention.
Small amounts of iron can be mixed in the lattice of layer silicate in addition.In addition, because its ion exchangeable layer silicate also may contain hydrogen ion, alkalimetal ion and alkaline-earth metal ions, particularly Na
+And Ca
++Usually water-content is 8-20% (weight), and is decided by swelling capacity and treatment technology.Layer silicate commonly used is substantially free of calcium ion and dark iron ion after by alkaline purification.
Suitable substituent or part substituent to phosphoric acid salt and zeolite is the lamellated water glass of crystalline, and its general formula is: NaMSi
xO
2x+1YH
2O, wherein M represents sodium or hydrogen atom, and X is 1.9 to 4 value, and Y is 0 to 20 value, and X preferably 2,3 or 4.Suitable crystallizing layer silicate is described in please EP-A-O-164 514 in the European patent.Preferred crystallizing layer silicate is that wherein M is a sodium, and X is 2 or 3, the sodium disilicate Na of β type and δ type
2Si
2O
5YH
2O is preferred especially.
These inorganic builders content are preferably 15 to 60% (weight) in premixture, and phosphate content below 15% (weight), is not have phosphatic washing assistant in the particularly preferred premixture preferably.
Useful organic washing-assisting detergent is poly carboxylic acid for example, and what preferably use is its sodium-salt form, as citric acid, and hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, saccharic acid, aminocarboxylic acid, triglycollamic acid (NTA), (its use do not have on the ecology dangerous) with and composition thereof.Preferred salt is polycarboxylate such as citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, salt of saccharic acid and composition thereof.
Suitable polymeric polycarboxylate is the sodium salt of polyacrylic acid or polymethyl acrylic acid for example, and for example having relative molecular weight is those compounds of 800 to 150,000 (based on acid).Suitable copolymerization polycarboxylate is the multipolymer of vinylformic acid and methacrylic acid and acrylic or methacrylic acid and toxilic acid particularly.The vinylformic acid that contains 50 to 90% (weight), the vinylformic acid of the toxilic acid of 50% to 10% (weight) and the interpolymer of toxilic acid are suitable especially.Their relative molecular weight in free acid, is generally 5000 to 200,000, and is preferred 10,000 to 120000, is more preferably 50,000 to 100,000.Biodegradable trimer for example contains those of the salt of the single aggressiveness of single aggressiveness of acrylate and maleate and vinyl alcohol or vinyl alcohol derivatives or vinylformic acid and 2-alkyl allyl sulphonic acid and sugar-derivative.(being total to) polymeric or trimeric polycarboxylate both can be Powdered, also can spraying drying or particulate state compound or use with aqueous solution form, and the aqueous solution of 20 to 55% (weight) preferably wherein.Polymerization (copolymerization) or the preferred maximum of the content of trimeric carboxylate salt in premixture can arrive 8% (weight), 0 to 5% (weight) preferably.
Other suitable washing assistant is a polyacetals, it can make by dialdehyde and the polyalcohols carboxylic acid reaction that contains 5-7 carbon atom and 3 hydroxyls at least, as in the type described in the european patent application ER-A-0280223, preferred polyacetals can be by dialdehyde, as oxalic dialdehyde, glutaraldehyde, terephthalic aldehyde and composition thereof and produce by polyalcohols carboxylic acid such as glyconic acid and/or glucose enanthic acid.
In the premixture other has water-soluble inorganic salt as two carbonate suitable the composition, carbonate, and amorphous silicate or its mixture, alkaline carbonate and amorphous alkali metal silicate, especially having mol ratio is Na
2O: SiO
2=1: 1 to 1: 4.5, the water glass that is preferably 1: 2 to 1: 3.5 was a particularly suitable.Sodium carbonate salt content preferably can be to reaching 20% (weight), preferably 2 to 15% (weight) in the premixture.Premixture mesosilicic acid sodium content can reach 10% (weight) usually at the most, is preferably 2 to 8% (weight).In a scheme of the present invention alkalimetal silicate preferably in the introducing method to small part be to be aqueous solution form, as the water glass solution of 10 to 45% (weight).
