WO1996030489A2 - Method of washing using non-aqueous liquid washing agents with separate bleach - Google Patents
Method of washing using non-aqueous liquid washing agents with separate bleach Download PDFInfo
- Publication number
- WO1996030489A2 WO1996030489A2 PCT/EP1996/001139 EP9601139W WO9630489A2 WO 1996030489 A2 WO1996030489 A2 WO 1996030489A2 EP 9601139 W EP9601139 W EP 9601139W WO 9630489 A2 WO9630489 A2 WO 9630489A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- washing
- mixing
- bleach
- component
- hollow body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00
- D06F39/02—Devices for adding soap or other washing agents
- D06F39/024—Devices for adding soap or other washing agents mounted on the agitator or the rotating drum; Free body dispensers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
- D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Definitions
- the present invention relates to a method for washing textile fabrics using a non-aqueous liquid detergent with separate bleach in a household washing machine and to a mixing and metering device which is used in this method.
- liquid detergents generally contain anionic and nonionic surfactants and water as a solvent.
- the incorporation of bleaching agent systems into these liquid detergents has proven to be difficult since the bleaching agent decomposes very easily in the presence of water.
- the bleaching agents in particular percarbonates, will clump when incorporated into the liquid formulations. These clumps can lead to high bleach concentrations locally, which can lead to spotting problems, particularly in the case of colored textiles, and thus a uniform bleaching performance in the wash liquor would no longer be guaranteed.
- European patent application 30 096 discloses non-aqueous liquid detergents made from liquid nonionic surfactants, which can contain 20 to 70% by weight builder substances and 1 to 20% by weight bleach in suspended form.
- anionic surfactants such as alkylbenzenesulfonates, olefin sulfonates, alkyl sulfates or soap, optical brighteners, dyes, fragrances or enzymes can be added to these agents.
- the bleaching agent has a particle size that no more than 30% of the particles are larger than 5 ⁇ m and particularly preferably no more than 10% larger than 10 ⁇ m.
- EP-B-0 460 810 describes a non-aqueous, liquid detergent composition for dishwashers which selects a non-aqueous, organic carrier liquid and at least one constituent selected from organic detergent, detergent builder, foam inhibitor and mixtures thereof, and a constituent from a non-abrasive amount of 0.5 to 10% of small, essentially water-insoluble particles of silicon dioxide, aluminum oxide or titanium oxide or mixtures thereof as anti-film-forming agents.
- the agent described may further contain 3 to 15% by weight of bleach
- WO 94/01524 describes an essentially non-aqueous liquid detergent which, in addition to nonionic surfactant, contains up to 60% by weight of builder substance and between 5 and 35% by weight of bleach.
- the liquid detergent composition described also contains a polymer compound which reduces the viscosity of the dispersion of the solid builders and bleaches in the nonionic surfactant in order to obtain a flowable and pourable composition.
- German patent application 36 26 572 describes a liquid detergent which contains builder substance, in particular polyacetal carboxylate, an agent which prevents gel formation and an agent which prevents settling, dispersed in a liquid nonionic surfactant.
- the solid particles should preferably have a particle size that no more than 10% of the particles are larger than 10 ⁇ m.
- So-called modular systems are also known on the market as an alternative to the detergents and cleaning agents consisting of several components.
- the individual system components which are generally in the form of solids, are metered in via the addition compartment of the washing machine and mixed in the washing drum.
- liquid components such as a liquid detergent without bleach and bleach present in solid form
- EP-A-0 288 345, EP-A-0 288 346 and EP-A-0 331 542 describe two-part containers in which a preferably liquid cleaning agent and one not with the cleaning agent are in each case provided via separate openings compatible additive, for example a bleach, are also preferably given in liquid form.
- the described containers consist of a larger container into which a further container or bag is inserted. Both containers or departments can be filled separately with the corresponding liquids.
- the filled container described in the above-mentioned documents is placed in the washing drum of a conventional household washing machine, and during the washing process the liquid components diffuse into the drum and are mixed there.
- this device has the disadvantage that the bleaching agent can only be uniformly dispensed in liquid form.
- the bleach is released undiluted and it can lead to spotting if it comes into direct contact with the laundry.
- Another economic and ecological disadvantage of this container is that it is only intended for single use.
- German utility model G 880 920.9 discloses a metering memory for receiving and dispensing laundry treatment agents, in particular liquid laundry treatment agents, in a washing machine or the like, which has at least two liquid-tight receiving chambers, each having at least one dispensing opening.
- the individual receiving chambers can contain various laundry treatment agents, such as are present, for example, as so-called “modular detergents”.
- module detergents With two receiving chambers, for example, one can hold a liquid laundry treatment agent and another the bleaching component.
- the substances are released into the wash water separately through the respective discharge openings of the dosing reservoir.
- existing bleaching agent is dispensed into the washing drum as an undiluted substance, which in turn can cause the "spotting problems" described above.
- the object of the present invention was to provide a method for washing textile fabrics using a non-aqueous liquid detergent with bleach in a household washing machine which does not have the above disadvantages.
- Another object of the present invention is to provide a metering device which makes it possible to use two incompatible, i.e. dosing detergent components that can be stored together in a recipe for a long time separately in a single device, then mixing in this device and metering the mixture obtained directly into the washing machine.
- the present invention relates to a process for washing textile fabrics in a household washing machine using a non-aqueous liquid detergent with separate bleach, characterized in that the non-aqueous liquid detergent with bleach consists of at least two components, one component being a contains liquid Ten ⁇ sid or a liquid surfactant mixture and a component B bleach, which are mixed before the washing process and placed in the washing machine.
- bleach-containing component B can be mixed in a simple manner with the liquid component A in the amount usually required for domestic washing machines and thus a non-aqueous liquid detergent with bleach. It was found that the disadvantages described in the prior art are not observed when this liquid detergent produced directly before the wash cycle is used.
- the method according to the invention for washing textile fabrics leads essentially to the same results as the known powdery universal detergents which contain bleaching agents.
- the system used according to the invention has the further advantage that the amount of bleaching agent, depending on the type of textiles to be cleaned and the type of soiling, the amount of bleaching agent can be metered accordingly.
- component A contains liquid surfactant or a liquid surfactant mixture.
- component A preferably contains nonionic surfactants, anionic surfactants and water-soluble builder substances.
- essentially not aqueous means that the agent preferably contains no free water which is not bound as water of crystallization or in a comparable form, to prevent decomposition of the peroxide bleach.
- small amounts of free water are tolerable, especially in amounts up to 5% by weight, the ratio of bleach to free water should be at least 3: 1.
- the nonionic surfactants used are preferably liquid, alkoxylated, preferably ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms (alkyl polyglycol ether) and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is linear or in 2-position may be methyl branched, or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 C atoms are preferred, e.g.
- the preferred ethoxylated alcohols include, for example, C] 2-C] 4-alcohols with 3 EO units or 7 EO units, C9-C] ⁇ - alcohols with 3 EO units, 5 EO units or 7 EO- Units and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO units and Ci 2-C ⁇ g alcohol with 5 EO units.
- the degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a special product.
- Preferred alcohol alkoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- the agent according to the invention can contain alkyl polyglycosides, fatty acid alkyl esters and polyhydroxy fatty acid amides as further nonionic surfactants.
- C6-C22-alkyl sulfates, Cg-Cjg-alkanesulfonates, alkylbenzenesulfonates and / or fatty acid soaps are preferably used as anionic surfactants.
- Particularly suitable alkyl sulfates are the sulfuric acid monoesters of C 1 -C 4 fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which also contain proportions of unsaturated alcohols, for example Oleyl alcohol can contain.
- Preferred mixtures are those in which the proportion of the alkyl radicals is 50 to 70% by weight on C 2, 18 to 30% by weight on C14, 5 to 15% by weight on CJ ⁇ , less than 3% by weight .-% are distributed on CJQ and less than 10% by weight on C j .
- Preferred surfactants of the sulfonate type are C9-C13-alkylbenzenesulfonates, C] 2-C ⁇ alkanesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from Cj2-C; ⁇ g-alkanes or Ci2 -C] g 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.
- Suitable soaps are in particular saturated fatty acid soaps, the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids.
- the sulfuric acid monoesters and the soaps can be present in total in an amount of 1 to 15% by weight, in particular 1 to 10% by weight, based on the sum of components A and B, alone or in any mixtures.
- the agent Cg-C ⁇ g-alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerin ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, amide acids, C6-C] g-fatty acid amide ethersulfate ethersulfates, C6-C] g fatty acid amide sulfates, Contain N-Cö-Cig-Acyl-Sarcosinate, N-C ⁇ -C i g-Acyl-Tauride, C $ -C ⁇ g-Alkyloligoglycosidsulfate, C ⁇ -C ⁇ g-Alkyl-Phosphate and their mixtures
- All water-soluble organic and inorganic builder substances are suitable as builder substances.
- Usable organic builder substances are, for example, mono- and / or polycarboxylates, preferably the polycarboxylic acids 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 an use is ecological from an ecological point of view For reasons not to be objectionable, as well as mixtures of these.
- NTA nitrilotriacetic acid
- Particularly preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof, with sodium citrate being particularly preferred as inorganic Builder substances are, in particular, crystalline, layered sodium silicates of the general formula (I) NaMSi x ⁇ 2 ⁇ + ] VH2O, 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 is preferred Values for x 2, 3 or 4 are such crystalline sheet silicates described for example in European patent application 164 514.
- polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof
- sodium citrate being particularly preferred as inorganic Builder substances
- Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na2Si2 ⁇ 5 VH2O are preferred
- the builders are preferably used in amounts such that the mixture prepared from components A and B contains the builder substances in an amount of 1 to less than 20% by weight, preferably 8 to less than 20% by weight.
- Suitable builder substances are, for example, amorphous silicates with a low water content, preferably with a water content below 15% by weight, and silicates in compound form, for example soda / silicate compounds.
- a mixture of mono- and / or polycarboxylates and crystalline, layered sodium silicates of the general formula (I) NaMSi x ⁇ 2 ⁇ +] VH2O is used in the process according to the invention as a builder, where M is sodium or hydrogen, x is a number of 1 , 9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4, and / or amorphous silicates.
