WO2004055143A2 - Emballage unidose en plastique contenant un produit nettoyant servant a enlever directement des salissures - Google Patents

Emballage unidose en plastique contenant un produit nettoyant servant a enlever directement des salissures Download PDF

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Publication number
WO2004055143A2
WO2004055143A2 PCT/EP2003/013811 EP0313811W WO2004055143A2 WO 2004055143 A2 WO2004055143 A2 WO 2004055143A2 EP 0313811 W EP0313811 W EP 0313811W WO 2004055143 A2 WO2004055143 A2 WO 2004055143A2
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WO
WIPO (PCT)
Prior art keywords
plastic container
dose plastic
cleaning agent
dose
acid
Prior art date
Application number
PCT/EP2003/013811
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German (de)
English (en)
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WO2004055143A3 (fr
Inventor
Wilfried Rähse
Sandra Hoffmann
Ulrike Ruffer
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU2003293781A priority Critical patent/AU2003293781A1/en
Publication of WO2004055143A2 publication Critical patent/WO2004055143A2/fr
Publication of WO2004055143A3 publication Critical patent/WO2004055143A3/fr

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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/09—Ampoules
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser

Definitions

  • the invention relates to a single-dose plastic container containing a liquid, foam-like or gel-like cleaning agent for the direct removal of dirt.
  • wet cleaning wipes are known from the prior art which can be used for direct stain removal from textiles. These cleaning wipes have the disadvantage, among other things, that the amount of liquid is too small to be able to remove stubborn dirt. Furthermore, direct skin contact with the damp cleaning cloth is essential during the entire cleaning process, i.e. When the cleaning cloth is unpacked, i.e. before the actual cleaning begins, the user is contacted with the cleaning agent. In addition, in order to avoid drying out, such cleaning wipes have to be packaged in a complex manner.
  • cleaning agents including sprays, which are suitable for removing numerous stains from textile supports are known.
  • Such agents are not pre-portioned as a single dose unit, so that exact dosing is difficult.
  • Another disadvantage is that after such stain removal agents have been opened once, by penetrating air, oxygen-sensitive cleaning substances can be oxidized during storage.
  • fragrances can be released over a prolonged period of time, which can lead to a change in the smell of the agent and, when used, has an immediate effect on the textile to be cleaned.
  • WO-A-02/079362 discloses a method and a device for stain cleaning a fabric by means of a liquid cleaning agent, suitable for multiple use Use, wherein the device comprises more than one absorbent for absorbing at least a portion of the detergent used from the tissue and a storage means for absorbing more than one absorbent.
  • WO-A-02/079363 discloses a device for stain cleaning a fabric using a liquid detergent composition, the device comprises a reservoir for receiving the composition, an applicator suitable for applying the composition to the fabric and an absorbent for absorbing at least one Part of the composition of the fabric.
  • WO 01/79413 discloses a method for removing a water stain from a fabric article, in which the fabric surface to be cleaned is placed on a hard surface, the soiled area is moistened with clean water, a clean cloth is placed on the soiled area and over the clean area Cloth irons.
  • a method for removing a water stain from a fabric article is described that involves wetting the soiled area with water and then drying it with a hair dryer or in a tumble dryer. The method described there does not relate to the use of a liquid, foam-like or gel-like cleaning agent for the direct removal of dirt.
  • EP 1 069 177 discloses a tissue treatment applicator with a tip containing a bleach and surfactant. This tissue treatment applicator is used for mechanical and chemical stain removal. A single-dose plastic container for a liquid, foam-like or gel-like cleaning agent for the direct removal of dirt, however, is not described.
  • the present invention relates to a single-dose plastic container containing a liquid, foam-like or gel-like cleaning agent for the direct removal of dirt at room temperature from hard or soft surfaces, characterized in that the single-dose plastic container has a filling volume of up to 5.0 ml detergent.
  • the single-dose plastic containers that can be used according to the invention serve to hold liquid, foam-like or gel-like cleaning agents for the direct removal of soiling, whereby for cleaning purposes the entire detergent content of the single-dose plastic container can be applied to the place of soiling to be cleaned, apart from practically no or only minimal residual fill quantities.
  • a single-dose plastic container is understood to mean a product which is suitable for absorbing an amount of cleaning agent which is sufficient for a single application.
  • a liquid, foam-like or gel-like cleaning agent for the direct removal of dirt is understood to mean a product for single use, in which the entire cleaning agent, after opening the single-dose plastic container, without further dilution, is applied directly to the hard or soft surface to be cleaned for the purpose of development the cleaning effect is applied.
  • liquid, foam-like or gel-like cleaning agents in which the formation of difficult-to-remove wreaths and edges around the original stains does not occur and practically no increased re-soiling occurs at the originally stained area.
  • the cleaning agent for the direct removal of dirt hereinafter also referred to as stain removal agent, which can be removed as a liquid, gel or foam from a single-dose plastic container that can be used according to the invention, is applied to the stain and, if necessary, with a cloth, a brush or a Sponge, which may be damp, rubbed into the stain.
  • stain removal agent which can be removed as a liquid, gel or foam from a single-dose plastic container that can be used according to the invention.
  • the degree to which the mechanical treatment of the stain must be selected in connection with the use of the cleaning agent also largely depends on the type and age of the stain and on the effectiveness of the agent. In mild cases, mechanical treatment can be dispensed with entirely. The residues of the cleaning agent are then removed mechanically.
  • An extraction and / or adsorbent can in particular be used to remove or suction the liquid, foam-like or gel-like cleaning agent.
  • Suitable absorbents and / or adsorbents are preferably based on woven or non-woven materials, selected from the group comprising paper towels, textile towels or microfiber towels.
  • the removal and / or adsorbent agent is particularly preferred, suitable for absorbing cleaning agents from the soft or hard surface to be cleaned, selected from the group comprising a cloth or a sponge.
  • the absorption and / or adsorbent is usually dry.
  • the reason for the excellent effectiveness of the agent which can be used according to the invention is, inter alia, suspects that the liquids and active ingredients contained in the cleaning agent convert the stain components into a mobile form and the stain components are then, in this form, distributed in the object to be cleaned, such as textile, 'oxidized, and / or by an absorption / adsorbent recorded and removed with this.
  • the single-dose plastic container is formed in one piece, preferably from a polymeric material.
  • Single-dose plastic containers suitable according to the invention are preferably made of polyethylene, particularly preferably low-density polyethylene (LDPE).
  • single-dose plastic containers that can be used according to the invention can also be formed from polypropylene or polypropylene-containing polymeric material.
  • single-dose plastic containers suitable according to the invention are preferably formed from a polymeric material which is free from plasticizers. According to the invention, however, the polymeric material can optionally also contain plasticizers and optionally pigments and / or other additives.
  • Single dose plastic container made of a polymeric material that is impermeable to UV radiation and / or air.