Can be by early stage German patent application P 43 19 578.4 by containing other carboxyl 2 to 11 carbon atoms and optional and/or amino no sulphur amino acid and/or its salt replacement alkaline carbonate.According to the present invention preferably by glycine or glycinate part or whole displacement-alkali metal carbonates.
In water, can produce H
2O
2Compound can be used as SYNTHETIC OPTICAL WHITNER with the Sodium peroxoborate of four Heshuis and monohydrate sodium stannate for the most meaningful.Other useful SYNTHETIC OPTICAL WHITNER is as SPC-D, pyrophosphate peroxide, citric acid perhydrate and generation H
2O
2Persalt or peracid, as peroxybenzoic acid salt, the peroxidation phthalate, two cross two n-nonanoic acids or two crosses the dodecyl diacid.The content of SYNTHETIC OPTICAL WHITNER 5 to 25% (weight) preferably are more preferably 10 to 20% (weight) in the premixture, advantageously use a water perborate.
In order when washing below 60 ℃ or 60 ℃, to reach bleaching action preferably, can in preparation, mix bleach-activating agent, the example of suitable bleach-activating agent is energy and H
2O
2The N-acyl group of formation organic peracid-or O-acyl compounds, preferably NN '-tetra-acylated diamines.The carboxylic acid anhydride and fat such as glucose penta acetic ester that also have many alcohol.The content of bleach-activating agent is the constant scope in containing the premixture of SYNTHETIC OPTICAL WHITNER, and preferably 1 to 10% (weight) is more preferably 3 to 8% (weight).Particularly preferred bleach activator is N, N, N ', N '-tetra acetyl ethylene diamine and 1,5-diacetyl-2,4-dioxy six hydrogen-1,3,5 triazines.
Premixture also can contain oil ﹠ fat in the eccysis yarn fabric is effectively formed in addition.When yarn fabric has repeated to wash with the washing composition of the present invention that contains this dissolving oil and fatty ingredient and when staiing and washing, then this effect is just obvious especially.Preferred dissolving oil and fatty ingredient be for example non-ionic celluloses ether as containing based on the methoxy group of 15 to 30% (weight) of nonionic cellulose ether and the methylhydroxypropylcellulose of 1 to 15% (weight) propoxyl group component, and the polymkeric substance or derivatives thereof of known phenylformic acid of prior art and/or terephthalic acid, the particularly polymkeric substance of vinyl terephthalate and/or polyoxyethylene glycol-terephthalate.
The function of burnt hair inhibitor is to make dirt by removing on the fiber that is suspended in the washings, thereby stops variable color.Suitable burnt hair inhibitor is water miscible, organic colloid normally, as the salt of water-soluble polymeric carboxylic acid, and glue, gelatin, the salt of the acid sulfate of the ether carboxylate of starch or ether sulfonate or Mierocrystalline cellulose or Mierocrystalline cellulose or starch.
The water soluble polyamide that contains acidic-group also is suitable for this.Solvability starch preparation and other non-above-mentioned starch product, as degradable starch, starch aldehyde or the like also can use.It also is suitable that polyvinyl is given a tongue-lashing pyrrolidone.Ether of cellulose, as carboxymethyl cellulose, methylcellulose gum, hydroxy alkyl cellulose and mixed ether thereof, as methyl hydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethyl cellulose and composition thereof and polyvinyl are given a tongue-lashing pyrrolidone and also can be used, and its usage quantity is 0.1 to 5% (weight).
Suitable foam inhibiting agent is for example to have high-content C
18-C
14The soap class of the natural source of lipid acid or synthetic source.The foam inhibiting agent of suitable nonsurfactant is, for example silicic acid and the paraffinic hydrocarbons of organopolysiloxane and it and trickle siliconization, paraffin, the mixture of Microcrystalline Wax and it and the silica of silanization or the mixture of two stearyl ethylene diamides.The mixture of various foam inhibiting agents, siloxanes for example, the mixture of paraffinic hydrocarbons or paraffin also help using.On that foam inhibiting agent, the foam inhibiting agent that particularly contains siloxanes or paraffinic hydrocarbons preferably are fixed to granular water soluble or the dispersible carrier of water, the mixture of paraffinic hydrocarbons and two stearyl oxalamides is preferred especially.
