EP0893492B1 - Process for making a storage stable and flowable granulate from anionic detergent compositions - Google Patents
Process for making a storage stable and flowable granulate from anionic detergent compositions Download PDFInfo
- Publication number
- EP0893492B1 EP0893492B1 EP98113138A EP98113138A EP0893492B1 EP 0893492 B1 EP0893492 B1 EP 0893492B1 EP 98113138 A EP98113138 A EP 98113138A EP 98113138 A EP98113138 A EP 98113138A EP 0893492 B1 EP0893492 B1 EP 0893492B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- acid
- weight
- neutralizate
- surfactants
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000008187 granular material Substances 0.000 title claims abstract description 29
- 239000003599 detergent Substances 0.000 title claims abstract description 26
- 230000009969 flowable effect Effects 0.000 title claims description 3
- 239000000203 mixture Substances 0.000 title description 31
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 39
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 9
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000344 soap Substances 0.000 claims description 12
- 229920005646 polycarboxylate Polymers 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- 235000012211 aluminium silicate Nutrition 0.000 claims 1
- 238000010348 incorporation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
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- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
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- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 3
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- 238000005406 washing Methods 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Chemical class CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- 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
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
-
- 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
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the invention relates to a method for producing a storable and free-flowing granulate of detergents and cleaning agents containing anionic surfactants with a bulk density above 600 g / l as well as washing and cleaning agents containing anionic and non-ionic surfactants.
- Patent specification EP 0 642 576 B1 describes a two-stage process for the production of Granules known.
- the use of zeolites or Phosphates are described as builder substances. Phosphates are used as builders from environmental biology Reasons used less preferred. Even the absence of zeolites is preferred as builder components because of their poor solubility.
- WO 93/23520 From the teaching of WO 93/23520 is a process for the preparation of anionic surfactants Detergents and cleaning agents known. Here, a neutralizate that contains anionic surfactants is prepared separately. This then becomes a solid or placed in a mixer added to a solid mixture and granulated in the same mixer. By teaching this document shows excessive heat buildup due to the neutralization reaction avoided. However, the choice of solids proves to be disadvantageous with this procedure. Either builders from the zeolite or phosphate groups are not omitted or it is the commercially available crystalline alkali silicates, optionally in combination with alkali carbonates. By applying the neutralization medium to the Solid and the granulation in the same mixer, however, becomes a poorly pourable Product received.
- the object of the invention is therefore to provide a method that the above Does not have disadvantages. It is said to be a process for producing a granulate of detergents and cleaning agents that are made available by the inventive Process steps neither glued nor greased, to water-insoluble ones Zeolites and phosphates as builder components can be dispensed with, however Detergent and cleaning agent, based on anionic surfactants, with excellent detergent properties and delayed release speed of the builder components.
- the invention relates to a process for producing a storable and free-flowing granulate of detergents and cleaning agents containing anionic surfactants with a bulk density above 600 g / l, characterized in that firstly (a) at least one completely neutralized neutralizate containing at least one anionic surfactant acid a non-ionic surfactant and sodium hydroxide solution, (b) applied to a water-soluble silicate builder to produce a precursor, (c) mixed with other conventional detergent ingredients and finally (d) granulated with a granulating liquid, the preparation of the precursor and the granules are produced spatially separated and continuously.
- the process is carried out continuously.
- at least two mixers connected in series.
- the primary product is in the first mixer manufactured, i.e. the neutralisate, which in turn is produced separately, is there on the silicate builder applied.
- a second mixer In a second mixer, the other solids and / or liquids become the preliminary product added and the granulation step carried out.
- the following, if applicable Powdering with flow improver takes place either in the discharge zone of the second mixer or separately in a downstream third mixer.
- a so-called Schugi mixer is preferred as the third mixer for this purpose.
- a method which provides that the silicate builder treated with neutralisate (the preliminary product) initially with others Substances are encased.
- Suitable coating substances are water-soluble detergent components, those in the form of their aqueous solution on the silicate treated with neutralizate Builder are sprayed on (fluidized bed coating). During this application process excess water is evaporated. This is preferably achieved with disilicate and / or Polycarboxylate solutions, e.g. in a fluid bed dryer from Glatt, Aeromatic or Escher-Wyss.
- this "coated" intermediate product after adding other common detergent ingredients in a granulation step granulated or mixed in a (dry) mixing step.
- the preliminary product is converted into a free-flowing compound that can be ensiled, which can now be stored temporarily.
- the neutralisates can be prepared in a stirred tank or in all conventional, customary ones Mixers are made and carried out separately.
- concentrated sodium hydroxide solution is used.
- the concentrated sodium hydroxide solution contains between 30 and 60% by weight sodium hydroxide, preferably between 45 and 55% by weight.
- the anionic surfactant acid (s) is (are) usually specified and the sodium hydroxide solution as Neutralization medium added. A reverse procedure is also possible.
- the nonionic surfactant component (s) given the anionic surfactants added in their acid form and finally the neutralization was carried out with concentrated sodium hydroxide solution.
- the three components of the neutralizate become continuous and synchronous introduced in the mixing process.
- the neutralizate contains one or more anionic surfactants between 10 and 99% by weight, one or more non-ionic surfactants between 1 and 90 wt .-% (each based on the neutralizate) and the lowest possible water content.
- the usable water content depends on the type and amount of nonionic surfactant used. The water content should be determined in any case so that after the neutralization of the anionic surfactant a liquid phase is retained.
- the anionic surfactant-containing mixtures prepared according to this preferred embodiment are preferably at temperatures between 5 and 20 ° C, in particular between 8 and 15 ° C, flowable and pumpable.
- the known sulfonates and sulfates and soaps made from preferably natural fatty acids or fatty acid mixtures are suitable as anionic surfactants.
- sulfo fatty acids and fatty acids are preferably converted into their anionic surfactants.
- the use of saturated and unsaturated fatty acids with C 8 -C 18 chain lengths in the form of their mixtures and / or the ⁇ -sulfofatty acids of saturated C 8 -C 18 fatty acids is preferred.
- Anionic surfactants in their acid form of the sulfonic acid type include alkylbenzenesulfonic acids, olefin sulfonic acids, ie mixtures of alkene and hydroxyalkanesulfonic acids, and the sulfonic acids obtained, for example, from C 12 -C 18 monoolefins with terminal and internal double bonds by sulfonating with gaseous sulfur trioxide consideration.
- alkanesulfonic acids which are obtainable from C 12 -C 18 alkanes by sulfochlorination and sulfoxidation and by subsequent hydrolysis or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids, e.g. B. the ⁇ -sulfonated methyl ester of hydrogenated coconut, palm kernel, or tallow fatty acids.
- Suitable alkyl sulfuric acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, especially from fatty alcohols, e.g. B.
- coconut fatty alcohols coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
- the anionic surfactants mentioned in their acid form for example fatty acid and alkylbenzenesulfonic acid or fatty acid and sulfofatty acids of saturated and / or unsaturated fatty acids or sulfofatty acid alkyl esters of saturated and / or unsaturated fatty acids. It is particularly advantageous if the fatty acids are first added to the ethoxylated nonionic surfactant and then the further sulfonated anionic surfactants in their acid form.
- the neutralizate used is made from alkylbenzenesulfonic acid, sodium hydroxide solution and at least one nonionic surfactant.
- Alkylbenzenesulfonic acids having a C 9 -C 15 alkyl group are particularly preferred.
- the neutralizate is composed of alkylbenzenesulfonic acid, Sodium hydroxide solution and non-ionic surfactants from the group of ethoxylated nonionic surfactants manufactured.
- the ethoxylated nonionic surfactants are derived from primary alcohols having preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol radical can be linear or methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture , as they are usually present in oxo alcohol residues.
- linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. coconut oil, tallow fat or oleyl alcohol.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE).
- alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
- the preferred ethoxylated alcohols include, for example, C 9 -C 11 oxo alcohol with 7 EO, C 13 -C 15 oxo alcohol with 3 EO, 5 EO, 7 EO or 8 EO and in particular C 12 -C 14 alcohols with 3 EO or 4 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
- This mixture of anionic surfactant in acid form and ethoxylated nonionic surfactants can be combined in one broad weight ratio, preferably in a weight ratio of anionic surfactant in acid form to ethoxylated nonionic surfactant from 1: 0.5 to 1:30, in particular up to 1:20 become.
- Mixtures are advantageously used in the case of complete neutralization used in which the weight ratio of anionic surfactant in acid form to ethoxylated nonionic surfactant is less than 1, preferably 1: 2 to 1:20 and in particular less than 1: 5.
- the metering takes place with the mixer and knife ring running. Suitable mixers are e.g. Eirich mixer the R and RV series, manufactured by the machine factory Gustav Eirich, Hardheim, Germany, the Fukae FS-G mixer, manufactured by the Fukae Powtech Kogyo Co., Japan, the Lödige FM, KM and CB mixers, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany, or the Drais series T or K-T by Drais Maschinene GmbH, Mannheim, Germany.
- the neutralisate preferably introduced into the mixer via nozzles. The addition can also - if also less preferred - manually, for example by pouring.