  • the polymeric material used for single-dose plastic containers which can be used according to the invention has a modulus of elasticity of at most 500 N / mm 2 .
  • the elasticity of the polymeric material used particularly preferably corresponds to a 1% Secant modulus of approximately 10 MPa to 500 MPa, in particular up to 300 MPa, preferably 30 MPa to 200 MPa, particularly preferably 50 MPa to 100 MPa.
  • the Secant module is an idealized modulus of elasticity derived from a secant that is drawn between the origin and any point on a non-linear stress-strain curve. For materials whose modulus changes with the stress, the Secant modulus is the average between the zero point of the stress and the point considered as the maximum of the stress.
  • the filling quantity or the filling volume of the single-dose plastic containers suitable according to the invention is up to 5.0 ml, preferably 4 ml, more preferably 0.3 to 3 ml and particularly preferably 1 to 2 ml.
  • the filling quantity is particularly preferably liquid or gel-like Cleaning agents for the direct removal of contaminants according to the invention up to 2.5 ml, particularly preferably up to 1.5 ml.
  • the filling amount is preferably between 1 and 3 ml, while in the case of gel-type cleaning agents for the direct removal of contaminants the filling amount is preferably between 0.5 and 2.5 ml.
  • the single-dose plastic containers according to the present invention have a width in the area for liquid absorption of 3 mm to 30 mm, in particular 6 mm to 20 mm, and a length of 10 mm to 80 mm, in particular 15 mm up to 40 mm.
  • Single-dose plastic containers suitable according to the invention have an outlet opening with a diameter of 0.1 mm to 5 mm, preferably of 0.5 to 3 mm, particularly preferably of 1.2 mm to 2 mm.
  • Preferred single-dose plastic containers have a bottle-like shape.
  • Single-dose plastic containers that are spherical or have the shape of a vial are particularly suitable.
  • angular moldings are also suitable.
  • different geometrical configurations of the hollow body such as for example Santa Clauses, Easter bunnies or other figures, can be shaped.
  • Preferred single-dose plastic containers are without integral compartmentalization devices, but can also have such for the establishment of internal, separate chambers.
  • Single dose plastic containers can have a flag, for example.
  • a flag is an elongated surface element arranged on the single-dose plastic container, in particular on the outer container base, which is suitable for applying information.
  • single-dose plastic containers that do not have a flag are preferred.
  • the single-dose plastic containers can be embossed and / or decorated in the mold during manufacture, in particular blow molding.
  • a motif can be transferred to the single-dose plastic container in mirror image.
  • the surface of the single-dose plastic container can be designed practically as desired.
  • information such as calibration marks, application notes, hazard symbols, brands, weight, filling quantity, expiry date, pictures, etc. can be applied to it.
  • information can also, if necessary additionally, be applied in the form of an applied, preferably adhesive, pre-printed label.
  • the wall of the single-dose plastic containers can be in the middle, i.e. have at least one, preferably at least two, opposing waists between the bottle neck and the bottom of the single-dose plastic container. Such waists of the wall of the single-dose plastic container can make emptying the direct, liquid cleaning agent considerably easier.
  • the single-dose plastic containers can have grooves and / or grooves and / or roughening on their outer sides which prevent fingers from slipping off the container during the stain treatment and / or Increase grip.
  • such grooves and / or grooves and / or roughening can be formed in the region of the waist (s). .
  • Single-dose plastic containers which can be used according to the invention have an at least partially, preferably completely unscrewable and / or tear-off closure flap.
  • FIG. 1 shows a single-dose plastic container that can be used according to the invention.
  • FIG. 2 shows single-dose plastic containers which are connected in blocks and can be used according to the invention.
  • the single-dose plastic container according to FIG. 1, which can be used according to the invention, allows the container to be completely emptied, that is to say a more precise dosing of liquid, foam-like or gel-like cleaning agents for the direct removal of contaminants, since practically no or only minimal residual fill quantities remain in the plastic container.
  • the plastic container has a twist-off / tear-off closure flap 1.
  • this closure cap is designed in such a way that it can be easily twisted off or torn off from the single-dose plastic container with the thumb and forefinger.
  • the single-dose plastic container according to the present invention is connected to a large number of further aforementioned single-dose plastic containers to form blocks. Blocks of 2, 3, 4, 5, 6, 8, 10, 12 or 15 single-dose plastic containers are particularly preferred.
  • the respective plastic containers are preferably connected via at least one connecting member, the connecting member preferably being made of polymer.
  • the connecting link is preferably designed as a web.
  • the connection of the plastic containers by means of web (s) to a block is designed in such a way that the respective plastic container can be easily twisted off or torn off from the block of single-dose plastic containers with thumbs and fingers.
  • blocks consisting of the single-dose plastic containers that can be used according to the invention are shown by way of example.
  • Single-dose plastic containers which are suitable according to the invention can be produced by blow extrusion with subsequent filling and sealing, but particularly preferably according to the blow-fill-seal method, in particular in.
  • the Bottlepack® machines from Rommelag or Cooker plastic. It is an industrial process for the rational packaging of, among other things, individually dosed cleaning agents for the direct removal of dirt, in which single-dose plastic containers are produced, filled and sealed immediately in an automatic machine.
  • the containers are usually made of plastic granulate by extrusion blowing, vented via a blowing and filling mandrel with an exhaust air line and at the same time filled with the desired amount of liquid or gel using a piston metering machine and three-way valve connected to the mandrel.
  • the container After removing the dome, the container is welded with separate head tools. In this way, hermetically sealed single-dose plastic containers filled with cleaning agent in the desired shape are obtained to a desired degree of filling.
  • the molding tools or the method can be designed in such a way that blocks are obtained from interconnected single-dose plastic containers.
  • Single-dose plastic containers suitable according to the invention are preferably made of polyethylene, particularly preferably low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • the LDPE with the trade name Lupolen 3040 D sold by the Mariac company or the LDPE with the trade name Escorene LD 100 MED sold by Exxon Chemical are suitable as polymeric material.
  • Cleaning agents suitable for filling the single-dose plastic containers which can be used according to the invention are, in particular, liquid, foam-like or gel-like tissue treatment agents.
  • a combination of anionic and nonionic surface-active substances, such as surfactants, and a solvent, in particular a non-aqueous solvent, furthermore particularly preferably one having a low vapor pressure under ambient conditions, or an aqueous solvent are preferred.
  • the nonionic surfactant is preferably an ethoxylated alcohol with an alcohol chain length of 11-16 carbon atoms and a proportion of 1.6-7 moles of ethylene oxide.
  • the anionic surface-active substance is preferably taken from the group consisting of alkyl alcohol sulfates, alcohol ethoxy sulfates, alkyl alcohol benzene sulfonates or mixtures of these compounds.
  • the cleaning agent which can be used according to the invention can be used for cleaning hard surfaces and / or soft surfaces and particularly preferably for removing dirt from textiles.
