EP0716684B1 - Builder component for washing or cleaning products - Google Patents
Builder component for washing or cleaning products Download PDFInfo
- Publication number
- EP0716684B1 EP0716684B1 EP94926862A EP94926862A EP0716684B1 EP 0716684 B1 EP0716684 B1 EP 0716684B1 EP 94926862 A EP94926862 A EP 94926862A EP 94926862 A EP94926862 A EP 94926862A EP 0716684 B1 EP0716684 B1 EP 0716684B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- quantities
- sodium
- additives
- roll
- 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
- 238000004140 cleaning Methods 0.000 title claims 5
- 238000005406 washing Methods 0.000 title abstract description 11
- 150000004760 silicates Chemical class 0.000 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 239000004615 ingredient Substances 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 239000003599 detergent Substances 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 235000005985 organic acids Nutrition 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000007519 polyprotic acids Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 4
- 238000009826 distribution Methods 0.000 claims 2
- 239000011362 coarse particle Substances 0.000 claims 1
- 239000010419 fine particle Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims 1
- 239000012459 cleaning agent Substances 0.000 abstract description 16
- 239000004115 Sodium Silicate Substances 0.000 abstract description 3
- 235000019351 sodium silicates Nutrition 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000009490 roller compaction Methods 0.000 description 7
- 229910052615 phyllosilicate Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004753 textile Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 optical brighteners Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- 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
-
- 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
- C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- 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
Definitions
- the invention relates to a builder component with a very high bulk density and to detergents or cleaning agents which contain this component.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
- both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
- ⁇ -sodium disilicate is commercially available under the name SKS 7 (R)
- ⁇ -sodium disilicate is available under the name SKS 6 (R) (commercial products from Hoechst AG, Federal Republic of Germany).
- SKS 7 (R) commercial products from Hoechst AG, Federal Republic of Germany.
- crystalline layered silicates according to the disclosure of the international patent application WO-A-92/18594 spray-drying detergent-containing slurries suffer losses in their washing action caused by the destruction of their physical structure, they should preferably be used by other process methods in washing or cleaning agents can be incorporated. However, due to their high proportion of fine grains and thus their dusty structure, these powders are also unsuitable for use as an admixing component with other granular components of detergents or cleaning agents. In addition, since crystalline layered silicates such as crystalline disilicates have a lower dissolution rate in water than amorphous silicates, local deposits on the textiles can lead to an increase in the pH value to values above 12, which can damage the textile fibers.
- the crystalline layered silicates are used in the form of a granular builders component which contains at least 10% by weight of crystalline layered silicates and 5 to 90% by weight in water Form of ions of organic acids and / or inorganic or organic salts present, the material used should not, however, exceed an average size of 300 ⁇ m, and optionally contain further binders, surfactants and other common ingredients of detergents or cleaning agents.
- a preferred way of producing this builder component is roller compaction, in which a pressure of 10 to 50 kN / cm roller length and preferably around 25 kN / cm roller length is used.
- Such builders components still have high pH values in 1% aqueous solution; however, since these components have a higher dissolution rate than the powder, the risk of local deposits on textiles and thus damage to textile fibers is reduced.
- this invention is limited to builder components which contain a maximum of 95% by weight of crystalline layered silicates.
- the object of the invention was to further develop methods of roller compacting builders components containing crystalline phyllosilicates in such a way that, on the one hand, the most effective, i.e. concentrated builders components are obtained and on the other hand an improvement in the dissolving behavior of builders components which contain crystalline phyllosilicates above 95% by weight is achieved.
- the builders components should therefore contain as little as possible of additives.
- the invention accordingly relates to a process for the preparation of a builder component which contains crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number of 0 to 20, by roller compacting at pressures up to 50 kN / cm roller length, the crystalline layered silicates in amounts of more than 95% by weight to 99.8% by weight and customary solid ingredients of detergents or cleaning agents as additives in Amounts of 0.2 to less than 5 wt .-% are used.
- Disilicates particularly ⁇ -sodium disilicates and ⁇ -sodium disilicate, are used as particularly preferred crystalline sheet silicates.
- Which conventional solid ingredients of washing or cleaning agents can in principle be used can be found, for example, in international patent application WO-A-92/18594.
- the invention particularly includes a method for roller compaction, in which 96 to 99% by weight of crystalline phyllosilicates are compacted in a mixture with additives, which are either organic acids, preferably polybasic organic acids, and / or salts of inorganic and / or organic acids, preferably polybasic acids. It was particularly surprising that even small amounts of these preferred additives are sufficient to bring about a significantly improved dissolving behavior of the builders components compared to a 100% by weight roll-compacted crystalline layered silicate granulate.
- additives which are either organic acids, preferably polybasic organic acids, and / or salts of inorganic and / or organic acids, preferably polybasic acids.
- additives are sulfates, in particular sodium sulfate and carbonates
- the preferred organic additives include citric acid, tartaric acid, succinic acid, glutaric acid, adipic acid and sugar acids and their salts. These additives can be used alone or in a mixture with each other.
- sulfate and / or citrate can be used with preference for their sodium salts or combinations of two or three with polybasic organic acids with preference for citric acid. Due to the small amount of additives that is used in total, in most cases only one selected compound or a maximum of two selected compounds will be compacted in a mixture with the crystalline layered silicates.
- the roller pressing itself can be carried out without or with a pre-compression of the premixed powdery material.
- the pair of rollers can be arranged in any spatial direction, in particular thus vertically or horizontally to one another.
- the mixture to be compacted or the sole powder of crystalline layered silicate is then fed to the roll gap either by gravity filling or by means of a suitable device, for example by means of a stuffing screw.