- Granular sodium and / or potassium silicates obtained by spray drying, compression and grinding with a molar SiO 2 : M 2 O ratio of preferably 2.0 to 3.0, in particular sodium silicates with a certain water content, are used as silicate builder components.
- the water content is preferably between 15 and 22% by weight. Only granular silicates are used in the context of the invention. In particular, the use of alkali carbonates is dispensed with.
- Granular silicates selected from the commercially available granular Britesil (R) disilicates (commercial products from AKZO-PQ Silica) of the type H20 (module 2.0), H20 Plus (module 2.0) and H24 (module 2, 4), which are suitable as substitutes for zeolites and / or crystalline layered disilicates.
- the detergents and cleaning agents produced in accordance with the process contain at least 15% by weight, in particular 30 to 60% by weight, based on the total detergent or cleaning agent formulation, of these granular silicates.
- These water-soluble amorphous, granular silicates are particularly preferred over ground water glass. Compared to water glass, they show a significantly delayed dissolving behavior. This means that the alkali silicates mentioned also do justice to their builder effect, but without leaving behind insoluble washing or cleaning residues.
- the builder treated with neutralized at least one further anionic surfactant component and / or one soap component added alongside other typical detergent components.
- the surfactants used here are preferably surfactants of the sulfonate type, particularly preferably C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered.
- alkanesulfonates obtained from C 12 -C 18 alkanes for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
- Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
- sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a restricted homolog distribution, are particularly preferred.
- esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
- the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
- 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN (R) , are also suitable anionic surfactants.
- the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the anionic surfactants are preferably used in amounts of 3 to 25% by weight, in particular in Quantities of 10 to 20% by weight, based in each case on the sum of the constituents used, used. However, their content can also exceed 15% by weight.
- preferred Anionic surfactants are fatty alkyl sulfates, alkyl benzene sulfonates, sulfosuccinates and mixtures from these, such as mixtures of fatty alkyl sulfates and sulfosuccinates or fatty alkyl sulfates and fatty alkyl benzene sulfates, especially in combination with soap. It is special preferred that at least some of the sulfonate and / or sulfate surfactants are not as solid Component, but used in liquid form as part of the granulating liquid becomes.
- Suitable surfactants are soaps, either alone or in combination with the anionic surfactants mentioned.
- Saturated fatty acid soaps such as salts of myristic, lauric, palmitic or stearic acid, are particularly suitable.
- Unsaturated fatty acids derived, for example, from oleic acid are also suitable.
- Fatty acid mixtures which can be extracted from natural resources, for example coconut, palm kernel or tallow fatty acids, are also suitable.
- those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 18 fatty acid soaps.
- the soaps are preferably present in amounts of 0.5 to 8% by weight.
- detergents and cleaning agents are, for example organic cobuilders, graying inhibitors, such as anionic and / or non-ionic Cellulose derivatives, especially carboxymethyl cellulose (CMC) and / or methyl cellulose (MC), and polyvinyl pyrrolidone (PVP) or foam inhibitors such as silicones or paraffin oils used on granular carriers and fatty alkyl phosphoric acid esters.
- graying inhibitors such as anionic and / or non-ionic Cellulose derivatives, especially carboxymethyl cellulose (CMC) and / or methyl cellulose (MC)
- PVP polyvinyl pyrrolidone
- foam inhibitors such as silicones or paraffin oils used on granular carriers and fatty alkyl phosphoric acid esters.
- Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
- the acids themselves can also be used.
- the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of detergents or cleaning agents.
- citric acid succinic acid, glutaric acid, adipic acid, To name gluconic acid and any mixtures of these.
- dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
- DE dextrose equivalent
- Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
- a preferred dextrin is described in British patent application 94 19 091.
- the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608 are known.
- a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
- Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.
- Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid).
- Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
- Their relative molecular weight, based on free acids is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.
- homopolymeric salts of acrylic acid with relative molecular weights between about 2000 and about 15,000, especially between 4,000 and 10,000, are suitable.
- the (co) polymeric polycarboxylates can either be as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
- Polymers composed of more than two different monomer units are also particularly preferred, for example those which, according to DE-A-43 00 772, are monomers as salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
- copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those used in the international Patent application WO-A-93/08251 can be described or their preparation is described, for example, in international patent application WO-A-93/16110. Oxidized oligosaccharides according to the earlier German patent application are also suitable P 196 00 018.1.
- polymeric aminodicarboxylic acids their To name salts or their precursors.
- Polyaspartic acids are particularly preferred or their salts and derivatives, of which in German patent application P 195 40 086.0 discloses that in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
- polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 described, can be obtained.
- Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- the other granular components include, for example, compact ones Bleaching agent or bleach activator granules, enzyme granules, foam inhibitor granules, preferably concentrated foam inhibitor granules and granular carriers for color and Fragrances.
- bleach activators for example, with H 2 O 2 which form organic peracids N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, also carboxylic anhydrides and esters of polyols such as glucose pentaacetate.
- the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 2 and 8% by weight.
- Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED) and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT).
- TAED N, N ', N'-tetraacetylethylene diamine
- DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
- Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question.
- Bacterial strains or are particularly well suited Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are enzymatic Agents.
- Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Your share can about 0.2 to about 2% by weight.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
- stabilizers in particular for per-compounds and enzymes the salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP) into consideration.
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
- Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes, are also advantageously used.
- Bleaching agents can be added to the preliminary product as further typical detergent components become.
- perborates and / or percarbonates are used in particular as bleaching agents.
- Sodium perborate tetrahydrate and sodium perborate monohydrate are preferably used.
- sodium percarbonates are preferably used.
- peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids for example perbenzoates and / or peroxaphthalates.
- the proportion of the bleaching agents, based on the finished product is 5 to 25% by weight, in particular 10 to 20% by weight.
- the bleaching agents are added to the treated builder for the production of the intermediate product in addition to the other usual detergent components mentioned above. If appropriate, the bleaching agents can also be added in whole or in part in a preparation step downstream of the granulation.
- the preliminary product or the preliminary product further treated by "coating” and / or dewatering is mixed in the second mixer with other common detergent raw materials and under Addition of liquid (s) granulated.
- the use of polycarboxylate solution is preferred as granulation liquid.
- a mixture of optical brighteners and polycarboxylate solution is added as the granulation liquid in the granulation step.
- Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts are suitable as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Particularly uniform white granules are obtained if, in addition to the usual brighteners, the agents are used in customary amounts, for example between 10 -6 to 10 -3 % by weight, preferably between 0.1 and 0.3% by weight, even small amounts. contains, for example, 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye.
- a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
- the granulation is carried out as mixing, pressing or roller granulation in the Mixers, extruders or roller presses familiar to those skilled in the art.
- the granulation however, it is particularly preferably carried out in a mixer / granulator.
- a suitable mixer e.g. Eirich mixers of the R and RV series, manufactured by the machine factory Gustav Eirich, Hardheim, Germany, the Fukae FS-G mixer, manufactured by the Fukae Powtech Kogyo Co., Japan, the Lödige FM, KM and CB mixers, manufactured by the Lödige Maschinenbau GmbH, Paderborn, Germany, or the Drais series T or K-T by Drais Maschinene GmbH, Mannheim, Germany.
- Intensive mixer too Company IMCATEC Germany
- the usual one needed for granulation Residence time in these mixers is in the range of one minute to approximately 10 minutes.
- the granulate produced according to the invention is under Using flow improvers, powdered and dried at the end of the granulation.
- Amorphous and / or crystalline aluminum silicates are particularly preferred as flow improvers as well as silicas.
- Zeolite A and / or X is among the aluminum silicates and / or P, for example Wessalith P® (commercial product from Degussa, Germany), and particularly preferred among the silicas Sipernat®.
- the flow improver are usually mixed into the granulate. Your share, based on the finished product, is between 0.5 and 8% by weight.
- a proportion of the silicas is particularly preferred between 0.5 and 3% by weight and / or a proportion of the zeolites between 1.5 and 7.5 Wt .-%.
- the intermediate typically contains between 0 and 10% by weight nonionic surfactant, of 40 up to 65% by weight disilicate, from 5 to 15% by weight ABS, from 2 to 10% by weight flow improver, from 0 to 20% by weight of polycarboxylate and water.
- the drying step is carried out in the fluidized bed, especially at supply air temperatures below of 180 ° C.
- Products manufactured in accordance with the invention have a Bulk density of more than 600 g / l.
- the granules produced according to the invention are pourable and pourable, non-sticky and almost dust-free.
- the granular detergents and cleaning agents, produced according to the invention preferably contain between 3 and 12% by weight, in particular between 3 and 6% by weight nonionic surfactants, 10 to 60% by weight, in particular between 30 and 60% by weight Alkali silicates as a solid and 10 to 35 wt .-%, in particular between 15 and 35% by weight of anionic surfactants.
- the granules produced according to the invention have one Bulk density above 600 g / l, preferably between 700 and 1000 g / l.
- the granules with a weight ratio of FAS: ABS of about 3.3: 1 were easy to pour and had a bulk density of 810 g / l.
- the granules obtained were also free-flowing and had a bulk density of 920 g / l.
- This granulate was produced in the "one-step process", i.e. this processing was carried out in the same mixer without separating preproduction and granulation.
