WO2000032734A1 - Production of brightening agent-containing detergent granulates - Google Patents
Production of brightening agent-containing detergent granulates Download PDFInfo
- Publication number
- WO2000032734A1 WO2000032734A1 PCT/EP1999/009006 EP9909006W WO0032734A1 WO 2000032734 A1 WO2000032734 A1 WO 2000032734A1 EP 9909006 W EP9909006 W EP 9909006W WO 0032734 A1 WO0032734 A1 WO 0032734A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- microns
- powder
- detergent particles
- coarse
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 40
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- 238000005282 brightening Methods 0.000 title abstract 2
- 239000008187 granular material Substances 0.000 title description 16
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- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000010670 sage oil Substances 0.000 description 1
- 239000010671 sandalwood oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 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 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 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
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
Definitions
- the present invention relates to a brightener-containing powder, a process for its preparation and the use of these powder for powdering detergents with a high bulk density.
- the present invention also relates to a process for producing coarse-grained detergents which contain optical brighteners.
- Granular detergents usually contain, in addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, other components that can be summarized under the term washing aids and that include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors.
- Such auxiliary substances also include substances which are absorbed onto the fibers of washed, clean textiles and which are intended to compensate for the weak yellow coloration of originally white textiles which is usually present after washing. These substances are called optical brighteners. They usually work in the desired sense by converting part of the invisible ultraviolet radiation into longer-wave blue light. The yellowish tone of washed laundry can be attributed to the partial absorption of light in the blue region from the spectrum of white light.
- optical brightener This partial absorption is compensated for by the increased emission of blue light by the optical brightener, so that the result is the impression of bright white laundry.
- a side effect of the use of optical brighteners is that the granular detergent containing them also appears bright white, which is positively received by the consumer.
- Optical brighteners are commercially available either as suspensions or as spray-dried products.
- the optical brightener is usually added in the form of the commercially available suspension spraying aqueous slurry of the detergent ingredients incorporated. It is known that the achievable bulk density of the granular products produced is limited in this production method. So it is normally not possible to produce detergents with bulk densities above approx. 500 g / 1 by spray drying alone. On the other hand, as compact as possible detergents are required by the consumer.
- An economically advantageous possibility of introducing optical brighteners via the preparation in the production of compact detergents should now be found, which meets all quality requirements with regard to homogeneity, aspect and flowability of the end product.
- the disadvantages of the cleaning effort of apparatus, the yellowish or greenish product color and the stickiness or tendency to clump the products should be minimized or completely avoided.
- the advantages of using non-ionic surfactants to improve the whiteness of the end products should be exploited without having to accept the disadvantages of sticking and clumping.
- An object of the present invention is therefore a powder for coarse detergents containing
- the powder has maximum primary particle sizes below 50 microns.
- Preferred powdering agents have even smaller particle sizes, which makes them even more suitable for homogeneous powdering.
- Preferred powdering agents have maximum primary particle sizes below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
- the powdering agent according to the invention contains 40 to 95% by weight of one or more pure white carrier materials.
- pure white in the context of the present invention means that the carrier materials used have a so-called whiteness, which according to Berger (see A. Berger, A. Brockes: “Color Measurement in the Textile Industry", BAYER Maschinen Revue, Special Issue 3/1, 1971) with the help of filter color measuring devices, for example the Spectroflash 500 from datacolor international, CH-8305 Dietlihon, of over 60, in particular over 70.
- this method for whiteness determination on textiles was developed and is suitable but also excellent for whiteness measurement of powders or granular substances, whiteness can also be determined using the Ganz / Griesser method, the basics of color measurement are described in DIN standard 5033.
- a number of substances are suitable as pure white carriers, it being preferred to use substances which, in addition to their function as powdering agents, perform further functions, for example builder action, in the later detergent.
- a large number of substances are suitable as a carrier material.
- inorganic as well as organic substances that are sufficiently white in color. Examples include finely divided substances that are obtained by precipitation.
- silicates, aluminosilicates, alkali silicates and alkali carbonates or bicarbonates are used as substances.
- Diatomaceous earth (diatomaceous earth) and finely divided cellulose fibers or derivatives thereof can also be used in the context of the present invention.
- finely divided zeolites can be used, but also pyrogenic silicas (Aerosil ® ) or silicas obtained by precipitation.
- Powdering agents preferred in the context of the present invention contain 55 to 85% by weight, preferably 60 to 80% by weight and in particular 65 to 75% by weight of one or more pure white carrier materials, wherein carrier materials from the group of the carbonates, the sulfates, the phosphates, the citrates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y, are preferred.
- carrier materials from the group of the carbonates, the sulfates, the phosphates, the citrates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y are preferred.
- the carrier material contained in the powdering agents according to the invention preferably has an oil absorption capacity of at least 20 g / 100 g. However, even more preferably, oil absorption components are used which have a higher oil absorption capacity. Powdering agents are preferred in which the carrier material contained therein has an oil absorption capacity of at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular at least 140g / 100g.
- the oil absorption capacity is a physical property of a substance that can be determined using standardized methods.
- the British standard methods BS1795 and BS3483: Part B7.1982 exist, both of which refer to Noim ISO 787/5.
- a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93) "3" is added dropwise from a burette.
- the powder is mixed intensively with the oil using a spatula, the addition of oil is continued until a paste of smooth consistency is obtained. This paste should flow or flow without crumbling.
- the oil absorption capacity is now the amount of the added dropwise. ten oil, based on 100g absorbent and is given in ml / 100g or g / lOOg, whereby conversions about the density of linseed oil are possible without any problems.
- the powdering agents according to the invention contain one or more optical brighteners.
- These fabrics which are also called “whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge.
- Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers.
- the commercially available brighteners suitable for incorporation in detergents essentially comprise five structural groups: the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems.
- An overview of common brighteners can be found, for example, in G. Jakobi, A. Lschreib “Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are e.g.
- brighteners of the substituted diphenylstyryl type may be present, e.g.
- Powdering agents preferred in the context of the present invention contain 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight, of one or more optical brighteners, brighteners of the dimorpholine type and of distilbene -Type or mixtures of these are preferred.
- the powdering agents according to the invention can optionally contain up to 10% by weight of further active ingredients and auxiliaries.
- a content of such substances comes about, for example, from the fact that certain commercial brightener preparations contain substances which are neither attributable to the carriers nor to the brighteners.
- Such active substances or auxiliaries originate, for example, from the groups of polymers, surfactants, non-aqueous solvents, etc.
- the powdering agents according to the invention preferably contain less than 7.5% by weight, preferably even less than 5% by weight, of further auxiliaries - or active ingredients, particularly preferred powdering agents being free of such substances.
- Another object of the present invention is a process for the preparation of powdering agents for coarse detergents, in which a mixture of
- Comminution machines with very different embodiments come into consideration as mills for the method according to the invention. It is common to all mills that they effect the comminution by means of impact, impact, pressure, friction, shear, etc. of grinding elements which perform rotating, oscillating, tumbling or reciprocating movements.
- the ball mill is preferably used, in which steel, porcelain or flint balls are rolled in a rotating grinding drum, which shatter the ground material as it rolls along or falls down.
- a sieve ball mill the falling, ground particles are still removed by a drum sieving sieve.
- Variants of this type of mill are the vibrating ball mills and the circulation mills, the latter being a combination of ball mill and air classifier.
- So-called cutting mills are also suitable for carrying out the method according to the invention. They consist of a horizontally or vertically arranged rotor, which is equipped with knives that work against knives anchored in the housing of the mill.
- fine impact mills can also be used, which include pin mills, mills with a peripheral grinding path and jet mills, for example the cross-flow mill and the spiral jet mill.
- roller, tube, disc, toothed disc, vibration, bell, spring force, centrifugal, cross, and other mills can also be used for the method according to the invention.
- the mixture is ground in a ball mill, an annular gap ball mill, a mortar mill or a pin disc mill to maximum primary particle sizes below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
- the process according to the invention it is preferred that 55 to 85% by weight, preferably 60 to 80% by weight and in particular 65 to 75% by weight, of one or more pure white support materials, preferably support materials from the group of the carbonates, of Sulfates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y, and 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight one or more optical brighteners, preferably brighteners of the dimorpholine type and of the distilbene type or mixtures thereof, and up to 10% by weight, preferably up to 7.5% by weight and in particular up to 5% by weight .-% of other auxiliaries or active ingredients are mixed and ground.
- the powdering agents according to the invention are outstandingly suitable for powdering large-scale detergent particles, so that the present invention further relates to
- the coarse-particle detergent particles have average particle diameters above 700 ⁇ m, preferably above 800 ⁇ m and in particular above 1000 ⁇ m, and the powder medium has a maximum primary particle size below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- Preferred ethoxylated alcohols include, for example, C 12 _ 14 - alcohols with 3 EO or 4 EO, C. 9 ⁇ alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C I2. , 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12.14 alcohol with 3 EO and C 12 8 alcohol with 5 EO.
- 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 narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90713533.
- alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
- Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
- Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
- Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
- RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
- R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
- [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
- C,. 4 -alkyl or phenyl radicals are preferred
- [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups. is or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- Nonionic surfactants preferably contained in the coarse-particle detergent particles come from the group of alkoxylated alcohols. These compounds, also known as fatty alcohol polyglycol ethers or alkyl polyglycol ethers, represent a group of nonionic surfactants which, by alkoxylation, but preferably ethoxylation, of primary fatty alcohols or oxoalcohols in the presence of basic or acidic catalysts at temperatures of 150-200 ° and pressures of 1-10 won in cash.
- a polyglycol ether mixture of homologs of different degrees of alkoxylation is formed, the distribution of which, depending on the catalyst and the amount of alkoxide, between a Gaussian and the corresponding statistic. of an unselective Schulz-Flory curve can vary. For example, a broad homolog distribution is obtained in the presence of sodium hydroxide and a narrow-range homolog distribution using alkaline earth metal salts.
- basic catalysts for example sodium methylate in methanol, are preferably used in industry.
- fatty alcohol ethoxylates are contained in the coarse-particle detergent particles, preference is given to using products with degrees of ethoxylation below 10, for example with average degrees of ethoxylation of 5, 6, 7 or 8.
- Medium degrees of ethoxylation can also be fractional numbers, although lower degrees such as 1.5 or medium degrees of 5.5 can also be set.
- the chain length of the fatty alcohols which are converted to the ethoxylates is usually in the range from 8 to 22, preferably from 10 to 20 and in particular from 12 to 18 carbon atoms.
- a preferred use of the powdering agents according to the invention in the context of the present invention is characterized in that the coarse-particle detergent particles, based on the non-powdered particles, are at least 2.5% by weight, preferably at least 5% by weight and in particular at least 7 5% by weight of nonionic surfactant (s), preferably ethoxylated alcohols.
- nonionic surfactant preferably ethoxylated alcohols.
- the coarse-particle detergent particles coated with brightener-containing powder can contain further surface-active substances from the group of anionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their performance spectrum.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C 9 . 13 - Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C 12 . ⁇ 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration.
- Alkanesulfonates which are derived from C 12 are also suitable.
- esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
- Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- alk (en) yl sulfates are the alkali and especially 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, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- the C, 2 -C 16 alkyl sulfates and C 12 -C ] 5 alkyl sulfates and C ! 4 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
- 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
- Suitable 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 . 18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Soaps are particularly suitable as further anionic surfactants.
- Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- builders are the most important ingredients in detergents and cleaning agents.
- the detergent particles powdered with the powdering agents according to the invention can contain all builders commonly used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates .
- the builders described below are also particularly suitable as a carrier material in the powder compositions according to the invention.
- Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + , ⁇ 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.
- M sodium or hydrogen
- x is a number from 1.9 to 4
- y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicate Na ⁇ i ⁇ '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.
- Amorphous sodium silicates with a modulus Na, O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties.
- the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
- amorphous is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are also suitable.
- Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
- Suitable zeolites preferably have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
- the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
- Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this.
- 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 coarse-shaped detergent particles to be powdered can of course contain further ingredients of detergents and cleaning agents, with specific ingredients being described in detail below.
- Another object of the present invention is a process for the preparation of brightener-hooked detergents, which comprises the steps
- Process step a) comprises the known production of detergent particles for which there is a wide range of prior art.
- Step a) of the process according to the invention can thus be carried out in a large number of customary mixing and granulating devices.
- Suitable mixers and granulators are disclosed, for example, Eirich ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan ), the Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais- Maschinene GmbH, Mannheim).
- press agglomeration is another possible method for carrying out process step a).
- the premix for the coarse-particle detergent particles is compressed and plasticized under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner.
- the most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
- preferred press agglomeration processes are extrusion, roller compaction and pelletization.
- the premix for the coarse-particle detergent particles is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with a co-rotating or counter-rotating screw guide, its housing and its extruder pelletizing head on the predetermined extrusion temperature can be heated.
- the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the ex under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used - Trudat preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives.
- the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
- the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
- particle diameters up to at most 8 mm are preferred.
- Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
- the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
- small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
- step c ie the powdering with the brightener-containing powder detergent, in the rounding device.
- This shaping / powdering can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage.
- Extrusion as a manufacturing process for detergents and cleaning agents is described in detail, for example, in European Patent EP 486 592 (Henkel KGaA).
- extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (extrusion press from Amandus Kahl, Reinbek near Hamburg) or in the extruder (Hosokawa Bepex).
- Kahl press extrusion press from Amandus Kahl, Reinbek near Hamburg
- Hosokawa Bepex it is also preferred in the other production processes to feed the resulting primary granules / compactates to a further shaping processing step, in particular a rounding, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.