- the material to be compacted is then pressed through the gap of a pair two rollers running in opposite directions at approximately the same circumferential speed and thereby compacted into a plate-like or band-shaped material to be pressed, which is also referred to as a sliver belt.
- Preferred press pressures are between 7 and 30 kN / cm roll length and in particular press presses between 10 and 25 kN / cm roll length. Press pressures between 12 and 20 kN / cm roll length are particularly advantageous.
- the shoulder strap is then subjected to a comminution process.
- This comminution or grinding can take place, for example, in a mill.
- the comminuted material is then expediently subjected to a screening process, coarse material being separated off and returned to the comminution device, while material which is too fine is added again to the batch of the powdery mixture or the powdered layered silicate and is again fed to the compacting in the nip.
- the sliver belt is preferably made by conventional grinding into granules with a particle size range of 0.05 mm to 2 mm, preferably with a particle size range that consists of at least 70% by weight of granules with a particle diameter between 0.1 and 1.6 mm , is set, while fine-grain fractions with granule diameters below 0.05 mm are returned to the compacting and coarse-grained fractions with granule diameters above 2 mm are returned to the grinding.
- a granular builder component is obtained which has a bulk density between 800 and 1100 g / l.
- the granular builder components obtained are selected in a subsequent step with further ingredients of washing or cleaning agents, preferably with impregnating agents, from the group of ethoxylated nonionic surfactants, mixtures of nonionic and anionic surfactants, pasty aqueous nonionic and / or anionic surfactants, the water possibly being subsequently dried off, and the silicone oils and paraffin oils, in particular with nonionic surfactants.
- the builders components can then additionally with powdery solids, be powdered in particular with powdered crystalline layered silicates.
- the invention relates to a washing or cleaning agent which contains the builders components according to the invention.
- these agents preferably contain the builder components according to the invention in amounts of 10 to 70% by weight and in particular in amounts of 20 to 60% by weight.
- the washing or cleaning agents contain other customary inorganic and / or organic builders, contents of 25 to 50% by weight of the builders components according to the invention are particularly advantageous.
- the washing or cleaning agents can contain all the usual ingredients such as anionic, nonionic, amphoteric, cationic and / or zwitterionic surfactants, other builders such as zeolite and / or phosphates, phyllosilicates such as bentonites, polycarboxylates such as citrates etc., polymeric polycarboxylates such as salts of homo- or copolymers of acrylic acid, bleaching agents and bleach activators, graying inhibitors such as cellulose ether or polyvinylpyrrolidone, optical brighteners, dyes and fragrances, and enzymes and enzyme stabilizers. Foam inhibitors can also be included.
- other builders such as zeolite and / or phosphates, phyllosilicates such as bentonites, polycarboxylates such as citrates etc., polymeric polycarboxylates such as salts of homo- or copolymers of acrylic acid, bleaching agents and bleach activators, graying inhibitors such as cellulose
- the agents can consist of a base granulate or of a multicomponent mixture, whereby multicomponent mixtures can be advantageous.
- enzyme granules and, for example, bleach activator granules, but also foam inhibitor granules or individual constituents such as sodium carbonate, sodium silicate or polycarboxylate are subsequently mixed in.
- the individual components can be made by spray drying, granulation, extrusion or other conventional techniques.
- the agents have a bulk density above 650 g / l, preferably above 700 g / l.
- detergents or cleaning agents with bulk densities above 800 g / l can also be produced without these agents tending to separate.
- These agents are also suitable for concentrates with high surfactant contents.
- a high anionic surfactant content can be achieved by admixing a highly concentrated anionic surfactant compound, for example by spray drying, spray neutralization or by granulation and simultaneous drying in a fluidized bed was obtained, and a high nonionic surfactant content can be achieved by admixing the builder components according to the invention with high nonionic surfactant contents. Washing or cleaning agents with 15 to 40% by weight, in particular with 18 or 20 to 35% by weight, anionic and nonionic surfactants are preferred.
- roller-compacted granules produced according to the invention are mixed into extruded granules which may contain highly concentrated anionic surfactant compounds and are preferably low in nonionic to nonionic in particular.
- Crystalline layered silicates of the type SKS 6 (R) ( ⁇ -sodium disilicate, commercial product from Hoechst AG, Germany) and the inorganic or organic salts of polybasic acids specified below were pressed at a pressure of 17 kN / cm on a roller press of the type WR 50 N / 75 (Alexanderwerk AG, Germany) at 20 ° C to form crusts of approx. 1 mm thickness. After comminution into granules with an average particle size range of 0.1 to 1.6 mm, products with the bulk densities specified below were obtained. The dissolving speeds given in the table were determined for the sieve fraction 0.6 to 0.8 mm according to the following test:
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Die Erfindung betrifft eine Gerüststoffkomponente mit sehr hohem Schüttgewicht sowie Wasch- oder Reinigungsmittel, welche diese Komponente enthalten.The invention relates to a builder component with a very high bulk density and to detergents or cleaning agents which contain this component.