- the Recipe of the mixture used in the present comparative example and the ones used Raw materials, compounds and granulating liquids correspond to the recipe and the Starting materials of Example 1.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines lager- und rieselfähigen Granulats von aniontensidhaltigen Wasch- und Reinigungsmitteln mit einer Schüttdichte oberhalb von 600 g/l sowie verfahrensgemäß hergestellte anion- und niotensidhaltige Wasch- und Reinigungsmittel.The invention relates to a method for producing a storable and free-flowing granulate of detergents and cleaning agents containing anionic surfactants with a bulk density above 600 g / l as well as washing and cleaning agents containing anionic and non-ionic surfactants.
Aus dem Stand der Technik sind zahlreiche Verfahren bekannt, die entweder im kontinuierlichen oder im schrittweisen Betrieb die Herstellung von verdichteten Granulaten erlauben. So etwa beschreibt die Lehre der EP-A-420 317 eine Kombination aus schnellaufendem Mischer/Granulator, wobei zunächst die Aniontenside in ihrer Säureform neutralisiert werden und nachgeschaltet durch die Zugabe weiterer Bestandteile ein Granulat geformt wird. Dieses Granulat ist in plastischem Zustand, weswegen weitere Verfahrensschritte erforderlich sind, etwa ein Verdichtungs- und ein Trocknungsschritt. Dieses Verfahren besitzt jedoch den Nachteil, daß die Granulate zwar einerseits eine hohe Schüttdichte aufweisen, andererseits jedoch zum Verbacken, Verkleben und Verfetten neigen, wenn nicht bestimmte Randbedingungen beachtet werden. So muß das Verfahren nahezu wasserfrei und/oder frei von nicht-ionischen Tensiden und/oder in einem bestimmten Temperaturbereich durchgeführt werden.Numerous processes are known from the prior art, which are carried out either continuously or allow the production of compacted granules in gradual operation. So the teaching of EP-A-420 317 describes a combination of a high-speed mixer / granulator, the anionic surfactants are first neutralized in their acid form and a granulate is formed downstream by the addition of further constituents. This Granules are in a plastic state, which is why further process steps are required are, for example, a compression and a drying step. However, this method has the Disadvantage that the granules have a high bulk density on the one hand, on the other hand however, they tend to cake, stick together and become greasy, if not certain boundary conditions get noticed. So the process must be almost anhydrous and / or free of non-ionic Surfactants and / or be carried out in a certain temperature range.
Aus der Patentschrift EP 0 642 576 B1 ist ein zweistufiges Verfahren zur Herstellung von Granulaten bekannt. In der Lehre dieses Dokuments wird der Einsatz von Zeolithen oder Phosphaten als Buildersubstanzen beschrieben. Phosphate werden als Builder aus umweltbiologischen Gründen jedoch weniger bevorzugt eingesetzt. Auch der Verzicht auf Zeolithe als Builderkomponenten ist auf Grund ihrer schlechten Löslichkeit bevorzugt.Patent specification EP 0 642 576 B1 describes a two-stage process for the production of Granules known. In the teaching of this document the use of zeolites or Phosphates are described as builder substances. Phosphates are used as builders from environmental biology Reasons used less preferred. Even the absence of zeolites is preferred as builder components because of their poor solubility.
Aus der Lehre der WO 93/23520 ist ein Verfahren zur Herstellung aniontensidhaltiger Wasch- und Reinigungsmittel bekannt. Hierbei wird ein Neutralisat, das Aniontenside enthält, separat zubereitet. Dieses wird dann zu einem in einem Mischer vorgelegten Feststoff oder einer Feststoffmischung zugegeben und in demselben Mischer granuliert. Durch die Lehre dieses Dokuments wird eine übermäßige Wärmetönung durch die Neutralisationsreaktion vermieden. Nachteilig erweist sich bei dieser Vorgehensweise jedoch die Wahl der Feststoffe. Entweder wird auf Builder aus den Gruppen der Zeolithe oder Phosphate nicht verzichtet oder es werden die handelsüblichen kristallinen Alkalisilikate, gegebenenfalls in Kombination mit Alkalicarbonaten, eingesetzt. Durch das Auftragen des Neutralisationsmediums auf den Feststoff und die Granulierung in demselben Mischer wird jedoch ein nur schlecht rieselfähiges Produkt erhalten.From the teaching of WO 93/23520 is a process for the preparation of anionic surfactants Detergents and cleaning agents known. Here, a neutralizate that contains anionic surfactants is prepared separately. This then becomes a solid or placed in a mixer added to a solid mixture and granulated in the same mixer. By teaching this document shows excessive heat buildup due to the neutralization reaction avoided. However, the choice of solids proves to be disadvantageous with this procedure. Either builders from the zeolite or phosphate groups are not omitted or it is the commercially available crystalline alkali silicates, optionally in combination with alkali carbonates. By applying the neutralization medium to the Solid and the granulation in the same mixer, however, becomes a poorly pourable Product received.
Aufgabe der Erfindung ist es daher, ein Verfahren zur Verfügung zu stellen, daß die genannten Nachteile nicht aufweist. Es soll demnach ein Verfahren zur Herstellung eines Granulats von Wasch- und Reinigungsmitteln zur Verfügung gestellt werden, daß durch die erfindungsgemäßen Verfahrensschritte weder verklebt noch verfettet, auf wasserunlösliche Zeolithe und auf Phosphate als Builderkomponenten verzichten kann, gleichwohl aber Wasch- und Reinigungsmittel, basierend auf Aniontensiden, mit hervorragenden Waschmitteleigenschaften und verzögerter Lösegeschwindigkeit der Builderkomponenten bereitstellt.The object of the invention is therefore to provide a method that the above Does not have disadvantages. It is said to be a process for producing a granulate of detergents and cleaning agents that are made available by the inventive Process steps neither glued nor greased, to water-insoluble ones Zeolites and phosphates as builder components can be dispensed with, however Detergent and cleaning agent, based on anionic surfactants, with excellent detergent properties and delayed release speed of the builder components.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines lager- und rieselfähigen Granulats von aniontensidhaltigen Wasch- und Reinigungsmitteln mit einer Schüttdichte oberhalb von 600 g/l, dadurch gekennzeichnet, daß zunächst (a) ein vollständig neutralisiertes Neutralisat, enthaltend mindestens eine anionische Tensidsäure, mindestens ein nicht-ionisches Tensid und Natronlauge, hergestellt, (b) dieses auf einen wasserlöslichen silikatischen Builder zur Herstellung eines Vorprodukts aufgetragen, (c) mit weiteren üblichen Waschmittelbestandteilen vermengt und schließlich (d) mit einer Granulierflüssigkeit granuliert wird, wobei die Herstellung des Vorprodukts und die Herstellung des Granulats räumlich getrennt und kontinuierlich erfolgen.The invention relates to a process for producing a storable and free-flowing granulate of detergents and cleaning agents containing anionic surfactants with a bulk density above 600 g / l, characterized in that firstly (a) at least one completely neutralized neutralizate containing at least one anionic surfactant acid a non-ionic surfactant and sodium hydroxide solution, (b) applied to a water-soluble silicate builder to produce a precursor, (c) mixed with other conventional detergent ingredients and finally (d) granulated with a granulating liquid, the preparation of the precursor and the granules are produced spatially separated and continuously.
Das Verfahren wird erfindungsgemäß kontinuierlich durchgeführt. Zu diesem Zweck werden mindestens zwei Mischer hintereinandergeschaltet. In dem ersten Mischer wird das Vorprodukt hergestellt, d.h. das Neutralisat, das wiederum separat hergestellt wird, wird dort auf den silikatischen Builder aufgetragen.According to the invention, the process is carried out continuously. For this purpose at least two mixers connected in series. The primary product is in the first mixer manufactured, i.e. the neutralisate, which in turn is produced separately, is there on the silicate builder applied.
In einem zweiten Mischer werden die weiteren Feststoffe und/oder Flüssigkeiten zum Vorprodukt hinzugefügt und der Granulationsschritt durchgeführt. Die gegebenenfalls nachfolgende Abpuderung mit Fließverbesserem erfolgt entweder in der Austragungszone des zweiten Mischers oder aber separat in einem nachgeschalteten dritten Mischer. Besonders bevorzugt ist als dritter Mischer zu diesem Zweck ein sogenannter Schugi-Mischer.In a second mixer, the other solids and / or liquids become the preliminary product added and the granulation step carried out. The following, if applicable Powdering with flow improver takes place either in the discharge zone of the second mixer or separately in a downstream third mixer. Especially a so-called Schugi mixer is preferred as the third mixer for this purpose.