- step a) of the method according to the invention is carried out by means of roller compaction.
- the premix for the coarse-particle detergent particles is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
- the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
- smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later coarse-particle detergent particles can be specified.
- the sliver belt is subsequently broken up into smaller pieces by a knock-off and comminution device and can be processed into granules in this way, which can be further tempered by further surface treatment processes, in particular brought into an approximately spherical shape and subsequently powdered (process step c)).
- step a) of the method according to the invention is carried out by means of pelleting.
- the premix for the coarse-particle detergent particles is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
- the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
- the most varied configurations of the pressure roller and perforated die are conceivable here.
- step a) of the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
- the ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
- the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
- the coarse-particle detergent particles produced in process step a) are produced by granulation, agglomeration or press agglomeration, in particular by wet granulation, roller compaction, pelleting or extrusion.
- the preferred ranges already mentioned for the use according to the invention apply to the particle sizes of particles to be powdered and powdering agent.
- the coarse-particle detergent particles produced in step a) have average particle diameters above 700 ⁇ m, preferably above 800 ⁇ m and in particular above 1000 ⁇ m
- the powder agent produced in step b) has a maximum primary particle size below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
- the coarse-particle detergent particles produced in step a) preferably contain surfactants, a content of at least at least 2.5% by weight, preferably at least 5% by weight and in particular at least 7.5% by weight, of one or more nonionic surfactants, preferably ethoxylated alcohols, is preferred.
- step a) it is preferred to produce the detergent particles, which preferably contain surfactants, in step a) in a mixer / granulator.
- This procedure has the advantage that the powder to be applied can be introduced into the same apparatus. In this way, only one mixer / granulator is required for process steps a) and c).
- Methods according to the invention are preferred in which steps a) and c) are carried out in a mixer / granulator (in the sense of one and the same).
- Particularly preferred are processes in which process steps a) and c) are carried out in a slow-running mixer, e.g. a Lödige ploughshare mixer, at speeds of 80 to 300 rpm for the mixing tools.
- this mixer It is particularly advantageous to divide this mixer into two chambers.
- the granulation takes place in the larger chamber, while the granules are powdered in the smaller chamber.
- liquids can be injected into this second mixer in order to enhance the effect of the solid coating with an additional coating.
- Additional coating materials are preferably polymer or water glass solutions.
- Another possibility is to operate the Lödige mixer in batches, the finely divided powder containing Auheller being added separately at the end of the granulation.
- the contents of the mixer can then be discharged into an interim storage facility or onto a conveyor belt, from where the downstream parts of the system (fluidized bed dryer, sieve, etc.) continue to be operated.
- Process step b) the production of the brightener-containing powder, has already been described in detail as a separate process according to the invention, reference being made to the above statements.
- process step c) of the process according to the invention the finely divided brightener-containing powder is applied to the coarse-particle detergent particles, it being possible to use the powdering methods familiar to the person skilled in the art.
- the powdering agents produced in step b) are applied to the laundry detergent particles produced in step a) by mixing in the weight ratio of laundry detergent particles to powdering agent from 400: 1 to 25: 1, preferably from 200: 1 to 50: 1 and in particular from 150: 1 to 75: 1.
- the detergent particles produced in step a) can contain further detergent ingredients, in particular from the groups of bleaching agents, bleach activators, enzymes, pH regulators, dyes, foam inhibitors, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures be mixed in from this.
- the detergent particles produced in step a) contain surfactant (s), in particular nonionic surfactant (s) and, preferably, ethoxylated alcohols, this does not result in the other granular components of the preparation are covered by the powder, but only the detergent particles containing surfactant are powdered off. Due to the interaction of nonionic surfactant and powder agent described above, the initially pale greenish color of the powdered detergent particles in the further product path changes to a bright white color within a few minutes.
- ingredients described below can also be added to the detergent particles that have already been powdered only after carrying out process step c).
- bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedi- acid.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimoxyhexanoic acid [hexoxyacid] oxaloacetic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocyseboxyacid, diperoxyacid acid, diperoxyacid acid, diperoxy acid, Decy
- bleach activators can be incorporated.
- Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- TAED tetraacety
- Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof.
- Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable enzymatic agents.
- Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
- Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
- components can also be included which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
- the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
- Colorants and fragrances can be added to the detergent particles in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
- Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
- Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- the ethers include, for example, benzyl ethyl ether
- the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal
- the ketones include, for example, the ionone, c-isomethyl ionone and methyl cedryl ketone
- the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
- the hydrocarbons mainly include the terpenes such as limonene and pinene.
- Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
- the colorant content of detergents and cleaning agents is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.
- the fragrances can be incorporated directly into the detergents, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to a slower fragrance release.
- Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
- dyes In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes.
- Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them. Examples:
- the base granules contain approximately 4% nonionic surfactant (3.5% via extrusion + ethoxylated tallow alcohol from the tower powder). Another 0.4% nonionic surfactant is sprayed onto the surface via a suspension of brightener in nonionic surfactant.
- the total amount of nonionic surfactant can and should be quite higher, with no product caking according to the above statements.
- the extrudate contains approximately 7.5% non-ionic surfactants:
- a tower powder of the following composition was produced by spray drying and served as the basis for a premix to be extruded:
- This tower powder was mixed with other substances and in a Lihotzky-2 screw extruder at a temperature of 80 ° C to crude extrudates with a medium Extruded particle size of 1.2 mm.
- the premix / extrudate composition was as follows:
- the surface of the extrudate particles was evenly coated with brightener powder in this mixing process. It is striking that the other granular components of the preparation were not covered by the powder.
- the initially pale greenish color of the extrudate particles at the mixer outlet turned into a brilliant white color within a few minutes.
- the Berger whiteness was above 100.
- the whitening powder used was previously prepared by grinding the raw materials listed below together in a pin disc mill in a circuit up to a maximum particle size below 5 ⁇ m (primary particles according to SEM image):
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Abstract
Powdering agents for coarse-grain detergents which confer excellent optical properties to detergent particles to be powdered, especially surfactant-containing detergent particles contain 5 to 80 wt.- % of one or more optical brightening agents and up to 15 wt.- % of other adjuvants or substances and have maximum primary particle sizes of less than 50 νm.
Description
"Herstellung Aufheller-haltiger Waschmittel-Granulate " "Production of detergent granules containing brighteners"
Die vorliegende Erfindung betrifft ein Aufheller-haltiges Pudermittel, ein Verfahren zu dessen Herstellung sowie die Verwendung dieser Pudermittel zum Abpudern von Waschmitteln mit hoher Schüttdichte. Ein Verfahren zur Herstellung grobkörniger Waschmittel, die optischen Aufheller enthalten, ist ebenfalls Gegenstand der vorliegenden Erfindung.The present invention relates to a brightener-containing powder, a process for its preparation and the use of these powder for powdering detergents with a high bulk density. The present invention also relates to a process for producing coarse-grained detergents which contain optical brighteners.
Granuläre Waschmittel enthalten normalerweise neben den für den Waschprozess unverzichtbaren Inhaltsstoffen wie Tensiden und Buildermaterialien in der Regel weitere Bestandteile, die man unter dem Begriff Waschhilfsstoffe zusammenfassen kann und die so unterschiedliche Wirkstoffgruppen wie Schaumregulatoren, Vergrauungsinhibitoren, Bleichmittel, Bleichaktivatoren und Farbübertragungsinhibitoren umfassen. Zu derartigen Hilfsstoffen gehören auch Substanzen, welche auf die Fasern gewaschener, sauberer Textilien aufziehen und die nach dem Waschen üblicherweise vorhandene schwache Gelbfärbung ursprünglich weißer Textilien kompensieren sollen. Diese Substanzen werden als optische Aufheller bezeichnet. Sie wirken im gewünschten Sinne normalerweise dadurch, daß sie einen Teil der unsichtbaren ultravioletten Stahlung in längerwelliges blaues Licht umwandeln. Der gelbliche Ton gewaschener Wäsche kann auf die partielle Absorption von Licht des blauen Bereichs aus dem Spektrum von weißem Licht zurückgeführt werden. Durch die erhöhte Emission blauen Lichtes durch den optischen Aufheller wird diese partielle Absorption ausgeglichen, so daß sich in der Summe der Eindruck strahlend weißer Wäsche ergibt. Ein Nebeneffekt des Einsatzes optischer Aufheller besteht darin, daß auch das granuläre Waschmittel, welches diesen enthält, leuchtend weiß erscheint, was vom Verbraucher positiv aufgenommen wird.Granular detergents usually contain, in addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, other components that can be summarized under the term washing aids and that include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliary substances also include substances which are absorbed onto the fibers of washed, clean textiles and which are intended to compensate for the weak yellow coloration of originally white textiles which is usually present after washing. These substances are called optical brighteners. They usually work in the desired sense by converting part of the invisible ultraviolet radiation into longer-wave blue light. The yellowish tone of washed laundry can be attributed to the partial absorption of light in the blue region from the spectrum of white light. This partial absorption is compensated for by the increased emission of blue light by the optical brightener, so that the result is the impression of bright white laundry. A side effect of the use of optical brighteners is that the granular detergent containing them also appears bright white, which is positively received by the consumer.
Optische Aufheller werden im Handel entweder als Suspensionen oder als sprühgetrocknete Produkte angeboten. Bei der Herstellung sprühgetrockneter Waschmittelpulver wird der optische Aufheller üblicherweise in Form der handelsüblichen Suspension in die zu
versprühende wäßrige Aufschlämmung der Waschmittelbestandteile eingearbeitet. Bekanntlich ist bei dieser Herstellungsweise das erreichbare Schüttgewicht der hergestellten granulären Produkte beschränkt. So ist es normalerweise nicht möglich, Waschmittel mit Schüttgewichten über ca. 500 g/1 allein durch Sprühtrocknen herzustellen. Andererseits werden vom Verbraucher möglichst kompakte Waschmittel gefordert. Im Zuge der steigenden Verbreitung von aufhellerfreien Waschmitteln (Feinwaschmittel, Colorwaschmit- tel) neben den weiterhin aufhellerhaltigen Universalwaschmitteln besteht aber auch ein wirtschaftliches Interesse, die Sprühtürme bei Produktwechseln nicht intensiv von Aufhellerrückständen reinigen zu müssen. Dies wurde im Stand der Technik dadurch gelöst, daß handelsübliche sprühgetrocknete Aufheller erst nachträglich zugemischt werden. Diese letzte - als Aufbereitung bezeichnete und ohnehin vorhandene - Prozeßstufe dient ansonsten der Zumischung empfindlicher Bestandteile wie beispielsweise Enzymen, Bleichmitteln, Bleichaktivatoren, Schauminhibitoren und Duftstoffen. Der Reinigungsaufwand der verwendeten Apparate reduziert sich nunmehr auf diese Aufbereitungsstufe und spart die Spühtrocknungsanlage mit ihren reinigungsintensiven Filtersystemen aus. Ermöglicht wird diese Vorgehensweise dadurch, daß handelsübliche Aufheller und Basiswaschpulver ähnliche Teilchengröße und -Struktur besitzen. Dies gewährleistet die Gleichverteilung des Aufhellers im Endprodukt, ohne daß bei Abfüllung und Transport die Gefahr der Entmischung besteht.Optical brighteners are commercially available either as suspensions or as spray-dried products. In the production of spray-dried detergent powder, the optical brightener is usually added in the form of the commercially available suspension spraying aqueous slurry of the detergent ingredients incorporated. It is known that the achievable bulk density of the granular products produced is limited in this production method. So it is normally not possible to produce detergents with bulk densities above approx. 500 g / 1 by spray drying alone. On the other hand, as compact as possible detergents are required by the consumer. In the course of the increasing spread of brightener-free detergents (mild detergents, color detergents) in addition to the universal detergents that still contain brighteners, there is also an economic interest in not having to intensively clean the spray towers of brightener residues when changing products. This has been solved in the prior art in that commercially available spray-dried brighteners are only added subsequently. This last process stage, which is referred to as preparation and is already present, is otherwise used to admix sensitive components such as enzymes, bleaching agents, bleach activators, foam inhibitors and fragrances. The cleaning effort of the equipment used is now reduced to this treatment level and spares the spray drying system with its cleaning-intensive filter systems. This procedure is made possible by the fact that commercial brighteners and basic washing powders have a similar particle size and structure. This ensures that the brightener is evenly distributed in the end product without the risk of segregation during filling and transport.
In grobgranularen Waschmitteln sind die handelsüblichen feingranularen sprühgetrockneten Aufheller wegen der zwangsläufigen Entmischung nicht als Zumischkomponenten einsetzbar.In coarse-grained detergents, the commercially available fine-granular spray-dried brighteners cannot be used as admixing components because of the inevitable segregation.
So ist in der internationalen Patentanmeldung WO 95/1358 AI vorgeschlagen worden, granuläre Mittel mit erhöhtem Schüttgewicht durch verdichtende Agglomeration herzustellen, wobei der optische Aufheller den flüssigen Komponenten beigemischt werden soll, die mit Feststoffen derart vermischt werden, daß die Feststoffpartikel miteinander verkleben und das Mittel mit hohem Schüttgewicht ergeben.