  • the cleaning agent which can be used according to the invention can contain from 0.001 to 2% by weight, preferably from 0.01 to 1.5% by weight, preferably from 0.05 to 0.9% by weight, of an aromatic or zwitterionic surfactant; from 0.001 to 2% by weight, preferably from 0.01 to 1.5% by weight, preferably from 0.05 to 0.9% by weight, of a nonionic surfactant; from 0 to 2% by weight, preferably from 0.01 to 1.5% by weight, preferably from 0.05 to 0.9% by weight, of an anionic surfactant.
  • the cleaning agent which can be used according to the invention is preferably aqueous, although a non-aqueous or essentially non-aqueous cleaning agent can also be suitable.
  • the cleaning agent which can be used according to the invention can have a water content of less than 99% by weight, preferably less than 50% by weight, more preferably less than 25% by weight, in particular less than 20% by weight, less than 15% by weight, less than 10% by weight or even less than 5% by weight, based on the total weight of the cleaning agent.
  • organic solvent In the case of an aqueous cleaning agent which can be used according to the invention, it is also preferred to add an organic solvent.
  • organic solvents are alcohol, ketones, esters, paraffins, alcohols, especially C to C chain alcohols, petrol, fluorinated and chlorinated hydrocarbons, butyl acetate, petroleum ether, glycol ether and Mixtures of these are selected.
  • the proportion of organic solvent in the Detergent composition advantageously makes up 0.1 to 75% by weight, preferably 1% to 10% by weight, based on the total weight of the detergent.
  • the proportion of surfactant advantageously makes up 0.00001% by weight to 20% by weight, preferably 0.0001% by weight to 10% by weight, particularly preferably 0.001% by weight, to 1% by weight based on the total weight of the detergent.
  • cleaning agent compositions disclosed in WO-A-02/079362 and WO-A-02/079363, to which full reference is made, can also be suitable as cleaning agents which can be used according to the invention.
  • the constituents contained in the cleaning agents which can be used according to the invention are preferably selected from the group comprising surfactants, fragrances, dyes, enzymes, enzyme stabilizers, builders, substances for adjusting the pH, bleaching agents, bleach activators, dirt-repellent substances, optical brighteners, graying inhibitors, disintegration aids , usual ingredients and / or mixtures thereof.
  • Anionic, cationic, ampho- and / or nonionic surfactants can be used as surfactants for the production of the cleaning agents.
  • anionic surfactants of the sulfonate and sulfate type can be used.
  • Suitable surfactants of the sulfonate type are preferably C 9-13 -Alkylben- sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 12 ⁇ 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, (n.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids
  • Sulfonation products of unsaturated fatty acids for example oleic acid
  • ⁇ -sulfofatty acid alkyls ter which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl ester, ethyl ester, propyl ester and butyl ester.
  • the methyl esters of ⁇ -sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Fatty acid derivatives of amino acids for example of N-methyl acid (tauride) and / or of N-methyl glycine (sarcoside) are suitable as further anionic surfactants.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants, including the soaps can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or tri-ethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the anionic surfactants are present in the cleaning agents which can be used according to the invention preferably in amounts of 0.05 to 30% by weight and in particular in amounts of 0.1 to 10% by weight and preferably 1 to 5% by weight.
  • alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598.
  • Preferred nonionic surfactants are C 12 -C 18 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO in particular can be used as surfactants.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously for the production of cleaning agents are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Symbol is that for a glycose unit with 5 or 6 carbon atoms, preferably for Glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-di- m 'ethylaminoxid and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable for production of the detergents.
  • gemini surfactants are suitable as further surfactants for the preparation of the cleaning agents which can be used according to the invention. These are generally understood to mean compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another.
  • Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants is understood to mean not only dimers but also trimer surfactants.
  • Gemini surfactants for the production of cleaning agents are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE-A-195 03 061.
  • End group-blocked dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 391 are distinguished in particular by their bi- and multifunctionality.
  • the end group-closed surfactants mentioned have good wetting properties and are low-foaming.
  • the cleaning agents which can be used according to the invention can optionally also contain cationic surfactants.
  • Suitable cationic surfactants are, for example, surface-active quaternary compounds, in particular with an ammonium .sulfonium, phosphonium, iodonium or arsonium group, as described, for example, by KH Wall conferenceußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene” (5th ed - Stuttgart; New York: Thieme, 1995) as antimicrobial agents writes.
  • KH Wallnosußer a quaternary
  • the agent can be designed with an antimicrobial effect on surface-active compounds with an antimicrobial effect or its antimicrobial effect which may already be present due to other ingredients can be improved.
  • Particularly preferred cationic surfactants are the quaternary, partly antimicrobial ammonium compounds (QAV; INCI Quaternary Ammonium Compounds) 'according to the general formula (R I ) (R ") (R I ") (R IV ) N * X-, in which R 1 to R ⁇ v identical or different C -22- alkyl radicals, C -28- aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, as in pyridine, even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or imidazolinium compound formation, form, represent and X ⁇ are halide ions, sulfate ions, hydroxide ions or similar anions.
  • QAV quaternary, partly antimicrobial ammonium compounds
  • At least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QAV can be prepared by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzyl ammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No . 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzalkonium chloride N-alkyl-N, N-dimethyl-benzyl ammonium chloride, CAS No. 8001-54-5
  • benzalkon B m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No . 58390
  • Benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1, 1, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloric, 1-cetylpyridinium chloride (CAS No.
  • QACs are the benzalkonium chlorides with C 8 -C 18 -alkyl radicals, in particular C 12 -C 1 -alkyl-benzyl-dimethylammoni- monium chloride.
  • a particularly preferred QAV cocospentaethoxymethylammonium methosulfate (INCI PEG-5 Qocomonium methosulfate; Rewoquat ® CPEM).
  • anionic surfactants that are as compatible as possible and / or as little as possible cationic surfactant are used or, in a particular embodiment of the invention, no cationic surfactants with an antimicrobial effect are used.
  • Parabens, benzoic acid and / or benzoate, lactic acid and / or lactates can be used as antimicrobial substances. Benzoic acid and / or lactic acid are particularly preferred.
  • the cleaning agents which can be used according to the invention can contain one or more cationic surfactants in amounts, based on the total composition, of from 0 to 5% by weight, greater than 0 to 5% by weight, preferably 0.01 to 3% by weight, in particular 0 Contain 1 to 1 wt .-%.
  • the cleaning agents which can be used according to the invention can also contain amphoteric surfactants.
  • Suitable amphoteric surfactants are, for example, betaines of the formula '(R 1 ) (R 2 ) (R 3 ) N + CH 2 CO ⁇ , in which R 1 is an alkyl radical with 8 to 25, preferably 10 to, optionally interrupted by heteroatoms or heteroatom groups 21 carbon atoms and R 2 and R 3 are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 22 -alkyldimethylcarboxymethylbetaine and C ⁇ C 17 - alkylamidopropyldimethylcarboxymethylbetaine.