Kristalline schichtförmige Natriumsilikate der Formel NaMSixO2x+1·yH2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind, haben sich als geeignete Substitute oder Teilsubstitute für die etablierten Gerüststoffe Phosphate und Zeolithe erwiesen. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5·yH2O bevorzugt, wobei ß-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO-A-91/ 08171 beschrieben ist. β-Natriumdisilikat ist unter der Bezeichnung SKS 7(R), δ-Natriumdisilikat ist unter der Bezeichnung SKS 6(R) im Handel erhältlich (Handelsprodukte der Hoechst AG, Bundesrepublik Deutschland). Diese Pulver weisen im allgemeinen ein Schüttgewicht unter 600 g/l auf und besitzen hohe Feinkornanteile, üblicherweise mehr als 30 Gew.-%, mit einer Teilchengröße unterhalb 0,1 mm. Da kristalline Schichtsilikate gemäß der Offenbarung der internationalen Patentanmeldung WO-A-92/18594 bei der Sprühtrocknung Wasch- oder Reinigungsmittel-haltiger Slurries Verluste in ihrer Waschwirkung, hervorgerufen durch die Zerstörung ihrer physikalischen Struktur, erleiden, sollten sie vorzugsweise über andere Verfahrensmethoden in Wasch- oder Reinigungsmittel eingearbeitet werden. Aufgrund ihres hohen Feinkornanteils und damit ihrer staubigen Struktur sind diese Pulver jedoch auch nicht geeignet, als Zumischkomponente zu anderen granularen Bestandteilen von Wasch- oder Reinigungsmitteln zu dienen. Da zudem kristalline Schichtsilikate wie kristalline Disilikate eine geringere Lösegeschwindigkeit in Wasser aufweisen als amorphe Silikate, kann es durch lokale Ablagerungen auf den Textilien zu einem Anstieg des pH-Werts auf Werte oberhalb von 12 kommen, wodurch Beschädigungen der Textilfasern entstehen können.Crystalline layered sodium silicates of the formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 have proven to be suitable substitutes or partial substitutes for the established builders phosphates and zeolites. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171. β-sodium disilicate is commercially available under the name SKS 7 (R) , δ-sodium disilicate is available under the name SKS 6 (R) (commercial products from Hoechst AG, Federal Republic of Germany). These powders generally have a bulk density of less than 600 g / l and have high fines content, usually more than 30% by weight, with a particle size below 0.1 mm. Since crystalline layered silicates according to the disclosure of the international patent application WO-A-92/18594 spray-drying detergent-containing slurries suffer losses in their washing action caused by the destruction of their physical structure, they should preferably be used by other process methods in washing or cleaning agents can be incorporated. However, due to their high proportion of fine grains and thus their dusty structure, these powders are also unsuitable for use as an admixing component with other granular components of detergents or cleaning agents. In addition, since crystalline layered silicates such as crystalline disilicates have a lower dissolution rate in water than amorphous silicates, local deposits on the textiles can lead to an increase in the pH value to values above 12, which can damage the textile fibers.
Die internationale Patentanmeldung WO-A-92/18594 beschreibt, wie diese Nachteile vermieden werden können: Die kristallinen Schichtsilikate werden in Form einer granularen Gerüststoffkomponente eingesetzt, die mindestens 10 Gew.-% kristalline Schichtsilikate, 5 bis 90 Gew.-% in Wasser in Form von Ionen vorliegender organischer Säuren und/oder anorganischer oder organischer Salze, wobei das eingesetzte Material allerdings eine Größe von im Durchschnitt 300 µm nicht überschreiten soll, sowie gegebenenfalls weitere Bindemittel, Tenside und weitere übliche Inhaltsstoffe von Wasch-oder Reinigungsmitteln enthalten. Eine bevorzugte Art der Herstellung dieser Gerüststoffkomponente ist die Walzenkompaktierung, wobei ein Preßdruck von 10 bis 50 kN/cm Walzenlänge und vorzugsweise um 25 kN/cm Walzenlänge aufgewendet werden. Derartige Gerüststoffkomponenten weisen zwar in 1%iger wäßriger Lösung immer noch hohe pH-Werte auf; da diese Komponenten jedoch gegenüber dem Pulver eine höhere Lösegeschwindigkeit besitzen, wird das Risiko der lokalen Ablagerungen auf Textilien und damit der Beschädigungen von Textilfasern verringert. Diese Erfindung ist jedoch auf Gerüststoffkomponenten beschränkt, die maximal 95 Gew.-% kristalline Schichtsilikate enthalten.International patent application WO-A-92/18594 describes how these disadvantages can be avoided: the crystalline layered silicates are used in the form of a granular builders component which contains at least 10% by weight of crystalline layered silicates and 5 to 90% by weight in water Form of ions of organic acids and / or inorganic or organic salts present, the material used should not, however, exceed an average size of 300 μm, and optionally contain further binders, surfactants and other common ingredients of detergents or cleaning agents. A preferred way of producing this builder component is roller compaction, in which a pressure of 10 to 50 kN / cm roller length and preferably around 25 kN / cm roller length is used. Such builders components still have high pH values in 1% aqueous solution; however, since these components have a higher dissolution rate than the powder, the risk of local deposits on textiles and thus damage to textile fibers is reduced. However, this invention is limited to builder components which contain a maximum of 95% by weight of crystalline layered silicates.