- the mono- and / or polycarboxylates and the crystalline phyllosilicates are preferably in a ratio of 4: 1 to 1: 4, preferably 3: 1 to 1: 3 and particularly preferably 1.2: 1 to 1: 1, 2 before.
- enzymes are used as a component of component A in the process according to the invention. Their proportion can be 0.2 to 4% by weight, based on the sum of components A and B.
- Suitable enzymes are those from the class of proteases, lipases, amylases and cellulases or mixtures thereof. Enzymatic active substances obtained from bacterial strains or fungi, such as Bacillus subtiles, Bacillus licheniformes and Streptomyces griseus, are particularly suitable.
- the enzymes can be adsorbed onto carrier substances in a manner known per se and / or embedded in coating substances.
- Component A may also contain stabilizers for the enzymes.
- the stabilizers which are also suitable as stabilizers for per-compounds are the salts of polyphosphonic acids, in particular l-hydroxyethane-1,1-diphosphonic acid (HEDP).
- HEDP l-hydroxyethane-1,1-diphosphonic acid
- the polyphosphonic acids mentioned above are also suitable for binding traces of heavy metal.
- Suitable complexing agents for heavy metals are, for example, the above-mentioned HEDP and ethylenetriaminepentamethylenephosphonic acid (DTPMP).
- Component A can also contain dirt-removing polymers.
- the dirt-releasing polymers are preferably in an amount of 0.01% by weight to 5% by weight, based on the sum of components A and B, preferably 0.05% by weight to about 3% by weight. contain.
- Preferred soil release polymers are those polymers which contain ethylene glycol terephthalate groups and polyethylene glycol terephthalate groups, each having 17 to 110 ethylene glycol groups, the molar ratio of ethylene glycol terephthalate to polyethylene glycol terephthalate in the polymer being from 50:50 to 90:10. In these compounds, the molecular weight of the linking polyethylene glycol units is in the range from 750 to 5000.
- the polymers can have an average molecular weight from approximately 5000 to approximately 200000. Ethylene glycol terephthalate and polyethylene glycol terephthalate can be present in an arbitrarily distributed manner in the polymer.
- Preferred polymers are those with molar ratios of ethylene glycol terephthalate / polyethylene glycol terephthalate from 65:35 to 90:10, preferably from 65:35 to 80:20, the linking polyethylene glycol units having a molecular weight of 750 to 5000, preferably 1000 to 3000 and the polymer has a molecular weight of 10,000 to 50,000.
- An example of commercially available polymers of this type is the product sold under the trade name "Repel-O-Tex SRP3" by Rhône-Poulenc, France.
- the dirt-removing polymers which are preferably used can be prepared by known polymerization processes, the starting materials being used in amounts such that the abovementioned ratios of ethylene glycol terephthalate to polyethylene glycol terephthalate are obtained.
- the processes described in US Pat. No. 3,479,212 can be used to produce suitable polymers.
- component A can contain further inorganic substances.
- the alkali carbonates eg. B. soda, alkali hydrogen carbonates, alkali sulfates, phosphates.
- Such additional inorganic material can be contained in amounts up to 10 wt .-%, based on the sum of components A and B.
- component A can contain optical brighteners and graying inhibitors, foam inhibitors, and colorants and fragrances.
- component A can be prepared in a manner known per se by simple mixing and subsequent wet grinding.
- Component B used in the process according to the invention contains bleaching agents.
- Compounds that serve as bleaching agents and supply H2O2 in water are, in particular, sodium carbonate, sodium borates, especially sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid, are suitable. Because of the good environmental compatibility, sodium percarbonate is particularly preferred.
- Components A and B are mixed in such proportions that an effective amount of bleaching agent is present in the process according to the invention.
- Components A and B are preferably mixed in such proportions that the mixture obtained contains the bleaching agent in an amount of more than 20 to 35% by weight, preferably more than 20 to 30% by weight.
- component A is facilitated if the bleaching agent and preferably the solid particles optionally present have a particle size which is not more than 30% of the particles larger than 5 ⁇ m and particularly preferably not more than 10% larger than 10 ⁇ m.
- bleach activators can be used.
- these are the N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
- the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight, based on the sum of components A and B, and in particular between 3 and 8% by weight, based on the total of components A and B.
- Particularly preferred bleach activators are NNN ' ⁇ ' - tetraacetylethylene diamine (TAED) and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triacine (DAHT).
- TAED NNN ' ⁇ ' - tetraacetylethylene diamine
- DAHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triacine
- component B can contain conventional ingredients, which are present in solid or liquid form and are usually present in detergents. Attention is drawn here in particular to the above anionic surfactants and water-soluble and also water-insoluble builder substances and the inorganic substances described above.
- Components A and B are added together in the appropriate amounts before the washing process and mixed thoroughly, so that the bleaching agent is distributed as evenly as possible in the liquid surfactant phase. Then the mixture of components A and B 10
- the washing process is fed via the metering device located in the washing machine, or the mixture is fed directly, possibly via a special metering device, into the washroom, usually a washing drum.
- the washing water can slowly rinse the detergent out of the dosing device
- Another object of the present invention is a mixing and dosing device for multi-component detergent systems, which consists of a plurality of hollow bodies which can be connected to one another in each case by means of a displaceable or rotatable locking device, the hollow bodies opening on the surface which abuts another hollow body have, which can be brought into alignment with each other by moving or rotating the hollow body
- individual detergent components that are usually incompatible with one another over a long period of time and cannot be stored in the mixture can be pre-dosed and mixed directly before dosing into the washing machine.
- a liquid detergent which can be easily metered and which contains no bleaching agent can be metered into a bleaching agent present in solid form, for example in the form of powder or granules, in separate hollow bodies of the device and then mixed by opening the connection between the hollow bodies.
- the mixture obtained can then be metered into the washing machine.
- Such a procedure has the advantage that the bleaching agent is evenly distributed in the liquid detergent and is added to the washing machine in dilute form. This prevents high bleaching agent concentrations directly from the textiles to be treated Come into contact, which prevents spotting
- the hollow bodies contain at least one opening on each of the surfaces abutting another hollow body.
- the hollow body can be filled with the respective detergent component via these openings, on the other hand, the openings serve to align them with each other when the hollow bodies are rotated, so that a common cavity is created.
- the individual components can enter the respective adjacent cavity via the opening, so that the individual components can be mixed
- the individual hollow bodies are connected via a rotatable or displaceable closure.
- the hollow bodies are releasably connected to one another.
- the detachable connection has the advantage that the hollow bodies can be filled separately with the respective detergent components.
- the hollow bodies are detachably connected to one another via a screw or bayonet connection.
- the mixing and dosing device according to the invention is generally made of plastic. Injectable or pourable materials are preferred for cost reasons. For easier dosing, it is preferred that the hollow bodies have a scale clearly visible on their outer wall.
- the mixing and dosing container 1 consists of two hollow bodies 1 and 2.
- the hollow bodies 1 and 2 have openings 6, 6 'and 7, 7' on their respective abutting surfaces 4 and 5.
- the hollow bodies each have two openings 6, 6 'and 7, 7' arranged opposite one another on the surfaces 4 and 5.
- the openings 6 and 6 'or 7 and 7' can each be arranged at an angle of 170 ° to 190 ° (mean value 180 °) to one another.
- the hollow body 1 is preferably a pot-shaped container with a removable lid 3, via which the hollow body can be filled.
- the hollow body 2, into which the liquid component can be filled, is preferably a hollow cylinder which is closed except for the openings (7, 7 ').
- the hollow body 1 has a centering edge 8 which projects towards the hollow body 2 and which is placed on the hollow body 2 when the hollow bodies 1, 2 are assembled. In this way, the two hollow bodies 1, 2 are centered with respect to one another.
- the centering edge 8 receives the element 9 of a rotary bayonet belonging to the hollow body 1.
- the elements 10 of the rotary bayonet belonging to the hollow body 2 are located on the upper edge of the hollow body 2, overlapped by the centering edge 9.
- the cutouts 6,6 'and 7,7' assume an angle of 85 ° to 95 ° (mean value 90 °) to each other.
- the two hollow bodies 1, 2 are then not connected to one another. If the hollow body is rotated by a relative angle of 90 °, the openings 6 and 7 or 6 'and 7' are aligned, so that a continuous cavity is created.
- the detergent components located in the hollow bodies 1 and 2 can be mixed by simple shaking. For emptying the device, the hollow bodies 1, 2 can be separated again and the emptying takes place via the cutouts 6, 6 'and 7, 7', usually into the detergent compartment of a household washing machine.
- the individual components are mixed in the washing drum by their movement.
- the hollow body 1 has a perforated cover 3. This embodiment can be used if the device is to be emptied directly in the washing drum. Water can enter the mixing and dosing device through the openings and remove the detergent.
- Components A and B which contained the constituents given below, were combined in a weight ratio of 2.6 to 1 shortly before washing in the metering device according to the invention, mixed thoroughly and placed in the washing machine.
- Component A contained the following components:
- Dehydol ( R ) LT7 is an ethoxylated Ci2-C ⁇ g fatty alcohol with an average of 7 EO units (commercial product from Henkel, Düsseldorf)
- Dehydol ( R ) LST 80/20 is a mixture of 80% of an ethoxylated C ⁇ -Cig fatty alcohol with an average of 5 EO units and 20% of an ethoxylated Ci2-Ci4 fatty alcohol with an average of 3 EO units (commercial product from Henkel, Düsseldorf).