  • alkylamidoalkylamines alkyl-substituted amino acids, acylated amino acids or biosurfactants as amphoteric surfactants in the cleaning agents which can be used according to the invention is conceivable.
  • the cleaning agents which can be used according to the invention can contain one or more amphoteric surfactants in amounts, based on the overall composition, of 0 to 5% by weight, greater than 0 to 5% by weight, preferably 0.01 to 3% by weight, in particular 0 Contain 1 to 1 wt .-%.
  • the agents can also be acidic
  • the cleaning agents which can be used according to the invention can contain, as builders or builders, all builders customarily used in cleaning agents, in particular thus zeolites, silicates, carbonates, soda, organic cobuilders and also the phosphates. To avoid particulate residues on textiles, it is particularly advantageous to use builders which are completely water soluble, such as soda or the like.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 • yH 2 O are preferred.
  • Amorphous sodium silicates with a Na 2 O: SiO 2 modulus from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6 can also be used.
  • Amorphous silicates are particularly preferred.
  • a usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • zeolite X and zeolite A (about 80% by weight of zeolite X)
  • VEGOBOND AX ® a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X)
  • VEGOBOND AX ® a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X)
  • VEGOBOND AX ® nNa 2 O • (1-n) K 2 O ⁇ AI 2 O 3 • (2 - 2.5) SiO 2 • ( 3.5 - 5.5) H 2 O
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. .
  • Organic cobuilders which can be used in the cleaning agents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotniacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 2,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
  • Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • a preferred dextrin is described in British patent application 94 19 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608 are known.
  • a product oxidized at C6 of the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders.
  • Ethylene diamine N, N'-disuccinate is preferably used in the form of its sodium or magnesium salts.
  • EDDS Ethylene diamine N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups.
  • Such cobuilders are described, for example, in international patent application WO-A-95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the cleaning agents also contain bleach, it may be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned for the preparation of the agents.
  • Suitable polymeric polycarboxylates for the preparation of the center which can be used according to the invention! are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, as monomers DE-C-42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those which are described in the German patent applications' DE-A-43 03 320 and DE-A-44 17 734 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Suitable builder substances for producing the cleaning agents which can be used according to the invention are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or their preparation, for example, in international patent application WO-A-93 / 16110.
  • Oxidized oligosaccharides according to German patent application DE-A-196 00 018 are also suitable.
  • polyacetals which are obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 can.
  • Preferred polyacetals are made from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the cleaning agents can also contain bleaching agents.
  • it can be an aqueous hydrogen peroxide solution.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Bleaching agents from the group of organic bleaching agents can also be used to produce the cleaning agents.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) ie aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimido -peroxycaproic acid [phthaloiminoper-oxyhexanoic acid (PAP)] “o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoper-adipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperainic acid, diperoxyacid, diperoxyacid, ocysebacic acid, diperoxybrassylic acid, the diperoxy-phthalic acids
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the cleaning agents which can be used according to the invention.
  • Suitable materials that release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with catio- such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • the bleach content is preferably 0 to 25% by weight and in particular 1 to 20% by weight, based on the overall composition of the cleaning agent.
  • bleach activators can be included.
  • Bleach activators for the preparation of the cleaning agents which can be used according to the invention can be compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (T ⁇ ED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) are preferred.
  • T ⁇ ED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU tetraacetylglycoluril
  • N-acylimides especially N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, especially acylated polyhydric alcohols , Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • NOSI N-nonanoyl succinimide
  • acylated phenol sulfonates especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS)
  • carboxylic acid anhydrides especially phthalic anhydride, especially acylated polyhydric alcohols
  • bleach catalysts can also be used for the production of cleaning agents which can be used according to the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are also used as bleaching catalysts usable.
  • Bleach activators which can be used to prepare the cleaning agents which can be used according to the invention are also those from German patent applications DE-A-196 16 693 and DE- A-196 16 767 known enol esters as well as acetylated sorbitol and mannitol or their mixtures described in the European patent application EP-A-0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acetone optionally N-alkyl-glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94 / 28103, WO-A-95/00626,
  • hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are also preferred for the preparation of the cleaning agents that can be used according to the invention.
  • the conventional known from German patent application DE-A-4443 177 known combinations bleach activators can be used for the preparation of the medium according to the invention can be used cleaning.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, possibly signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica or bistearylethylenediamide.
  • Suitable enzymes for the preparation of the cleaning agents are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains.
  • Oxidoreductases can also be used for bleaching.
  • Particularly suitable for the production of the cleaning agents are those derived from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferred.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing enzymes Mixtures or mixtures with lipolytically active enzymes of particular interest.
  • lipolytically active enzymes are the known cutinases.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Oxireductases are also suitable.
  • cellulases can also be used for the production of the cleaning agents. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the proportion of the enzymes or enzyme mixtures can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight, based on the total weight of the detergent composition.
  • the cleaning agents can also contain further enzyme stabilizers.
  • the cleaning agents can contain sodium formate.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron compounds, is particularly advantageous. oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7).
  • the cleaning agents can also contain graying inhibitors.
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric qarboxylic acids, glue, gelatin salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g.
  • polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone are preferably used in the cleaning agents which can be used according to the invention.
  • dirt-repellent substances can be used to produce the cleaning agents, which have a positive influence on the oil and fat washability from textiles (so-called soil repellents).
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • Optical brighteners are organic dyes that unite Convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made, for example, depending on the “fibers to be dyed”