Die Walzenkompaktierung von Wasch- oder Reinigungsmitteln oder einzelner Komponenten von Wasch- oder Reinigungsmitteln ist gesicherter Stand des technischen Wissens. Bereits aus der europäischen Patentanmeldung EP-A-0 253 323 ist bekannt, daß Gerüststoffe wie Zeolith und/oder Phosphat durch Walzenkompaktierung in Granulate mit hohem Schüttgewicht und sehr guten anwendungstechnischen Eigenschaften überführt werden können. In diesem druckschriftlichen Stand der Technik werden ausführlich die Bedingungen geschildert, unter denen eine Walzenkompaktierung üblicherweise durchgeführt wird. Dabei wird ausgeführt, daß der Preßdruck im Walzenspalt und die Verweildauer des Materials in dem Bereich des Preßdrucks so einzustellen sind, daß ein gut ausgebildetes Schülpenband mit hoher Dichte erzeugt wird. Der hohe Verdichtungsgrad ist dabei nicht nur im Hinblick auf moderne Wasch- oder Reinigungsmittel mit hohem Schüttgewicht, sondern auch hinsichtlich einer erhöhten Abriebstabilität der Granulate erwünscht. Dabei muß allerdings beachtet werden, daß zu hohe Preßdrucke die Verfahrenssicherheit beeinträchtigen, da bei ihrem Einsatz das Material auf den Walzen plastifiziert wird und zu Anklebungen führen kann. Dieser unerwünschte Effekt tritt dann auf, wenn eine Erhöhung des Preßdrucks keine weitere Verdichtung des Materials mehr bewirkt und die jetzt zusätzlich eingetragene Preßkraft überwiegend die Erwärmung und Plastifizierung des Materials
- beispielsweise durch partielles Aufschmelzen wasserhaltiger Bestandteile
- verursacht. Dies ist auch der Grund dafür, daß Walzenkompaktierungen üblicherweise bei nicht zusätzlich extern erhöhten Temperaturen, sondern bei Umgebungstemperatur durchgeführt werden.
- for example by partially melting water-containing components
- caused. This is also the reason why roller compaction is usually carried out at temperatures which are not additionally increased externally, but at ambient temperature.
Die Aufgabe der Erfindung bestand nun darin, daß Verfahren der Walzenkompaktierung von Gerüststoffkomponenten, welche kristalline Schichtsilikate enthalten, dahingehend weiterzuentwickeln, daß zum einen möglichst effektive, d.h. konzentrierte Gerüststoffkomponenten erhalten werden und zum anderen auch eine Verbesserung des Löseverhaltens von Gerüststoffkomponenten, welche kristalline Schichtsilikate oberhalb 95 Gew.-% enthalten, erreicht wird. Die Gerüststoffkomponenten sollten also so wenig wie möglich an Zuschlagstoffen enthalten.The object of the invention was to further develop methods of roller compacting builders components containing crystalline phyllosilicates in such a way that, on the one hand, the most effective, i.e. concentrated builders components are obtained and on the other hand an improvement in the dissolving behavior of builders components which contain crystalline phyllosilicates above 95% by weight is achieved. The builders components should therefore contain as little as possible of additives.
Überraschenderweise wurde festgestellt, daß derartige Gerüststoffkomponenten bereits schon dann eine signifikante Verbesserung des Löseverhaltens aufweisen, wenn sie nur sehr geringe Mengen an Zuschlagstoffen enthalten.Surprisingly, it was found that such builders components already show a significant improvement in the dissolving behavior when they contain only very small amounts of additives.
Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung einer Gerüststoffkomponente, welche kristalline Schichtsilikate der Formel NaMSixO2x+1·yH2O enthält, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist, durch Walzenkompaktierung bei Preßdrucken bis 50 kN/cm Walzenlänge, wobei die kristallinen Schichtsilikate in Mengen von mehr als 95 Gew.-% bis 99,8 Gew.-% und übliche feste Inhaltsstoffe von Wasch- oder Reinigungsmitteln als Zuschlagstoffe in Mengen von 0,2 bis weniger als 5 Gew.-% eingesetzt werden.The invention accordingly relates to a process for the preparation of a builder component which contains crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number of 0 to 20, by roller compacting at pressures up to 50 kN / cm roller length, the crystalline layered silicates in amounts of more than 95% by weight to 99.8% by weight and customary solid ingredients of detergents or cleaning agents as additives in Amounts of 0.2 to less than 5 wt .-% are used.
Als besonders bevorzugte kristalline Schichtsilikate werden Disilikate und dabei vor allem ß-Natriumdisilikate und δ-Natriumdisilikate eingesetzt. Welche übliche feste Inhaltsstoffe von Wasch- oder Reinigungsmitteln im Prinzip eingesetzt werden können, kann beispielsweise der internationalen Patentanmeldung WO-A-92/18594 entnommen werden.Disilicates, particularly β-sodium disilicates and δ-sodium disilicate, are used as particularly preferred crystalline sheet silicates. Which conventional solid ingredients of washing or cleaning agents can in principle be used can be found, for example, in international patent application WO-A-92/18594.