In der Patentanmeldung DE 196 22 443 (Henkel) wurde vorgeschlagen, die Aufheller in der Aufbereitung als Suspension auf extrudierte grobkörnige Waschmittel-Partikel aufzusprühen. Als Suspensionsflüssigkeiten wurden bevorzugt nichtionische Tenside verwendet, weil diese Kombinationen gegenüber anderen Systemen den besonderen Vorteil bieten, statt eines Grünstiches hervorragende Weißgrade auf der Granulatoberfläche zu erzeugen.Thus, it has been proposed in international patent application WO 95/1358 AI to produce granular agents with increased bulk density by compacting agglomeration, the optical brightener being mixed with the liquid components which are mixed with solids in such a way that the solid particles stick to one another and the agent result with high bulk density. In patent application DE 196 22 443 (Henkel) it was proposed to spray the brighteners in the preparation as a suspension onto extruded coarse-grained detergent particles. Nonionic surfactants were preferably used as suspension liquids because these combinations offer the particular advantage over other systems of producing excellent whiteness on the granulate surface instead of a green tinge.
Die vorstehend genannten Lösungswege weisen jedoch entscheidende Nachteile auf: So wird die Klebrigkeit der Granulat-Oberfläche auch mit Abpuderungsmitteln nicht ausreichend sicher beherrscht, so daß Produktverbackungen in den Verkaufsgebinden auftreten können. Auch die Herstell- bzw. Einsatzkosten der Suspension liegen weitaus höher, als die Einsparung der Reinigungskosten für Sprühturm und Extrusionsanlage eingebracht hätten. Aus diesen Gründen haben sich die vorstehend genannten Lösungsansätze nicht durchgesetzt. Ein weiteres Problem, das es bei der Einarbeitung von optischen Aufhellern zu lösen gilt, ist die Eigenfarbe der Aufheller, die je nach eingesetztem Typ zwischen schwach gelb (Morpholintyp) und intensiv Signalgrün (Distilben-Typ) variiert. Dies führt bei der Zumischung von Aufheller-Teilchen zu Produkten, die nicht strahlend weiß erscheinen und somit vom Verbraucher weniger akzeptiert werden.However, the solutions mentioned above have decisive disadvantages: the stickiness of the granulate surface is not adequately controlled even with powdering agents, so that product caking can occur in the sales containers. The manufacturing and operating costs of the suspension are also much higher than the savings in cleaning costs for the spray tower and extrusion system would have brought. For these reasons, the approaches mentioned above have not become established. Another problem that has to be solved when incorporating optical brighteners is the inherent color of the brightener, which varies depending on the type used between pale yellow (morpholine type) and intense signal green (distilbene type). When admixing brightener particles, this leads to products that do not appear bright white and are therefore less accepted by the consumer.
Es sollte nun eine wirtschaftlich vorteilhafte Möglichkeit der Einbringung optischer Aufheller über die Aufbereitung bei der Herstellung von kompakten Waschmitteln gefunden werden, die alle Qualitätsanforderungen bezüglich Homogenität, Aspekt und Rieselfähigkeit des Endproduktes erfüllt. Hierbei sollten insbesondere die Nachteile des Reinigungsaufwands von Apparaten, der gelblichen bzw. grünlichen Produktfarbe und der Klebrigkeit bzw. Klumpneigung der Produkte minimiert bzw. völlig vermieden werden. Die Vorteile des Einsatzes von nichtionischen Tensiden zur Weißgradverbesserung der Endprodukte sollten dabei nutzbar gemacht werden, ohne die Nachteile von Verklebung und Klumpneigung in Kauf nehmen zu müssen.
Ein Gegenstand der vorliegenden Erfindung ist somit ein Pudermittel für grobteilige Waschmittel, enthaltendAn economically advantageous possibility of introducing optical brighteners via the preparation in the production of compact detergents should now be found, which meets all quality requirements with regard to homogeneity, aspect and flowability of the end product. In particular, the disadvantages of the cleaning effort of apparatus, the yellowish or greenish product color and the stickiness or tendency to clump the products should be minimized or completely avoided. The advantages of using non-ionic surfactants to improve the whiteness of the end products should be exploited without having to accept the disadvantages of sticking and clumping. An object of the present invention is therefore a powder for coarse detergents containing
a) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie c) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe,a) 40 to 95% by weight of one or more pure white carrier materials, b) 5 to 80% by weight of one or more optical brighteners and c) up to 15% by weight of other auxiliaries or active ingredients,
wobei das Pudermittel maximale Primärteilchengrößen unterhalb von 50 μm aufweist.wherein the powder has maximum primary particle sizes below 50 microns.
Bevorzugte Pudermittel weisen dabei noch geringere Teilchengrößen auf, was sie für eine homogene Abpuderung noch besser geeignet macht. Bevorzugte Pudermittel weisen maximale Primärteilchengrößen unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, auf.Preferred powdering agents have even smaller particle sizes, which makes them even more suitable for homogeneous powdering. Preferred powdering agents have maximum primary particle sizes below 20 μm, preferably below 10 μm and in particular below 5 μm.
Das erfindungsgemäße Pudermittel enthält 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien. Der Begriff "reinweiß" bedeutet dabei im Rahmen der vorliegenden Erfindung, daß die eingesetzten Trägermaterialien einen sogenannten Weißgrad, der gemäß Berger (siehe A. Berger, A. Brockes: „Farbmessung in der Textilindustrie", BAYER Farben Revue, Sonderheft 3/1, 1971) mit Hilfe von Filterfarbmeßgeräten, zum Beispiel dem Gerät Spectroflash 500 der Firma datacolor international, CH — 8305 Dietlihon, bestimmt werden kann, von über 60, insbesondere über 70, besitzen. Ursprünglich wurde diese Methode zur Weißgradbestimmung an Textilien entwickelt; sie eignet sich aber ebenfalls hervorragend zur Weißgradmessung von Pulvern oder granulären Substanzen. Weißgrade lassen sich auch mit der Methode nach Ganz/Griesser bestimmen; die Grundlagen der Farbmessung sind in der DIN-Norm 5033 beschrieben.The powdering agent according to the invention contains 40 to 95% by weight of one or more pure white carrier materials. The term "pure white" in the context of the present invention means that the carrier materials used have a so-called whiteness, which according to Berger (see A. Berger, A. Brockes: "Color Measurement in the Textile Industry", BAYER Farben Revue, Special Issue 3/1, 1971) with the help of filter color measuring devices, for example the Spectroflash 500 from datacolor international, CH-8305 Dietlihon, of over 60, in particular over 70. Originally, this method for whiteness determination on textiles was developed and is suitable but also excellent for whiteness measurement of powders or granular substances, whiteness can also be determined using the Ganz / Griesser method, the basics of color measurement are described in DIN standard 5033.
Als reinweiße Trägerstoffe eignen sich eine Reihe von Substanzen, wobei es bevorzugt ist, Stoffe zu verwenden, die im späteren Waschmittel neben ihrer Funktion als Pudermittel weitere Funktionen, beispielsweise Builderwirkung, wahrnehmen. Als Trägermaterial eignen sich eine Vielzahl von Stoffen. Es existiert eine große Anzahl sowohl anorganischer
als auch organischer Substanzen, die eine genügend weiße Farbe aufweisen. Beispielhaft seien hier feinteilige Stoffe, die durch Fällung gewonnen werden, genannt. Als Substanzen finden beispielsweise Silikate, Aluminosilikate, Alkalisilikate und Alkalicarbonate bzw. -hydrogencarbonate Verwendung. Aber auch Kieselgur (Diatomeenerde) und feinteilige Cellulosefasern bzw. Derivate hiervon sind im Rahmen der vorliegenden Erfindung einsetzbar. So kommen beispielsweise feinteilige Zeolithe in Frage, aber auch pyrogene Kieselsäuren (Aerosil®) oder Kieselsäuren, die durch Fällung erhalten wurden. Im Rahmen der vorliegenden Erfindung bevorzugte Pudermittel enthalten 55 bis 85 Gew.-%, vorzugsweise 60 bis 80 Gew.-% und insbesondere 65 bis 75 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, wobei Trägermaterialien aus der Gruppe der Carbonate, der Sulfate, der Phosphate, der Citrate, der Silikate, insbesondere Kieselsäuren, und der Aluminiumsilikate, insbesondere Zeolithe A, P, X und Y, bevorzugt sind. Die genannten Stoffe werden weiter unten ausführlich beschrieben.A number of substances are suitable as pure white carriers, it being preferred to use substances which, in addition to their function as powdering agents, perform further functions, for example builder action, in the later detergent. A large number of substances are suitable as a carrier material. There are a large number of both inorganic as well as organic substances that are sufficiently white in color. Examples include finely divided substances that are obtained by precipitation. For example, silicates, aluminosilicates, alkali silicates and alkali carbonates or bicarbonates are used as substances. Diatomaceous earth (diatomaceous earth) and finely divided cellulose fibers or derivatives thereof can also be used in the context of the present invention. For example, finely divided zeolites can be used, but also pyrogenic silicas (Aerosil ® ) or silicas obtained by precipitation. Powdering agents preferred in the context of the present invention contain 55 to 85% by weight, preferably 60 to 80% by weight and in particular 65 to 75% by weight of one or more pure white carrier materials, wherein carrier materials from the group of the carbonates, the sulfates, the phosphates, the citrates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y, are preferred. The substances mentioned are described in detail below.
Das in den erfindungsgemäßen Pudermitteln enthaltene Trägermaterial weist vorzugsweise eine Ölabsorptionskapazität von mindestens 20g/ 100g auf. Noch weiter bevorzugt werden jedoch Ölabsorptionskomponenten eingesetzt, die eine höhere Ölabsorptionskapazität besitzen. Es sind dabei Pudermittel bevorzugt, bei denen das in ihnen enthaltene Trägermaterial eine Ölabsorptionskapazität von mindestens 50g/100g, vorzugsweise mindestens 80g/ 100g, besonders bevorzugt mindestens 120g/ 100g und insbesondere mindestens 140g/l 00g aufweist.The carrier material contained in the powdering agents according to the invention preferably has an oil absorption capacity of at least 20 g / 100 g. However, even more preferably, oil absorption components are used which have a higher oil absorption capacity. Powdering agents are preferred in which the carrier material contained therein has an oil absorption capacity of at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular at least 140g / 100g.
Die Ölabsorptionskapazität ist dabei eine physikalische Eigenschaft eines Stoffes, die sich nach genormten Methoden bestimmen läßt. So existieren beispielsweise die britischen Standardmethoden BS1795 und BS3483:Part B7.1982, die beide auf die Noim ISO 787/5 verweisen. Bei den Testmethoden wird eine ausgewogene Probe des betreffenden Stoffes auf einen Teller aufgebracht und tropfenweise mit raffiniertem Leinsamenöl (Dichte: 0,93 gern"3) aus einer Bürette versetzt. Nach jeder Zugabe wird das Pulver mit dem Öl unter Verwendung eines Spatels intensiv vermischt, wobei die Zugabe von Öl fortgesetzt wird, bis eine Paste von geschmeidiger Konsistenz erreicht ist. Diese Paste sollte fließen bzw. verlaufen, ohne zu krümeln. Die Ölabsorptionskapazität ist nun die Menge des zugetropf-
ten Öls, bezogen auf 100g Absorptionsmittel und wird in ml/ 100g oder g/lOOg angegeben, wobei Umrechnungen über die Dichte des Leinsamenöls problemlos möglich sind.The oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7.1982 exist, both of which refer to Noim ISO 787/5. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93) "3" is added dropwise from a burette. After each addition, the powder is mixed intensively with the oil using a spatula, the addition of oil is continued until a paste of smooth consistency is obtained. This paste should flow or flow without crumbling. The oil absorption capacity is now the amount of the added dropwise. ten oil, based on 100g absorbent and is given in ml / 100g or g / lOOg, whereby conversions about the density of linseed oil are possible without any problems.
Als zweite Komponente enthalten die erfindungsgemäßen Pudermittel einen oder mehrere optische(n) Aufheller. Diese Stoffe, die auch "Weißtöner" genannt werden, werden in modernen Waschmittel eingesetzt, da sogar frisch gewaschene und gebleichte weiße Wäsche einen leichten Gelbstich aufweist. Optische Aufheller sind organische Farbstoffe, die einen Teil der unsichtbaren UV-Strahlung des Sonnenlichts in längerwelliges blaues Licht umwandeln. Die Emission dieses blauen Lichts ergänzt die "Lücke" im vom Textil reflektierten Licht, so daß ein mit optischem Aufheller behandeltes Textil dem Auge weißer und heller erscheint. Da der Wirkungsmechanismus von Aufhellern deren Aufziehen auf die Fasern voraussetzt, unterscheidet man je nach "anzufärbenden" Fasern beispielsweise Aufheller für Baumwolle, Polyamid- oder Polyesterfasern. Die handelsüblichen für die Inkorporation in Waschmittel geeigneten Aufheller gehören dabei im wesentlichen fünf Strukturgruppen an Der Stilben-, der Diphenylstilben-, der Cumarin-Chinolin-, der Diphenylpy- razolingruppe und der Gruppe der Kombination von Benzoxazol oder Benzimidazol mit konjugierten Systemen. Ein Überblick über gängige Aufheller ist beispielsweise in G. Ja- kobi, A.Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, Seiten 94 bis 100, zu finden. Geeignet sind z.B. Salze der 4,4'-Bis[(4-anilino-6-morpholino-s- triazin-2-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 der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4- Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden.As a second component, the powdering agents according to the invention contain one or more optical brighteners. These fabrics, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners suitable for incorporation in detergents essentially comprise five structural groups: the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners can be found, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are e.g. Salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or similarly structured compounds which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.