Suitable enzyme is from proteolytic enzyme, lipase, starch (saccharification) enzyme, Mierocrystalline cellulose enzyme and composition thereof.By bacterial strain or fungi such as Bacillus subtilus, the lichens bacillus, the enzyme of producing in the grey mold streptomycete is suitable especially.What preferably use is the proteolytic enzyme of subtilysin type, and the proteolytic enzyme of being produced by crystalline bacillus (BaCillus lentus) is suitable especially.Enzyme mixture, as proteolytic enzyme and starch (saccharification) enzyme or proteolytic enzyme and lipase or proteolytic enzyme and cellulase or cellulase and ester fat enzyme or by proteolytic enzyme, starch (saccharification) enzyme and lipase or proteolytic enzyme, the mixture of the mixture of lipase and cellulase, particularly cellulase is a particularly advantageous.And (mistake) oxydase is also suiting in some cases.Enzyme is adsorbable to carrier and/or be encapsulated in the shelly material, can be for example about 0.1 to 5% (weight) with the content that stops their premature decomposition enzymes, enzyme mixture or enzyme pellet, is preferably 0.1 to about 2% (weight).
Suitable stabilizers, the stablizer of particularly crossing compound and enzyme has the salt of polyphosphonic acid, sodium salt after the preferred neutral reaction is 1-hydroxyl ethane-1 for example, the neutral reaction sodium salt of 1-diphosphonate and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt, its content is 0.1 to 1.5% (weight), be more preferably 1-hydroxyl ethane-1,1 diphosphonate.For example sodium formiate also can be used as stablizer.Soluble calcium salt stable with calcium content be that base is about 1.2% proteolytic enzyme and also can uses with the enzyme.But the particularly advantageous boron compound that is to use is as boric acid, boron oxide, borax and other alkali-metal borate such as orthoboric acid salt (H
3BO
3), metaborate (HBO
2) and pyroborate (tetraboric acid H
2B
4O
7) with stabilized enzyme.
The derivative of diaminostilbene disulfonic acid or its an alkali metal salt can be used as white dyes, suitable white dyes is just like 4,4 '-two (2-anilinos-4-morpholino-1,3,5-triazine-6-amino) stilbene-2,2 '-compound of stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate or similar composition, it contains a diethanolamino group, a methylamino group, an aniline group or a 2-methoxy ethyl amino group are to replace the morpholino group.The white dyes of the diphenyl benzene vinyl-type that replaces, as 4,4 '-two (2-sulfonic acid styryl)-biphenyl, 4,4 '-an alkali metal salt of two (4-chloro-3 sulfo group styryls) biphenyl or 4-(4-chloro-styrene base)-4 '-(2-sulfo group styryl) biphenyl also can exist.The also mixture of available above-mentioned white dyes.Discovery except with common amount as 0.1 to 0.5% (weight), being preferably 0.1 to 0.3% (weight) adds outside the general white dyes, washing composition also can contain a small amount of as 10-6 to 10-3% (weight), and a kind of blue pigments of preferred 10-5% (weight) can obtain uniform white extrudate.Particularly preferred pigment is Tinolux
R(Ciba Geigy product).