Die Erfindung umfaßt dabei insbesondere ein Verfahren zur Walzenkompaktierung, bei dem 96 bis 99 Gew.-% kristalline Schichtsilikate in Mischung mit Zuschlagstoffen kompaktiert werden, welche entweder organische Säuren, vorzugsweise mehrbasige organische Säuren, und/oder Salze anorganischer und/oder organischer Säuren, vorzugsweise mehrbasiger Säuren, sind. Dabei war es insbesondere überraschend, daß bereits geringe Mengen dieser bevorzugten Zuschlagstoffe ausreichen, um ein signifikant verbessertes Löseverhalten der Gerüststoffkomponenten gegenüber einem 100 Gew.-%igen walzenkompaktierten kristallinen Schichtsilikat-Granulat herbeizuführen. Ebenso war es sehr überraschend, daß bereits durch Mengen um 0,2 bis weniger als 5 Gew.-% und vorzugsweise zwischen 1 und 4 Gew.-% an Zuschlagstoffen eine Verbesserung des Löseverhaltens bewirkt wird, die nicht nur gleichzusetzen ist, sondern teilweise sogar signifikant besser ist als die Verbesserung des Löseverhaltens derartiger Gerüststoffkomponenten, welche wesentlich mehr Zuschlagstoffe, beispielsweise zwischen 10 und 30 Gew.-%, enthalten. Bevorzugte anorganische Zuschlagstoffe sind Sulfate, insbesondere Natriumsulfat und Carbonate, während zu den bevorzugten organischen Zuschlagstoffen Citronensäure, Weinsäure, Bernsteinsäure, Glutarsäure, Adipinsäure und Zuckersäuren sowie deren Salze zählen. Diese Zuschlagstoffe können dabei allein oder in Mischung miteinander eingesetzt werden. So können beispielsweise Sulfat und/oder Citrat mit Bevorzugung ihrer Natriumsalze oder Zweier- bzw. Dreierkombinationen mit mehrbasigen organischen Säuren mit Bevorzugung der Citronensäure eingesetzt werden. Aufgrund der geringen Menge an Zuschlagstoffen, die insgesamt eingesetzt wird, werden in den meisten Fällen nur eine ausgewählte Verbindung oder maximal zwei ausgewählte Verbindungen in Mischung mit den kristallinen Schichtsilikaten kompaktiert werden.The invention particularly includes a method for roller compaction, in which 96 to 99% by weight of crystalline phyllosilicates are compacted in a mixture with additives, which are either organic acids, preferably polybasic organic acids, and / or salts of inorganic and / or organic acids, preferably polybasic acids. It was particularly surprising that even small amounts of these preferred additives are sufficient to bring about a significantly improved dissolving behavior of the builders components compared to a 100% by weight roll-compacted crystalline layered silicate granulate. It was also very surprising that quantities of 0.2 to less than 5% by weight and preferably between 1 and 4% by weight of additives lead to an improvement in the dissolving behavior, which is not only equivalent, but sometimes even is significantly better than the improvement in the dissolving behavior of such builders components which contain significantly more additives, for example between 10 and 30% by weight. Preferred inorganic additives are sulfates, in particular sodium sulfate and carbonates, while the preferred organic additives include citric acid, tartaric acid, succinic acid, glutaric acid, adipic acid and sugar acids and their salts. These additives can be used alone or in a mixture with each other. For example, sulfate and / or citrate can be used with preference for their sodium salts or combinations of two or three with polybasic organic acids with preference for citric acid. Due to the small amount of additives that is used in total, in most cases only one selected compound or a maximum of two selected compounds will be compacted in a mixture with the crystalline layered silicates.
Die Walzenverpressung selber kann ohne oder mit einer Vorverdichtung des vorgemischten pulverförmigen Gutes erfolgen. Das Walzenpaar kann dabei in jeder beliebigen Raumrichtung, insbesondere also vertikal oder horizontal zueinander angeordnet sein. Die zu kompaktierende Mischung oder das alleinige Pulver aus kristallinem Schichtsilikat wird dann entweder durch Schwerkraftfüllung oder mittels einer geeigneten Einrichtung, beispielsweise mittels einer Stopfschnecke dem Walzenspalt zugeführt. Das zu kompaktierende Gut wird dann unter Preßdruck durch den Spalt eines Paares zweier mit etwa gleicher Umfangsgeschwindigkeit gegensinnig laufender Walzen geführt und dabei zu einem plattenförmigen bzw. bandförmigen Preßgut, das auch als Schülpenband bezeichnet wird, verdichtet. Bevorzugte Preßdrucke liegen dabei zwischen 7 und 30 kN/cm Walzenlänge und insbesondere bei Preßdrucken zwischen 10 und 25 kN/cm Walzenlänge. Besonders vorteilhaft sind dabei Preßdrucke zwischen 12 und 20 kN/cm Walzenlänge.The roller pressing itself can be carried out without or with a pre-compression of the premixed powdery material. The pair of rollers can be arranged in any spatial direction, in particular thus vertically or horizontally to one another. The mixture to be compacted or the sole powder of crystalline layered silicate is then fed to the roll gap either by gravity filling or by means of a suitable device, for example by means of a stuffing screw. The material to be compacted is then pressed through the gap of a pair two rollers running in opposite directions at approximately the same circumferential speed and thereby compacted into a plate-like or band-shaped material to be pressed, which is also referred to as a sliver belt. Preferred press pressures are between 7 and 30 kN / cm roll length and in particular press presses between 10 and 25 kN / cm roll length. Press pressures between 12 and 20 kN / cm roll length are particularly advantageous.
Das Schülpenband wird anschließend einem Zerkleinerungsverfahren unterworfen. Diese Zerkleinerung oder Mahlung kann dabei beispielsweise in einer Mühle erfolgen. Zweckmäßigerweise wird das zerkleinerte Material anschließend einem Sichtungsprozeß zugeführt, wobei grobes Material abgetrennt und in die Zerkleinerungsvorrichtung zurückgeführt wird, während zu feines Material dem Ansatz der pulverförmigen Mischung oder dem pulverförmigen Schichtsilikat wieder beigegeben und erneut der Kompaktierung im Walzenspalt zugeführt wird. Vorzugsweise wird dabei das Schülpenband durch übliche Mahlung in Granulate mit einem Kornspektrum von 0,05 mm bis 2 mm, vorzugsweise mit einem Kornspektrum, das zu mindestens 70 Gew.-% aus Granulaten mit einem Teilchendurchmesser zwischen 0,1 und 1,6 mm besteht, eingestellt, während Feinkornanteile mit Granulatdurchmessern unterhalb 0,05 mm in die Kompaktierung zurückgeführt und Grobkornanteile mit Granulatdurchmessern oberhalb 2 mm in die Mahlung zurückgeführt werden.The shoulder strap is then subjected to a comminution process. This comminution or grinding can take place, for example, in a mill. The comminuted material is then expediently subjected to a screening process, coarse material being separated off and returned to the comminution device, while material which is too fine is added again to the batch of the powdery mixture or the powdered layered silicate and is again fed to the compacting in the nip. The sliver belt is preferably made by conventional grinding into granules with a particle size range of 0.05 mm to 2 mm, preferably with a particle size range that consists of at least 70% by weight of granules with a particle diameter between 0.1 and 1.6 mm , is set, while fine-grain fractions with granule diameters below 0.05 mm are returned to the compacting and coarse-grained fractions with granule diameters above 2 mm are returned to the grinding.