- MaranilW A is a C ⁇ j-Ciss-alkylbenzenesulfonate (commercial product from Hüls, Mari)
- Edenor R) HT 35 is a Ci6-C ⁇ g fatty acid (commercial product from Henkel, Düsseldorf)
- VP 1132 is a silicone oil (commercial product from Dow Corning)
- Tu ⁇ inalW 2 NZ is a hydroxyethyl diphosphonate (commercial product from Henkel, Düsseldorf)
- BLAP ( R ) 140 is a protease (commercial product from Henkel, Düsseldorf) Component B:
- the detergent components could be mixed well in the device according to the invention; the bleaching agent was dispersed uniformly in the liquid phase without clumping. The resulting mixture was quickly flushed out of the device from the water entering the washing machine. No spotting effects were observed for the washed laundry.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatment Of Fiber Materials (AREA)
Abstract
Description
Verfahren zum Waschen von teitilen Geweben unter Anwendung eines nicht-wäßrieen Process for washing teitile fabrics using a non-aqueous
Flüssigwaschmittels mit BleicheLiquid detergent with bleach
Die vorliegende Erfindung betrifft ein Verfahren zum Waschen von textilen Geweben unter An¬ wendung eines nicht-wäßrigen Flüssigwaschmittels mit separater Bleiche in einer Haushalts¬ waschmaschine sowie eine Misch- und Dosiervorrichtung, welche bei diesem Verfahren eingesetzt wird.The present invention relates to a method for washing textile fabrics using a non-aqueous liquid detergent with separate bleach in a household washing machine and to a mixing and metering device which is used in this method.
Handelsübliche Flüssigwaschmittel enthalten im allgemeinen anionische und nichtionische Tenside sowie Wasser als Lösungsmittel. Das Einarbeiten von Bleichmittelsystemen in diese Flüssig¬ waschmittel hat sich als schwierig erwiesen, da sich das Bleichmittel in Gegenwart von Wasser sehr leicht zersetzt. Hinzukommt, daß die Gefahr besteht, daß die Bleichmittel, insbesondere Per- carbonate, beim Einarbeiten in die flüssigen Formulierungen verklumpen. Durch diese Verklum- pungen kann es lokal zu hohen Bleichmittelkonzentrationen kommen, welche insbesondere bei bunten Textilien zu Spotting-Problemen fuhren können und somit wäre eine gleichmäßige Bleichleistung in der Waschflotte nicht mehr gewährleistet.Commercial liquid detergents generally contain anionic and nonionic surfactants and water as a solvent. The incorporation of bleaching agent systems into these liquid detergents has proven to be difficult since the bleaching agent decomposes very easily in the presence of water. In addition, there is a risk that the bleaching agents, in particular percarbonates, will clump when incorporated into the liquid formulations. These clumps can lead to high bleach concentrations locally, which can lead to spotting problems, particularly in the case of colored textiles, and thus a uniform bleaching performance in the wash liquor would no longer be guaranteed.
In der Literatur werden verschiedene flüssige Waschmittelzusammensetzungen beschrieben, die Bleichmittel enthalten können.Various liquid detergent compositions which can contain bleaches are described in the literature.
Aus der europäischen Patentanmeldung 30 096 sind beispielsweise nicht- wäßrige Flüssigwa¬ schmittel aus flüssigen nichtionischen Tensiden bekannt, die 20 bis 70 Gew.-% Buildersubstanzen und 1 bis 20 Gew.-% Bleichmittel in suspendierter Form enthalten können. Falls erwünscht, kön¬ nen diesen Mitteln anionische Tenside, wie Alkylbenzolsulfonate, Olefinsulfonate, Alkylsulfate oder Seife, optische Aufheller, Farbstoffe, Duftstoffe oder Enzyme zugesetzt werden. Es ist be¬ vorzugt, daß das Bleichmittel eine Teilchengröße aufweist, daß nicht mehr als 30 % der Teilchen größer als 5 μm und besonders bevorzugt nicht mehr als 10 % größer als 10 μm sind. In der EP-B-0 460 810 wird eine nicht-wäßrige, flüssige Reinigungsmittelzusammensetzung für Geschirrspülmaschinen beschrieben, die eine nicht-wäßrige, organische Trägerflüssigkeit und mindestens einen Bestandteil ausgewählt aus organischem Reinigungsmittel, Reinigungsmittel- Builder, Schauminhibitor und Mischungen derselben sowie einen Bestandteil ausgewählt aus einer nicht-scheuernden Menge von 0,5 bis 10% von kleinen, im wesentlichen wasserunlöslichen Teil¬ chen aus Siliciumdioxid, Aluminiumoxid oder Titanoxid oder Mischungen derselben als Anti- Filmbildungsmittel enthält. Das beschriebene Mittel kann ferner 3 bis 15 Gew.-% Bleichmittel enthaltenEuropean patent application 30 096, for example, discloses non-aqueous liquid detergents made from liquid nonionic surfactants, which can contain 20 to 70% by weight builder substances and 1 to 20% by weight bleach in suspended form. If desired, anionic surfactants such as alkylbenzenesulfonates, olefin sulfonates, alkyl sulfates or soap, optical brighteners, dyes, fragrances or enzymes can be added to these agents. It is preferred that the bleaching agent has a particle size that no more than 30% of the particles are larger than 5 μm and particularly preferably no more than 10% larger than 10 μm. EP-B-0 460 810 describes a non-aqueous, liquid detergent composition for dishwashers which selects a non-aqueous, organic carrier liquid and at least one constituent selected from organic detergent, detergent builder, foam inhibitor and mixtures thereof, and a constituent from a non-abrasive amount of 0.5 to 10% of small, essentially water-insoluble particles of silicon dioxide, aluminum oxide or titanium oxide or mixtures thereof as anti-film-forming agents. The agent described may further contain 3 to 15% by weight of bleach
In der WO 94/01524 wird ein im wesentlichen nicht-wäßriges Flüssigwaschmittel beschrieben, das neben nichtionischem Tensid bis zu 60 Gew.-% Buildersubstanz und zwischen 5 und 35 Gew.-% Bleichmittel enthält. Die beschriebene flüssige Waschmittelzusammensetzung enthält außerdem eine Polymerverbindung, die die Viskosität der Dispersion der festen Buildersubstanzen und Bleichmittel im nichtionischen Tensid reduziert, um eine fließ- und gießfähige Zusammensetzung zu erhalten.WO 94/01524 describes an essentially non-aqueous liquid detergent which, in addition to nonionic surfactant, contains up to 60% by weight of builder substance and between 5 and 35% by weight of bleach. The liquid detergent composition described also contains a polymer compound which reduces the viscosity of the dispersion of the solid builders and bleaches in the nonionic surfactant in order to obtain a flowable and pourable composition.
In der deutschen Patentanmeldung 36 26 572 wird ein Flüssigwaschmittel beschrieben, das Buil¬ dersubstanz, insbesondere Polyacetalcarboxylat, ein die Gelbildung verhinderndes Mittel und ein das Absetzen verhinderndes Mittel, dispergiert in einem flüssigen nichtionischen Tensid, enthält.German patent application 36 26 572 describes a liquid detergent which contains builder substance, in particular polyacetal carboxylate, an agent which prevents gel formation and an agent which prevents settling, dispersed in a liquid nonionic surfactant.
In der Literatur wird zwar beschrieben, daß für eine stabile Dispersion der Feststoffteilchen in flüssigen Tensiden die Feststoffteilchen bevorzugt eine Teilchengröße aufweisen sollten, daß nicht mehr als 10 % der Teilchen größer sind als 10 μm. Es hat sich aber als schwierig erwiesen, die Bleichmittel gleichmäßig und ohne Verklumpungen in der flüssigen Phase zu dispergieren und ein bleichmittelhaltiges nicht-wäßriges Flüssigwaschmittel herzustellen, welches über einen längeren Zeitraum lagerstabil ist.In the literature it is described that for a stable dispersion of the solid particles in liquid surfactants, the solid particles should preferably have a particle size that no more than 10% of the particles are larger than 10 μm. However, it has proven difficult to disperse the bleaches uniformly and without lumps in the liquid phase and to produce a non-aqueous liquid detergent containing bleach which is stable in storage over a longer period of time.
Als Alternative zu den aus mehreren Komponenten bestehenden Wasch- und Reinigungsmitteln sind auf dem Markt auch sogenannte Baukastensysteme bekannt. Die einzelnen Systemkompo¬ nenten, die in der Regel als Feststoffe vorliegen, werden über das Zugabefach der Waschmaschine zudosiert und in der Waschtrommel vermischt. Liegen aber flüssige Komponenten und bei¬ spielsweise bei längerer Lagerung mit dem Flüssigwaschmittel nicht verträgliche Komponenten vor, so wäre es vorteilhaft, die einzelnen Komponenten, wie zum Beispiel ein Flüssigwaschmittel ohne Bleichmittel und in fester Form vorliegendes Bleichmittel separat zuzugeben. Besonders vorteilhaft ist es, das Flüssigwaschmittel und die festen Komponenten vor Zugabe zur Waschma¬ schine zu vermischen, um eine gleichmäßige Verteilung des Bleichmittels im Waschmittel zu er¬ reichen.So-called modular systems are also known on the market as an alternative to the detergents and cleaning agents consisting of several components. The individual system components, which are generally in the form of solids, are metered in via the addition compartment of the washing machine and mixed in the washing drum. However, if there are liquid components and, for example, components which are incompatible with the liquid detergent for prolonged storage, it would be advantageous to add the individual components, such as a liquid detergent without bleach and bleach present in solid form, separately. Especially It is advantageous to mix the liquid detergent and the solid components before adding them to the washing machine in order to achieve a uniform distribution of the bleaching agent in the detergent.
In der Literatur werden verschiedene Dosiersysteme für Wasch- und Reinigungsmittel beschrie¬ ben. In den europäischen Patentanmeldungen EP-A-0 288 345, EP-A-0 288 346 und EP-A-0 331 542 werden zweiteilige Behälter beschrieben, in welchen jeweils über separate Öffnungen ein be¬ vorzugt flüssiges Reinigungsmittel und ein mit dem Reinigungsmittel nicht verträgliches Additiv, beispielsweise ein Bleichmittel, ebenfalls bevorzugt in flüssiger Form gegeben werden. Die be¬ schriebenen Behälter bestehen aus einem größeren Behälter, in den ein weiterer Behälter oder Beutel eingesetzt wird. Beide Behälter bzw. Abteilungen sind separat mit den entsprechenden Flüssigkeiten füllbar.Various dosing systems for detergents and cleaning agents are described in the literature. European patent applications EP-A-0 288 345, EP-A-0 288 346 and EP-A-0 331 542 describe two-part containers in which a preferably liquid cleaning agent and one not with the cleaning agent are in each case provided via separate openings compatible additive, for example a bleach, are also preferably given in liquid form. The described containers consist of a larger container into which a further container or bag is inserted. Both containers or departments can be filled separately with the corresponding liquids.