Last washing composition or cleanser compositions product can be made of the extrudate that contains said components fully.But extrudate produces with other composition of washing composition or sanitising agent in another program of the present invention.Washing composition or cleanser compositions can be made of multiple different granule mixtures, and are major ingredient by this extrudate of the present invention.So bleach-activating agent such as N; N '-tetra-acetylatedization diamines; as N; N; N ', the tetra-acetylated ethylene diamine of N ', the enzyme pellet, particularly proteolytic enzyme that contain enzyme and/or lipase and/or cellulase and/or amylase; wherein useful especially is 2 or the mixture of 3 kind of enzyme, preferably adds spices in step thereafter.Extrudate also can be before adding enzyme and other composition, with other fine grain powder treatment of exsiccant.Suitable dry powder example has zeolite, silica and soap, and as calcium stearate, the mixture of one of bleach-activating agent or zeolite and described other powder.Also find, if foam inhibiting agent, for example organopolysiloxane or itself and fine particles, the randomly silica of silanization and paraffinic hydrocarbons in addition, paraffin, the mixture of the mixture of Microcrystalline Wax and itself and silylation silica or two stearyl ethylene diamides is to have at least the part end to extrude, and just has and influences but mix then the lathering property of washing composition mutually with extrudate thereafter.For example at first topped according to the surface of extrudate of the present invention in this case with zeolite or a kind of mixture that contains zeolite, use foam inhibiting agent topped then.Can further improve the rinsing performance of extrudate by these measures.Apparent specific gravity by the extrudate of the present invention preparation is 600 to 2000 grams per liters.Wherein apparent specific gravity be 700 to 1000 grams per liters particularly preferably in 750 to 950 grams per liters for most preferably.
Embodiment
In the unitary batch mixer of pulverizing that the cutting knife head is installed by international monopoly WO-A-91/02047, premixture M1 to M5 of the present invention and reference premixture V1 to V2 are extruded.Dry extrudate, but no longer continue to handle.The composition of extrudate is shown in table 1 and table 3, and its apparent specific gravity and solvability are listed in table 2 and table 4.By using the most nearly C of 30% (weight)
8-C
12The basic sulphate moiety of the alkane of alkyl-sulphate (alkene) can further improve redispersibility.As use the tallow aliphatic alcohol sulfate, then to replace PEG 400 suitable equally tallow Fatty Alcohol(C12-C14 and C12-C18) 40 EO.
Used abbreviation has following meaning in the table: ABS C
9-C
13The alkyl benzene sulphonate (ABS) sodium salt is represented with 100% active substance, with
90% weight powder (Maranil A
R) the form use.TAS91 tallow aliphatic alcohol sulfate is represented with 100% active substance, and is (heavy with 91%
Amount) pellet uses, and it contains yellow soda ash as carrier and less than 1% (weight)
Combination water non-chemically, it is by International Patent Application WO-A-93/04162 side
The method preparation.TAS84 tallow aliphatic alcohol sulfate is represented with 84% (weight) with 100% active substance
Pellet use, it contains yellow soda ash and makes carrier and have to be less than 1% non-chemically
Combination water, it is by International Patent Application WO-A-93/04162 method preparation.TAS47 tallow aliphatic alcohol sulfate is represented with 100% active substance, and is (heavy with 47%
Amount) pellet form is used, and it contains yellow soda ash and makes carrier and have to be less than 1%
(weight) is combination water non-chemically, and it is by International Patent Application WO-A-93/04162
The method preparation.FA5EO contains the C of 5 ethylene oxide groups (EO)
12-C
18Fatty Alcohol(C12-C14 and C12-C18) TA5EO contains the saturated C of 5EO tallow Fatty Alcohol(C12-C14 and C12-C18) soap class
12-C
18-fatty acid sodium salt Zeolites Zeolites represents that with anhydrous active substance soda yellow soda ash Sil 2.0 contains Na
2O: SiO
2Weight ratio is 1: 2.0 water glass vitriol sulfuric acid sodium and is the foam inhibiting agent particle of base and the perborate CP5 Sokalan CP5 that contains vitriol PBMH one water of 15% (weight) silicone oil with soda from the salt SIK of solution
R, the copolymer p EG400 of acrylate and toxilic acid contains the polyoxyethylene glycol HEDP 1-hydroxyl ethane-1 of relative molecular weight 400,1-di 2 ethylhexyl phosphonic acid-tetra-na salt
A kind of 20% (weight) Sokatan CP5 that in premixture M1-M3, except adding nonionogenic tenside, also adds 2.8% (weight) as plastic agent and/or lubricant
RA kind of 34% (weight) sodium silicate solution (1: 2.2) of solution and 4.1% (weight).At M4, add 4.3% water in the premixture of M5 and V2 on the contrary.