Im Rahmen der vorliegenden Erfindung bevorzugte Pudermittel enthalten 7,5 bis 50 Gew.- %, vorzugsweise 10 bis 40 Gew.-% und insbesondere 15 bis 30 Gew.-% eines oder mehrerer optischer Aufheller, wobei Aufheller vom Dimorpholin-Typ und vom Distilben-Typ bzw. Mischungen aus diesen, bevorzugt sind.
Optional können die erfindungsgemäßen Pudermittel bis zu 10 Gew.-% weiterer Wirk- und Hilfsstoffe enthalten. Ein Gehalt an solchen Stoffen kommt beispielsweise dadurch zustande, daß bestimmte handelsübliche Aufhellerzubereitungen Stoffe enthalten, die weder den Trägerstoffen noch den Aufhellern zuzurechnen sind. Solche Wirk- bzw. Hilfsstoffe stammen beispielsweise aus den Gruppen der Polymere, der Tenside, der nichtwäßrigen Lösungsmittel usw. Bevorzugt enthalten die erfindungsgemäßen Pudermittel allerdings weniger als 7,5 Gew.-%, vorzugsweise sogar weniger als 5 Gew.-% an weiteren Hilfs- oder Wirkstoffen, wobei besonders bevorzugte Pudermittel frei von solchen Stoffen sind.Powdering agents preferred in the context of the present invention contain 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight, of one or more optical brighteners, brighteners of the dimorpholine type and of distilbene -Type or mixtures of these are preferred. The powdering agents according to the invention can optionally contain up to 10% by weight of further active ingredients and auxiliaries. A content of such substances comes about, for example, from the fact that certain commercial brightener preparations contain substances which are neither attributable to the carriers nor to the brighteners. Such active substances or auxiliaries originate, for example, from the groups of polymers, surfactants, non-aqueous solvents, etc. However, the powdering agents according to the invention preferably contain less than 7.5% by weight, preferably even less than 5% by weight, of further auxiliaries - or active ingredients, particularly preferred powdering agents being free of such substances.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Pudermitteln für grobteilige Waschmittel, bei dem man ein Gemisch ausAnother object of the present invention is a process for the preparation of powdering agents for coarse detergents, in which a mixture of
a) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie c) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe,a) 40 to 95% by weight of one or more pure white carrier materials, b) 5 to 80% by weight of one or more optical brighteners and c) up to 15% by weight of other auxiliaries or active ingredients,
in einer Mühle vermischt und auf maximale Primärteilchengrößen unterhalb von 50 μm aufmahlt.mixed in a mill and ground to maximum primary particle sizes below 50 μm.
Die Inhaltsstoffe, die vermischt und anschließend vermählen werden, wurden vorstehend bereits beschrieben. Als Mühlen kommen für das erfindungsgemäße Verfahren Zerkleinerungsmaschinen mit sehr unterschiedlichen Ausführungsformen in betracht. Allen Mühlen gemeinsam ist, daß sie die Zerkleinerung durch Stoß, Schlag, Druck, Reibung, Scherung usw. von Mahlorganen bewirken, die rotierende, schwingende, taumelnde oder hin- und hergehende Bewegungen ausführen.The ingredients that are mixed and then ground have already been described above. Comminution machines with very different embodiments come into consideration as mills for the method according to the invention. It is common to all mills that they effect the comminution by means of impact, impact, pressure, friction, shear, etc. of grinding elements which perform rotating, oscillating, tumbling or reciprocating movements.
Für die Feinzerkleinerung harter Stoffe findet bevorzugt die Kugelmühle Verwendung, bei der in einer rotierenden Mahltrommel Stahl-, Porzellan- oder Flintkugeln mitgerollt werden, die das Mahlgut beim Mitrollen oder Herabfallen zertrümmern. Bei einer Siebkugel- Mühle werden die abfallenden, zermahlenen Teilchen noch durch ein die Trommel umge-
benden Sieb gesiebt. Varianten dieses Mühlen-Typs stellen die Schwingkugelmühlen und die Umlaufmühlen dar, letztere sind eine Kombination aus Kugelmühle und Windsichter. Auch sogenannte Schneidmühlen sind zur Durchführung des erfindungsgemäßen Verfahrens geeignet. Sie bestehen aus einem horizontal oder vertikal angeordneten Rotor, der mit Messern bestückt ist, die gegen im Gehäuse der Mühle verankerte Messer arbeiten. Im erfindungsgemäßen Verfahren können auch Feinprallmühlen Anwendung finden, zu denen u.a. Stiftmühlen, Mühlen mit einer peripheren Mahlbahn und Strahlmühlen gehören, z.B. die Querstrom-Mühle und die Spiralstrahl-Mühle. Auch Walzen-, Rohr-, Scheiben-, Zahnscheiben-, Schwing-, Glocken-, Federkraftroll-, Fliehkraftroll-, Schlagkreuz- und andere Mühlen sind für das erfindungsgemäße Verfahren einsetzbar.For the fine comminution of hard materials, the ball mill is preferably used, in which steel, porcelain or flint balls are rolled in a rotating grinding drum, which shatter the ground material as it rolls along or falls down. In the case of a sieve ball mill, the falling, ground particles are still removed by a drum sieving sieve. Variants of this type of mill are the vibrating ball mills and the circulation mills, the latter being a combination of ball mill and air classifier. So-called cutting mills are also suitable for carrying out the method according to the invention. They consist of a horizontally or vertically arranged rotor, which is equipped with knives that work against knives anchored in the housing of the mill. In the process according to the invention, fine impact mills can also be used, which include pin mills, mills with a peripheral grinding path and jet mills, for example the cross-flow mill and the spiral jet mill. Roller, tube, disc, toothed disc, vibration, bell, spring force, centrifugal, cross, and other mills can also be used for the method according to the invention.
In bevorzugten Varianten des erfindungsgemäßen Verfahrens wird das Gemisch in einer Kugelmühle, einer Ringspaltkugelmühle, einer Mörsermühle oder einer Stiftscheibenmühle auf maximale Primärteilchengrößen unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, vermählen.In preferred variants of the method according to the invention, the mixture is ground in a ball mill, an annular gap ball mill, a mortar mill or a pin disc mill to maximum primary particle sizes below 20 μm, preferably below 10 μm and in particular below 5 μm.
Hinsichtlich der bevorzugten Mengen und Substanzklassen von Trägermaterial, Aufheller und Hilfsstoffen sei auf die vorstehenden Angaben verwiesen. Auch bei den erfindungsgemäßen Verfahren ist es bevorzugt, daß 55 bis 85 Gew.-%, vorzugsweise 60 bis 80 Gew.- % und insbesondere 65 bis 75 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, vorzugsweise Trägermaterialien aus der Gruppe der Carbonate, der Sulfate, der Silikate, insbesondere Kieselsäuren, und der Aluminiumsilikate, insbesondere Zeolithe A, P, X und Y, und 7,5 bis 50 Gew.-%, vorzugsweise 10 bis 40 Gew.-% und insbesondere 15 bis 30 Gew.-% eines oder mehrerer optischer Aufheller, vorzugsweise Aufheller vom Dimorpho- lin-Typ und vom Distilben-Typ bzw. Mischungen aus diesen, sowie bis zu 10 Gew.-%, vorzugsweise bis zu 7,5 Gew.-% und insbesondere bis zu 5 Gew.-% weiterer Hilfs- oder Wirkstoffe vermischt und vermählen werden.
Die erfindungsgemäßen Pudermittel eignen sich hervorragend zum Abpudern von grobtei- ligen Waschmittel-Partikeln, so daß ein weiterer Gegenstand der vorliegenden Erfindung die Verwendung von Pudermitteln mit einem Gehalt anWith regard to the preferred amounts and substance classes of carrier material, brightener and auxiliary substances, reference is made to the above information. In the process according to the invention, too, it is preferred that 55 to 85% by weight, preferably 60 to 80% by weight and in particular 65 to 75% by weight, of one or more pure white support materials, preferably support materials from the group of the carbonates, of Sulfates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y, and 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight one or more optical brighteners, preferably brighteners of the dimorpholine type and of the distilbene type or mixtures thereof, and up to 10% by weight, preferably up to 7.5% by weight and in particular up to 5% by weight .-% of other auxiliaries or active ingredients are mixed and ground. The powdering agents according to the invention are outstandingly suitable for powdering large-scale detergent particles, so that the present invention further relates to the use of powdering agents containing
a) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie c) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe,a) 40 to 95% by weight of one or more pure white carrier materials, b) 5 to 80% by weight of one or more optical brighteners and c) up to 15% by weight of other auxiliaries or active ingredients,
und maximalen Primärteilchengrößen unterhalb von 50 μm zur Abpuderung grobteihger Waschmittel-Partikel ist.and maximum primary particle sizes below 50 μm for powdering coarse detergent particles.
Bevorzugte Ausführungsformen der erfindungsgemäßen Verwendung sehen dabei vor, daß die grobteiligen Waschmittel-Partikel mittlere Partikeldurchmesser oberhalb von 700 μm, vorzugsweise oberhalb von 800 μm und insbesondere oberhalb von 1000 μm aufweisen und das Pudermittel eine maximale Primärteilchengröße unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, besitzt.Preferred embodiments of the use according to the invention provide that the coarse-particle detergent particles have average particle diameters above 700 μm, preferably above 800 μm and in particular above 1000 μm, and the powder medium has a maximum primary particle size below 20 μm, preferably below 10 μm and in particular below 5 μm.
Wie bereits vorstehend erwähnt, lassen sich durch die Kombination von nichtionischen Tensiden mit den Aufhellern Farbvorteile erzielen, weshalb es bevorzugt ist, daß die grob- teiligen Waschmittel-Partikel solche nichtionischen Tenside enthalten.As already mentioned above, color combinations can be achieved by combining nonionic surfactants with the brighteners, which is why it is preferred that the coarse-particle detergent particles contain such nonionic surfactants.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxy- lierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C- Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalko- holresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C- Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12_14- Alkohole mit 3 EO oder 4 EO, C9.π-Alkohol mit 7 EO, C13.15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, CI2.
,8-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12.14-Alkohol mit 3 EO und C12_ι8-Alkohol mit 5 EO. Die angegebenen Ethoxy- lierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Taigfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO.The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C 12 _ 14 - alcohols with 3 EO or 4 EO, C. 9 π alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C I2. , 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12.14 alcohol with 3 EO and C 12 8 alcohol with 5 EO. 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 narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und pro- poxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkyl- kette, insbesondere Fettsäuremethyl ester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90713533 beschriebenen Verfahren hergestellt werden.Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90713533.
Eine weitere Klasse von nichtionischen Tensiden, die vorteilhaft eingesetzt werden kann, sind die Alkylpolyglycoside (APG). Einsetzbare Alkypolyglycoside genügen der allgemeinen Formel RO(G)z, in der R für einen linearen oder verzweigten, insbesondere in 2- Stellung methylverzweigten, gesättigten oder ungesättigten, aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glyko- seeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Glycosidierungs- grad z liegt dabei zwischen 1,0 und 4,0, vorzugsweise zwischen 1,0 und 2,0 und insbesondere zwischen 1,1 und 1,4.Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
Bevorzugt eingesetzt werden lineare Alkylpolyglucoside, also Alkylpolyglycoside, in denen der Polyglycosylrest ein Glucoserest und der Alkylrest ein n-Alkylrest ist.Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N- dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealka- nolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vor-
zugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I),Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
RJ R J
R-CO-N-[Z] (I)R-CO-N- [Z] (I)
in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuk- kers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylie- rung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II),The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
RΪ-O-R^R Ϊ -OR ^
R-CO-N-[Z] (II)R-CO-N- [Z] (II)
in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R1 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C,.4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substitu-
iert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, where C,. 4 -alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups. is or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Anmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
Bevorzugt in den grobteiligen Waschmittel-Partikeln enthaltene nichtionische Tenside stammen aus der Gruppe der alkoxylierten Alkohole. Diese auch als Fettalkoholpolygly- kolether oder Alkylpolyglykolether bezeichneten Verbindungen stellen eine Gruppe nichtionischer Tenside dar, die durch Alkoxylierung, vorzugsweise jedoch Ethoxylierung von primären Fett- bzw. Oxoalkoholen in Gegenwart basischer oder saurer Katalysatoren bei Temperaturen von 150-200° und Drücken von 1-10 bar gewonnen wird. Bei der Umsetzung des Alkohols mit dem Alkoxid entsteht ein Polyglykolether-Gemisch unterschiedlich hoch alkoxylierter Homologer, deren Verteilung in Abhängigkeit des Katalysators und der Alkoxid-Menge zwischen einer der Statistik entsprechenden Gauss- u. einer unselektiven Schulz-Flory-Kurve variieren kann. So wird z.B. in Gegenwart von Natriumhydroxid eine breite, unter Verwendung von Erdalkali-Salzen eine eingeengte (narrow-range) Homologen- Verteilung erhalten. Infolge der durch saure Ethoxylierungskatalysatoren begünstigten Bildung von 1,4-Dioxan als unerwünschtem Nebenprodukt, werden in der Technik bevorzugt basische Katalysatoren, z.B. Natriummethylat in Methanol, eingesetzt. Wenn Fettalkoholethoxylate in den grobteiligen Waschmittel-Partikeln enthalten sind, so werden bevorzugt Produkte mit Ethoxylierungsgraden unter 10, beispielsweise mit mittleren Ethoxylierungsgraden von 5, 6, 7 oder 8, eingesetzt. Mittlere Ethoxylierungsgrade können auch gebrochene Zahlen sein, wobei auch niedrigere Grade wie 1,5 oder mittlere Grade von 5,5 eingestellt werden können. Die Kettenlänge der Fettalkohole, die zu den Ethoxylaten umgesetzt werden, liegt üblicherweise im Bereich von 8 bis 22, vorzugsweise von 10 bis 20 und insbesondere von 12 bis 18 Kohlenstoffatomen.