Der in den voranstehend genannten Druckschriften beschriebene gefüllte Behälter wird in die Waschtrommel einer üblichen Haushaltswaschmaschine gegeben, und während des Waschvor¬ gangs diffundieren die flüssigen Komponenten in die Trommel und werden dort vermischt. Diese Vorrichtung hat jedoch den Nachteil, daß eine gleichmäßige Abgabe des Bleichmittels nur in flüs¬ siger Form erfolgen kann. Hinzukommt, daß das Bleichmittel unverdünnt abgegeben wird, und es bei direktem Kontakt mit dem Waschgut zu Spotting führen kann. Ein weiterer wirtschaftlicher und auch ökologischer Nachteil dieses Behälters ist, daß er nur für den einmaligen Gebrauch ge¬ dacht ist.The filled container described in the above-mentioned documents is placed in the washing drum of a conventional household washing machine, and during the washing process the liquid components diffuse into the drum and are mixed there. However, this device has the disadvantage that the bleaching agent can only be uniformly dispensed in liquid form. In addition, the bleach is released undiluted and it can lead to spotting if it comes into direct contact with the laundry. Another economic and ecological disadvantage of this container is that it is only intended for single use.
Das deutsche Gebrauchsmuster G 880 920.9 offenbart einen Dosierspeicher zur Aufnahme und Abgabe von Wäschebehandlungsmitteln, insbesondere flüssigen Wäschebehandlungsmitteln, in ei¬ ner Waschmaschine oder dergleichen, der mindestens zwei zueinander flüssigkeitsdichte Auf ah- mekammern, die jeweils mindestens eine Abgabeöfihung aufweist. Die einzelnen Aufhahmekam- mern können verschiedene Wäschebehandlungsmittel, wie sie zum Beispiel als sogenannte "Baukasten-Waschmittel" vorliegen, enthalten. Bei zwei Aufhahmekammern kann beispielsweise eine ein flüssiges Wäschebehandlungsmittel und eine andere die Bleichkomponente aufnehmen. Die Substanzen werden getrennt durch die jeweiligen Abgabeöffhungen des Dosierspeichers in das Waschwasser abgegeben. Auch mit Hilfe des in dem Gebrauchsmuster beschriebenen Do¬ sierspeichers wird vorhandenes Bleichmittel als unverdünnte Substanz in die Waschtrommel ab¬ gegeben, wodurch wiederum die oben beschriebenen "Spotting-Probleme" auftreten können. Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein Verfahren zum Waschen von textilen Geweben unter Anwendung eines nicht-wäßrigen Flüssigwaschmittels mit Bleiche in einer Haus- haltswaschmachine zur Verfügung zu stellen, welches die obigen Nachteile nicht aufweist.German utility model G 880 920.9 discloses a metering memory for receiving and dispensing laundry treatment agents, in particular liquid laundry treatment agents, in a washing machine or the like, which has at least two liquid-tight receiving chambers, each having at least one dispensing opening. The individual receiving chambers can contain various laundry treatment agents, such as are present, for example, as so-called “modular detergents”. With two receiving chambers, for example, one can hold a liquid laundry treatment agent and another the bleaching component. The substances are released into the wash water separately through the respective discharge openings of the dosing reservoir. With the aid of the dosage storage described in the utility model, existing bleaching agent is dispensed into the washing drum as an undiluted substance, which in turn can cause the "spotting problems" described above. The object of the present invention was to provide a method for washing textile fabrics using a non-aqueous liquid detergent with bleach in a household washing machine which does not have the above disadvantages.
Eine weitere Aufgabe der vorliegenden Erfindung ist es, eine Dosiervorrichtung zur Verfügung zu stellen, welche es ermöglicht, zwei miteinander nicht verträgliche, d.h. über längere Zeit gemein¬ sam in einer Rezeptur lagerbare, Waschmittelkomponenten getrennt in einer einzigen Vorrichtung zu dosieren, anschließend in dieser Vorrichtung zu vermischen und das erhaltene Gemisch direkt in die Waschmaschine zu dosieren.Another object of the present invention is to provide a metering device which makes it possible to use two incompatible, i.e. dosing detergent components that can be stored together in a recipe for a long time separately in a single device, then mixing in this device and metering the mixture obtained directly into the washing machine.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Waschen von textilen Geweben in einer Haushaltswaschmaschine unter Anwendung eines nicht-wäßrigen Flüssigwaschmittels mit separater Bleiche, daß dadurch gekennzeichnet ist, daß das nicht-wäßrige Flüssigwaschmittel mit Bleiche aus mindestens zwei Komponenten besteht, wobei eine Komponente A ein flussiges Ten¬ sid oder eine flüssige Tensidmischung und eine Komponente B Bleichmittel enthält, die vor dem Waschvorgang vermischt und in die Waschmaschine gegeben werden.The present invention relates to a process for washing textile fabrics in a household washing machine using a non-aqueous liquid detergent with separate bleach, characterized in that the non-aqueous liquid detergent with bleach consists of at least two components, one component being a contains liquid Ten¬ sid or a liquid surfactant mixture and a component B bleach, which are mixed before the washing process and placed in the washing machine.
Überraschenderweise wurde festgestellt, daß sich die bleichmittelhaltige Komponente B in einfa¬ cher Weise in der üblicherweise für Haushaltswaschmaschinen benötigten Menge mit der flüssigen Komponente A vermischen lassen und somit ein nicht-wäßriges Flüssigwaschmittel mit Bleiche ergeben. Es wurde festgestellt, daß bei der Anwendung dieses direkt vor dem Waschgang herge¬ stellten Flüssigwaschmittels die aus dem Stand der Technik beschriebenen Nachteile nicht beob¬ achtet werden. Das erfindungsgemäße Verfahren zum Waschen von textilen Geweben führt im wesentlichen zu den gleichen Ergebnissen wie die bekannten pulverförmigen Uni¬ versalwaschmittel, die Bleichmittel enthalten. Das erfindungsgemäß eingesetzte System hat den weiteren Vorteil, daß die Menge des Bleichmittels je nach Art der zu reinigenden Textilien und der Art der Verschmutzungen die Menge des Bleichmittels entsprechend dosiert werden können.Surprisingly, it was found that bleach-containing component B can be mixed in a simple manner with the liquid component A in the amount usually required for domestic washing machines and thus a non-aqueous liquid detergent with bleach. It was found that the disadvantages described in the prior art are not observed when this liquid detergent produced directly before the wash cycle is used. The method according to the invention for washing textile fabrics leads essentially to the same results as the known powdery universal detergents which contain bleaching agents. The system used according to the invention has the further advantage that the amount of bleaching agent, depending on the type of textiles to be cleaned and the type of soiling, the amount of bleaching agent can be metered accordingly.
Das im erfindungsgemäßen Verfahren eingesetzte nicht-wäßrige Flüssigwaschmittel mit separater Bleiche besteht aus mindestens zwei Komponenten. Die Komponente A enthält erfindungsgemäß flüssiges Tensid bzw. eine flüssige Tensidmischung. Bevorzugt enthält die Komponente A nich¬ tionische Tenside, anionische Tenside und wasserlösliche Buildersubstanzen.The non-aqueous liquid detergent with separate bleach used in the process according to the invention consists of at least two components. According to the invention, component A contains liquid surfactant or a liquid surfactant mixture. Component A preferably contains nonionic surfactants, anionic surfactants and water-soluble builder substances.
"Im wesentlichen nicht wäßrig" bedeutet im Rahmen dieser Erfindung, daß das Mittel vorzugs¬ weise kein freies, nicht als Kristallwasser oder in vergleichbarer Form gebundenes Wasser enthält, um eine Zersetzung des Peroxid-Bleichmittels zu verhindern. In einigen Fällen sind geringe Men¬ gen an freiem Wasser tolerierbar, insbesondere in Mengen bis zu 5 Gew.-%, wobei das Verhältnis von Bleichmittel zu freiem Wasser mindestens 3 : 1 betragen sollte.In the context of this invention, "essentially not aqueous" means that the agent preferably contains no free water which is not bound as water of crystallization or in a comparable form, to prevent decomposition of the peroxide bleach. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight, the ratio of bleach to free water should be at least 3: 1.
Als nichtionische Tenside werden vorzugsweise flüssige, alkoxylierte, bevorzugt ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C- Atomen (Alkylpolyglykolether) und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Al¬ koholrest linear oder in 2-Stellung methylverzweigt sein kann, bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbe¬ sondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C- Atomen bevorzugt, z.B. aus Kokos-, Taigfett- oder Oleylalkohol, die durchschnittlich 2 bis 8 EO-Einheiten pro Mol Alkohol haben können. Zu den bevorzugten ethoxylierten Alkoho¬ len gehören beispielsweise C ] 2-C ] 4- Alkohole mit 3 EO-Einheiten oder 7 EO-Einheiten, C9-C ] \ - Alkohole mit 3 EO-Einheiten, 5 EO-Einheiten oder 7 EO-Einheiten und Mischungen aus diesen, wie Mischungen aus Ci2-Ci4-Alkohol mit 3 EO-Einheiten und Ci 2-Cιg-Alkohol mit 5 EO-Ein¬ heiten. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spe¬ zielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholalkoxylate weisen eine eingeengte Homologenverteilung auf (Narrow Range Ethoxylates, NRE).The nonionic surfactants used are preferably liquid, alkoxylated, preferably ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms (alkyl polyglycol ether) and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is linear or in 2-position may be methyl branched, or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 C atoms are preferred, e.g. from coconut, tallow or oleyl alcohol, which can have an average of 2 to 8 EO units per mole of alcohol. The preferred ethoxylated alcohols include, for example, C] 2-C] 4-alcohols with 3 EO units or 7 EO units, C9-C] \ - alcohols with 3 EO units, 5 EO units or 7 EO- Units and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO units and Ci 2-Cιg alcohol with 5 EO units. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a special product. Preferred alcohol alkoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
Als weitere nichtionische Tenside kann das erfindungsgemäße Mittel Alkylpolyglykoside, Fettsäu- realkylester sowie Polyhydroxyfettsäureamide enthalten.The agent according to the invention can contain alkyl polyglycosides, fatty acid alkyl esters and polyhydroxy fatty acid amides as further nonionic surfactants.