In einer bevorzugten Ausführungsform wird ein Verfahren beansprucht, das vorsieht, daß die mit Neutralisat behandelten, silikatischen Builder (das Vorprodukt) zunächst mit weiteren Substanzen umhüllt werden. Geeignete Hüllsubstanzen sind wasserlösliche Waschmittelbestandteile, die in Form ihrer wäßrigen Lösung auf den mit Neutralisat behandelten, silikatischen Builder aufgesprüht werden (Wirbelschichtcoating). Während dieses Auftragungsvorgangs wird überschüssiges Wasser verdampft. Vorzugsweise gelingt dies mit Disilikatund/oder Polycarboxylat-Lösungen, z.B. in einem Fließbetttrockner der Firmen Glatt, Aeromatic oder Escher-Wyss. Schließlich wird - wie oben beschrieben - dieses "gecoatete" Vorprodukt nach Zugabe weiterer üblicher Waschmittelbestandteile in einem Granulationsschritt granuliert oder in einem (Trocken)Mischschritt zugemischt. Durch dieses als "Coating" bezeichnete Verfahren wird das Vorprodukt in ein silierbares, rieselfähiges Compound überführt, das nun auch zwischengelagert werden kann.In a preferred embodiment, a method is claimed which provides that the silicate builder treated with neutralisate (the preliminary product) initially with others Substances are encased. Suitable coating substances are water-soluble detergent components, those in the form of their aqueous solution on the silicate treated with neutralizate Builder are sprayed on (fluidized bed coating). During this application process excess water is evaporated. This is preferably achieved with disilicate and / or Polycarboxylate solutions, e.g. in a fluid bed dryer from Glatt, Aeromatic or Escher-Wyss. Finally - as described above - this "coated" intermediate product after adding other common detergent ingredients in a granulation step granulated or mixed in a (dry) mixing step. Through this referred to as "coating" The preliminary product is converted into a free-flowing compound that can be ensiled, which can now be stored temporarily.
In einer ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung wird anstelle des "Coatings" oder zusätzlich nach dem Coating des Vorprodukts mit z.B. Wasserglas und/oder Polycarboxylatlösung das Vorprodukt mit Fließverbesserern abgepudert. Hierfür sind insbesondere Wessalith und/oder Fällungskieselsäuren geeignet.In a very particularly preferred embodiment of the present invention, instead of of the "coating" or additionally after coating the preliminary product with e.g. water glass and / or polycarboxylate solution powdered the preliminary product with flow improvers. Therefor Wessalith and / or precipitated silicas are particularly suitable.
Sowohl beim "Coating" des Vorprodukts als auch alternativ beim Abpudem des Vorprodukts ohne "Coating" bzw. bei der Kombination von "Coating" und Abpudern ist - je nach Wassergehalt - zumindest ein teilweises Verdampfen der über das Neutralisat eingebrachten Wasseranteile wünschenswert bis erforderlich.Both in the "coating" of the preliminary product and alternatively in the degreasing of the preliminary product without "coating" or with the combination of "coating" and powdering - depending on the water content - At least a partial evaporation of the water components introduced via the neutralizate desirable to necessary.
Die Herstellung der Neutralisate kann im Rührkessel oder in allen herkömmlichen, gewöhnlichen Mischern erfolgen und wird separat durchgeführt. Zur Neutralisierung der Aniontensidsäure(n) wird konzentrierte Natronlauge eingesetzt. Die konzentrierte Natronlauge enthält zwischen 30 und 60 Gew.-% Natriumhydroxid, vorzugsweise zwischen 45 und 55 Gew.-%. Üblicherweise wird (werden) die Aniontensidsäure(n) vorgegeben und die Natronlauge als Neutralisationsmedium hinzugefügt. Auch eine umgekehrte Vorgehensweise ist möglich. In einer anderen Ausführungsform zur Herstellung des Neutralisats wird (werden) die Niotensidkomponente(n) vorgegeben, die Anionentenside in ihrer Säureform hinzugegeben und schließlich die Neutralisierung mit konzentrierter Natronlauge durchgeführt. In einer weiteren Ausführungsform werden die drei Komponenten des Neutralisats kontinuierlich und synchron in den Mischungsprozeß eingeführt.The neutralisates can be prepared in a stirred tank or in all conventional, customary ones Mixers are made and carried out separately. To neutralize the anionic surfactant acid (s) concentrated sodium hydroxide solution is used. The concentrated sodium hydroxide solution contains between 30 and 60% by weight sodium hydroxide, preferably between 45 and 55% by weight. The anionic surfactant acid (s) is (are) usually specified and the sodium hydroxide solution as Neutralization medium added. A reverse procedure is also possible. In In another embodiment for producing the neutralizate, the nonionic surfactant component (s) given, the anionic surfactants added in their acid form and finally the neutralization was carried out with concentrated sodium hydroxide solution. In another Embodiment, the three components of the neutralizate become continuous and synchronous introduced in the mixing process.
Das Neutralisat enthält ein oder mehrere anionische Tenside zwischen 10 und 99 Gew.-%, ein oder mehrere nicht-ionische Tenside zwischen 1 und 90 Gew.-% (jeweils bezogen auf das Neutralisat) und einen möglichst geringen Wasseranteil. Der einsetzbare Wassergehalt ist dabei abhängig von der Art und der Menge des eingesetzten Niotensids. Der Wassergehalt soll auf jeden Fall so zu bestimmen sein, daß nach der Neutralisation der Aniontensidsäure eine Flüssigphase erhalten bleibt.The neutralizate contains one or more anionic surfactants between 10 and 99% by weight, one or more non-ionic surfactants between 1 and 90 wt .-% (each based on the neutralizate) and the lowest possible water content. The usable water content depends on the type and amount of nonionic surfactant used. The water content should be determined in any case so that after the neutralization of the anionic surfactant a liquid phase is retained.
Die nach dieser bevorzugten Ausführungsform hergestellten aniontensidhaltigen Mischungen sind vorzugsweise bei Temperaturen zwischen 5 und 20 °C, insbesondere zwischen 8 und 15 °C, fließ- und pumpfähig.The anionic surfactant-containing mixtures prepared according to this preferred embodiment are preferably at temperatures between 5 and 20 ° C, in particular between 8 and 15 ° C, flowable and pumpable.
Als Aniontenside kommen die bekannten Sulfonate und Sulfate sowie Seifen aus vorzugsweise natürlichen Fettsäuren bzw. Fettsäuregemischen in Betracht. Vorzugsweise werden in der Ausführungsform der vollständigen Neutralisation Sulfofettsäuren und Fettsäuren in ihre Aniontenside überführt. Insbesondere ist der Einsatz von gesättigten und ungesättigten Fettsäuren mit C8-C18-Kettenlängen in Form ihrer Gemische und/oder der α-Sulfofettsäuren gesättigter C8-C18-Fettsäuren bevorzugt. Mit besonderem Vorteil können auch Mischungen der genannten Fettsäuren und α-Sulfofettsäuren mit weiteren Sulfonsäuren und Alkylschwefelsäuren, beispielsweise Alkylbenzolsulfonsäuren und Fettalkylschwefelsäuren, eingesetzt werden.The known sulfonates and sulfates and soaps made from preferably natural fatty acids or fatty acid mixtures are suitable as anionic surfactants. In the embodiment of complete neutralization, sulfo fatty acids and fatty acids are preferably converted into their anionic surfactants. In particular, the use of saturated and unsaturated fatty acids with C 8 -C 18 chain lengths in the form of their mixtures and / or the α-sulfofatty acids of saturated C 8 -C 18 fatty acids is preferred. Mixtures of the fatty acids and α-sulfo fatty acids mentioned with other sulfonic acids and alkylsulfuric acids, for example alkylbenzenesulfonic acids and fatty alkylsulfuric acids, can also be used with particular advantage.
Als Aniontenside in ihrer Säureform vom Sulfonsäuretyp kommen neben Alkylbenzolsulfonsäuren, Olefinsulfonsäuren, d.h. Gemische aus Alken- und Hydroxyalkansulfonsäuren sowie die Sulfonsäuren, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- und innenständiger Doppelbindung durch Sulfonieren mit gasförmigen Schwefeltrioxid erhält, in Betracht. Geeignet sind auch die Alkansulfonsäuren, die aus C12-C18-Alkanen durch Sulfochlorierung und Sulfoxidation und durch eine anschließende Hydrolyse bzw. durch Bisulfitaddition an Olefine erhältlich sind, sowie insbesondere die Ester von α-Sulfofettsäuren, z. B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkem-, oder Talgfettsäuren. Geeignete Alkylschwefelsäuren sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs, insbesondere aus Fettalkoholen, z. B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, Lauryl-, Myristyl-, Palmityl- oder Stearylalkohol, oder den C10-C20-Oxoalkoholen, und diejenigen sekundärer Alkohole dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten Alkohole, wie 2-Methyl-verzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid sind geeignet. Insbesondere ist es bevorzugt, mindestens zwei der genannten Aniontenside in ihrer Säureform, beispielsweise Fettsäure und Alkylbenzolsulfonsäure oder Fettsäure und Sulfofettsäuren von gesättigten und/oder ungesättigten Fettsäuren bzw. Sulfofettsäurealkylester gesättigter und/oder ungesättigter Fettsäuren, einzusetzen. Dabei ist es von besonderem Vorteil, wenn zunächst die Fettsäuren zu dem vorgelegten ethoxylierten Niotensid und anschließend die weiteren sulfierten Aniontenside in ihrer Säureform hinzugegeben werden.Anionic surfactants in their acid form of the sulfonic acid type include alkylbenzenesulfonic acids, olefin sulfonic acids, ie mixtures of alkene and hydroxyalkanesulfonic acids, and the sulfonic acids obtained, for example, from C 12 -C 18 monoolefins with terminal and internal double bonds by sulfonating with gaseous sulfur trioxide consideration. Also suitable are the alkanesulfonic acids which are obtainable from C 12 -C 18 alkanes by sulfochlorination and sulfoxidation and by subsequent hydrolysis or by bisulfite addition to olefins, and in particular the esters of α-sulfofatty acids, e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel, or tallow fatty acids. Suitable alkyl sulfuric acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, especially from fatty alcohols, e.g. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 moles of ethylene oxide, are also suitable. In particular, it is preferred to use at least two of the anionic surfactants mentioned in their acid form, for example fatty acid and alkylbenzenesulfonic acid or fatty acid and sulfofatty acids of saturated and / or unsaturated fatty acids or sulfofatty acid alkyl esters of saturated and / or unsaturated fatty acids. It is particularly advantageous if the fatty acids are first added to the ethoxylated nonionic surfactant and then the further sulfonated anionic surfactants in their acid form.