Eine im Rahmen der vorliegenden Erfindung bevorzugte Verwendung der erfindungsgemäßen Pudermittel ist dadurch gekennzeichnet, daß die grobteiligen Waschmittel-Partikel, bezogen auf die nicht abgepuderten Partikel, mindestens 2,5 Gew.-%, vorzugsweise mindestens 5 Gew.-% und insbesondere mindestens 7,5 Gew.-% nichtionische(s) Tensid(e), vorzugsweise ethoxylierte Alkohole, enthalten.Nonionic surfactants preferably contained in the coarse-particle detergent particles come from the group of alkoxylated alcohols. These compounds, also known as fatty alcohol polyglycol ethers or alkyl polyglycol ethers, represent a group of nonionic surfactants which, by alkoxylation, but preferably ethoxylation, of primary fatty alcohols or oxoalcohols in the presence of basic or acidic catalysts at temperatures of 150-200 ° and pressures of 1-10 won in cash. When the alcohol is reacted with the alkoxide, a polyglycol ether mixture of homologs of different degrees of alkoxylation is formed, the distribution of which, depending on the catalyst and the amount of alkoxide, between a Gaussian and the corresponding statistic. of an unselective Schulz-Flory curve can vary. For example, a broad homolog distribution is obtained in the presence of sodium hydroxide and a narrow-range homolog distribution using alkaline earth metal salts. As a result of the formation of 1,4-dioxane as an undesirable by-product, which is favored by acidic ethoxylation catalysts, basic catalysts, for example sodium methylate in methanol, are preferably used in industry. If fatty alcohol ethoxylates are contained in the coarse-particle detergent particles, preference is given to using products with degrees of ethoxylation below 10, for example with average degrees of ethoxylation of 5, 6, 7 or 8. Medium degrees of ethoxylation can also be fractional numbers, although lower degrees such as 1.5 or medium degrees of 5.5 can also be set. The chain length of the fatty alcohols which are converted to the ethoxylates is usually in the range from 8 to 22, preferably from 10 to 20 and in particular from 12 to 18 carbon atoms. A preferred use of the powdering agents according to the invention in the context of the present invention is characterized in that the coarse-particle detergent particles, based on the non-powdered particles, are at least 2.5% by weight, preferably at least 5% by weight and in particular at least 7 5% by weight of nonionic surfactant (s), preferably ethoxylated alcohols.
Zur Entfaltung der Waschleistung können die erfindungsgemäß mit Aufheller-haltigem Pudermittel beschichteten grobteiligen Waschmittel-Partikel weitere grenzflächenaktive Substanzen aus der Gruppe der anionischen, zwitterionischen oder kationischen Tenside enthalten, wobei anionische Tenside aus ökonomischen Gründen und aufgrund ihres Leistungsspektrums deutlich bevorzugt sind.To develop the washing performance, the coarse-particle detergent particles coated with brightener-containing powder can contain further surface-active substances from the group of anionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their performance spectrum.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9.13- Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansul- fonaten sowie Disulfonaten, wie man sie beispielsweise aus C12.ι8-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12.18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren geeignet.Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C 9 . 13 - Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C 12 .ι 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration. Alkanesulfonates which are derived from C 12 are also suitable. 18 -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglyce- rinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fett-
säuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Ca- prinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf pe- trochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C,2-C16-Alkylsulfate und C12-C]5- Alkylsulfate sowie C!4-C15-Alkylsulfate 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® erhalten werden können, sind geeignete Aniontenside.As alk (en) yl sulfates are the alkali and especially 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, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C, 2 -C 16 alkyl sulfates and C 12 -C ] 5 alkyl sulfates and C ! 4 -C 15 alkyl sulfates are preferred from the point of view of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7.2,-Alkohole, wie 2-Methyl-verzweigte C9.,,-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12.18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.The sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with 1 to 6 mol of ethylene oxide. 2 , -alcohols, such as 2-methyl-branched C 9. ,, - alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8.18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist
es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Other suitable 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 . 18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. Likewise it is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Taigfettsäuren, abgeleitete Seifengemische.Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kaliumoder 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, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Neben den waschaktiven Substanzen sind Gerüststoffe die wichtigsten Inhaltsstoffe von Wasch- und Reinigungsmitteln. In den mit den erfindungsgemäßen Pudermitteln abgepuderten Waschmittel-Partikeln können dabei alle üblicherweise in Wasch- und Reinigungsmitteln eingesetzten Gerüststoffe enthalten sein, insbesondere also Zeolithe, Silikate, Car- bonate, organische Cobuilder und - wo keine ökologischen Vorurteile gegen ihren Einsatz bestehen - auch die Phosphate. Wie vorstehend erwähnt, eignen sich die nachfolgend beschriebenen Gerüststoffe auch in besonderer Weise als Trägermaterial in den erfindungsgemäßen Pudermitteln.In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. The detergent particles powdered with the powdering agents according to the invention can contain all builders commonly used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates . As mentioned above, the builders described below are also particularly suitable as a carrier material in the powder compositions according to the invention.
Geeignete kristalline, schichtfbrmige Natriumsilikate besitzen die allgemeine Formel NaMSixO2x+, Η2O, 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. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A- 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate Na^i^ ' yH2O bevorzugt, wobei ß-Natrium- disilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO-A-91/08171 beschrieben ist.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na,O : SiO2 von 1 :2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/ Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, daß die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige sogenannte röntgenamor- phe Silikate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, werden beispielsweise in der deutschen Patentanmeldung DE-A- 44 00 024 beschrieben. Insbesondere bevorzugt sind verdichtete kompaktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate.Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + , Η 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. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ^ i ^ '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. Amorphous sodium silicates with a modulus Na, O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith A und oder P. Als Zeolith P wird Zeolith MAP® (Handelsprodukt der Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X und/oder P. Kommerziell erhältlich und im Rahmen der vorliegenden Erfindung bevorzugt einsetzbar ist beispielsweise auch ein Co-Kristallisat aus Zeolith X und Zeolith A (ca. 80 Gew.-% Zeolith X), das von der Firma CONDEA Augusta S.p.A. unter dem Markennamen VEGOBOND AX® vertrieben wird und durch die FormelThe finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
nNa • (l-n)K2O • Al2O3 ■ (2 - 2,5)SiO2 ■ (3,5 - 5,5) H2O
beschrieben werden kann. Geeignete Zeolithe weisen vorzugsweise eine mittlere Teilchengröße von weniger als 10 μm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22 Gew.-%, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.nNa • (ln) K 2 O • Al 2 O 3 ■ (2 - 2.5) SiO 2 ■ (3.5 - 5.5) H 2 O can be described. Suitable zeolites preferably have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
Selbstverständlich ist auch ein Einsatz der allgemein bekannten Phosphate als Buildersub- stanzen möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden sollte. Geeignet sind insbesondere die Natriumsalze der Orthophosphate, der Py- rophosphate und insbesondere der Tripolyphosphate.It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutar- säure, 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.Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this. 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.
Neben Tensid(en) und Gerüststoff(en) können die abzupudernden grobkörmigen Waschmittel-Partikel selbstverständlich weitere Inhaltsstoffe von Wasch- und Reinigungsmitteln enthalten, wobei für spezielle Inhaltsstoffe weiter unten ausführlich beschrieben werden.In addition to surfactant (s) and builder (s), the coarse-shaped detergent particles to be powdered can of course contain further ingredients of detergents and cleaning agents, with specific ingredients being described in detail below.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung Aufheller-hakiger Waschmittel, das durch die SchritteAnother object of the present invention is a process for the preparation of brightener-hooked detergents, which comprises the steps
a) Herstellung grobteihger Waschmittel-Partikel in an sich bekannter Weise b) Herstellung von Pudermitteln mit einer maximalen Primärteilchengrößen unterhalb von 50 μm durch Vermischen und Vermählen eines Gemischs aus bl) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b2) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie
b3) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe, c) Aufbringen der in Schritt b) hergestellten Pudermittel auf die in Schritt a) gebildeten Waschmittel-Partikela) Production of coarse detergent particles in a manner known per se b) Production of powdering agents with a maximum primary particle size below 50 μm by mixing and grinding a mixture of bl) 40 to 95% by weight of one or more pure white carrier materials, b2) 5 up to 80% by weight of one or more optical brighteners and b3) up to 15% by weight of further auxiliaries or active ingredients, c) applying the powdering agents prepared in step b) to the detergent particles formed in step a)
gekennzeichnet ist.is marked.
Der Verfahrensschritt a) umfaßt dabei die an sich bekannte Herstellung von Waschmittel- Partikeln, für die ein breiter Stand der Technik existiert. So läßt sich Schritt a) des erfindungsgemäßen Verfahrens in einer Vielzahl üblicher Misch- und Granuliervorrichtungen durchführen. Geeignete Mischer bzw. Granulatoren sind beispielsweise Eirich®-Mischer der Serien R oder RV (Warenzeichen der Maschinenfabrik Gustav Eirich, Hardheim), der Schugi® Flexomix, die Fukae® FS-G-Mischer (Warenzeichen der Fukae Powtech, Kogyo Co., Japan), die Lödige® FM-, KM- und CB-Mischer (Warenzeichen der Lödige Maschinenbau GmbH, Paderborn) oder die Drais®-Serien T oder K-T (Warenzeichen der Drais- Werke GmbH, Mannheim).Process step a) comprises the known production of detergent particles for which there is a wide range of prior art. Step a) of the process according to the invention can thus be carried out in a large number of customary mixing and granulating devices. Suitable mixers and granulators are disclosed, for example, Eirich ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan ), the Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais- Werke GmbH, Mannheim).
Neben der Granulation oder Agglomeration ist die Preßagglomeration ein weiteres mögliches Verfahren für die Durchführung des Verfahrensschritts a). Bei dem Verfahren der Preßagglomeration wird das Vorgemisch für die grobteiligen Waschmittel-Partikel unter Druck und unter Einwirkung von Scherkräften verdichtet und plastifiziert, dabei homogenisiert und anschließend formgebend aus den Apparaten ausgetragen. Die technisch bedeutsamsten Preßagglomerationsverfahren sind die Extrusion, die Walzenkompaktierung, die Pelletierung und das Tablettieren. Im Rahmen der vorliegenden Erfindung bevorzugte Preßagglomerationsverfahren sind die Extrusion, die Walzenkompaktierung und die Pelletierung.In addition to granulation or agglomeration, press agglomeration is another possible method for carrying out process step a). In the press agglomeration process, the premix for the coarse-particle detergent particles is compressed and plasticized under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner. The most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting. In the context of the present invention, preferred press agglomeration processes are extrusion, roller compaction and pelletization.
In einer bevorzugten Ausführungsform der Erfindung wird dabei das Vorgemisch für die grobteiligen Waschmittel-Partikel vorzugsweise kontinuierlich einem Planetwalzenextruder oder einem 2-Wellen-Extruder bzw. 2-Schnecken-Extruder mit gleichlaufender oder gegenlaufender Schneckenfuhrung zugeführt, dessen Gehäuse und dessen Extruder- Granulierkopf auf die vorbestimmte Extrudiertemperatur aufgeheizt sein können. Unter der
Schereinwirkung der Extruderschnecken wird das Vorgemisch unter Druck, der vorzugsweise mindestens 25 bar beträgt, bei extrem hohen Durchsätzen in Abhängigkeit von dem eingesetzten Apparat aber auch darunter liegen kann, verdichtet, plastifiziert, in Form feiner Stränge durch die Lochdüsenplatte im Extruderkopf extrudiert und schließlich das Ex- trudat mittels eines rotierenden Abschlagmessers vorzugsweise zu etwa kugelförmigen bis zylindrischen Granulatkörnern verkleinert. Der Lochdurchmesser der Lochdüsenplatte und die Strangschnittlänge werden dabei auf die gewählte Granulatdimension abgestimmt. In dieser Ausfuhrungsform gelingt die Herstellung von Granulaten einer im wesentlichen gleichmäßig vorherbestimmbaren Teilchengröße, wobei im einzelnen die absoluten Teilchengrößen dem beabsichtigten Einsatzzweck angepaßt sein können. Im allgemeinen werden Teilchendurchmesser bis höchstens 8 mm bevorzugt. Wichtige Ausführungsformen sehen hier die Herstellung von einheitlichen Granulaten im Millimeterbereich, beispielsweise im Bereich von 0,5 bis 5 mm und insbesondere im Bereich von etwa 0,8 bis 3 mm vor. Das Länge/Durchmesser- Verhältnis der abgeschlagenen primären Granulate liegt dabei in einer wichtigen Ausführungsform im Bereich von etwa 1 :1 bis etwa 3:1. Weiterhin ist es bevorzugt, das noch plastische Primärgranulat einem weiteren formgebenden Verarbeitungsschritt zuzuführen; dabei werden am Rohextrudat vorliegende Kanten abgerundet, so daß letztlich kugelförmig bis annähernd kugelförmige Extrudatkömer erhalten werden können. Falls gewünscht können in dieser Stufe geringe Mengen an Trockenpulver, beispielsweise Zeolithpulver wie Zeolith NaA-Pulver, mitverwendet werden. Falls die grobteiligen Waschmittel-Partikel durch Extrusion hergestellt werden, ist es auch möglich, Verfahrensschritt c), d.h. die Abpuderung mit dem Aufheller-haltigen Pudermittel, im Ron- diergerät vorzunehmen. Diese Formgebung/ Abpuderung kann in marktgängigen Rondier- geräten erfolgen. Dabei ist darauf zu achten, daß in dieser Stufe nur geringe Mengen an Feinkornanteil entstehen. Die Extrusion als Herstellungsprozess für Wasch- und Reinigungsmittel ist beispielsweise im europäischen Patent EP 486 592 (Henkel KGaA) ausführlich beschrieben.In a preferred embodiment of the invention, the premix for the coarse-particle detergent particles is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with a co-rotating or counter-rotating screw guide, its housing and its extruder pelletizing head on the predetermined extrusion temperature can be heated. Under the Shear of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the ex under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used - Trudat preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 8 mm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. In an important embodiment, the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred to feed the still plastic primary granulate to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. If the coarse-particle detergent particles are produced by extrusion, it is also possible to carry out process step c), ie the powdering with the brightener-containing powder detergent, in the rounding device. This shaping / powdering can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Extrusion as a manufacturing process for detergents and cleaning agents is described in detail, for example, in European Patent EP 486 592 (Henkel KGaA).