Als anionische Tenside werden C6-C22- Alkylsulfate, Cg-Cjg-Alkansulfonate, Alkylbenzolsul¬ fonate und/oder Fettsäureseifen bevorzugt eingesetzt. Als Alkylsulfate eignen sich insbesondere die Schwefelsäuremonoester der C^-Cig-Fettalkohole, wie Lauryl-, Myristyl-, Cetyl- oder Ste- arylalkohol oder der aus Kokosöl, Palm- und Palmkernöl gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, z.B. an Oleylalkohol, enthalten können. Be¬ vorzugte Gemische sind solche, in denen der Anteil der Alkylreste zu 50 bis 70 Gew.-% auf C 2, zu 18 bis 30 Gew.-% auf C14, zu 5 bis 15 Gew.-% auf CJÖ, unter 3 Gew.-% auf CJQ- und unter 10 Gew.-% auf Cj verteilt sind.C6-C22-alkyl sulfates, Cg-Cjg-alkanesulfonates, alkylbenzenesulfonates and / or fatty acid soaps are preferably used as anionic surfactants. Particularly suitable alkyl sulfates are the sulfuric acid monoesters of C 1 -C 4 fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which also contain proportions of unsaturated alcohols, for example Oleyl alcohol can contain. Preferred mixtures are those in which the proportion of the alkyl radicals is 50 to 70% by weight on C 2, 18 to 30% by weight on C14, 5 to 15% by weight on CJÖ, less than 3% by weight .-% are distributed on CJQ and less than 10% by weight on C j .
Als Tenside vom Sulfonat-Typ kommen vorzugsweise C9-C 13- Alkylbenzolsulfonate, C]2-Cι - Alkansulfonate, Olefinsulfonate, d. h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Cj2-C;ιg-Alkanen bzw. Ci2-C]g-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht.Preferred surfactants of the sulfonate type are C9-C13-alkylbenzenesulfonates, C] 2-Cι alkanesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from Cj2-C; ιg-alkanes or Ci2 -C] g 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.
Als Seifen sind insbesondere gesättigte Fettsäureseifen, die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie insbesondere aus natürlichen Fettsäuren, z.B Kokos-, Palmkern- oder Taigfettsäuren, abgeleitete Seifengemische, geeignet. Die Schwefelsäuremo¬ noester und die Seifen können insgesamt in einer Menge von 1 bis 15 Gew.-%, insbesondere 1 bis 10 Gew.-%, bezogen auf die Summe der Komponenten A und B, alleine oder in beliebigen Mi¬ schungen vorliegen.Suitable soaps are in particular saturated fatty acid soaps, the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids. The sulfuric acid monoesters and the soaps can be present in total in an amount of 1 to 15% by weight, in particular 1 to 10% by weight, based on the sum of components A and B, alone or in any mixtures.
Als weitere anionische Tenside kann das erfindungsgemäße Mittel Cg-C \ g- Alkyl- polyglykolethersulfonate, Glycerinethersulfonate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglyceridsulfate, Sulfosuccinate, Sulfotriglyceride, Amidsäuren, C6-C]g-Fettsaureamid- Ethersulfate, Cö-Cig-Alkylcarboxylate, Fettsaureisethionate, N-Cö-Cig-Acyl-Sarcosinate, N-Cό- C i g- Acyl-Tauride, C$-C \ g-Alkyloligoglycosidsulfate, CÖ-C \ g-Alkyl-Phosphate sowie deren Mi¬ schungen enthaltenThe agent Cg-C \ g-alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerin ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, amide acids, C6-C] g-fatty acid amide ethersulfate ethersulfates, C6-C] g fatty acid amide sulfates, Contain N-Cö-Cig-Acyl-Sarcosinate, N-Cό-C i g-Acyl-Tauride, C $ -C \ g-Alkyloligoglycosidsulfate, C Ö -C \ g-Alkyl-Phosphate and their mixtures
Als Buildersubstanz sind alle wasserlöslichen organischen und anorganischen Buildersubstanzen geeignet. Brauchbare organische Buildersubstanzen sind beispielsweise Mono und/oder Polycar- boxylate, bevorzugt die in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronen- saure, Adipinsaure, Bernsteinsäure, Glutarsäure, Weinsaure, Zuckersäuren, Aminocarbonsauren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu be¬ anstanden ist, sowie Mischungen aus diesen Besonders bevorzugte Salze sind die Salze der Poly¬ carbonsäuren wie Citronensaure, Adipinsaure, Bernsteinsaure, Glutarsäure, Weinsaure, Zucker¬ säuren und Mischungen aus diesen, wobei Natriumeitrat besonders bevorzugt ist Als anorgani¬ sche Buildersubstanzen sind insbesondere kristalline, schichtfbrmige Natriumsilikate der allgemei¬ nen Formel (I) NaMSixθ2χ+] VH2O, 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 Derar¬ tige kristalline Schichtsilikate werden beispielsweise in der europaischen Patentanmeldung 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der Formel (I) sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt Insbesondere sind sowohl ß- als auch δ- Natriumdisilikate Na2Si2θ5 VH2O bevorzugt Die Builder werden bevorzugt in Mengen eingesetzt, daß das aus den Komponenten A und B hergestellte Gemisch die Buildersubstanzen in einer Menge von 1 bis weniger als 20 Gew.-%, be¬ vorzugt 8 bis weniger als 20 Gew.-% enthält.All water-soluble organic and inorganic builder substances are suitable as builder substances. Usable organic builder substances are, for example, mono- and / or polycarboxylates, preferably the polycarboxylic acids 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 an use is ecological from an ecological point of view For reasons not to be objectionable, as well as mixtures of these. Particularly preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof, with sodium citrate being particularly preferred as inorganic Builder substances are, in particular, crystalline, layered sodium silicates of the general formula (I) NaMSi x θ2 χ + ] VH2O, 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 is preferred Values for x 2, 3 or 4 are such crystalline sheet silicates described for example in European patent application 164 514. Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na2Si2θ5 VH2O are preferred The builders are preferably used in amounts such that the mixture prepared from components A and B contains the builder substances in an amount of 1 to less than 20% by weight, preferably 8 to less than 20% by weight.
Weitere geeignete Buildersubstanzen sind beispielsweise amorphe Silikate mit einem niedrigen Wassergehalt, bevorzugt mit einem Wassergehalt unter 15 Gew.-%, und Silikate in Compound- Form, beispielsweise Soda/Silikat-Compounds.Further suitable builder substances are, for example, amorphous silicates with a low water content, preferably with a water content below 15% by weight, and silicates in compound form, for example soda / silicate compounds.
Im erfindungsgemäßen Verfahren wird in einer bevorzugten Ausführungsform als Builder ein Gemisch aus Mono- und/oder Polycarboxylaten und kristallinen, schichtförmigen Natriumsilikaten der allgemeinen Formel (I) NaMSixθ2χ+] VH2O eingesetzt, 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, und/oder amorphen Silikaten. Bevorzugt liegen die Mono- und/oder Polycarboxyla- te und die kristallinen Schichtsilikate in einem Verhältnis von 4 : 1 bis 1 : 4, bevorzugt von 3 : 1 bis 1 : 3 und besonders bevorzugt von 1,2 : 1 bis 1 : 1,2 vor.In a preferred embodiment, a mixture of mono- and / or polycarboxylates and crystalline, layered sodium silicates of the general formula (I) NaMSi x θ2χ +] VH2O is used in the process according to the invention as a builder, where M is sodium or hydrogen, x is a number of 1 , 9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4, and / or amorphous silicates. The mono- and / or polycarboxylates and the crystalline phyllosilicates are preferably in a ratio of 4: 1 to 1: 4, preferably 3: 1 to 1: 3 and particularly preferably 1.2: 1 to 1: 1, 2 before.
In einer bevorzugten Ausführungsform werden im erfindungsgemäßen Verfahren Enzyme als Be¬ standteil der Komponente A eingesetzt. Ihr Anteil kann 0,2 bis 4 Gew.-%, bezogen auf die Sum¬ me der Komponenten A und B, betragen. Als Enzyme kommen solche aus der Klasse der Protea- sen, Lipasen, Amylasen und Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtiles, Bacillus licheniformes und Strep- tomyces griseus gewonnene enzymatische Wirkstoffe. Die Enzyme können in an sich bekannter Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein.In a preferred embodiment, enzymes are used as a component of component A in the process according to the invention. Their proportion can be 0.2 to 4% by weight, based on the sum of components A and B. Suitable enzymes are those from the class of proteases, lipases, amylases and cellulases or mixtures thereof. Enzymatic active substances obtained from bacterial strains or fungi, such as Bacillus subtiles, Bacillus licheniformes and Streptomyces griseus, are particularly suitable. The enzymes can be adsorbed onto carrier substances in a manner known per se and / or embedded in coating substances.
Weiterhin kann die Komponente A Stabilisatoren für die Enzyme enthalten. Als Stabilisatoren, die auch als Stabilisatoren für Perverbindungen geeignet sind, kommen die Salze von Polyphos¬ phonsäuren, insbesondere l-Hydroxyethan-l,l-Diphosphonsäure (HEDP) in Betracht. Die vor¬ anstehend genannten Polyphosphonsäuren sind auch geeignet, um Spuren von Schwermetall zu binden. Als geeignete Komplexbildner für Schwermetalle sind beispielsweise die voranstehend genannte HEDP und die Ethylentriaminpentamethylenphosphonsäure (DTPMP) geeignet.Component A may also contain stabilizers for the enzymes. The stabilizers which are also suitable as stabilizers for per-compounds are the salts of polyphosphonic acids, in particular l-hydroxyethane-1,1-diphosphonic acid (HEDP). The polyphosphonic acids mentioned above are also suitable for binding traces of heavy metal. Suitable complexing agents for heavy metals are, for example, the above-mentioned HEDP and ethylenetriaminepentamethylenephosphonic acid (DTPMP).