In einer bevorzugten Ausführungsform wird das eingesetzte Neutralisat aus Alkylbenzolsulfonsäure, Natronlauge und mindestens einem nicht-ionischen Tensid hergestellt ist. Insbesondere bevorzugt sind hierbei Alkylbenzolsulfonsäuren mit einer C9-C15-Alkylgruppe.In a preferred embodiment, the neutralizate used is made from alkylbenzenesulfonic acid, sodium hydroxide solution and at least one nonionic surfactant. Alkylbenzenesulfonic acids having a C 9 -C 15 alkyl group are particularly preferred.
In einer weiteren bevorzugten Ausführungsform wird das Neutralisat aus Alkylbenzolsulfonsäure, Natronlauge und nicht-ionischen Tensiden aus der Gruppe der ethoxylierten Niotenside hergestellt.In a further preferred embodiment, the neutralizate is composed of alkylbenzenesulfonic acid, Sodium hydroxide solution and non-ionic surfactants from the group of ethoxylated nonionic surfactants manufactured.
Die ethoxylierten Niotenside leiten sich von primären Alkoholen mit vorzugsweise 9 bis 18 Kohlenstoffatomen und durchschnittlich 1 bis 12 Mol Ethylenoxid pro Mol Alkohol ab, in denen der Alkoholrest linear oder in 2-Stellung methylverzweigt sein kann, bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch lineare Reste aus Alkoholen nativen Ursprungs mit 12 bis 18 Kohlenstoffatomen bevorzugt, wie z. B. Kokos-, Talgfett oder Oleylalkohol. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeschränkte Homologenverteilung (Narrow range ethoxylates, NRE) auf. Insbesondere sind Alkoholethoxylate bevorzugt, die durchschnittlich 2 bis 8 Ethylenoxidgruppen aufweisen. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C9-C11-Oxoalkohol mit 7 EO, C13-C15-Oxoalkohol mit 3 EO, 5 EO, 7 EO oder 8 EO und insbesondere C12-C14-Alkohole mit 3 EO oder 4 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 5 EO.The ethoxylated nonionic surfactants are derived from primary alcohols having preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol radical can be linear or methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture , as they are usually present in oxo alcohol residues. In particular, linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. coconut oil, tallow fat or oleyl alcohol. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups. The preferred ethoxylated alcohols include, for example, C 9 -C 11 oxo alcohol with 7 EO, C 13 -C 15 oxo alcohol with 3 EO, 5 EO, 7 EO or 8 EO and in particular C 12 -C 14 alcohols with 3 EO or 4 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
Diese Mischung aus Aniontensid in Säureform und ethoxylierten Niotensiden kann in einem breiten Gewichtsverhältnis, vorzugsweise in einem Gewichtsverhältnis Aniontensid in Säureform zu ethoxyliertem Niotensid von 1 : 0,5 bis 1 : 30, insbesondere bis 1 : 20, hergestellt werden. Dabei werden vorteilhafterweise im Fall der vollständigen Neutralisation Mischungen eingesetzt, in denen das Gewichtsverhältnis Aniontensid in Säureform zu ethoxyliertem Niotensid kleiner als 1, vorzugsweise 1 : 2 bis 1 : 20 und insbesondere kleiner als 1 : 5 ist.This mixture of anionic surfactant in acid form and ethoxylated nonionic surfactants can be combined in one broad weight ratio, preferably in a weight ratio of anionic surfactant in acid form to ethoxylated nonionic surfactant from 1: 0.5 to 1:30, in particular up to 1:20 become. Mixtures are advantageously used in the case of complete neutralization used in which the weight ratio of anionic surfactant in acid form to ethoxylated nonionic surfactant is less than 1, preferably 1: 2 to 1:20 and in particular less than 1: 5.
In einer bevorzugten Ausführungsform wird bei einer Temperatur von mindestens 50 °C das separat hergestellte Neutralisat auf den silikatischen Builder im ersten Mischer aufgebracht. Insbesondere bevorzugt sind hierbei Temperaturen zwischen 70 °C und 90 °C. Die Zudosierung erfolgt bei laufendem Mischer und Messerkranz. Als geeignete Mischer seien z.B. Eirich-Mischer der Serien R und RV, hergestellt durch die Maschinenfabrik Gustav Eirich, Hardheim, Deutschland, die Fukae FS-G Mischer, hergestellt durch die Fukae Powtech Kogyo Co., Japan, die Lödige FM, KM und CB Mischer, hergestellt durch die Lödige Maschinenbau GmbH, Paderborn, Deutschland, oder die Drais Serien T oder K-T, hergestellt durch die Drais Werke GmbH, Mannheim, Deutschland, genannt. Dabei wird das Neutralisat vorzugsweise über Düsen in den Mischer eingeführt. Die Zugabe kann aber auch - wenn auch weniger bevorzugt - manuell, etwa durch Schütten, erfolgen.In a preferred embodiment, the at a temperature of at least 50 ° C. separately prepared neutralisate applied to the silicate builder in the first mixer. Temperatures between 70 ° C. and 90 ° C. are particularly preferred. The metering takes place with the mixer and knife ring running. Suitable mixers are e.g. Eirich mixer the R and RV series, manufactured by the machine factory Gustav Eirich, Hardheim, Germany, the Fukae FS-G mixer, manufactured by the Fukae Powtech Kogyo Co., Japan, the Lödige FM, KM and CB mixers, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany, or the Drais series T or K-T by Drais Werke GmbH, Mannheim, Germany. The neutralisate preferably introduced into the mixer via nozzles. The addition can also - if also less preferred - manually, for example by pouring.
Als silikatische Builderkomponenten werden granulare, durch Sprühtrocknung, Verdichtung und Vermahlen erhaltene Natrium- und/oder Kaliumsilikate mit einem molaren SiO2:M2O-Verhältnis von vorzugsweise 2,0 bis 3,0, insbesondere Natriumsilikate mit einem gewissen Wassergehalt eingesetzt. Der Wassergehalt liegt vorzugsweise zwischen 15 und 22 Gew.-%. Im Rahmen der Erfindung werden nur granulare Silikate verwendet. Insbesondere wird auf den Einsatz von Alkalicarbonaten verzichtet. Insbesondere bevorzugt sind granulare Silikate, ausgewählt aus den käuflich erwerbbaren granularen Britesil(R)-Disilikaten (Handelsprodukte von AKZO-PQ Silica) des Typs H20 (Modul 2,0), H20 Plus (Modul 2,0) und H24 (Modul 2,4), welche sich als Substitute für Zeolithe und/oder kristalline schichtförmige Disilikate eignen. Die verfahrensgemäß hergestellten Wasch- und Reinigungsmittel enthalten mindestens 15 Gew.-%, insbesondere 30 bis 60 Gew.-%, bezogen auf die gesamte Wasch- oder Reinigungsmittelrezeptur, dieser granularen Silikate. Diese wasserlösliche amorphen, granularen Silikate sind insbesondere auch gegenüber vermahlenem Wasserglas bevorzugt. Sie weisen, verglichen mit Wasserglas, ein deutlich verzögertes Löseverhalten auf. Damit werden die genannten Alkalisilikate auch ihrer Builderwirkung gerecht, ohne jedoch unlösliche Wasch- oder Reinigungsrückstände zu hinterlassen.Granular sodium and / or potassium silicates obtained by spray drying, compression and grinding with a molar SiO 2 : M 2 O ratio of preferably 2.0 to 3.0, in particular sodium silicates with a certain water content, are used as silicate builder components. The water content is preferably between 15 and 22% by weight. Only granular silicates are used in the context of the invention. In particular, the use of alkali carbonates is dispensed with. Granular silicates, selected from the commercially available granular Britesil (R) disilicates (commercial products from AKZO-PQ Silica) of the type H20 (module 2.0), H20 Plus (module 2.0) and H24 (module 2, 4), which are suitable as substitutes for zeolites and / or crystalline layered disilicates. The detergents and cleaning agents produced in accordance with the process contain at least 15% by weight, in particular 30 to 60% by weight, based on the total detergent or cleaning agent formulation, of these granular silicates. These water-soluble amorphous, granular silicates are particularly preferred over ground water glass. Compared to water glass, they show a significantly delayed dissolving behavior. This means that the alkali silicates mentioned also do justice to their builder effect, but without leaving behind insoluble washing or cleaning residues.