Alternativ können Extrusionen/Verpressungen auch in Niedrigdruckextrudern, in der Kahl- Presse (Strangpresse der Firma Amandus Kahl, Reinbek bei Hamburg) oder im Bextruder (Firma Hosokawa Bepex) durchgeführt werden.
Ebenso wie im Extrusionsverfahren ist es auch in den anderen Herstellungsverfahren bevorzugt, die entstandenen Primärgranulate/Kompaktate einem weiteren formgebenden Verarbeitungsschritt, insbesondere einer Verrundung, zuzuführen, so daß letztlich kugelförmige bis annähernd kugelförmige (perlenförmige) Körner erhalten werden können.Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (extrusion press from Amandus Kahl, Reinbek near Hamburg) or in the extruder (Hosokawa Bepex). Just as in the extrusion process, it is also preferred in the other production processes to feed the resulting primary granules / compactates to a further shaping processing step, in particular a rounding, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.
In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung wird Schritt a) des erfmdungsgemäßen Verfahrens mittels einer Walzenkompaktierung durchgeführt. Hierbei wird das Vorgemisch für die grobteiligen Waschmittel-Partikel gezielt zwischen zwei glatte oder mit Vertiefungen von definierter Form versehene Walzen eindosiert und zwischen den beiden Walzen unter Druck zu einem blattförmigen Kompaktat, der sogenannten Schülpe, ausgewalzt. Die Walzen üben auf das Vorgemisch einen hohen Liniendruck aus und können je nach Bedarf zusätzlich geheizt bzw. gekühlt werden. Bei der Verwendung von Glattwalzen erhält man glatte, unstrukturierte Schülpenbänder, während durch die Verwendung strukturierter Walzen entsprechend strukturierte Schülpen erzeugt werden können, in denen beispielsweise bestimmte Formen der späteren grobteiligen Waschmittel-Partikel vorgegeben werden können. Das Schülpenband wird nachfolgend durch eine Abschlag- und Zerkleinerungsvorrichtung in kleinere Stücke gebrochen und kann auf diese Weise zu Granulatkörnern verarbeitet werden, die durch weitere Oberflächenbehandlungsverfahren weiter vergütet, insbesondere in annähernd kugelförmige Gestalt gebracht und nachfolgend abgepudert (Verfahrensschritt c)) werden können.In a further preferred embodiment of the present invention, step a) of the method according to the invention is carried out by means of roller compaction. Here, the premix for the coarse-particle detergent particles is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later coarse-particle detergent particles can be specified. The sliver belt is subsequently broken up into smaller pieces by a knock-off and comminution device and can be processed into granules in this way, which can be further tempered by further surface treatment processes, in particular brought into an approximately spherical shape and subsequently powdered (process step c)).
In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung wird Schritt a) des erfindungsgemäßen Verfahrens mittels einer Pelletierung durchgeführt. Hierbei wird das Vorgemisch für die grobteiligen Waschmittel-Partikel auf eine perforierte Fläche aufgebracht und mittels eines druckgebenden Körpers unter Plastifizierung durch die Löcher gedrückt. Bei üblichen Ausführungsformen von Pelltpressen wird das Vorgemisch unter Druck verdichtet, plastifiziert, mittels einer rotierenden Walze in Form feiner Stränge durch eine perforierte Fläche gedrückt und schließlich mit einer Abschlagvorrichtung zu Granulatkörnern zerkleinert. Hierbei sind die unterschiedlichsten Ausgestaltungen von Druckwalze und perforierter Matrize denkbar. So finden beispielsweise flache perforierte
Teller ebenso Anwendung wie konkave oder konvexe Ringmatrizen, durch die das Material mittels einer oder mehrerer Druckwalzen hindurchgepreßt wird. Die Preßrollen können bei den Tellergeräten auch konisch geformt sein, in den ringförmigen Geräten können Matrizen und Preßrolle(n) gleichläufigen oder gegenläufigen Drehsinn besitzen. Ein zur Durchführung des Schritts a) des erfindungsgemäßen Verfahrens geeigneter Apparat wird beispielsweise in der deutschen Offenlegungsschrift DE 38 16 842 (Schlüter GmbH) beschrieben. Die in dieser Schrift offenbarte Ringmatrizenpresse besteht aus einer rotierenden, von Preßkanälen durchsetzten Ringmatrize und wenigstens einer mit deren Innenfläche in Wirkverbindung stehenden Preßrolle, die das dem Matrizenraum zugeführte Material durch die Preßkanäle in einen Materialaustrag preßt. Hierbei sind Ringmatrize und Preßrolle gleichsinnig antreibbar, wodurch eine verringerte Scherbelastung und damit geringere Temperaturerhöhung des Vorgemischs realisierbar ist. Selbstverständlich kann aber auch bei der Pelletierung mit heiz- oder kühlbaren Walzen gearbeitet werden, um eine gewünschte Temperatur des Vorgemischs einzustellen.In a further preferred embodiment of the present invention, step a) of the method according to the invention is carried out by means of pelleting. The premix for the coarse-particle detergent particles is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, find flat perforated ones Plates as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out step a) of the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix.
In bevorzugten Verfahren werden die in Verfahrensschritt a) hergestellten grobteiligen Waschmittel-Partikel durch Granulation, Agglomeration oder Preßagglomeration, insbesondere durch Naßgranulation, Walzenkompaktierung, Pelletierung oder Extrusion, hergestellt.In preferred processes, the coarse-particle detergent particles produced in process step a) are produced by granulation, agglomeration or press agglomeration, in particular by wet granulation, roller compaction, pelleting or extrusion.
Auch im erfindungsgemäßen Verfahren gelten die bereits bei der erfindungsgemäßen Verwendung genannten bevorzugten Bereiche für die Teilchengrößen von abzupuderndem Partikel und Pudermittel. So sind Verfahren bevorzugt, bei denen die in Schritt a) hergestellten grobteiligen Waschmittel-Partikel mittlere Partikeldurchmesser oberhalb von 700 μm, vorzugsweise oberhalb von 800 μm und insbesondere oberhalb von 1000 μm aufweisen und das in Schritt b) hergestellte Pudermittel eine maximale Primärteilchengröße unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, besitzt.Also in the process according to the invention, the preferred ranges already mentioned for the use according to the invention apply to the particle sizes of particles to be powdered and powdering agent. Thus, methods are preferred in which the coarse-particle detergent particles produced in step a) have average particle diameters above 700 μm, preferably above 800 μm and in particular above 1000 μm, and the powder agent produced in step b) has a maximum primary particle size below 20 μm, preferably below 10 μm and in particular below 5 μm.
Ebenfalls vorstehend erwähnt wurde die Tatsache, daß die in Schritt a) hergestellten grobteiligen Waschmittel-Partikel vorzugsweise tensidhaltig sind, wobei ein Gehalt von minde-
stens 2,5 Gew.-%, vorzugsweise mindestens 5 Gew.-% und insbesondere mindestens 7,5 Gew.-% an einem oder mehreren nichtionischen Tensiden, vorzugsweise ethoxylierten Alkoholen, bevorzugt ist.Also mentioned above was the fact that the coarse-particle detergent particles produced in step a) preferably contain surfactants, a content of at least at least 2.5% by weight, preferably at least 5% by weight and in particular at least 7.5% by weight, of one or more nonionic surfactants, preferably ethoxylated alcohols, is preferred.
So ist es im Rahmen der vorliegenden Erfindung bevorzugt, die vorzugsweise tensidhalti- gen Waschmittel-Partikel in Schritt a) in einem Mischer/Granulator herzustellen. Diese Vorgehensweise hat den Vorteil, daß das aufzubringende Pudermittel in den gleichen Apparat eingebracht werden kann. Auf diese Weise wird für die Verfahrensschritte a) und c) lediglich ein Mischer/Granulator benötigt. So sind erfindungsgemäße Verfahren bevorzugt, bei denen die Schritte a) und c) in einem (im Sinne von ein- und demselben) Mischer/Granulator durchgeführt werden. Besonders bevorzugt sind Verfahren, bei denen die Verfahrensschritte a) und c) in einem langsamlaufenden Mischer, z.B. einem Lödige- Pflugscharmischer, bei Umlaufgeschwindigkeiten der Mischwerkzeuge von 80 bis 300 U/min durchgeführt werden.In the context of the present invention, it is preferred to produce the detergent particles, which preferably contain surfactants, in step a) in a mixer / granulator. This procedure has the advantage that the powder to be applied can be introduced into the same apparatus. In this way, only one mixer / granulator is required for process steps a) and c). Methods according to the invention are preferred in which steps a) and c) are carried out in a mixer / granulator (in the sense of one and the same). Particularly preferred are processes in which process steps a) and c) are carried out in a slow-running mixer, e.g. a Lödige ploughshare mixer, at speeds of 80 to 300 rpm for the mixing tools.
Es ist besonders vorteilhaft, diesen Mischer in zwei Kammern aufzuteilen. In der größeren Kammer erfolgt die Granulation, während in der kleineren Kammer die Abpuderung des Granulats erfolgt. Zusätzlich können in diesem zweiten Mischer Flüssigkeiten eingedüst werden, um den Effekt des Feststoffcoatings mit einem zusätzlichen Coating zu verstärken. Zusätzliche Coatingmaterialien sind dabei vorzugsweise Polymer- oder Wasserglaslösungen.It is particularly advantageous to divide this mixer into two chambers. The granulation takes place in the larger chamber, while the granules are powdered in the smaller chamber. In addition, liquids can be injected into this second mixer in order to enhance the effect of the solid coating with an additional coating. Additional coating materials are preferably polymer or water glass solutions.
Eine weitere Möglichkeit besteht darin, den Lödige-Mischer batchweise zu betreiben, wobei die feinteiligen Auheller-haltigen Pudermittel getrennt am Ende der Granulation zugegeben werden. Der Mischerinhalt kann dann in ein Zwischenlager oder auf ein Transportband abgelassen werden, von wo aus die nachgeschalteten Anlagenteile (Wirbelschichttrockner, Sieb etc.) kontinuierlich weiterbetrieben werden.Another possibility is to operate the Lödige mixer in batches, the finely divided powder containing Auheller being added separately at the end of the granulation. The contents of the mixer can then be discharged into an interim storage facility or onto a conveyor belt, from where the downstream parts of the system (fluidized bed dryer, sieve, etc.) continue to be operated.
Der Verfahrensschritt b), die Herstellung der Aufheller-haltigen Pudermittel, ist als separates erfindungsgemäßes Verfahren bereits ausführlich beschrieben worden, wobei auf die vorstehenden Ausführungen verwiesen wird.
In Verfahrensschritt c) des erfindungsgemäßen Verfahrens wird das feinteilige Aufheller- haltige Pudermittel auf die grobteiligen Waschmittel-Partikel aufgebracht, wobei auf die dem Fachmann geläufigen Abpuderangsmethoden zurückgegriffen werden kann. In bevorzugten Verfahren erfolgt das Aufbringen der in Schritt b) hergestellten Pudermittel auf die in Schritt a) hergestellten Waschmittel-Partikel durch Vermischen im Gewichtsverhältnis Waschmittel-PartikehPudermittel von 400:1 bis 25:1, vorzugsweise von 200:1 bis 50:1 und insbesondere von 150:1 bis 75:1.Process step b), the production of the brightener-containing powder, has already been described in detail as a separate process according to the invention, reference being made to the above statements. In process step c) of the process according to the invention, the finely divided brightener-containing powder is applied to the coarse-particle detergent particles, it being possible to use the powdering methods familiar to the person skilled in the art. In preferred processes, the powdering agents produced in step b) are applied to the laundry detergent particles produced in step a) by mixing in the weight ratio of laundry detergent particles to powdering agent from 400: 1 to 25: 1, preferably from 200: 1 to 50: 1 and in particular from 150: 1 to 75: 1.