Die Komponente A kann weiterhin schmutzablösende Polymere enthalten. Die schmutzablösen¬ den Polymere sind bevorzugt in einer Menge von 0,01 Gew.-% bis 5 Gew.-%, bezogen auf die Summe der Komponenten A und B, vorzugsweise 0,05 Gew.-% bis etwa 3 Gew.-% enthalten. Bevorzugte schmutzablösende Polymere sind solche Polymere, welche Ethylenglykolterephthalat- gruppen und Polyethylenglykolterephthalatgruppen, die jeweils 17 bis 110 Ethylenglykolgruppen aufweisen, enthalten, wobei das Molverhältnis von Ethylenglykolterephthalat zu Polyethylengly- kolterephthalat im Polymeren von 50:50 bis 90: 10 beträgt. In diesen Verbindungen liegt das Mo¬ lekulargewicht der verknüpfenden Polyethylenglykoleinheiten in dem Bereich von 750 bis 5000. Die Polymeren können ein durchschnittliches Molekulargewicht von etwa 5000 bis etwa 200000 besitzen. Im Polymer können Ethylenglykolterephthalat und Polyethylenglykolterephthalat will¬ kürlich verteilt vorliegen.Component A can also contain dirt-removing polymers. The dirt-releasing polymers are preferably in an amount of 0.01% by weight to 5% by weight, based on the sum of components A and B, preferably 0.05% by weight to about 3% by weight. contain. Preferred soil release polymers are those polymers which contain ethylene glycol terephthalate groups and polyethylene glycol terephthalate groups, each having 17 to 110 ethylene glycol groups, the molar ratio of ethylene glycol terephthalate to polyethylene glycol terephthalate in the polymer being from 50:50 to 90:10. In these compounds, the molecular weight of the linking polyethylene glycol units is in the range from 750 to 5000. The polymers can have an average molecular weight from approximately 5000 to approximately 200000. Ethylene glycol terephthalate and polyethylene glycol terephthalate can be present in an arbitrarily distributed manner in the polymer.
Bevorzugte Polymere sind solche mit Molverhältnissen Ethylenglykoltereph- thalat/Polyethylenglykolterephthalat von 65:35 bis 90:10, vorzugsweise von 65:35 bis 80:20, wo¬ bei die verknüpfenden Polyethylenglykoleinheiten ein Molekulargewicht von 750 bis 5000, bevor¬ zugt 1000 bis 3000 und das Polymere ein Molekulargewicht von 10000 bis 50000 aufweist. Ein Beispiel für handelsübliche Polymere dieser Art ist das unter der Handelsbezeichnung "Repel-O- Tex SRP3" von Rhöne-Poulenc, Frankreich vertriebene Produkt.Preferred polymers are those with molar ratios of ethylene glycol terephthalate / polyethylene glycol terephthalate from 65:35 to 90:10, preferably from 65:35 to 80:20, the linking polyethylene glycol units having a molecular weight of 750 to 5000, preferably 1000 to 3000 and the polymer has a molecular weight of 10,000 to 50,000. An example of commercially available polymers of this type is the product sold under the trade name "Repel-O-Tex SRP3" by Rhône-Poulenc, France.
Die bevorzugt eingesetzten schmutzablösenden Polymere können durch bekannte Polymerisati¬ onsverfahren hergestellt werden, wobei die Ausgangsmaterialien in solchen Mengen eingesetzt werden, um die oben genannten Verhältnisse von Ethylengylkolterephthalat zu Polyethylengly¬ kolterephthalat zu erhalten. Beispielsweise können die in der US-PS 3479212 beschriebenen Ver¬ fahren zur Herstellung geeigneter Polymere verwendet werden.The dirt-removing polymers which are preferably used can be prepared by known polymerization processes, the starting materials being used in amounts such that the abovementioned ratios of ethylene glycol terephthalate to polyethylene glycol terephthalate are obtained. For example, the processes described in US Pat. No. 3,479,212 can be used to produce suitable polymers.
Zusätzlich zu den oben genannten Buildersubstanzen kann die Komponente A weitere anorgani¬ sche Substanzen enthalten. Als geeignete Substanzen können in diesem Zusammenhang die Alka- licarbonate, z. B. Soda, Alkalihydrogencarbonate, Alkalisulfate, Phosphate genannt werden. Der¬ artiges zusätzliches anorganisches Material kann in Mengen bis zu 10 Gew.-%, bezogen auf die Summe der Komponenten A und B, enthalten sein.In addition to the builder substances mentioned above, component A can contain further inorganic substances. In this context, the alkali carbonates, eg. B. soda, alkali hydrogen carbonates, alkali sulfates, phosphates. Such additional inorganic material can be contained in amounts up to 10 wt .-%, based on the sum of components A and B.
Als weitere Bestandteile kann die Komponente A optische Aufheller sowie Vergrauungsinhibito- ren, Schauminhibitoren, sowie Färb- und Duftstoffe enthalten.As further constituents, component A can contain optical brighteners and graying inhibitors, foam inhibitors, and colorants and fragrances.
Die Bestandteile der Komponente A können in an sich bekannter Weise durch einfaches Vermi¬ schen und anschließendes Naßmahlen hergestellt werden.The components of component A can be prepared in a manner known per se by simple mixing and subsequent wet grinding.
Die im erfindungsgemäßen Verfahren eingesetzte Komponente B enthält Bleichmittel. Als Bleichmittel dienende, in Wasser H2O2 liefernde Verbindungen sind insbesondere Natriumper- carbonat, Natriumborate, insbesondere das Natriumperborattetrahydrat und das Natriumperbo- ratmonohydrat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure oder Diperdodecandisäure, geeignet. Wegen der guten Umweltverträglichkeit wird Natriumpercarbonat besonders bevorzugt eingesetzt.Component B used in the process according to the invention contains bleaching agents. Compounds that serve as bleaching agents and supply H2O2 in water are, in particular, sodium carbonate, sodium borates, especially sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid, are suitable. Because of the good environmental compatibility, sodium percarbonate is particularly preferred.
Die Komponenten A und B werden in solchen Mengenverhältnissen vermischt, daß im erfin- dungsgmäßen Verfahren eine wirksame Menge Bleichmittel vorliegt. Bevorzugt werden die Komponenten A und B in solchen Mengenverhältnissen vermischt, daß das erhaltene Gemisch das Bleichmittel in einer Menge von über 20 bis 35 Gew.-%, bevorzugt über 20 bis 30 Gew.-%, ent¬ hält.Components A and B are mixed in such proportions that an effective amount of bleaching agent is present in the process according to the invention. Components A and B are preferably mixed in such proportions that the mixture obtained contains the bleaching agent in an amount of more than 20 to 35% by weight, preferably more than 20 to 30% by weight.
Das Einarbeiten des Komponente A wird erleichtert, wenn das Bleichmittel und bevorzugt die gegebenenfalls enthaltenen Feststoffteilchen eine Teilchengröße aufweisen, das nicht mehr als 30 % der Teilchen größer als 5 μm und besonders bevorzugt nicht mehr als 10 % größer als 10 μm sind.The incorporation of component A is facilitated if the bleaching agent and preferably the solid particles optionally present have a particle size which is not more than 30% of the particles larger than 5 μm and particularly preferably not more than 10% larger than 10 μm.
Um beim Waschen bei Temperaturen von 60°C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren werden. Beispiele hierfür sind die mit H2O2 organische Per¬ säuren bildende N-Acyl- bzw. O-Acyl- Verbindungen, vorzugsweise N, N'-tetraacylierte Diamine, ferner Carbonsäureanhydride und Ester von Polyolen wie Glucosepentaacetat. Der Gehalt der bleichmittelhaltigen Mittel an Bleichaktivatoren liegt in dem üblichen Bereich, vorzugsweise zwi¬ schen 1 und 10 Gew.-%, bezogen auf die Summe der Komponenten A und B, und insbesondere zwischen 3 und 8 Gew.-%, bezogen auf die Summe der Komponenten A und B. Besonders be¬ vorzugte Bleichaktivatoren sind N.N.N'^'-Tetraacetylethylendiamin (TAED) und 1,5-Diacetyl- 2,4-Dioxo-Hexahydro-l,3,5-Triacin (DAHT).In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be used. Examples of these are the N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight, based on the sum of components A and B, and in particular between 3 and 8% by weight, based on the total of components A and B. Particularly preferred bleach activators are NNN '^' - tetraacetylethylene diamine (TAED) and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triacine (DAHT).
Als weitere Bestandteile kann die Komponente B übliche, in fester oder flüssiger Form vorliegen¬ de Inhaltsstoffe enthalten, die üblicherweise in Waschmitteln vorliegen. Hier sei insbesondere auf die voranstehenden anionischen Tenside, sowie wasserlösliche und auch wasserunlösliche Builder¬ substanzen sowie die oben beschriebenen anorganischen Substanzen hingewiesen.As further constituents, component B can contain conventional ingredients, which are present in solid or liquid form and are usually present in detergents. Attention is drawn here in particular to the above anionic surfactants and water-soluble and also water-insoluble builder substances and the inorganic substances described above.
Die Komponenten A und B werden vor dem Waschvorgang in den entsprechenden Mengen zu¬ sammen gegeben und sorgfältig vermischt, so daß das Bleichmittel möghchst gleichmäßig in der flüssigen Tensidphase verteilt ist. Anschließend kann das Gemisch aus den Komponenten A und B 10Components A and B are added together in the appropriate amounts before the washing process and mixed thoroughly, so that the bleaching agent is distributed as evenly as possible in the liquid surfactant phase. Then the mixture of components A and B 10
dem Waschvorgang über die in der Waschmaschine befindliche Dosiervorrichtung zugeführt wer¬ den, oder das Gemisch wird direkt, ggf. über eine spezielle Dosiervorrichtung, in den Waschraum, in der Regel Waschtrommel, gegeben.the washing process is fed via the metering device located in the washing machine, or the mixture is fed directly, possibly via a special metering device, into the washroom, usually a washing drum.