In einer weiteren bevorzugten Ausführungsform wird dem mit Neutralisat behandelten Builder mindestens eine weitere anionische Tensidkomponente und/oder eine Seifenkomponente neben anderen typischen Waschmittelkomponenten zugesetzt.In a further preferred embodiment, the builder treated with neutralized at least one further anionic surfactant component and / or one soap component added alongside other typical detergent components.
Hierbei kommen als Tenside bevorzugt Tenside vom Sulfonat-Typ, insbesondere bevorzugt C9-C13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit endoder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind aber auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden.The surfactants used here are preferably surfactants of the sulfonate type, particularly preferably C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. However, alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
Bevorzugte Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobemsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8-C18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeschränkter Homologenverteilung ableiten, besonders bevorzugt. Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a restricted homolog distribution, are particularly preferred.
Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkem- oder Talgfettsäuren.The esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate insbesondere bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN(R) erhalten werden können, sind geeignete Aniontenside.The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN (R) , are also suitable anionic surfactants.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten Alkohole, wie 2-Methyl-verzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid, sind geeignet.The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Die Aniontenside werden vorzugsweise in Mengen von 3 bis 25 Gew.-%, insbesondere in Mengen von 10 bis 20 Gew.-%, jeweils bezogen auf die Summe der eingesetzten Bestandteile, eingesetzt. Ihr Gehalt kann jedoch auch über 15 Gew.-% hinausgehen. Bevorzugte Aniontenside sind Fettalkylsulfate, Alkylbenzolsulfonate, Sulfosuccinate sowie Mischungen aus diesen, wie Mischungen aus Fettalkylsulfaten und Sulfosuccinaten oder Fettalkylsulfaten und Fettalkylbenzolsulfaten, insbesondere in Kombination mit Seife. Dabei ist es insbesondere bevorzugt, daß wenigstens ein Teil der Sulfonat- und/oder Sulfat-Tenside nicht als.fester Bestandteil, sondern in flüssiger Form als Bestandteil der Granulierflüssigkeit eingesetzt wird. The anionic surfactants are preferably used in amounts of 3 to 25% by weight, in particular in Quantities of 10 to 20% by weight, based in each case on the sum of the constituents used, used. However, their content can also exceed 15% by weight. preferred Anionic surfactants are fatty alkyl sulfates, alkyl benzene sulfonates, sulfosuccinates and mixtures from these, such as mixtures of fatty alkyl sulfates and sulfosuccinates or fatty alkyl sulfates and fatty alkyl benzene sulfates, especially in combination with soap. It is special preferred that at least some of the sulfonate and / or sulfate surfactants are not as solid Component, but used in liquid form as part of the granulating liquid becomes.
Als weitere Tenside kommen Seifen, entweder allein oder in Kombination mit den genannten anionischen Tensiden, in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie Salze der Myristin-, Laurin-, Palmitin- oder Stearinsäure. Ebenfalls geeignet sind ungesättigte Fettsäuren, die sich beispielsweise von der Ölsäure ableiten. Geeignet sind auch Fettsäuregemische, die sich aus natürlichen Resourcen extrahieren lassen, z.B. Kokos-, Palmkern- oder Talgfettsäuren. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten C12-C18-Fettsäureseifen zusammengesetzt sind. Die Seifen liegen vorzugsweise in Mengen von 0,5 bis 8 Gew.-% vor.Other suitable surfactants are soaps, either alone or in combination with the anionic surfactants mentioned. Saturated fatty acid soaps, such as salts of myristic, lauric, palmitic or stearic acid, are particularly suitable. Unsaturated fatty acids derived, for example, from oleic acid are also suitable. Fatty acid mixtures which can be extracted from natural resources, for example coconut, palm kernel or tallow fatty acids, are also suitable. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 18 fatty acid soaps. The soaps are preferably present in amounts of 0.5 to 8% by weight.
Als weitere typische Komponenten von Wasch- und Reinigungsmitteln werden beispielsweise organische Cobuilder, Vergrauungsinhibitoren, wie etwa anionische und/oder nicht-ionische Cellulosederivate, insbesondere Carboxymethylcellulose (CMC) und/oder Methylcellulose (MC), und Polyvinylpyrrolidon (PVP) oder Schauminhibitoren, wie etwa Silikone oder Paraffinöle auf granularen Trägern und Fettalkylphosphorsäureestem eingesetzt.Other typical components of detergents and cleaning agents are, for example organic cobuilders, graying inhibitors, such as anionic and / or non-ionic Cellulose derivatives, especially carboxymethyl cellulose (CMC) and / or methyl cellulose (MC), and polyvinyl pyrrolidone (PVP) or foam inhibitors such as silicones or paraffin oils used on granular carriers and fatty alkyl phosphoric acid esters.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen.Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, To name gluconic acid and any mixtures of these.
Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500000. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 bis 30000. Ein bevorzugtes Dextrin ist in der britischen Patentanmeldung 94 19 091 beschrieben. Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Derartige oxidierte Dextrine und Verfahren ihrer Herstellung sind beispielsweise aus den europäischen Patentanmeldungen EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 und EP-A-0 542 496 sowie den internationalen Patentanmeldungen WO-A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 und WO-A-95/20608 bekannt. Ein an C6 des Saccharidrings oxidiertes Produkt kann besonders vorteilhaft sein.Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for is the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608 are known. A product oxidized at C 6 of the saccharide ring can be particularly advantageous.
Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten. Derartige Cobuilder werden beispielsweise in der internationalen Patentanmeldung WO-A-95/20029 beschrieben.Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups. Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.
Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Auch homopolymere Salze der Acrylsäure mit relativen Molekülmassen zwischen etwa 2000 und etwa 15000, insbesondere zwischen 4000 und 10000 sind geeignet.Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular weight, based on free acids, is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000. Also homopolymeric salts of acrylic acid with relative molecular weights between about 2000 and about 15,000, especially between 4,000 and 10,000, are suitable.
Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden, wobei 20 bis 55 Gew.-%ige wäßrige Lösungen bevorzugt sind.The (co) polymeric polycarboxylates can either be as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
Insbesondere bevorzugt sind auch Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die gemäß der DE-A-43 00 772 als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder gemäß der DE-C-42 21 381 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten.Polymers composed of more than two different monomer units are also particularly preferred, for example those which, according to DE-A-43 00 772, are monomers as salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE-A-43 03 320 und DE-A-44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Other preferred copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
Weitere geeignete Buildersubstanzen sind Oxidationsprodukte von carboxylgruppenhaltigen Polyglucosanen und/oder deren wasserlöslichen Salzen, wie sie beispielsweise in der internationalen Patentanmeldung WO-A-93/08251 beschrieben werden oder deren Herstellung beispielsweise in der internationalen Patentanmeldung WO-A-93/16110 beschrieben wird. Ebenfalls geeignet sind auch oxidierte Oligosaccharide gemäß der älteren deutschen Patentanmeldung P 196 00 018.1.Other suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those used in the international Patent application WO-A-93/08251 can be described or their preparation is described, for example, in international patent application WO-A-93/16110. Oxidized oligosaccharides according to the earlier German patent application are also suitable P 196 00 018.1.
Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate, von denen in der deutschen Patentanmeldung P 195 40 086.0 offenbart wird, daß sie neben Cobuilder-Eigenschaften auch eine bleichstabilisierende Wirkung aufweisen.Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, of which in German patent application P 195 40 086.0 discloses that in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP-A-0 280 223 beschrieben, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 described, can be obtained. Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
Zu den weiteren granularen Bestandteilen gehören beispielsweise auch kompaktierte Bleichmittel- bzw. Bleichaktivatorgranulate, Enzym-Granulate, Schauminhibitor-Granulate, vorzugsweise konzentrierte Schauminhibitor-Granulate sowie granulare Träger für Farb- und Duftstoffe.The other granular components include, for example, compact ones Bleaching agent or bleach activator granules, enzyme granules, foam inhibitor granules, preferably concentrated foam inhibitor granules and granular carriers for color and Fragrances.
Als Bleichaktivatoren dienen beispielsweise mit H2O2 organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N'-tetraacylierte Diamine, ferner Carbonsäureanhydride und Ester von Polyolen wie Glucosepentaacetat. Der Gehalt der bleichmittelhaltigen Mittel an Bleichaktivatoren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 2 und 8 Gew.-%. Besonders bevorzugte Bleichaktivatoren sind N,N,N',N'-Tetraacetylethylendiamin (TAED) und 1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazin (DADHT).Serve as bleach activators, for example, with H 2 O 2 which form organic peracids N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, also carboxylic anhydrides and esters of polyols such as glucose pentaacetate. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 2 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED) and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT).
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Ihr Anteil kann etwa 0,2 bis etwa 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are enzymatic Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Your share can about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
Als Stabilisatoren insbesondere für Perverbindungen und Enzyme kommen beispielsweise die Salze von Polyphosphonsäuren, insbesondere 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) in Betracht.Examples of stabilizers, in particular for per-compounds and enzymes the salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP) into consideration.
Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an C18-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure. Mit Vorteil werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche, aus Silikonen, Paraffinen oder Wachsen.Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes, are also advantageously used.
Als weitere typische Waschmittelkomponenten können Bleichmittel dem Vorprodukt zugesetzt werden.Bleaching agents can be added to the preliminary product as further typical detergent components become.
In einer bevorzugten Ausführungsform werden als Bleichmittel insbesondere Perborate und/oder Percarbonate eingesetzt. Vorzugsweise werden Natriumperborattetrahydrat und Natriumperboratmonohydrat verwendet. Unter den Percarbonaten werden vorzugsweise Natriumpercarbonate verwendet. Neben oder anstatt den (der) Perborate(n) und den (der) Percarbonate(n) können gegebenenfalls auch Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, etwa Perbenzoate und/oder Peroxaphthalate, zum Einsatz kommen. Der Anteil der Bleichmittel, bezogen auf das fertige Produkt, beträgt 5 bis 25 Gew.-%, insbesondere 10 bis 20 Gew.-%. Erfindungsgemäß werden die Bleichmittel neben den anderen oben genannten üblichen Waschmittelkomponenten dem behandelten Builder zur Herstellung des Vorprodukts zugesetzt. Gegebenenfalls kann die Zugabe der Bleichmittel ganz oder teilweise aber auch in einem der Granulation nachgeschalteten Aufbereitungsschritt erfolgen.In a preferred embodiment, perborates and / or percarbonates are used in particular as bleaching agents. Sodium perborate tetrahydrate and sodium perborate monohydrate are preferably used. Among the percarbonates, sodium percarbonates are preferably used. In addition to or instead of the perborate (s) and the percarbonate (s), it is also possible, if appropriate, to use peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, for example perbenzoates and / or peroxaphthalates. The proportion of the bleaching agents, based on the finished product, is 5 to 25% by weight, in particular 10 to 20% by weight. According to the invention, the bleaching agents are added to the treated builder for the production of the intermediate product in addition to the other usual detergent components mentioned above. If appropriate, the bleaching agents can also be added in whole or in part in a preparation step downstream of the granulation.
Das Vorprodukt oder das durch "Coating" und/oder Abpudem weiterbehandelte Vorprodukt wird in dem zweiten Mischer mit weiteren üblichen Waschmittelrohstoffen vermischt und unter Zugabe von Flüssigkeit(en) granuliert. Bevorzugt ist hierbei der Einsatz von Polycarboxylat-Lösung als Granulationsflüssigkeit.The preliminary product or the preliminary product further treated by "coating" and / or dewatering is mixed in the second mixer with other common detergent raw materials and under Addition of liquid (s) granulated. The use of polycarboxylate solution is preferred as granulation liquid.
In einer weiteren bevorzugten Ausführungsform wird als Granulationsflüssigkeit im Granulationsschritt eine Mischung aus optischen Aufhellern und Polycarboxylat-Lösung zugesetzt. Als optische Aufheller kommen Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze in Betracht. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4'-Distyryl-di-phenyls anwesend sein, z.B. die Verbindung 4,4'-Bis(4-chlor-3-sulfostyryl)diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden. Besonders einheitlich weiße Granulate werden erhalten, wenn die Mittel außer den üblichen Aufhellern in üblichen Mengen, beispielsweise zwischen 10 -6 bis 10 -3 Gew.-%, vorzugsweise zwischen 0,1 und 0,3 Gew.-%, auch geringe Mengen, beispielsweise 10-6 bis 10-3 Gew.-%, vorzugsweise um 10-5 Gew.%, eines blauen Farbstoffes enthält. Ein besonders bevorzugter Farbstoff ist Tinolux® (Handelsprodukt der Ciba-Geigy).In a further preferred embodiment, a mixture of optical brighteners and polycarboxylate solution is added as the granulation liquid in the granulation step. Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts are suitable as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Particularly uniform white granules are obtained if, in addition to the usual brighteners, the agents are used in customary amounts, for example between 10 -6 to 10 -3 % by weight, preferably between 0.1 and 0.3% by weight, even small amounts. contains, for example, 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
Die Granulation wird erfindungsgemäß als Misch-, Preß- oder Walzengranulation in dem Fachmann geläufigen Mischern, Extrudern oder Walzenpressen durchgeführt. Die Granulation erfolgt jedoch insbesondere bevorzugt in einem Mischer/Granulator. Als geeignete Mischer seien z.B. Eirich-Mischer der Serien R und RV, hergestellt durch die Maschinenfabrik Gustav Eirich, Hardheim, Deutschland, die Fukae FS-G Mischer, hergestellt durch die Fukae Powtech Kogyo Co., Japan, die Lödige FM, KM und CB Mischer, hergestellt durch die Lödige Maschinenbau GmbH, Paderborn, Deutschland, oder die Drais Serien T oder K-T, hergestellt durch die Drais Werke GmbH, Mannheim, Deutschland, genannt. Auch Intensivmischer der Firma IMCATEC (Deutschland) kommen in Betracht. Die übliche, zur Granulation benötigte Verweilzeit in diesen Mischern liegt im Bereich von einer Minute bis ca. 10 Minuten.According to the invention, the granulation is carried out as mixing, pressing or roller granulation in the Mixers, extruders or roller presses familiar to those skilled in the art. The granulation however, it is particularly preferably carried out in a mixer / granulator. As a suitable mixer e.g. Eirich mixers of the R and RV series, manufactured by the machine factory Gustav Eirich, Hardheim, Germany, the Fukae FS-G mixer, manufactured by the Fukae Powtech Kogyo Co., Japan, the Lödige FM, KM and CB mixers, manufactured by the Lödige Maschinenbau GmbH, Paderborn, Germany, or the Drais series T or K-T by Drais Werke GmbH, Mannheim, Germany. Intensive mixer too Company IMCATEC (Germany) are considered. The usual one needed for granulation Residence time in these mixers is in the range of one minute to approximately 10 minutes.
In einer bevorzugten Ausführungsform wird das erfindungsgemäß hergestellte Granulat unter Verwendung von Fließverbesserern am Ende der Granulierung abgepudert und getrocknet. Insbesondere bevorzugt sind hierbei als Fließverbesserer amorphe und/oder kristalline Aluminiumsilikate sowie Kieselsäuren. Unter den Aluminiumsilikaten ist Zeolith A und/oder X und/oder P, beispielsweise Wessalith P® (Handelsprodukt der Firma Degussa, Deutschland), und unter den Kieselsäuren Sipernat® ganz besonders bevorzugt. Die Fließverbesserer werden dem Granulat üblicherweise untergemischt. Ihr Anteil, bezogen auf das Fertigprodukt, beträgt zwischen 0,5 und 8 Gew.-%. Insbesondere bevorzugt ist ein Anteil der Kieselsäuren zwischen 0,5 und 3 Gew.-% und/oder ein Anteil der Zeolithe zwischen 1,5 und 7,5 Gew.-%.In a preferred embodiment, the granulate produced according to the invention is under Using flow improvers, powdered and dried at the end of the granulation. Amorphous and / or crystalline aluminum silicates are particularly preferred as flow improvers as well as silicas. Zeolite A and / or X is among the aluminum silicates and / or P, for example Wessalith P® (commercial product from Degussa, Germany), and particularly preferred among the silicas Sipernat®. The flow improver are usually mixed into the granulate. Your share, based on the finished product, is between 0.5 and 8% by weight. A proportion of the silicas is particularly preferred between 0.5 and 3% by weight and / or a proportion of the zeolites between 1.5 and 7.5 Wt .-%.
Das Zwischenprodukt enthält typischerweise zwischen 0 und 10 Gew.-% Niotensid, von 40 bis 65 Gew.-% Disilikat, von 5 bis 15 Gew.-% ABS, von 2 bis 10 Gew.-% Fließverbesserer, von 0 bis 20 Gew.-% Polycarboxylat sowie Wasser.The intermediate typically contains between 0 and 10% by weight nonionic surfactant, of 40 up to 65% by weight disilicate, from 5 to 15% by weight ABS, from 2 to 10% by weight flow improver, from 0 to 20% by weight of polycarboxylate and water.
Der Trocknungsschritt wird in der Wirbelschicht insbesondere bei Zulufttemperaturen unterhalb von 180 °C durchgeführt. Derart erfindungsgemäß hergestellte Produkte weisen eine Schüttdichte von mehr als 600 g/l auf. Die erfindungsgemäß hergestellten Granulate sind schütt- und rieselfähig, nicht klebend und nahezu staubfrei.The drying step is carried out in the fluidized bed, especially at supply air temperatures below of 180 ° C. Products manufactured in accordance with the invention have a Bulk density of more than 600 g / l. The granules produced according to the invention are pourable and pourable, non-sticky and almost dust-free.
Hierauf folgt verfahrensgemäß die dem Fachmann geläufige Aufbereitung des Granulats zum Fertigprodukt.This is followed, in accordance with the process, by the preparation of the granules known to the person skilled in the art Finished product.