Deliquescent mensuration
In 1 liter of container, add 500 ml deionized water (20 ℃), start propeller type mixer and introducing and conductance measurement pond that per minute 900 changes.Add 5 gram extrudates then.Registering instrument is noted the variation of specific conductivity, continues to measure till specific conductivity no longer increases.The time that arrives constant conductance is the dissolution time (100%) of extrudate, the dissolution time when measuring 90% dissolving by calculating.
The composition (% weight) of table 1:M1 to M3 and V1
M1 M2 M3 V1ABS 10 10 20 2,0TA,S84 10---TAS91-10--TAS47---10FA5EO 222 2TA5EO 0.5 0.5 0.5 0.5 soap classes 1.0 1.0 1.0 1.0SIK 6.0 6.0 6.0 6.0 zeolites 20 20 20 20 soda 12 12 12 12Sil 2.0 3.5 3.5 3.5 3.5CP5 6.0 6.0 6.0 6.0PBMH, 18 18 18 18,DEG,400 2.0 2.0 2.0 2.0HEDP, 1.0 1.0 1.0 1.0 water and surplus surplus surplus surplus sulfate
Table 2: the apparent specific gravity of extrudate M1-M3 and V1 and dissolution time (90%)
M1 M2 M3 V1 apparent specific gravity (grams per liter) 830 808 795 810 dissolution times (second) 210 203 229 243
The composition (% (weight)) of table 3:M4 and M5 and V2
M4 M5 V2TAS84 9--TAS91-9-TAS47--9FA5EO 99 9FA5EO 111 and soap class 0.5 0.5 0.5 zeolites, 35 35 35 soda 14 14 14PBMH, 16 16 16 water and vitriol surplus surplus surplus
Table 4: the apparent specific gravity of extrudate M4-M5 and V2 and dissolution time (90%)
M4 M5 V2 apparent specific gravity (grams per liter) 820 812 800 dissolution times (second) 310 216 454
Claims (12)
1, produces the method for the extrudate of high density active washing composition and sanitising agent, wherein the solid premixture is to be squeezed into to be cut into the particle of pre-sizing by cutter unit after rod and rod leave extrusion die under pressure, it is characterized in that, it is that independent form with solid powdery or granular preparation adds premixture that premixture contains anion surfactant and nonionogenic tenside and anion surfactant, and anion surfactant is that part is introduced with the anion surfactant preparation with at least 50% (weight) (based on preparation) at least.
2, by claim 1 method, it is characterized in that, with at least 30% (weight), the anion surfactant of at least 50% (weight) (based on the anionic surfactant total amount) particularly, to have anionic surfactant concentration at least 50% (weight), be preferably 60 to 100% (weight), be preferably the solid of 70 to 95% (weight) especially, powdery or granular preparation are introduced in present method.
3, claim 1 or 2 described methods, it is characterized in that, anion surfactant is to introduce in present method by one or more solid preparations, and wherein each preparation contains at least 75% (weight), preferably one or more anion surfactants of at least 80% (weight).
By one or more described method of claim 1 to 3, it is characterized in that 4, the amount that adds the anion surfactant in the premixture is 5 to 30% (weight).
By one or more described method of claim 1 to 4, it is characterized in that 5, the basic vitriol of alkylbenzene sulfonate and/or alkane (alkene) is as anion surfactant.
6, the arbitrary described method of claim 1 to 5 is characterized in that, 8 to 25% (weight) alkylbenzene sulfonates and/or the basic vitriol of alkane (alkene) are added in the premixture.