  • Brighteners for cotton, polyamide or polyester fibers The commercially available brighteners suitable for the production of cleaning agents essentially include five ⁇ ⁇
  • Structural groups namely the stilbene, diphenylstilbene, coumarin-quinoline, diphenyl-pyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems.
  • An overview of common brighteners can be found, for example, in G. Jakobi, A. Lschreib “Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100.
  • Suitable are, for example, salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazine-2-yl) amino] -stilbenr2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the brighteners mentioned above may be used. 1
  • Fragrances can be added to the cleaning agents that can be used according to the invention in order to improve the aesthetic impression of the resulting agents and, in addition to the cleaning performance and the color impression, provide the consumer with a sensorically "typical and unmistakable" cleaning agent.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propylate propylateionate.
  • the ethers include, for example, benzylethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, oc-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and
  • the hydrocarbons mainly include terpenes such as limes and pines.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the cleaning agents can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high. Storage stability and insensitivity to the other ingredients of the cleaning agents and to light as well as no pronounced substantivity to textile fibers so as not to stain them.
  • Preferred for the production of the cleaning agents which can be used according to the invention are all coloring agents which can be oxidatively destroyed during cleaning, as well as mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or in liquid organic substances at room temperature.
  • anionic colorants for example anionic nitroso dyes, are suitable.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
  • Pigmosol ® Blue 6900 (Cl 74160), Pigmosol ® Green 8730 (Cl 74260), Basonyl ® Red 545 FL (Cl 45170), Sandolan ® Rhodamine EB400 (Cl 45100), Basacid ® Yellow 094 (Cl 47005), Sicovit ® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol ® Blau GLW (CAS 12219-32-8, Cl Acidblue 221 ), Nylosan ® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan ® Blue (Cl Acid Blue 182, CAS 12219-26-0).
  • the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers.
  • suitable colorants it must also be taken into account that colorants have different stabilities against oxidation.
  • water-insoluble colorants are more stable to oxidation than water-soluble colorants.
  • concentration of the colorant in the cleaning agents varies.
  • the above-mentioned Basacid ® Green or the above-mentioned Sandolan ® Blue are typically chosen dyestuff concentrations in the range of some 10 "2 to 10" 3 wt .-%, each based on the total detergent, .
  • the appropriate concentration of the colorant is in detergents, however, typically a few 10 "3 to 10" 4 wt .-%, based on all the detergent.
  • any liquid, foam-like or gel-like cleaning composition is suitable which, on the one hand, has excellent dirt removal properties and, on the other hand, leaves little or no visible residue on the treated fabric.
  • non-ionic surfactant is used alone, there may be a risk that it will leave an oily residue on the treated tissue. Therefore combinations of nonionic and anionic surfactants are preferred.
  • CMC critical micelle concentrations
  • the nonionic surfactant is an ethoxylated alcohol with a chain length of 12- 15 carbon atoms and 3-7 moles of ethylene oxide, preferably 3 to 5 moles of ethylene oxide.
  • examples of such preferred nonionic surface-active substances include the commercially available products Neodol 25-3, Neodol 23-3 (manufacturer: Shell Corp.), Surfonic L24-3, Surfonic L24-4 and Surfonic L1270-2 (manufacturer: Huntsman Corp. .) in question.
  • the proportion of the nonionic surface-active substance is desirable for the proportion of the nonionic surface-active substance to be between 0.05% by weight and 1.0% by weight, in each case based on the total composition.
  • a nonionic surfactant can be used in conjunction with at least one of the aforementioned categories of anionic surfactants.
  • Cleaning agents based on organic solvents and also those based on water are also suitable according to the invention.
  • the agents are applied as a liquid, gel or foam and should contain at least 70% by weight, preferably at least 80% by weight, of volatile constituents. Examples of such cleaning agents can be found in the relevant specialist literature.
  • Solvent-based cleaning agents also known as stain water, are mostly water-free and generally contain no surfactants.
  • the main solvents used are alcohols, petrol, chlorinated hydrocarbons, butyl acetate and similar volatile compounds, either alone or in mixtures.
  • Agents of this type are particularly suitable for removing grease stains and stains from felt-tip and ballpoint pens.
  • Cleaning agents in gel form consist of a mixture of very finely divided adsorbent such as silica or starch and organic solvents, especially gasoline and chlorinated hydrocarbons. These agents are also particularly suitable for grease and ballpoint stains.
  • Glycol ethers are preferably used as the sole organic solvent or as the main constituent of a mixture of organic solvents. These materials are lower (alkoxy) - or lower (alkoxy) lower (alkoxy) ether of ethanol or isopropanol. Some glycol ethers are available under the trade names Arcosolv ® (Arco Chemical Co.) or Qellosolve ® , Carbitol ® or Propasol ® (Union Carbide Corp.); these also include, for example, ButylCarbitol ® , HexylCarbitol ® , MethylCarbitol ® , and Carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • glycol ether can easily be made by the person skilled in the art on the basis of its volatility, water solubility, its weight percentage in the total dispersion and the like.
  • Pyrrolidone solvents such as N-alkylpyrrolidone, for example N-methyl-2-pyrrolidone or NC 8 -C 12 -alkylpyrrolidone, or 2-pyrrolidone can also be used.
  • glycerol derivatives in particular glycerol carbonate.
  • the alcohols which can be used as a cosolvent in the present invention include liquid polyethylene glycols with a low molecular weight, for example polyethylene glycols with a molecular weight of 200, 300, 400 or 600.
  • suitable cosolvents are other alcohols, for example (a) lower Alcohols such as ethanol, propanol, isopropanol and n-butanol, (b) ketones such as acetone and methyl ethyl ketone, (c) C 2 -C 4 polyols such as a diol or a triol, for example ethylene glycol, propylene glycol, glycerol or mixtures from that. From the class of diols, 1,2-octanediol is particularly preferred.
  • organic solvents which are suitable in principle are conventional chlorinated solvents, as are usually known from commercial chemical cleaning. These include the di- to tetrachlorinated derivatives of methane, the di- to pentachlorinated derivatives of ethane, the mono- to trichlorinated derivatives of cyclohexane and monochlorobenzene.
  • chlorinated hydrocarbons are less preferred for household use.
  • Organic solvents which are suitable for causing the agents to have two phases are, for example, hydrocarbons and alkyl ethers.
  • Particularly preferred hydrocarbons are those which have a boiling point above 150 ° C. and preferably above 180 ° C.
  • Particularly preferred multi-phase and in particular two-phase liquid and sprayable textile cleaning agents contain paraffins or isoparaffins with a boiling range between 200 and 300 ° C. In particular Isoparaffins are suitable as the only organic in the multi-phase cleaning agents
  • Solvents can be used, but it can be an advantage if the agents not only have hydrocarbons as organic solvents, but also one of the above-mentioned water-miscible organic solvents.
  • alkyl ethers are dialkyl ethers, especially C 6 -C 18 alkyl ethers, with particular preference for C 8 -C 12 alkyl ethers, for example dioctyl ether.
  • BPP butoxypropoxypropanols
  • emulsifiers For examples of possible emulsifiers, reference is made in full to the disclosure of WO 96/30580.
  • Water-based cleaning agents preferably contain tensides in amounts of about 0.4 to about 10 percent by weight, and in addition mostly additions of solvents which are readily soluble in water, such as lower alcohols, additions of salts, such as phosphates and borax, and other cleaning agents.
