EP0090311B1 - Agent for the care of textiles - Google Patents

Agent for the care of textiles Download PDF

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Publication number
EP0090311B1
EP0090311B1 EP83102772A EP83102772A EP0090311B1 EP 0090311 B1 EP0090311 B1 EP 0090311B1 EP 83102772 A EP83102772 A EP 83102772A EP 83102772 A EP83102772 A EP 83102772A EP 0090311 B1 EP0090311 B1 EP 0090311B1
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EP
European Patent Office
Prior art keywords
water
article
agents
container
fabric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83102772A
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German (de)
French (fr)
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EP0090311A1 (en
Inventor
Edgar Dr. Köppelmann
Werner Künzel
Klaus Dr. Schumann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT83102772T priority Critical patent/ATE20363T1/en
Publication of EP0090311A1 publication Critical patent/EP0090311A1/en
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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
    • 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
    • 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
    • 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
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/005—Compositions containing perfumes; Compositions containing deodorants
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process

Definitions

  • the invention relates to an object and a method for textile care during washing in household washing machines.
  • soiled textiles more advantageous usage properties, for example a softer feel, pleasant smell, antistatic properties, easy ironing, antimicrobial protection, in addition to washing by additional care measures.
  • liquid agents are often added to the last rinsing bath after the washing process.
  • these agents which mainly contain fabric softening and antistatic agents and fragrances, not only have to be evenly distributed in the cold washing liquor, but also have to be absorbed from the cold liquor onto the textiles in a short time.
  • containers or containers filled with textile care active ingredients or more or less absorbent rigid or flexible carrier materials impregnated with active ingredients are used, which are circulated together with the washed textiles in the tumble dryer during the drying process and thereby transfer active ingredients to the textiles.
  • the disadvantage here is that the transfer is often uneven and a sometimes not insignificant part of the active ingredients remains in the container or on the carrier material.
  • DE-OS 27 02 162 describes particulate textile conditioning agents made from a quaternary ammonium salt and hydrogenated castor oil, which are "smeared" onto the textiles in detergent-containing washing liquors and later evenly distributed and fixed in the tumble dryer.
  • DE-OS 27 49 555 describes an object which consists of two containers arranged one inside the other, an outer container made of a water-soluble or dispersible material and an inner container which consists at least in part of a water-soluble or dispersible material .
  • the inner container contains an effective amount of a textile conditioning agent and is located in the outer container together with an electrolyte and / or a pH regulator which render the inner container insoluble or undispersible in the wash liquor.
  • This complicated structure is put into the washing machine together with the textiles. removed after washing and rinsing or only after drying.
  • FR-A-1 328 999 relates to bags filled with soaking or detergent active substances, which consist of a material that dissolves in water at certain temperatures, as a result of which the active substances are released into the water. For active substances that are to be released at different temperatures, several bags made of different bag materials are selected according to the teaching of the French patent specification, which dissolve at the corresponding temperatures.
  • the invention is therefore based on the object of reducing or eliminating the disadvantages of the known laundry care products.
  • this object is achieved by a container which maintains textiles and consists of a closed container which contains textile-care agents and optionally fragrances for use during the washing process.
  • the object is characterized in that the container consists of a pillow-shaped structure made of two identical shaped, congruent superimposed and connected at the edges interconnected flexible parts or a sachet, of which in the case of the sachet the whole wall of the sachet or in the case of the pillow-shaped structure a part or both parts represent a waterproof, water-permeable sheet and optionally the second part a waterproof, water-impermeable sheet and the outer or the inner surface of one or the two water-permeable parts with a water-impermeable coating from a detachable at elevated temperature of the wash liquor and thereby the im Containing active ingredients and possibly fragrances are coated for transfer to the textiles-releasing material.
  • the container does not already contain its contents the still cold washing liquor, but only towards the end of the washing process when the temperature of the washing liquor has reached its highest value.
  • the textile care agents meet textiles that have already been largely freed of dirt and can deposit on them without any noticeable impairment by the surfactants, while on the other hand no deterioration in the washing result is observed due to the presence of textile care agents in the wash liquor.
  • This procedure also makes it possible to use active ingredients which care for textiles, the use of which in cold washing liquors or in the tumble dryer is not possible or is not economical.
  • the object according to the invention consists entirely or partially of a waterproof, water-permeable container in which the active ingredients and optionally fragrances are included.
  • a waterproof, water-permeable container in which the active ingredients and optionally fragrances are included.
  • at least the water-permeable part of the bag-like container possibly also the entire container on the inside and / or the outside, but preferably only on the outside, is provided with a coating which makes the water-permeable container material in the cold wash liquor impermeable makes. Only when an elevated washing liquor temperature is reached towards the end of the washing process does the coating gradually detach from the container material, which is water-permeable per se, and releases the contents, so that it can come into contact with the textiles which have already been largely or completely freed from dirt.