Vor der Durchführung des Verfahrensschrittes c) können den in Schritt a) hergestellten Waschmittel-Partikeln weitere Waschmittel-Inhaltsstoffe, insbesondere aus den Gruppen der Bleichmittel, Bleichaktivatoren, Enzyme, pH- Stellmittel, Farbstoffe, Schauminhibitoren, Antiredepositionsmittel, Vergrauungsinhibitoren, Farbübertragungsinhibitoren und Korrosionsinhibitoren sowie Mischungen hieraus zugemischt werden. In bevorzugten Verfahren, in denen die im Schritt a) hergestellten Waschmittel-Partikel Tensid(e), insbesondere nichtionische(s) Tensid(e) und darunter bevorzugt ethoxylierte Alkohole, enthalten, führt dies interessanterweise dazu, daß die anderen granulären Bestandteile der Aufbereitung nicht vom Puder belegt werden, sondern lediglich die tensidhaltigen Waschmittel- Partikel abgepudert werden. Durch die oben beschriebene Wechselwirkung von Niotensid und Pudermittel wechselt die anfangs blaß grünliche Farbe der abgepuderten Waschmittel- Partikel im weiteren Produktweg innerhalb weniger Minuten in einen strahlend weißen Farbton um.Before the process step c) is carried out, the detergent particles produced in step a) can contain further detergent ingredients, in particular from the groups of bleaching agents, bleach activators, enzymes, pH regulators, dyes, foam inhibitors, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures be mixed in from this. Interestingly, in preferred processes in which the detergent particles produced in step a) contain surfactant (s), in particular nonionic surfactant (s) and, preferably, ethoxylated alcohols, this does not result in the other granular components of the preparation are covered by the powder, but only the detergent particles containing surfactant are powdered off. Due to the interaction of nonionic surfactant and powder agent described above, the initially pale greenish color of the powdered detergent particles in the further product path changes to a bright white color within a few minutes.
Selbstverständlich können die nachfolgend beschriebenen Inhaltsstoffe auch erst nach der Durchführung des Verfahrensschritts c) den dann bereits abgepuderten Waschmittel- Partikeln zugemischt werden.Of course, the ingredients described below can also be added to the detergent particles that have already been powdered only after carrying out process step c).
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat, das Natriumperboratmonohydrat und das Natriumpercarbonat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyro- phosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Per- benzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandi-
säure. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylpero- xid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Bevorzugte Vertreter sind (a) die Peroxybenzoesäure und ihre ringsubstituierten Derivate, wie Alkyl- peroxybenzoesäuren, aber auch Peroxy-α-Naphtoesäure und Magnesium-monoperphthalat, (b) die aliphatischen oder substituiert aliphatischen Peroxysäuren, wie Peroxylaurinsäure, Peroxystearinsäure, ε-Phthalimidoperoxycapronsäure [Phthaloiminoperoxyhexansäure (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipinsäure und N- nonenylamidopersuccinate, und (c) aliphatische und araliphatische Peroxydicarbonsäuren, wie 1,12-Diperoxycarbonsäure, 1,9-Diperoxyazelainsäure, Diperocysebacinsäure, Diper- oxybrassylsäure, die Diperoxyphthalsäuren, 2-Decyldiperoxybutan-l,4-disäure, N,N- Terephthaloyl-di(ό-aminopercapronsäue) können eingesetzt werden.Among the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance. Further usable bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedi- acid. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexanoic acid [hexoxyacid] oxaloacetic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocyseboxyacid, diperoxyacid acid, diperoxyacid acid, diperoxy acid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (ό-aminopercapronic acid) can be used.
Um beim Waschen oder Reinigen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren eingearbeitet werden. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C- Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Tria- zinderivate, insbesondere l,5-Diacetyl-2,4-dioxohexahydro-l,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylengly- koldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran.In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C and below, bleach activators can be incorporated. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols and especially triacetyl, especially triacetin, 5-diacetoxy-2,5-dihydrofuran.
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. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere jedoch Cellulase-haltige Mischungen von besonderem Interesse. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable enzymatic agents. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
Zusätzlich können auch Komponenten enthalten sein, welche die Öl- und Fettaus- waschbarkeit aus Textilien positiv beeinflussen (sogenannte soil repellents). Dieser Effekt wird besonders deutlich, wenn ein Textil verschmutzt wird, das bereits vorher mehrfach mit einem erfindungsgemäßen Waschmittel, das diese öl- und fettlösende Komponente enthält, gewaschen wurde. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxy- propylcellulose mit einem Anteil an Methoxyl-Gruppen von 15 bis 30 Gew.-% und an Hy- droxypropoxyl-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethy- lenterephthalaten und/oder Polyethylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Besonders bevorzugt von diesen sind die sul- fonierten Derivate der Phthalsäure- und der Terephthalsäure-Polymere.In addition, components can also be included which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
Färb- und Duftstoffe können den Waschmittel-Partikeln zugesetzt werden, um den ästhetischen Eindruck der Produkte zu verbessern und dem Verbraucher neben der Weichheitsleistung ein visuell und sensorisch "typisches und unverwechselbares" Produkt zur Verfügung zu stellen. Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylace- tat, Dimethylbenzyl-carbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat,
Ethylmethylphenyl-glycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsa- licylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8-18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cy- clamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jono- ne, c -Isomethylionon und Methyl-cedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene wie Limonen und Pinen. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pine-, Citrus-, Jasmin-, Pat- chouly-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskateller, Salbeiöl, Ka- millenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl.Colorants and fragrances can be added to the detergent particles in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the ionone, c-isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
Üblicherweise liegt der Gehalt von Wasch- und Reinigungsmitteln an Farbstoffen unter 0,01 Gew.-%, während Duftstoffe bis zu 2 Gew.-% der gesamten Formulierung ausmachen können.The colorant content of detergents and cleaning agents is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.
Die Duftstoffe können direkt in die Waschmittel eingearbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, die die Haftung des Parfüms auf der Wäsche verstärken und durch eine langsamere Duftfreisetzung für langanhaltenden Duft der Textilien sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclo- dextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können.The fragrances can be incorporated directly into the detergents, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
Um den ästhetischen Eindruck der erfindungsgemäßen Mittel zu verbessern, können sie mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unemp- findlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasern, um diese nicht anzufärben.
Beispiele:In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them. Examples:
In dem Beispiel der DE 196 22 443 (Henkel) enthält das Grundgranulat ca. 4% nichtionisches Tensid (3,5% über Extrusion + ethoxylierten Talgalkohol aus dem Turmpulver). Über eine Suspension von Aufheller in nichtionischem Tensid werden nochmals 0,4% Niotensid auf die Oberfläche gesprüht.In the example of DE 196 22 443 (Henkel), the base granules contain approximately 4% nonionic surfactant (3.5% via extrusion + ethoxylated tallow alcohol from the tower powder). Another 0.4% nonionic surfactant is sprayed onto the surface via a suspension of brightener in nonionic surfactant.
In dem erfindungsgemäßen Verfahren der vorliegenden Erfindung kann und soll die Gesamtmenge Niotensid durchaus höher sein, wobei nach den vorstehenden Ausführungen keine Produktverbackung auftritt. In folgendem Beispiel enthält das Extrudat ca. 7,5% nichtionische Tenside:In the method according to the invention of the present invention, the total amount of nonionic surfactant can and should be quite higher, with no product caking according to the above statements. In the following example, the extrudate contains approximately 7.5% non-ionic surfactants:
Durch Sprühtrocknung wurde ein Turmpulver folgender Zusammensetzung hergestellt, das als Basis für ein zu extrudierendes Vorgemisch diente:A tower powder of the following composition was produced by spray drying and served as the basis for a premix to be extruded:
33,0% Zeolith 4A33.0% zeolite 4A
0,9% C12.18-Talgalkohol mit 5 EO0.9% C 12 . 18- tallow alcohol with 5 EO
1,0% C,2.,8-Fettsäure Natriumsalz1.0% C, 2nd , 8 -fatty acid sodium salt
17,3% C9.13-Alkylbenzolsulfonat17.3% C 9.13 alkyl benzene sulfonate
3,3% Natriumsulfat3.3% sodium sulfate
6,1% Acrylsäure-Maleinsäure-Copolymer (Sokalan® CP5, BASF)6.1% acrylic acid-maleic acid copolymer (Sokalan ® CP5, BASF)
1 ,2% Hydroxyethan- 1 , 1 -diphosphonsäure, Tetranatriumsalz1, 2% Hydroxyethan- 1, 1 -diphosphonic acid, tetrasodium salt
9,4% Wasser9.4% water
0,3% NaOH-Überschuß0.3% excess of NaOH
0,5% Salze aus Rohstoffen0.5% salts from raw materials
Dieses Turmpulver wurde mit weiteren Stoffen vermischt und in einem Lihotzky-2- Schnecken-Extruder bei einer Temperatur von 80 °C zu Rohextrudaten mit einer mittleren
Teilchengröße von 1,2 mm extrudiert. Die Zusammensetzung des Vorgemischs/Extrudats war folgende:This tower powder was mixed with other substances and in a Lihotzky-2 screw extruder at a temperature of 80 ° C to crude extrudates with a medium Extruded particle size of 1.2 mm. The premix / extrudate composition was as follows:
73,0%) Turmpulver (siehe oben)73.0%) tower powder (see above)
9,1% C12.18-Fettalkoholsulfat, 75% auf Natriumsulfat als Träger9.1% C 12.18 fatty alcohol sulfate, 75% on sodium sulfate as carrier
5,0% Natriumcitrat-Dihydrat5.0% sodium citrate dihydrate
2,6% Polyethylenglycol 40002.6% polyethylene glycol 4000
6,7% C12.18-Fettalkohol mit 7 EO6.7% C 12.18 fatty alcohol with 7 EO
3,6% Wessalith® P (Zeolith A, Degussa)3.6% Wessalith ® P (Zeolite A, Degussa)
In der Aufbereitung wurde das Extrudat mit folgenden Stoffen kontinuierlich in einem langsam laufenden Helix-Mischer gemischt:In the preparation, the extrudate was continuously mixed with the following substances in a slow-running helix mixer:
68,4% Extrudat (s.o.)68.4% extrudate (see above)
17.0%o Natriumcarbonat-Peroxyhydrat 90%ig17.0% o sodium carbonate peroxyhydrate 90%
7,4% TAED-Granulat7.4% TAED granules
4,0% Schauminhibitor4.0% foam inhibitor
1,1% Terephthalsäure-Ethylenglycol-Polyethylenglycolester, 70% auf Natriumsulfat1.1% terephthalic acid-ethylene glycol-polyethylene glycol ester, 70% on sodium sulfate
(Repel-O-Tex® SRP-4, Rhodia) 1,7% Enzyme 0,4% Parfümöl 1,0% Aufhellerpuder(Repel-O- Tex® SRP-4, Rhodia) 1.7% enzymes 0.4% perfume oil 1.0% brightener powder
Die Oberfläche der Extrudatpartikel wurde bei diesem Mischvorgang gleichmäßig mit Aufhellerpuder belegt. Auffällig ist, daß die anderen granulären Bestandteile der Aufbereitung nicht vom Puder belegt wurden. Die anfangs blaß grünliche Farbe der Extrudatpartikel am Mischeraustritt wandelte sich im weiteren Produktweg innerhalb weniger Minuten in einen strahlend weißen Farbton um. Der Weißgrad Berger lag oberhalb 100.The surface of the extrudate particles was evenly coated with brightener powder in this mixing process. It is striking that the other granular components of the preparation were not covered by the powder. The initially pale greenish color of the extrudate particles at the mixer outlet turned into a brilliant white color within a few minutes. The Berger whiteness was above 100.
Die Zubereitung des eingesetzten Aufhellerpuders erfolgte zuvor durch gemeinsames Vermählen der nachfolgend aufgeführten Rohstoffe in einer Stiftscheibenmühle im Kreislauf
bis zu einer maximalen Teilchengröße unterhalb 5 μm (Primärteilchen lt. REM- Aufhahme):The whitening powder used was previously prepared by grinding the raw materials listed below together in a pin disc mill in a circuit up to a maximum particle size below 5 μm (primary particles according to SEM image):
68,6% Zeolith A (Wessalith® P, Degussa) 27,0% Optiblanc® 2MG68.6% Zeolite A (Wessalith ® P, Degussa) 27.0% Optiblanc ® 2MG
(4,4'-Bis[(4-anilino-6-morpholino-s-triazin-2-yl)amino]-stilben-2,2'- disulfonsäure-Dinatriumsalz, Sigma) 4,4% Tinopal CBS-X(4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid disodium salt, Sigma) 4.4% Tinopal CBS-X
(4,4 '-Bis[2-sulfostyryl]biphenyl-Dinatriumsalz, Ciba)
(4,4'-bis [2-sulfostyryl] biphenyl disodium salt, Ciba)
Claims
1. Pudermittel für grobteilige Waschmittel, enthaltend1. Powder for coarse detergents containing
a) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie c) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe,a) 40 to 95% by weight of one or more pure white carrier materials, b) 5 to 80% by weight of one or more optical brighteners and c) up to 15% by weight of other auxiliaries or active ingredients,
wobei das Pudermittel maximale Primärteilchengrößen unterhalb von 50 μm aufweist.wherein the powder has maximum primary particle sizes below 50 microns.
2. Pudermittel nach Anspruch 1, dadurch gekennzeichnet, daß das Pudermittel maximale Primärteilchengrößen unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, aufweist.2. Powder according to claim 1, characterized in that the powder has maximum primary particle sizes below 20 microns, preferably below 10 microns and in particular below 5 microns.