  • solvents which are readily soluble in water
  • salts such as phosphates and borax
  • Such means are not only offered for individual types of stains, but are often advertised as universal means. They can be used directly as a liquid or, because of the easier spreadability, can be applied as a foam.
  • Stain-removing agents suitable according to the invention contain at least one organic liquid, selected from the group comprising gasoline, benzine, aromatics, trichloroethane, trichlorethylene, methylene chloride.
  • a stain removal agent can contain at least one organic liquid and at least one surfactant, in particular nonionic surfactant.
  • a stain removing agent preferred according to the invention has the following composition:
  • Anionic and nonionic surfactants are particularly suitable as surfactants for this agent.
  • Alkyl sulfates, alkyl sarcosides and alkyl sulfosuccinates with long-chain alkyl radicals which contain 8 to 18 carbon atoms are used as anionic surfactants.
  • alkanesulfonates with 12 to 18 carbon atoms monoalkyl polyethylene glycol ether sulfates with 10 to 20 carbon atoms in the alkyl part and 1 to 6 ethylene glycol units in the molecule, and also soaps, salts of fatty acid cyanamides or salts of long-chain ether carboxylic acids.
  • the anionic surfactants are preferably used in the form of the sodium salts.
  • Sodium alkyl sulfates, sodium alkyl sarcosides and sodium alkyl sulfosuccinates, of which in turn sodium alkyl sulfates with chain lengths of 12 to 16 carbon atoms, in particular technical sodium lauryl sulfate, can also be used as anionic surfactants.
  • the addition products of 1 to 30, preferably 4 to 15, moles of ethylene oxide and 1 mole of a long-chain compound having 10 to 20 carbon atoms from the group of alcohols, alkylphenols, carboxylic acids and carboxamides are suitable as nonionic surfactants.
  • the addition products of ethylene oxide with long-chain, primary or secondary alcohols, such as fatty alcohols or oxo alcohols with 10 to 20 C atoms and with mono- or dialkylphenols with 6 to 14 C atoms in the alkyl groups, are preferred.
  • the stain-removing effect of the surfactants can be significantly improved by adding certain water-soluble polymers.
  • These polymers which are added in small amounts up to about 0.1% by weight, are preferably the following types of compounds: polyethylene oxides with molecular weights between 200,000 and 5,000,000, nonionic cellulose ethers, such as methyl cellulose and hydroxyethyl cellulose, Polyvinyl alcohol, polyacrylamide and homopolymers of acrylic acid, methacrylic acid and maleic acid and copolymers of these compounds with suitable comonomers.
  • the amount of polymer used depends on the chemical composition of the polymer and can range up to a lower limit of about 0.001% by weight, based on the total agent.
  • the polyethylene oxides mentioned are preferably used in amounts between 0.001 and 0.01% by weight; the other polymers preferably in amounts between 0.01 and 0.05% by weight, based on the total agent.
  • the agents can contain up to 30% by weight of organic solvents to enhance the cleaning action, in particular grease stains and stains from Ballpoint or felt pens included.
  • organic solvents to enhance the cleaning action, in particular grease stains and stains from Ballpoint or felt pens included.
  • Both water-immiscible and water-miscible and limited water-soluble solvents are suitable, for example alcohols with 3 to 5 C atoms, acetone, glycol ethers with up to 10 C atoms and gasolines with boiling ranges from 100 to 280 ° C as well as terpenes in smaller quantities.
  • Alcohols with 2 and 3 carbon atoms and glycol ethers with 4 to 7 carbon atoms in particular ethanol, isopropanol, dipropylene glycol monomethyl ether and propylene glycol monoisobutyl ether, are particularly preferred.
  • the total solvent content is preferably between 5 and 25% by weight, based on the total agent.
  • the stain-removing agents can furthermore contain customary additives, such as salts, preservatives, perfume, thickeners and insoluble polymers with minimal film-forming temperatures above 70 ° C., for example polymethyl methacrylate.
  • customary additives such as salts, preservatives, perfume, thickeners and insoluble polymers with minimal film-forming temperatures above 70 ° C., for example polymethyl methacrylate.
  • the amount of these substances is usually not more than 5% by weight, preferably between 0.01 and 2% by weight.
  • anionic surfactant from the group of sodium alkyl sulfates, sodium alkyl sarcosides and sodium alkyl sulfosuccinates and mixtures thereof,
  • water-soluble polymer from the group of polyethylene oxides with molecular weights between 200,000 and 5,000,000, non-ionic cellulose ethers, polyvinyl alcohol, polyacrylamide, homo- and copolymers of acrylic acid, methacrylic acid and maleic acid, and mixtures thereof,
  • organic solvent from the group consisting of alcohols with 2 to 3 carbon atoms, glycol ethers with 4 to 7 carbon atoms and mixtures thereof,
  • additives from the group consisting of salts, preservatives, perfume, thickeners and insoluble polymers and
  • anionic or nonionic surfactant 0.05 to 10% by weight of anionic or nonionic surfactant
  • anionic surfactant from the group sodium alkyl sulfates, sodium alkyl sarcosides, sodium alkyl sulfosuccinates and mixtures thereof,
  • water-soluble polymer from the group consisting of polyethylene oxides with molecular weights between 200,000 and 5,000,000, nonionic cellulose ethers, polyvinyl alcohol, polyacrylamide, homo- and copolymers of acrylic acid, methacrylic acid and maleic acid, and mixtures thereof,
  • nonionic surfactants 0.05-10% by weight nonionic surfactants
  • White spirit * 1 paraffin cuts as used in the Sil white spirit spray products from Henkel KGaA. Paraffin mixtures of: a C12 / 14 iso cut (smells strongly gasoline) ISOPAR M, available from Exxon, and a C16-20 iso cut (little headspace) COBERSOL VP 1, available from the Cologne refinery.
  • Carragenan powder (Genu CSW-2 from Hercules), in a proportion of 0.25% by weight, based on the total agent.
  • the present invention further relates to a cleaning system comprising: at least one single-dose plastic container containing a cleaning agent, at least one absorbent and / or adsorbent, suitable for taking up cleaning agents from the soft or hard surface to be cleaned, preferably selected from the group comprising a cloth or a sponge, the absorption and / or adsorbent preferably being dry.
  • a means for mechanical processing of the dirt selected from the group comprising a cloth, a brush or a sponge, the means for mechanical processing optionally being moistened.
  • Another object of the present invention relates to a method for removing dirt, in particular stains, from hard or soft surfaces, characterized by the steps:
  • Separate or several connected single-dose plastic containers can be produced by means of injection molding, deep-drawing or blow molding, the respective single-dose plastic container being sealed with a sufficient amount of liquid, foam-like or gel-like cleaning agent for a single application for the direct removal of dirt at room temperature filled hard and / or soft surfaces, and taking the respective single-dose plastic container
  • the melt flow index of the blow molding material at 10 kg can be between 0.5 and 60, preferably between 5 and 30, particularly preferably between 10 and 20.
  • the single-dose plastic container is preferably formed in one piece.
  • a preform can be produced in a first step by means of extrusion, and in a second step the hollow body of the single-dose plastic container is blown in a cycle, preferably by means of a gas under pressure, preferably compressed air, preferably to the final one Hollow body geometry, and with the sufficient amount of liquid, foam or gel-like cleaning agent for a single application for direct removal Removal of dirt at room temperature from hard or soft surfaces, sealed liquid-tight and then demolded.
  • a gas under pressure preferably compressed air
  • single-dose plastic containers with at least one web (s) can be designed to form a one-piece block, see FIG. 2, the respective plastic container in a simple manner with the thumb and fingers from the block from single dose - Plastic containers can be twisted off or torn off.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Abstract