Die granularen Wasch- und Reinigungsmittel, hergestellt nach dem erfindungsgemäßen Verfahren, enthalten vorzugsweise zwischen 3 und 12 Gew.-%, insbesondere zwischen 3 und 6 Gew.-% Niotenside, 10 bis 60 Gew.-%, insbesondere zwischen 30 und 60 Gew.-% Alkalisilikate als vorgelegten Feststoff und 10 bis 35 Gew.-%, insbesondere zwischen 15 und 35 Gew.-% anionische Tenside. Die erfindungsgemäß hergestellten Granulate haben eine Schüttdichte oberhalb von 600 g/l, vorzugsweise zwischen 700 und 1000 g/l.The granular detergents and cleaning agents, produced according to the invention Processes preferably contain between 3 and 12% by weight, in particular between 3 and 6% by weight nonionic surfactants, 10 to 60% by weight, in particular between 30 and 60% by weight Alkali silicates as a solid and 10 to 35 wt .-%, in particular between 15 and 35% by weight of anionic surfactants. The granules produced according to the invention have one Bulk density above 600 g / l, preferably between 700 and 1000 g / l.
Die vorliegende Erfindung wird durch die nachfolgenden Ausführungsbeispiele näher erläutert: The present invention is explained in more detail by the following exemplary embodiments:
Das Granulat mit einem Gewichtsverhältnis FAS:ABS von etwa 3,3:1 war gut rieselfähig und wies eine Schüttdichte von 810 g/l auf.The granules with a weight ratio of FAS: ABS of about 3.3: 1 were easy to pour and had a bulk density of 810 g / l.
Die bereits in Ausführungsbeispiel 1 eingesetzten Komponenten wurden in dieser Rezeptur auf die gleiche Weise wie in Beispiel 1 verarbeitet. Abgesehen vom veränderten Verhältnis von FAS:ABS (1,2:1) und den daraus resultierenden Veränderungen in der Neutralisatzusammensetzung bzw. dem Neutralisatanteil wurden die gleichen Stoffmengen - insbesondere an Aniontensiden - wie in der Rezeptur des Beispiels 1 vorgelegt.The components already used in embodiment 1 were used in this recipe processed in the same manner as in Example 1. Apart from the changed relationship of FAS: ABS (1.2: 1) and the resulting changes in the neutralizate composition or the neutralizate portion were the same amounts of substance - especially on anionic surfactants - as presented in the formulation of Example 1.
Das erhaltene Granulat war ebenfalls gut rieselfähig und hatte eine Schüttdichte von 920 g/l. The granules obtained were also free-flowing and had a bulk density of 920 g / l.
Die Herstellung dieses Granulats erfolgte im "Einschrittverfahren", d.h. diese Verarbeitung erfolgte im gleichen Mischer ohne Trennung von Vorproduktherstellung und Granulation. Die Rezeptur der beim vorliegenden Vergleichsbeispiel eingesetzten Mischung und die eingesetzten Rohstoffe, Compounds und Granulierflüssigkeiten entsprechen der Rezeptur und den Einsatzstoffen des Beispiels 1.This granulate was produced in the "one-step process", i.e. this processing was carried out in the same mixer without separating preproduction and granulation. The Recipe of the mixture used in the present comparative example and the ones used Raw materials, compounds and granulating liquids correspond to the recipe and the Starting materials of Example 1.
Hierbei wurden Britesil®, Sokalan CP 5® als Pulver, Seife, Phosphonat, FAS und optischer Aufheller in der gleichen Weise wie in Beispiel 1 vorgelegt und zunächst (a) das Neutralisat und dann (b) die Copolymer-haltige Granulierflüssigkeit hinzugegeben. Es wurde danach über den gleichen Zeitraum wie bei den Beispielen 1 und 2 granuliert. Die weiteren Verfahrensschritte (Abpuderung mit Fließverbesserern und Trocknung) waren identisch mit dem Vorgehen in den Beispielen 1 und 2.Here, Britesil®, Sokalan CP 5® as powder, soap, phosphonate, FAS and optical Brightener presented in the same manner as in Example 1 and first (a) the neutralizate and then (b) adding the copolymer-containing granulating liquid. It became afterwards granulated over the same period as in Examples 1 and 2. The further process steps (Powdering with flow improvers and drying) were identical to that Procedure in Examples 1 and 2.
Das Granulat verklumpte im Trockner und bei der anschließenden Grobkornabsiebung, so daß Anbackungen entstanden. Eine betriebssichere Produktion war somit nicht möglich.The granules clumped in the dryer and during the subsequent coarse grain screening, see above that caking occurred. Reliable production was therefore not possible.
Claims (14)
- Process for the preparation of a storable and flowable granulate of detergents and cleaners containing anionic surfactant and having a bulk density above 600 g/l characterized in that firstly (a) a completely neutralized neutralizate comprising at least one anionic surfactant acid, at least one nonionic surfactant and sodium hydroxide solution is prepared, (b) applied to a water-soluble silicatic builder to prepare a preproduct, (c) this is combined with further customary detergent constituents and finally (d) granulated with a granulating liquid, whereby the preparation of the preproduct and the preparation of the granulate take place in a spatially separate manner and continuously.
- Process according to Claim 1, characterized in that, following the preparation of the nonflowable preproduct, it is treated by a coating with coating substances.
- Process according to Claim 1 or 2, characterized in that the preproduct is powdered prior to the granulation with flow improvers.
- Process according to one of the preceding claims, characterized in that the neutralizate used is prepared from alkylbenzenesulphonic acid, sodium hydroxide solution and at least one nonionic surfactant.
- Process according to Claim 4, characterized in that the neutralizate is prepared from alkylbenzenesulphonic acid, sodium hydroxide solution and nonionic surfactants from the group of ethoxylated nonionic surfactants.
- Process according to one of the preceding claims, characterized in that the metered addition of the neutralizate takes place at a temperature of at least 50°C and with the mixer running.
- Process according to one of the preceding claims, characterized in that, among the further detergent constituents, at least one further anionic surfactant and, or at least one further soap component is added to the builders obtained following treatment with the neutralizate.
- Process according to one of the preceding claims, characterized in that the bleaches used are perborates and/or percarbonates.
- Process according to one of the preceding claims, characterized in that, in the granulation step, a polycarboxylate solution is used as metered-in granulation liquid.
- Process according to Claim 9, characterized in that the polycarboxylate solution comprises optical brighteners.
- Process according to one of the preceding claims, characterized in that the granulated product is powdered by superficial incorporation of flow improvers.
- Process according to Claim 11, characterized in that the flow improvers used are zeolites and/or amorphous and/or crystalline aluminium silicates.
- Detergent and cleaner prepared according to one of the preceding claims, characterized in that it comprises 3 to 12% by weight of nonionic surfactants, 10 to 60% by weight of alkali metal silicates as initially charged solid and 10 to 35% by weight of anionic surfactants.
- Detergent and cleaner prepared by one of the preceding claims, characterized in that it comprises 3 to 12% by weight of nonionic surfactants, 30 to 60% by weight of alkali metal silicates as initially charged solid and 15 to 35% by weight of anionic surfactants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19731890A DE19731890A1 (en) | 1997-07-24 | 1997-07-24 | Process for the production of storable and free-flowing granules of detergents and cleaning agents containing anionic surfactants |
| DE19731890 | 1997-07-24 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0893492A2 EP0893492A2 (en) | 1999-01-27 |
| EP0893492A3 EP0893492A3 (en) | 1999-05-12 |
| EP0893492B1 true EP0893492B1 (en) | 2003-05-21 |
Family
ID=7836791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98113138A Expired - Lifetime EP0893492B1 (en) | 1997-07-24 | 1998-07-15 | Process for making a storage stable and flowable granulate from anionic detergent compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0893492B1 (en) |
| AT (1) | ATE241005T1 (en) |
| DE (2) | DE19731890A1 (en) |
| ES (1) | ES2200240T3 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8922018D0 (en) * | 1989-09-29 | 1989-11-15 | Unilever Plc | Detergent compositions and process for preparing them |
| DE4216629A1 (en) * | 1992-05-20 | 1993-11-25 | Henkel Kgaa | Process for the production of detergents and cleaning agents containing anionic surfactants |
| TW326472B (en) * | 1994-08-12 | 1998-02-11 | Kao Corp | Method for producing nonionic detergent granules |
| JPH09241695A (en) * | 1996-03-05 | 1997-09-16 | Lion Corp | Production of high-bulk density granular detergent composition with good color tone and its production |
-
1997
- 1997-07-24 DE DE19731890A patent/DE19731890A1/en not_active Withdrawn
-
1998
- 1998-07-15 EP EP98113138A patent/EP0893492B1/en not_active Expired - Lifetime
- 1998-07-15 AT AT98113138T patent/ATE241005T1/en not_active IP Right Cessation
- 1998-07-15 ES ES98113138T patent/ES2200240T3/en not_active Expired - Lifetime
- 1998-07-15 DE DE59808416T patent/DE59808416D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE241005T1 (en) | 2003-06-15 |
| DE59808416D1 (en) | 2003-06-26 |
| DE19731890A1 (en) | 1999-01-28 |
| EP0893492A2 (en) | 1999-01-27 |
| ES2200240T3 (en) | 2004-03-01 |
| EP0893492A3 (en) | 1999-05-12 |
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