In einer bevorzugten Ausführungform der Erfindung wird dabei eine granulare Gerüststoffkomponente erhalten, welche ein Schüttgewicht zwischen 800 und 1100 g/l aufweist.In a preferred embodiment of the invention, a granular builder component is obtained which has a bulk density between 800 and 1100 g / l.
In einer weiteren bevorzugten Ausführungsform der Erfindung werden die erhaltenen granularen Gerüststoffkomponenten, in einem anschließenden Schritt mit weiteren Inhaltsstoffen von Wasch- oder Reinigungsmitteln, vorzugweise mit Imprägnierungsmitteln ausgewählt aus der Gruppe der ethoxylierten nichtionischen Tenside, Mischungen aus nichtionischen und anionischen Tensiden, pastenförmigen wäßrigen nichtionischen und/oder anionischen Tensiden, wobei das Wasser gegebenenfalls nachträglich weggetrocknet wird, sowie der Silikonöle und Paraffinöle, insbesondere mit nichtionischen Tensiden, beaufschlagt. Im Anschluß an diese Imprägnierung können die Gerüststoffkomponenten dann zusätzlich mit pulverförmigen Feststoffen, insbesondere mit pulverförmigen kristallinen Schichtsilikaten abgepudert werden.In a further preferred embodiment of the invention, the granular builder components obtained are selected in a subsequent step with further ingredients of washing or cleaning agents, preferably with impregnating agents, from the group of ethoxylated nonionic surfactants, mixtures of nonionic and anionic surfactants, pasty aqueous nonionic and / or anionic surfactants, the water possibly being subsequently dried off, and the silicone oils and paraffin oils, in particular with nonionic surfactants. Following this impregnation, the builders components can then additionally with powdery solids, be powdered in particular with powdered crystalline layered silicates.
Gegenstand der Erfindung ist in einer weiteren Ausführungsform der Erfindung ein Wasch- oder Reinigungsmittel, welches die erfindungsgemäßen Gerüststoffkomponenten enthält. Vorzugsweise enthalten diese Mittel die erfindungsgemäßen Gerüststoffkomponenten in Mengen von 10 bis 70 Gew.-% und insbesondere in Mengen von 20 bis 60 Gew.-%. Insbesondere wenn die Wasch-oder Reinigungsmittel weitere übliche anorganische und/oder organische Gerüststoffe enthalten, sind Gehalte an den erfindungsgemäßen Gerüststoffkomponenten von 25 bis 50 Gew.-% besonders vorteilhaft. Ansonsten können die Wasch- oder Reinigungsmittel alle üblichen Inhaltsstoffe wie anionische, nichtionische, amphotere, kationische und/oder zwitterionische Tenside, weitere Gerüststoffe wie Zeolith und/oder Phosphate, Schichtsilikate wie Bentonite, Polycarboxylate wie Citrate etc., polymere Polycarboxylate wie Salze von Homo- oder Copolymeren der Acrylsäure, Bleichmittel und Bleichaktivatoren, Vergrauungsinhibitoren wie Celluloseether oder Polyvinylpyrrolidon, optische Aufheller, Farb- und Duftstoffe sowie Enzyme und Enzymstabilisatoren enthalten. Auch Schauminhibitoren können enthalten sein. Die Mittel können abgesehen von der zugemischten erfindungsgemäßen Gerüststoffkomponente aus einem Basisgranulat oder aus einem Mehrkomponentengemisch bestehen, wobei Mehrkomponentengemische von Vorteil sein können. Insbesondere werden dabei Enzymgranulate und beispielsweise Bleichaktivatorgranulate, aber auch Schauminhibitorgranulate oder einzelne Bestandteile wie Natriumcarbonat, Natriumsilikat oder Polycarboxylat nachträglich zugemischt. Die einzelnen Komponenten können durch Sprühtrocknung, Granulierung, Extrusion oder andere herkömmliche Techniken hergestellt werden. Insbesondere ist es bevorzugt, daß die Mittel insgesamt ein Schüttgewicht oberhalb 650 g/l, vorzugsweise oberhalb 700 g/l aufweisen. Durch den Einsatz der erfindungsgemäßen Gerüststoffkomponenten in hohen Mengen können auch Wasch- oder Reinigungsmittel mit Schüttgewichten oberhalb 800 g/l hergestellt werden, ohne daß diese Mittel zur Entmischung neigen. Diese Mittel eignen sich ebenfalls zu Konzentraten mit hohen Tensidgehalten. So kann beispielsweise ein hoher Aniontensidgehalt durch Zumischung eines hochkonzentrierten Aniontensid-Compounds, das beispielsweise durch Sprühtrocknung, Sprühneutralisation oder durch Granulierung und gleichzeitige Trocknung in einer Wirbelschicht erhalten wurde, und ein hoher Niotensidgehalt durch Zumischung der erfindungsgemäßen Gerüststoffkomponenten mit hohen Niotensidanteilen erreicht werden. Wasch- oder Reinigungsmittel mit 15 bis 40 Gew.-%, insbesondere mit 18 oder 20 bis 35 Gew.