Un premier aspect de l'invention concerne un emballage unidose en plastique contenant un produit nettoyant, sous forme liquide, sous forme de mousse ou sous forme de gel, servant à enlever directement des salissures à température ambiante sur des surfaces dures ou souples, cet emballage unidose en plastique pouvant contenir jusqu'à 5,0 ml de produit nettoyant. Un deuxième aspect de l'invention concerne un système de nettoyage comprenant au moins un emballage unidose en plastique contenant un produit nettoyant, au moins un moyen d'absorption et/ou d'adsorption conçu pour absorber et/ou adsorber le produit nettoyant appliqué sur la surface dure ou souple à nettoyer, ce moyen d'absorption et/ou d'adsorption étant de préférence sec, ainsi qu'éventuellement un moyen pour traiter mécaniquement la salissure.
PCT/EP2003/013811 2002-12-17 2003-12-06 Emballage unidose en plastique contenant un produit nettoyant servant a enlever directement des salissures WO2004055143A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003293781A AU2003293781A1 (en) 2002-12-17 2003-12-06 Single-dose plastic container provided with cleaning agent for directly removing dirt

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002159263 DE10259263A1 (de) 2002-12-17 2002-12-17 Eindosis-Kunststoffbehältnis mit Reinigungsmittel zur direkten Entfernung von Verschmutzungen
DE10259263.2 2002-12-17