7, the arbitrary described method of claim 1 to 6 is characterized in that, with alkylbenzene sulfonate and the basic vitriol of alkane (alkene) weight ratio with 0.5: 1 to 1.5: 1, is preferably 1.2: 1 weight ratios and is preferably about 1: 1 weight ratio especially and join in the premixture.
8, the arbitrary described method of claim 1 to 7, it is characterized in that, the basic vitriol of alkane (alkene) is used for premixture, wherein short-chain alkyl vitriol such as C12-alkyl-sulphate or more the alkyl-sulphate of short chain contain 30% (weight) at the most in the basic vitriol total amount of used alkane (alkene).
9, the arbitrary described method of claim 1 to 6 is characterized in that, alkylbenzene sulfonate is to use with single anion surfactant form in premixture, and it is a kind of highly enriched powder, preferably contains the powder that surpasses 85% (weight) active substance.
10, by the arbitrary described method of claim 1 to 9, it is characterized in that the add-on of nonionic surface active agent is 0.5 to 2.5% (weight) in premixture, be preferably 2 to 20% (weight), be preferably 5 to 15% (weight) especially.
11, by the described method of claim 10, it is characterized in that 50 to 100% (weight) of the nonionic surface active agent that is added are made up of the alcohols of ethoxylation.
12,, it is characterized in that prepared extrudate is that other composition with washing composition or sanitising agent is mixed together by the arbitrary described method of claim 1 to 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4325500.0 | 1993-07-29 | ||
| DE19934325500 DE4325500A1 (en) | 1993-07-29 | 1993-07-29 | Process for the production of extrudates that are active in washing or cleaning |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1127525A true CN1127525A (en) | 1996-07-24 |
Family
ID=6494018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94192872 Pending CN1127525A (en) | 1993-07-29 | 1994-07-21 | Process for preparing washing or detergent extrudates |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0711338A1 (en) |
| CN (1) | CN1127525A (en) |
| DE (1) | DE4325500A1 (en) |
| HU (1) | HUT73038A (en) |
| WO (1) | WO1995004129A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010142232A1 (en) * | 2009-06-09 | 2010-12-16 | 中轻化工股份有限公司 | Preparation method of spherical anionic surfactant |
| CN101240227B (en) * | 2007-02-09 | 2012-02-22 | 宝洁公司 | Slowly dissoluble, improved washing reagent rod fitting to human engineering |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19524722A1 (en) * | 1995-07-12 | 1997-01-16 | Henkel Kgaa | Granular washing or cleaning agent with high bulk density |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3824189A (en) * | 1972-05-11 | 1974-07-16 | G Borello | Detergent compositions and methods for making same |
| EP0486592B1 (en) * | 1989-08-09 | 1994-06-15 | Henkel Kommanditgesellschaft auf Aktien | Manufacture of compacted granules for washing agents |
| DE4124701A1 (en) * | 1991-07-25 | 1993-01-28 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED |
| DE4203031A1 (en) * | 1992-02-04 | 1993-08-05 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED |
-
1993
- 1993-07-29 DE DE19934325500 patent/DE4325500A1/en not_active Withdrawn
-
1994
- 1994-07-21 EP EP94924270A patent/EP0711338A1/en not_active Withdrawn
- 1994-07-21 CN CN 94192872 patent/CN1127525A/en active Pending
- 1994-07-21 WO PCT/EP1994/002403 patent/WO1995004129A1/en not_active Application Discontinuation
- 1994-07-21 HU HU9503968A patent/HUT73038A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240227B (en) * | 2007-02-09 | 2012-02-22 | 宝洁公司 | Slowly dissoluble, improved washing reagent rod fitting to human engineering |
| WO2010142232A1 (en) * | 2009-06-09 | 2010-12-16 | 中轻化工股份有限公司 | Preparation method of spherical anionic surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4325500A1 (en) | 1995-02-02 |
| HU9503968D0 (en) | 1996-03-28 |
| HUT73038A (en) | 1996-06-28 |
| WO1995004129A1 (en) | 1995-02-09 |
| EP0711338A1 (en) | 1996-05-15 |
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