3. Pudermittel nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß es 55 bis 85 Gew.-%, vorzugsweise 60 bis 80 Gew.-% und insbesondere 65 bis 75 Gew.-% eines oder mehrerer reinweißer Trägermaterialien enthält, wobei Trägermaterialien aus der Gruppe der Carbonate, der Sulfate, der Silikate, insbesondere Kieselsäuren, und der Aluminiumsilikate, insbesondere Zeolithe A, P, X und Y, bevorzugt sind.3. Powder agent according to one of claims 1 or 2, characterized in that it contains 55 to 85 wt .-%, preferably 60 to 80 wt .-% and in particular 65 to 75 wt .-% of one or more pure white carrier materials, wherein carrier materials from the group of carbonates, sulfates, silicates, especially silicas, and aluminum silicates, especially zeolites A, P, X and Y, are preferred.
4. Pudermittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es 7,5 bis 50 Gew.-%, vorzugsweise 10 bis 40 Gew.-% und insbesondere 15 bis 30 Gew.-% eines oder mehrerer optischer Aufheller enthält, wobei Aufheller vom Dimorpholin-Typ und vom Distilben-Typ bzw. Mischungen aus diesen, bevorzugt sind.4. Powder agent according to one of claims 1 to 3, characterized in that it contains 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight of one or more optical brighteners, whiteners of the dimorpholine type and of the distilbene type or mixtures thereof are preferred.
5. Verfahren zur Herstellung von Pudermitteln für grobteilige Waschmittel, dadurch gekennzeichnet, daß man ein Gemisch aus5. A process for the preparation of powder for coarse detergents, characterized in that a mixture of
a) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie c) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe, in einer Mühle vermischt und auf maximale Primärteilchengrößen unterhalb von 50 μm aufmahlt.a) 40 to 95% by weight of one or more pure white carrier materials, b) 5 to 80% by weight of one or more optical brighteners and c) up to 15% by weight of other auxiliaries or active ingredients, mixed in a mill and ground to maximum primary particle sizes below 50 μm.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Gemisch in einer Kugelmühle, einer Ringspaltkugelmühle, einer Mörsermühle oder einer Stiftscheibenmühle auf maximale Primärteilchengrößen unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, vermählen wird.6. The method according to claim 5, characterized in that the mixture is ground in a ball mill, an annular gap ball mill, a mortar mill or a pin disc mill to maximum primary particle sizes below 20 microns, preferably below 10 microns and in particular below 5 microns.
7. Verfahren nach einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, daß 55 bis 85 Gew.-%, vorzugsweise 60 bis 80 Gew.-% und insbesondere 65 bis 75 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, vorzugsweise Trägermaterialien aus der Gruppe der Carbonate, der Sulfate, der Silikate, insbesondere Kieselsäuren, und der Aluminiumsilikate, insbesondere Zeolithe A, P, X und Y, und 7,5 bis 50 Gew.-%, vorzugsweise 10 bis 40 Gew.-% und insbesondere 15 bis 30 Gew.-% eines oder mehrerer optischer Aufheller, vorzugsweise Aufheller vom Dimorpholin-Typ und vom Distilben-Typ bzw. Mischungen aus diesen, sowie bis zu 10 Gew.-%, vorzugsweise bis zu 7,5 Gew.-% und insbesondere bis zu 5 Gew.-% weiterer Hilfs- oder Wirkstoffe vermischt und vermählen werden.7. The method according to any one of claims 5 or 6, characterized in that 55 to 85 wt .-%, preferably 60 to 80 wt .-% and in particular 65 to 75 wt .-% of one or more pure white carrier materials, preferably carrier materials from the Group of the carbonates, the sulfates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y, and 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight of one or more optical brighteners, preferably brighteners of the dimorpholine type and of the distilbene type or mixtures thereof, and up to 10% by weight, preferably up to 7.5% by weight and in particular up to are mixed and ground to 5% by weight of further auxiliaries or active ingredients.
8. Verwendung von Pudermitteln mit einem Gehalt an8. Use of powder containing
a) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie c) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe,a) 40 to 95% by weight of one or more pure white carrier materials, b) 5 to 80% by weight of one or more optical brighteners and c) up to 15% by weight of other auxiliaries or active ingredients,
und maximalen Primärteilchengrößen unterhalb von 50 μm zur Abpuderung grobteihger Waschmittel-Partikel.and maximum primary particle sizes below 50 μm for powdering coarse detergent particles.
9. Verwendung nach Anspruch 8, dadurch gekennzeichnet, daß die grobteiligen Waschmittel-Partikel mittlere Partikeldurchmesser oberhalb von 700 μm, vorzugsweise ober- halb von 800 μm und insbesondere oberhalb von 1000 μm aufweisen und das Pudermittel eine maximale Primärteilchengröße unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, besitzt.9. Use according to claim 8, characterized in that the coarse-particle detergent particles average particle diameter above 700 microns, preferably upper have half of 800 microns and in particular above 1000 microns and the powder has a maximum primary particle size below 20 microns, preferably below 10 microns and in particular below 5 microns.
10. Verwendung nach einem der Ansprüche 8 oder 9, dadurch gekennzeichnet, daß die grobteiligen Waschmittel-Partikel, bezogen auf die nicht abgepuderten Partikel, mindestens 2,5 Gew.-%, vorzugsweise mindestens 5 Gew.-% und insbesondere mindestens 7,5 Gew.-% nichtionische(s) Tensid(e), vorzugsweise ethoxylierte Alkohole, enthalten.10. Use according to one of claims 8 or 9, characterized in that the coarse-particle detergent particles, based on the non-powdered particles, at least 2.5 wt .-%, preferably at least 5 wt .-% and in particular at least 7.5 % By weight of nonionic surfactant (s), preferably ethoxylated alcohols.
11. Verfahren zur Herstellung Aufheller-haltiger Waschmittel, gekennzeichnet durch die Schritte11. A process for producing brightener-containing detergents, characterized by the steps
a) Herstellung grobteihger Waschmittel-Partikel in an sich bekannter Weise b) Herstellung von Pudermitteln mit einer maximalen Primärteilchengrößen unterhalb von 50 μm durch Vermischen und Vermählen eines Gemischs aus bl) 40 bis 95 Gew.-% eines oder mehrerer reinweißer Trägermaterialien, b2) 5 bis 80 Gew.-% eines oder mehrerer optischer Aufheller sowie b3) bis zu 15 Gew.-% weiterer Hilfs- oder Wirkstoffe, c) Aufbringen der in Schritt b) hergestellten Pudermittel auf die in Schritt a) gebildeten Waschmittel-Partikel.a) Production of coarse detergent particles in a manner known per se b) Production of powdering agents with a maximum primary particle size below 50 μm by mixing and grinding a mixture of bl) 40 to 95% by weight of one or more pure white carrier materials, b2) 5 up to 80% by weight of one or more optical brighteners and b3) up to 15% by weight of further auxiliaries or active ingredients, c) applying the powdering agents prepared in step b) to the detergent particles formed in step a).
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die in Schritt a) hergestellten grobteiligen Waschmittel-Partikel mittlere Partikeldurchmesser oberhalb von 700 μm, vorzugsweise oberhalb von 800 μm und insbesondere oberhalb von 1000 μm aufweisen und das in Schritt b) hergestellte Pudermittel eine maximale Primärteilchengröße unterhalb von 20 μm, vorzugsweise unterhalb von 10 μm und insbesondere unterhalb von 5 μm, besitzt.12. The method according to claim 11, characterized in that the coarse-particle detergent particles produced in step a) have average particle diameters above 700 microns, preferably above 800 microns and in particular above 1000 microns and the powder produced in step b) a maximum Primary particle size below 20 microns, preferably below 10 microns and in particular below 5 microns.
13. Verfahren nach einem der Ansprüche 11 oder 12, dadurch gekennzeichnet, daß die in Schritt a) hergestellten grobteiligen Waschmittel-Partikel mindestens 2,5 Gew.-%, vor- zugsweise mindestens 5 Gew.-% und insbesondere mindestens 7,5 Gew.-% nichtioni- sche(s) Tensid(e), vorzugsweise ethoxylierte Alkohole, enthalten.13. The method according to any one of claims 11 or 12, characterized in that the coarse-particle detergent particles produced in step a) at least 2.5 wt .-%, pre- preferably contain at least 5% by weight and in particular at least 7.5% by weight of nonionic surfactant (s), preferably ethoxylated alcohols.
14. Verfahren nach einem der Ansprüche 11 bis 13, dadurch gekennzeichnet, daß die in Verfahrensschritt a) hergestellten grobteiligen Waschmittel-Partikel durch Granulation, Agglomeration oder Preßagglomeration, insbesondere durch Naßgranulation, Walzenkompaktierung, Pelletierung oder Extrusion, hergestellt werden.14. The method according to any one of claims 11 to 13, characterized in that the coarse-particle detergent particles produced in process step a) are produced by granulation, agglomeration or press agglomeration, in particular by wet granulation, roller compaction, pelleting or extrusion.
15. Verfahren nach einem der Ansprüche 11 bis 14, dadurch gekennzeichnet, daß das Aufbringen der in Schritt b) hergestellten Pudermittel auf die in Schritt a) hergestellten Waschmittel-Partikel durch Vermischen im Gewichtsverhältnis Waschmittel- Partike Pudermittel von 400:1 bis 25:1, vorzugsweise von 200:1 bis 50:1 und insbesondere von 150:1 bis 75:1, erfolgt.15. The method according to any one of claims 11 to 14, characterized in that the application of the powder agent prepared in step b) to the detergent particles produced in step a) by mixing in the weight ratio of detergent particles powder agent from 400: 1 to 25: 1 , preferably from 200: 1 to 50: 1 and in particular from 150: 1 to 75: 1.
16. Verfahren nach einem der Ansprüche 11 bis 15, dadurch gekennzeichnet, daß den in Schritt a) hergestellten Waschmittel-Partikeln vor dem Abpudern weitere Waschmittel- Inhaltsstoffe, insbesondere aus den Gruppen der Bleichmittel, Bleichaktivatoren, Enzyme, pH-Stellmittel, Farbstoffe, Schauminhibitoren, Antiredepositionsmittel, Ver- grauungsinhibitoren, Farbübertragungsinhibitoren und Korrosionsinhibitoren sowie Mischungen hieraus zugemischt werden. 16. The method according to any one of claims 11 to 15, characterized in that the detergent particles produced in step a) before powdering further detergent ingredients, in particular from the groups of bleaching agents, bleach activators, enzymes, pH adjusting agents, dyes, foam inhibitors , Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors as well as mixtures thereof.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1998155677 DE19855677A1 (en) | 1998-12-02 | 1998-12-02 | Production of detergent granules containing brighteners |
DE19855677.2 | 1998-12-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000032734A1 true WO2000032734A1 (en) | 2000-06-08 |
Family
ID=7889780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/009006 WO2000032734A1 (en) | 1998-12-02 | 1999-11-23 | Production of brightening agent-containing detergent granulates |
Country Status (2)
Country | Link |
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DE (1) | DE19855677A1 (en) |
WO (1) | WO2000032734A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10062007B4 (en) * | 2000-12-13 | 2010-03-18 | Henkel Ag & Co. Kgaa | Solid washing-active preparation with improved flushing behavior |
DE10148851A1 (en) * | 2001-10-04 | 2003-04-17 | Henkel Kgaa | Surface treatment to improve the storage stability and non-adhesiveness of active agents such as detergent ingredients or pharmaceuticals involves coating with a powder which has been milled under drying conditions |
DE10230416A1 (en) * | 2002-07-06 | 2004-02-12 | Henkel Kgaa | Detergent with a textile care component based on cellulose |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2217340A (en) * | 1988-04-14 | 1989-10-25 | Unilever Plc | Preparation of a granular detergent composition |
WO1990015856A1 (en) * | 1989-06-21 | 1990-12-27 | Novo Nordisk A/S | Detergent additive granulate and detergent |
EP0578872A1 (en) * | 1992-07-15 | 1994-01-19 | The Procter & Gamble Company | Detergent compositions |
EP0657527A1 (en) * | 1993-12-10 | 1995-06-14 | The Procter & Gamble Company | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions |
DE19622443A1 (en) * | 1996-06-05 | 1997-12-11 | Henkel Kgaa | Particulate washing agents for use as granular textile detergents |
DE19801186A1 (en) * | 1998-01-15 | 1999-07-22 | Henkel Kgaa | Production of colored laundry detergent particles for universal, colored or fine wash |
-
1998
- 1998-12-02 DE DE1998155677 patent/DE19855677A1/en not_active Withdrawn
-
1999
- 1999-11-23 WO PCT/EP1999/009006 patent/WO2000032734A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2217340A (en) * | 1988-04-14 | 1989-10-25 | Unilever Plc | Preparation of a granular detergent composition |
WO1990015856A1 (en) * | 1989-06-21 | 1990-12-27 | Novo Nordisk A/S | Detergent additive granulate and detergent |
EP0578872A1 (en) * | 1992-07-15 | 1994-01-19 | The Procter & Gamble Company | Detergent compositions |
EP0657527A1 (en) * | 1993-12-10 | 1995-06-14 | The Procter & Gamble Company | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions |
DE19622443A1 (en) * | 1996-06-05 | 1997-12-11 | Henkel Kgaa | Particulate washing agents for use as granular textile detergents |
DE19801186A1 (en) * | 1998-01-15 | 1999-07-22 | Henkel Kgaa | Production of colored laundry detergent particles for universal, colored or fine wash |
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DE19855677A1 (en) | 2000-06-08 |
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