-% anionischen und nichtionischen Tensiden sind dabei bevorzugt. In einer weiteren Ausführungsform der Erfindung werden die erfindungsgemäß hergestellten walzenkompaktierten, vorzugsweise mit Niotensiden beaufschlagten Granulate zu extrudierten Granulaten, welche gegebenenfalls hochkonzentrierte Aniontensid-Compounds enthalten und vorzugsweise Niotensid-arm bis insbesondere Niotensid-frei sind, hinzugemischt.In a further embodiment of the invention, the invention relates to a washing or cleaning agent which contains the builders components according to the invention. These agents preferably contain the builder components according to the invention in amounts of 10 to 70% by weight and in particular in amounts of 20 to 60% by weight. In particular, if the washing or cleaning agents contain other customary inorganic and / or organic builders, contents of 25 to 50% by weight of the builders components according to the invention are particularly advantageous. Otherwise, the washing or cleaning agents can contain all the usual ingredients such as anionic, nonionic, amphoteric, cationic and / or zwitterionic surfactants, other builders such as zeolite and / or phosphates, phyllosilicates such as bentonites, polycarboxylates such as citrates etc., polymeric polycarboxylates such as salts of homo- or copolymers of acrylic acid, bleaching agents and bleach activators, graying inhibitors such as cellulose ether or polyvinylpyrrolidone, optical brighteners, dyes and fragrances, and enzymes and enzyme stabilizers. Foam inhibitors can also be included. Apart from the admixed builder component according to the invention, the agents can consist of a base granulate or of a multicomponent mixture, whereby multicomponent mixtures can be advantageous. In particular, enzyme granules and, for example, bleach activator granules, but also foam inhibitor granules or individual constituents such as sodium carbonate, sodium silicate or polycarboxylate are subsequently mixed in. The individual components can be made by spray drying, granulation, extrusion or other conventional techniques. In particular, it is preferred that the agents have a bulk density above 650 g / l, preferably above 700 g / l. By using the builder components according to the invention in large quantities, detergents or cleaning agents with bulk densities above 800 g / l can also be produced without these agents tending to separate. These agents are also suitable for concentrates with high surfactant contents. For example, a high anionic surfactant content can be achieved by admixing a highly concentrated anionic surfactant compound, for example by spray drying, spray neutralization or by granulation and simultaneous drying in a fluidized bed was obtained, and a high nonionic surfactant content can be achieved by admixing the builder components according to the invention with high nonionic surfactant contents. Washing or cleaning agents with 15 to 40% by weight, in particular with 18 or 20 to 35% by weight, anionic and nonionic surfactants are preferred. In a further embodiment of the invention, the roller-compacted granules produced according to the invention, preferably loaded with nonionic surfactants, are mixed into extruded granules which may contain highly concentrated anionic surfactant compounds and are preferably low in nonionic to nonionic in particular.
Kristalline Schichtsilikate des Typs SKS 6(R) (δ-Natriumdisilikat, Handelsprodukt der Hoechst AG, Deutschland) und die unten angegebenen anorganischen bzw. organischen Salze mehrbasiger Säuren wurden bei einem Preßdruck von 17 kN/cm auf einer Walzenpresse des Typs WR 50 N/75 (Alexanderwerk AG, Deutschland) bei 20 °C zu Schülpen von ca. 1 mm Stärke verpreßt. Nach der Zerkleinerung zu einem Granulat mit einem mittleren Kornspektrum von 0,1 bis 1,6 mm wurden Produkte mit den unten angegebenen Schüttgewichten erhalten. Die in der Tabelle angegebenen Lösegeschwindigkeiten wurden für die Siebfraktion 0,6 bis 0,8 mm nach folgendem Test ermittelt:Crystalline layered silicates of the type SKS 6 (R) (δ-sodium disilicate, commercial product from Hoechst AG, Germany) and the inorganic or organic salts of polybasic acids specified below were pressed at a pressure of 17 kN / cm on a roller press of the type WR 50 N / 75 (Alexanderwerk AG, Germany) at 20 ° C to form crusts of approx. 1 mm thickness. After comminution into granules with an average particle size range of 0.1 to 1.6 mm, products with the bulk densities specified below were obtained. The dissolving speeds given in the table were determined for the sieve fraction 0.6 to 0.8 mm according to the following test:
In einem doppelwandigen und thermostatisierten 1-1-Gefäß wurden 500 ml demineralisiertes Wasser (20°C) eingefüllt, der Schrägblattrührer mit einer Drehzahl von 900 Umdrehungen pro Minute eingeschaltet und die Leitfähigkeitsmeßzelle eingetaucht. Danach wurden 5 g der Gerüststoffkomponente zugegeben. Die Änderung der Leitfähigkeit wurde über einen Schreiber festgehalten. Die Messung erfolgte, bis kein Anstieg der Leitfähigkeit mehr feststellbar war. Die Zeit zum Erreichen der Leitfähigkeitskonstanz ist die Lösezeit der Gerüststoffkomponente (100 %). Die Lösezeiten bei 80%iger, 90%iger und 95%iger Auflösung wurden rechnerisch ermittelt.
Claims (12)
- A process for the production of a builder component containing crystalline layer silicates corresponding to the formula NaMSixO2x+1·yH2O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, by roll compacting under pressures of up to 50 kN/cm roll length, characterized in that the crystalline layer silicates are used in quantities of more than 95% by weight to 99.8% by weight and typical solid ingredients of detergents or cleaning formulations are used as additives in quantities of 0.2 to less than 5% by weight.