Wird eine Dosiervorrichtung verwendet, kann das Waschwasser das Waschmittel langsam aus der Dosiervorrichtung spülenIf a dosing device is used, the washing water can slowly rinse the detergent out of the dosing device
Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Misch- und Dosiervorrichtung für Mehrkomponenten-Waschmittelsysteme, die aus mehreren jeweils über eine verschieb- oder ver¬ drehbare Verriegelvorrichtung miteinander verbindbaren Hohlkörpern besteht, wobei die Hohl¬ körper an den jeweils an einen anderen Hohlkörper anstoßenden Fläche Öffnungen aufweisen, die sich durch Verschieben oder Verdrehen der Hohlkörper relativ zueinander zur Fluchtung bringen lassenAnother object of the present invention is a mixing and dosing device for multi-component detergent systems, which consists of a plurality of hollow bodies which can be connected to one another in each case by means of a displaceable or rotatable locking device, the hollow bodies opening on the surface which abuts another hollow body have, which can be brought into alignment with each other by moving or rotating the hollow body
In der erfindungsgemäßen Misch- und Dosiervorrichtung können direkt vor dem Dosieren in die Waschmaschine einzelne, üblicherweise über einen längeren Zeitraum nicht miteinander ver¬ trägliche, d h im Gemisch nicht lagerbare Waschmittelkomponenten vordosiert und vermischt werden. Beispielsweise kann ein gut dosierbares Flussigwaschmittel, das kein Bleichmittel enthält, mit einem in fester Form, beispielsweise als Pulver oder Granulat, vorliegenden Bleichmittel je¬ weils in separaten Hohlkörpern der Vorrichtung dosiert und dann durch Öffnung der Verbindung zwischen den Hohlkörpern vermischt werden. Das erhaltene Gemisch kann dann in die Waschma¬ schine dosiert werden Eine derartige Vorgehensweise hat den Vorteil, daß das Bleichmittel gleichmaßig im Flussigwaschmittel verteilt vorliegt und in verdünnter Form in die Waschmaschine gegeben wird Dadurch wird vermieden, daß hohe Bleichmittelkonzentrationen direkt mit den zu behandelnden Textilien in Kontakt kommen, wodurch das Spotting vermieden werden kannIn the mixing and dosing device according to the invention, individual detergent components that are usually incompatible with one another over a long period of time and cannot be stored in the mixture can be pre-dosed and mixed directly before dosing into the washing machine. For example, a liquid detergent which can be easily metered and which contains no bleaching agent can be metered into a bleaching agent present in solid form, for example in the form of powder or granules, in separate hollow bodies of the device and then mixed by opening the connection between the hollow bodies. The mixture obtained can then be metered into the washing machine. Such a procedure has the advantage that the bleaching agent is evenly distributed in the liquid detergent and is added to the washing machine in dilute form. This prevents high bleaching agent concentrations directly from the textiles to be treated Come into contact, which prevents spotting
Erfindungsgemäß enthalten die Hohlkörper an den jeweils an einen anderen Hohlkörper ansto¬ ßenden Flachen mindestens eine Öffnung Über diese Öffnungen kann der Hohlkörper zum einen mit der jeweiligen Waschmittelkomponente gefüllt werden, zum anderen dienen die Öffnungen dazu, daß sie beim Verdrehen der Hohlkörper miteinander fluchten, so daß ein gemeinsamer Hohlraum entsteht. Über die Öffnung können die einzelnen Komponenten in den jeweils be¬ nachbarten Hohlraum gelangen, so daß das Vermischen der einzelnen Komponenten erfolgen kann Die Verbindung der einzelnen Hohlkörper erfolgt erfindungsgemäß über einen verdrehbaren oder verschiebbaren Verschluß. Die Hohlköφer sind lösbar miteinander verbunden. Die lösbare Ver¬ bindung hat den Vorteil, daß die Hohlkörper getrennt voneinander mit den jeweiligen Waschmit¬ telkomponenten gefüllt werden können. In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind die Hohlköφer über eine Schraub- oder Bajonettverbindung miteinander lösbar verbunden.According to the invention, the hollow bodies contain at least one opening on each of the surfaces abutting another hollow body. On the one hand, the hollow body can be filled with the respective detergent component via these openings, on the other hand, the openings serve to align them with each other when the hollow bodies are rotated, so that a common cavity is created. The individual components can enter the respective adjacent cavity via the opening, so that the individual components can be mixed According to the invention, the individual hollow bodies are connected via a rotatable or displaceable closure. The hollow bodies are releasably connected to one another. The detachable connection has the advantage that the hollow bodies can be filled separately with the respective detergent components. In a preferred embodiment of the present invention, the hollow bodies are detachably connected to one another via a screw or bayonet connection.
Die erfindungsgemäße Misch- und Dosiervorrichtung wird in der Regel aus Kunststoff hergestellt. Aus Kostengründen sind spritzbare oder gießbare Materialien bevorzugt. Zur leichteren Dosie¬ rung ist es bevorzugt, daß die Hohlköφer an ihrer Außenwand gut sichtbar eine Skala aufweisen.The mixing and dosing device according to the invention is generally made of plastic. Injectable or pourable materials are preferred for cost reasons. For easier dosing, it is preferred that the hollow bodies have a scale clearly visible on their outer wall.
Der Gegenstand der Erfindung ist in der beiliegenden Zeichnung in einem Ausführungsbeispiel dargestellt. Diese Zeichnung ist eine Explosionszeichnung der erfindungsgemäßen Misch- und Dosiervorrichtung.The object of the invention is shown in the accompanying drawing in one embodiment. This drawing is an exploded view of the mixing and dosing device according to the invention.
Der Misch- und Dosierbehälter 1 besteht aus zwei Hohlköφern 1 und 2. Die Hohlköφer 1 und 2 weisen an ihren jeweils aneinander stoßenden Flächen 4 und 5 Öffnungen 6,6' und 7,7' auf. In der hier dargestellten Ausführungsform weisen die Hohlköφer an den Flächen 4 und 5 jeweils zwei einander gegenüberliegend angeordnete Öffnungen 6,6' und 7,7' auf. Die Öffnungen 6 und 6' bzw. 7 und 7' können jeweils in einem Winkel von 170° bis 190° (Mittelwert 180°) zueinander an¬ geordnet sein.The mixing and dosing container 1 consists of two hollow bodies 1 and 2. The hollow bodies 1 and 2 have openings 6, 6 'and 7, 7' on their respective abutting surfaces 4 and 5. In the embodiment shown here, the hollow bodies each have two openings 6, 6 'and 7, 7' arranged opposite one another on the surfaces 4 and 5. The openings 6 and 6 'or 7 and 7' can each be arranged at an angle of 170 ° to 190 ° (mean value 180 °) to one another.
Der Hohlköφer 1 ist bevorzugt ein topfformiger Behälter mit entfernbarem Deckel 3, über den das Füllen des Holköφers erfolgen kann. Der Hohlköφer 2, in den die flüssige Komponente ge¬ füllt werden kann ist vorzugsweise ein bis auf die Öffnungen (7,7') verschlossener Hohlzylinder.The hollow body 1 is preferably a pot-shaped container with a removable lid 3, via which the hollow body can be filled. The hollow body 2, into which the liquid component can be filled, is preferably a hollow cylinder which is closed except for the openings (7, 7 ').
Der Hohlköφer 1 hat einen zum Hohlköφer 2 hin überstehenden Zentrierrand 8, der beim Zu¬ sammensetzen der Hohlköφer 1,2 auf den Hohlköφer 2 aufgesetzt wird. Auf diese Weise sind beide Hohlköφer 1,2 zueinander zentriert. In der in der Figur dargestellten Ausführungsform nimmt der Zentrierrand 8 das dem Hohlköφer 1 zugehörige Element 9 eines Drehbajonetts auf. Die dem Hohlköφer 2 zugehörigen Elemente 10 des Drehbajonetts befinden sich am oberen, durch den Zentrierrand 9 übergriffenen Rand des Hohlköφers 2.The hollow body 1 has a centering edge 8 which projects towards the hollow body 2 and which is placed on the hollow body 2 when the hollow bodies 1, 2 are assembled. In this way, the two hollow bodies 1, 2 are centered with respect to one another. In the embodiment shown in the figure, the centering edge 8 receives the element 9 of a rotary bayonet belonging to the hollow body 1. The elements 10 of the rotary bayonet belonging to the hollow body 2 are located on the upper edge of the hollow body 2, overlapped by the centering edge 9.
Steckt man die Hohlköφer 1 und 2 in der hier dargestellten Form zusammen, so werden die Öff¬ nungen 6,6' bzw. 7,7' durch die geschlossenen Flächen 5 und 4 des jeweils anderen Hohlköφers verschlossen. Dabei nehmen die Ausschnitte 6,6' und 7,7' einen Winkel von 85° bis 95° (Mittelwert 90°) zueinander an. Die beiden Hohlköφer 1,2 stehen dann nicht miteinander in Ver¬ bindung. Verdreht man die Hohlköφer um einen Relativwinkel von 90°, so fluchten die Öffnun¬ gen 6 und 7 bzw. 6' und 7', so daß ein kontinuierlicher Hohlraum entsteht. Durch einfaches Schütteln können die in den Hohlköφern 1 und 2 befindlichen Waschmittelkomponenten ver¬ mischt werden. Zum Entleeren der Vorrichtung können die Hohlköφers 1,2 wieder getrennt wer¬ den und die Entleerung erfolgt über die Ausschnitte 6,6' und 7,7' üblicherweise in das Waschmit¬ telfach einer Haushaltswaschmaschine.If the hollow bodies 1 and 2 are put together in the form shown here, the openings 6, 6 'and 7.7' through the closed surfaces 5 and 4 of the other hollow body locked. The cutouts 6,6 'and 7,7' assume an angle of 85 ° to 95 ° (mean value 90 °) to each other. The two hollow bodies 1, 2 are then not connected to one another. If the hollow body is rotated by a relative angle of 90 °, the openings 6 and 7 or 6 'and 7' are aligned, so that a continuous cavity is created. The detergent components located in the hollow bodies 1 and 2 can be mixed by simple shaking. For emptying the device, the hollow bodies 1, 2 can be separated again and the emptying takes place via the cutouts 6, 6 'and 7, 7', usually into the detergent compartment of a household washing machine.