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WO2004055143A2 true WO2004055143A2 (fr) 2004-07-01
WO2004055143A3 WO2004055143A3 (fr) 2004-11-11

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AU (1) AU2003293781A1 (fr)
DE (1) DE10259263A1 (fr)
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2016200775A1 (fr) 2015-06-11 2016-12-15 Tokitae Llc Récipients d'emballage multi-monodose
WO2016200771A1 (fr) 2015-06-11 2016-12-15 Tokitae Llc Récipients multi-monodoses
US11607369B2 (en) 2017-11-17 2023-03-21 Koska Family Limited Systems and methods for fluid delivery manifolds
USD992110S1 (en) 2021-08-10 2023-07-11 Koska Family Limited Sealed fluid container

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MX2007006781A (es) * 2004-12-07 2008-01-24 Graham Packaging Co Recipientes para servir sencillos de multiple embalaje.

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DE2430146A1 (de) * 1974-06-24 1976-01-15 Chemiro Ag Vorrichtung zur portionsweisen aufnahme eines vorzugsweise pastoesen fleckenentfernungsmittels
CH642928A5 (en) * 1978-11-21 1984-05-15 Richardson Gmbh Multipack and use thereof
US4671763A (en) * 1983-06-29 1987-06-09 Automatic Liquid Packaging, Inc. Container with a unitary but removable closure and method and apparatus therefor

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016200775A1 (fr) 2015-06-11 2016-12-15 Tokitae Llc Récipients d'emballage multi-monodose
WO2016200771A1 (fr) 2015-06-11 2016-12-15 Tokitae Llc Récipients multi-monodoses
CN107920953A (zh) * 2015-06-11 2018-04-17 脱其泰有限责任公司 多单剂量容器
EP3307626A4 (fr) * 2015-06-11 2018-12-12 Tokitae LLC Récipients d'emballage multi-monodose
EP3307226A4 (fr) * 2015-06-11 2019-04-17 Tokitae LLC Récipients multi-monodoses
US11607369B2 (en) 2017-11-17 2023-03-21 Koska Family Limited Systems and methods for fluid delivery manifolds
USD992110S1 (en) 2021-08-10 2023-07-11 Koska Family Limited Sealed fluid container

Also Published As

Publication number Publication date
AU2003293781A1 (en) 2004-07-09
AU2003293781A8 (en) 2004-07-09
DE10259263A1 (de) 2004-07-08
WO2004055143A3 (fr) 2004-11-11

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