- A process as claimed in claim 1, characterized in that the crystalline layer silicates are used in quantities of 96 to 99% by weight and in that organic acids, preferably polybasic organic acids, and/or salts of inorganic and/or organic acids, preferably polybasic acids, are used as additives.
- A process as claimed in claim 1 or 2, characterized in that the roll compacting is carried out under pressures of 7 to 30 kN/cm roll length, preferably under pressures of 10 to 25 kN/cm roll length and, more preferably, under pressures of 12 to 20 kN/cm roll length.
- A process as claimed in any of claims 1 to 3, characterized in that disilicates and, in particular, β-sodium disilicate and/or 6-sodium disilicate are used as the crystalline layer silicates.
- A process as claimed in any of claims 1 to 4, characterized in that one or more organic acids from the group consisting of citric acid, tartaric acid, succinic acid, glutaric acid, adipic acid and sugar acids, more particularly citric acid, is/are used as additives.
- A process as claimed in any of claims 1 to 5, characterized in that inorganic and/or organic salts of polybasic acids, sulfate and/or citrate, preferably sodium sulfate and/or sodium citrate, are used as additives.
- A process as claimed in any of claims 1 to 6, characterized in that the compactate is converted by grinding in the usual way into granules with a particle size distribution of 0.05 mm to 2 mm and preferably with a particle size distribution in which at least 70% by weight consists of granules between 0.1 and 1.6 mm in diameter, fine-particle fractions below 0.05 mm in diameter being returned to the compacting stage and coarseparticle fractions larger than 2 mm in diameter being returned to the grinding stage.
- A process as claimed in any of claims 1 to 7, characterized in that a granular builder component with an apparent density of 800 to 1100 g/l is obtained.
- A process as claimed in any of claims 1 to 8, characterized in that the granular builder components obtained are impregnated in a following step with further ingredients of detergents or cleaning formulations, more particularly with nonionic surfactants.
- A process as claimed in any of claims 1 to 9, characterized in that the roll-compacted granules obtained, preferably impregnated with nonionic surfactants, are added to extruded granules which contain optionally highly concentrated anionic surfactant compounds and which are preferably substantially free and, more preferably, completely free from nonionic surfactants.
- A detergent or cleaning formulation containing the builder components produced in accordance with a process claimed in any of claims 1 to 10.
- A detergent or cleaning formulation as claimed in claim 11, characterized in that it contains the builder components in quantities of 10 to 70% by weight, preferably in quantities of 20 to 60% by weight and more preferably in quantities of 25 to 50% by weight and optionally other typical inorganic and/or organic builders.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4329392A DE4329392A1 (en) | 1993-09-01 | 1993-09-01 | Builders component for detergents or cleaning agents |
DE4329392 | 1993-09-01 | ||
PCT/EP1994/002777 WO1995006707A1 (en) | 1993-09-01 | 1994-08-22 | Builder component for washing or cleaning products |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0716684A1 EP0716684A1 (en) | 1996-06-19 |
EP0716684B1 true EP0716684B1 (en) | 1997-04-09 |
Family
ID=6496502
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94926862A Expired - Lifetime EP0716684B1 (en) | 1993-09-01 | 1994-08-22 | Builder component for washing or cleaning products |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0716684B1 (en) |
JP (1) | JPH09501978A (en) |
KR (1) | KR960705018A (en) |
AT (1) | ATE151453T1 (en) |
DE (2) | DE4329392A1 (en) |
ES (1) | ES2100742T3 (en) |
WO (1) | WO1995006707A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19525197A1 (en) * | 1995-07-11 | 1997-01-16 | Hoechst Ag | Granular detergent builder |
DE19756696A1 (en) | 1997-12-19 | 1999-07-01 | Clariant Gmbh | Detergent and cleaning agent components containing layered silicate |
GB2339194A (en) * | 1998-07-08 | 2000-01-19 | Procter & Gamble | Layered crystalline silicate as detergent builder component |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3624336A1 (en) * | 1986-07-18 | 1988-01-28 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF GIANT ALKALINE CLEANING AGENTS BY COMPACTING GRANULATION |
DE3633519A1 (en) * | 1986-10-02 | 1988-04-14 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF GIANT, STABLE FOAM INHIBITOR CONCENTRATES BY COMPACTING GRANULATION |
GB9108639D0 (en) * | 1991-04-23 | 1991-06-12 | Procter & Gamble | Particulate detergent compositions |
-
1993
- 1993-09-01 DE DE4329392A patent/DE4329392A1/en not_active Withdrawn
-
1994
- 1994-08-22 WO PCT/EP1994/002777 patent/WO1995006707A1/en active IP Right Grant
- 1994-08-22 ES ES94926862T patent/ES2100742T3/en not_active Expired - Lifetime
- 1994-08-22 KR KR1019960701018A patent/KR960705018A/en not_active Application Discontinuation
- 1994-08-22 EP EP94926862A patent/EP0716684B1/en not_active Expired - Lifetime
- 1994-08-22 JP JP7507914A patent/JPH09501978A/en active Pending
- 1994-08-22 AT AT94926862T patent/ATE151453T1/en not_active IP Right Cessation
- 1994-08-22 DE DE59402397T patent/DE59402397D1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE4329392A1 (en) | 1995-03-02 |
KR960705018A (en) | 1996-10-09 |
ATE151453T1 (en) | 1997-04-15 |
JPH09501978A (en) | 1997-02-25 |
WO1995006707A1 (en) | 1995-03-09 |
DE59402397D1 (en) | 1997-05-15 |
ES2100742T3 (en) | 1997-06-16 |
EP0716684A1 (en) | 1996-06-19 |
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