In einer anderen Ausgestaltung der vorliegenden Erfindung erfolgt das Vermischen der einzelnen Komponenten in der Waschtrommel durch deren Bewegung. Der Hohlköφer 1 weist in der hier dargestellten Ausführungsform einen perforierten Deckel 3 auf. Diese Ausführungsform kann eingesetzt werden, wenn die Entleerung der Vorrichtung direkt in der Waschtrommel erfolgen soll. Durch die Öffnungen kann Wasser in die Misch- und Dosiervorrichtung eintreten und das Waschmittel herauslösen. In another embodiment of the present invention, the individual components are mixed in the washing drum by their movement. In the embodiment shown here, the hollow body 1 has a perforated cover 3. This embodiment can be used if the device is to be emptied directly in the washing drum. Water can enter the mixing and dosing device through the openings and remove the detergent.
BeispieleExamples
Die Komponenten A und B, die die unten angegebenen Bestandteile enthielten, wurden in einem Gewichtsverhältnis von 2,6 zu 1 kurz vor dem Waschen in der erfindungsgemäßen Dosiervor¬ richtung zusammengegeben, gründlich vermischt und in die Waschmaschine gegeben.Components A and B, which contained the constituents given below, were combined in a weight ratio of 2.6 to 1 shortly before washing in the metering device according to the invention, mixed thoroughly and placed in the washing machine.
Die Komponente A enthielt die folgenden Bestandteile:Component A contained the following components:
1) Dehydol(R) LT7 ist ein ethoxylierter Ci2-Cιg-Fettalhohol mit durchschnittlich 7 EO- Einheiten (Handelsprodukt der Fa. Henkel, Düsseldorf)1) Dehydol ( R ) LT7 is an ethoxylated Ci2-Cιg fatty alcohol with an average of 7 EO units (commercial product from Henkel, Düsseldorf)
2) Dehydol(R) LST 80/20 ist ein Gemisch aus 80% eines ethoxylierten C^-Cig-Fettalkohols mit durchschnittlich 5 EO-Einheiten und 20% eines ethoxylierten Ci2-Ci4-Fettalkohols mit durchschnittlich 3 EO-Einheiten (Handelsprodukt der Fa. Henkel, Düsseldorf).2) Dehydol ( R ) LST 80/20 is a mixture of 80% of an ethoxylated C ^ -Cig fatty alcohol with an average of 5 EO units and 20% of an ethoxylated Ci2-Ci4 fatty alcohol with an average of 3 EO units (commercial product from Henkel, Düsseldorf).
3) MaranilW A ist ein C\ j-Ciß-Alkylbenzolsulfonat (Handelsprodukt der Fa. Hüls, Mari)3) MaranilW A is a C \ j-Ciss-alkylbenzenesulfonate (commercial product from Hüls, Mari)
4) Edenor R) HT 35 ist eine Ci6-Cιg-Fettsäure (Handelsprodukt der Fa. Henkel, Düsseldorf)4) Edenor R) HT 35 is a Ci6-Cιg fatty acid (commercial product from Henkel, Düsseldorf)
5) VP 1132 ist ein Silikonöl (Handelsprodukt der Fa. Dow Corning)5) VP 1132 is a silicone oil (commercial product from Dow Corning)
6) TuφinalW 2 NZ ist ein Hydroxyethyldiphosphonat (Handelsprodukt der Fa. Henkel, Düs¬ seldorf)6) TuφinalW 2 NZ is a hydroxyethyl diphosphonate (commercial product from Henkel, Düsseldorf)
7) BLAP(R) 140 ist eine Protease (Handelsprodukt der Fa. Henkel, Düsseldorf) Komponente B:7) BLAP ( R ) 140 is a protease (commercial product from Henkel, Düsseldorf) Component B:
NatriumpercarbonatSodium percarbonate
Ergebnisse:Results:
Es wurde festgestellt, daß sich die Waschmittelkomponenten in der erfindungsgemäßen Vorrich¬ tung gut vermischen ließen, das Bleichmittel war gleichmäßig und ohne Verklumpungen in der flüssigen Phase dispergiert. Das erhaltene Gemisch wurde aus der Vorrichtung vom in die Waschmaschine eintretenden Wasser schnell herausgespült. Bei der gewaschenen Wäsche wurden keine Spotting-Effekte beochachtet. It was found that the detergent components could be mixed well in the device according to the invention; the bleaching agent was dispersed uniformly in the liquid phase without clumping. The resulting mixture was quickly flushed out of the device from the water entering the washing machine. No spotting effects were observed for the washed laundry.
BezugszeichenlisteReference list
1 Hohlköφer1 hollow body
2 Hohlköφer2 hollow bodies
3 perforierter Deckel3 perforated lids
4 Fläche des Hohlköφers 14 surface of the hollow body 1
5 Fläche des Hohlköφers 25 area of the hollow body 2
6,6' Öffnungen in der Fläche 46.6 'openings in area 4
7,7' Öffnungen in der Fläche 57,7 'openings in area 5
8 Zentrierrand8 centering edge
9 Element des Drehbajonetts am Hohlköφer 19 Element of the rotating bayonet on the hollow body 1
10 Element des Drehbajonetts am Hohlköφer 2 10 element of the rotating bayonet on the hollow body 2
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19511192.3 | 1995-03-27 | ||
| DE19511192A DE19511192A1 (en) | 1995-03-27 | 1995-03-27 | Process for washing textile fabrics using a non-aqueous liquid detergent with bleach |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1996030489A2 true WO1996030489A2 (en) | 1996-10-03 |
| WO1996030489A3 WO1996030489A3 (en) | 1996-11-21 |
Family
ID=7757872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1996/001139 Ceased WO1996030489A2 (en) | 1995-03-27 | 1996-03-15 | Method of washing using non-aqueous liquid washing agents with separate bleach |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE19511192A1 (en) |
| WO (1) | WO1996030489A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001090475A1 (en) * | 2000-05-22 | 2001-11-29 | The Procter & Gamble Company | A method for caring for a fabric article and for providing a system therefor |
| WO2001090294A1 (en) * | 2000-05-22 | 2001-11-29 | The Procter & Gamble Company | A kit for caring for a fabric article |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10340683A1 (en) * | 2003-09-04 | 2005-04-07 | Henkel Kgaa | Washing or cleaning agents |
| WO2005026307A1 (en) * | 2003-09-12 | 2005-03-24 | Reckitt Benckiser (Uk) Limited | Cleaning method and cleaning composition |
| GB2447496B (en) * | 2007-03-14 | 2009-09-30 | Pauline Harkins | Laundry detergent dispenser |
| DE102012015826A1 (en) | 2012-08-09 | 2014-02-13 | Clariant International Ltd. | Liquid surfactant-containing alkanolamine-free compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2554592C3 (en) * | 1975-12-04 | 1981-11-26 | Bosch-Siemens Hausgeräte GmbH, 7000 Stuttgart | Washing process for textiles to be carried out in an automatic washing machine and the device for carrying it out |
| IT1200285B (en) * | 1986-08-12 | 1989-01-12 | Mira Lanza Spa | NON-Aqueous LIQUID DETERGENT AND PROCEDURE FOR ITS MANUFACTURE |
| EP0490436A1 (en) * | 1990-12-10 | 1992-06-17 | Unilever N.V. | Use of non-aqueous detergent compositions |
-
1995
- 1995-03-27 DE DE19511192A patent/DE19511192A1/en not_active Withdrawn
-
1996
- 1996-03-15 WO PCT/EP1996/001139 patent/WO1996030489A2/en not_active Ceased
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001090475A1 (en) * | 2000-05-22 | 2001-11-29 | The Procter & Gamble Company | A method for caring for a fabric article and for providing a system therefor |
| WO2001090294A1 (en) * | 2000-05-22 | 2001-11-29 | The Procter & Gamble Company | A kit for caring for a fabric article |
| US7531493B2 (en) | 2000-05-22 | 2009-05-12 | The Procter & Gamble Company | Kit for caring for a fabric article |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996030489A3 (en) | 1996-11-21 |
| DE19511192A1 (en) | 1996-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0595946B1 (en) | Method of producing high-bulk-density washing agents with improved dissolving speed | |
| DE69216191T2 (en) | Detergent powder and process for its manufacture | |
| DE69221681T2 (en) | Detergent compositions | |
| DE3518100A1 (en) | FABRIC SOFTENING POWDERED DETERGENT | |
| EP0424403A1 (en) | Granular adsorbant with improved ease of rinsing | |
| EP0777722A1 (en) | Liquid washing or cleaning product with bleaching power | |
| DE3835918A1 (en) | METHOD FOR PRODUCING TENSIDE CONTAINING GRANULES | |
| WO1993015180A1 (en) | Process for producing solid washing and cleaning agents with a high powder density and improved rates of dissolution | |
| EP0648259B1 (en) | Solid detergent composition with improved washing-in behaviour | |
| DE1617140A1 (en) | Bleaching granular detergent and process for making the same | |
| EP0720644B1 (en) | Detergent mixtures and washing or cleaning agents with improved solvent properties | |
| DE2055423A1 (en) | Washing compositions - containing water-insoluble crosslinked cation -exchange polymers especially crosslinked polystyrene,polyacrylic acid | |
| DE3544762A1 (en) | LIQUID SOLID DETERGENT | |
| WO1996030489A2 (en) | Method of washing using non-aqueous liquid washing agents with separate bleach | |
| EP0327684A2 (en) | Process for machine washing textiles | |
| EP0623593A2 (en) | Process for neutralising the acid form of anionic surfactant, agglomerates and detergent thereby obtained | |
| EP0675947A1 (en) | Granulated washing and/or cleaning agents | |
| EP0804535B1 (en) | Granular bleaching washing and cleaning agent | |
| DE69633113T2 (en) | Detergent compositions | |
| EP0804534B1 (en) | Enzyme-containing bleaching washing agent | |
| EP1232239A1 (en) | Method for the production of particulate washing or cleaning agents | |
| DE3518656A1 (en) | BLEACHING DETERGENT | |
| DE19600466A1 (en) | Process for the production of granular washing or cleaning agents or components therefor | |
| DE3518295A1 (en) | DETERGENT WITH A BUILDER AND SURFACTANT CONTENT | |
| EP0971999A1 (en) | Granulated detergents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| 122 | Ep: pct application non-entry in european phase |