  • the temperature at which the coating peels depends on the type of coating material and can be adjusted to the desired wash liquor temperature, which is between about 30 to a maximum of about 100 ° C., by selecting the melting point of the coating material.
  • Nonwoven or non-woven material for example woven or knitted fabrics made of natural and / or synthetic fibers, e.g. made of cellulose, wool, silk, linen, jute, sisal, polyamide, polyester, polyacrylonitrile, polyvinyl derivatives, polyolefins, rayon.
  • Foams or sponges made of viscose or synthetic polymers, in particular polyurethane, are also suitable.
  • Suitable film materials are, for example, polyolefin, polyvinyl derivatives, polyester, polyamide, cellulose esters.
  • Open-cell foams with a thickness of 0.5 mm to 3 mm are preferably used.
  • the density of suitable foams is preferably in the range from 0.01 to 0.04 g per cm 3.
  • Particularly preferred are 0.05 mm to 2 mm thick nonwovens, in particular made of polyester and / or cellulose, the nonwovens having a basis weight between 10 and 100 g per m 2 .
  • Suitable water-impermeable, waterproof materials are flexible films made of, for example, polyolefin, polyvinyl derivatives, polyester, polyamide, cellulose esters or similar polymers. They have a thickness of 0.03 mm to 0.15 mm, preferably 0.05 to 0.08 mm.
  • flexible metal foils and composite foils for example made of metal and organic polymers, can also be used.
  • Polyolefin films are particularly preferred as the water-impermeable film material.
  • the container or the container generally has the shape of a pillow; however, it can also have the shape of a small bag. In the latter case, the wall material is expediently completely permeable to water.
  • the container consists of two superimposed flat structures, one or both of which consist of a water-permeable material. They have a size of preferably about 30 cm 2 to 400 cm 2 . They are bonded together at the edges. Suitable connection techniques are all those that lead to a waterproof connection and do not come loose due to the action of mechanical forces during the washing process. Examples of suitable joining techniques are gluing, embossing, welding, sewing, of which welding and sewing are preferred. If the container has the shape of a bag, sewing, pinching with clips or tying are also included Twine possible types of closures.
  • the container is filled with the active ingredients and, if appropriate, fragrances, it being possible for the fragrances to be bound to an absorbent carrier material which is introduced into the container after impregnation or other impregnation with the fragrance.
  • Suitable backing materials are absorbent nonwovens, paper, foams, sponges or textiles of the appropriate size.
  • the container in the preferred pillow form is expediently made by first making the water-permeable material water-impermeable, drying or solidifying, for example by knife coating, dipping or spraying with the coating material liquefied by melting or dissolving, the material optionally together with the water-impermeable material in cuts or punches suitable pieces and closes them on all sides after application or introduction of the active ingredients and, if appropriate, fragrances, so that the pillow consists either of one or of two water-impermeable, water-permeable layers.
  • Another way of producing the agent according to the invention is that the container is first made from uncoated material and, after filling and sealing, is coated with the coating, for example by dipping. In this case the cover is only or predominantly on the outside.
  • the coating there is no harm in applying the coating by thoroughly soaking the material with the coating compound. If you apply the cover before closing, you can also apply the cover to the inside of the container material. It is advisable not to use more coating material than is necessary to make the pouch impervious. If the application of coating material is too large, this can lead to a delayed or incomplete release of the active ingredients.
  • the cheapest order quantity also depends on the type of coating material, the container material and the application technique. A suitable order quantity can easily be determined by tests.
  • the type of water-impermeable coating material depends on the wash liquor temperature at which the coating material is to separate from the water-permeable container wall.
  • the melting point of the coating material must be similar to the wash liquor temperature at which the active ingredient and fragrance are to be released. Materials which are insoluble in cold water and therefore have a melting point in the range of the washing temperatures, ie about 30 ° C. to about 100 ° C., are suitable.
  • Paraffinic hydrocarbons, saturated and unsaturated fatty alcohols and fatty acids, a-o-alkanediols, fatty acid esters, amides of unsaturated fatty acids and the mixtures of the substances mentioned have proven themselves. Paraffin hydrocarbons, fatty alcohols, fatty acid amides and mixtures thereof with a melting point between about 30 ° C. and 100 ° C. are particularly suitable and therefore preferred.
  • the main active substances are textile softeners and textile antistatic agents.
  • soil release substances, textile stiffeners, ironing aids, antimicrobials and to a lesser extent impregnating agents, flame retardants and moth protection agents are suitable active ingredients. They are used individually or in a mixture.
  • the quaternary ammonium compounds with preferably two long-chain, preferably saturated aliphatic radicals each having 14-26, preferably 16-20, carbon atoms and at least one quaternary nitrogen atom in the molecule are suitable as fabric softening agents.
  • the long-chain aliphatic radicals can be straight-chain or branched and can accordingly be derived from fatty acids, or from fatty amines, Guerbetamines, or from the alkylamines obtainable by reduction of nitroparaffins.
  • quaternary ammonium compounds are, in particular, derivatives of ammonia, that is to say the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for example, the compounds distearyldimethylammonium chloride or ditalgalkyldimethylammonium chloride, or those by reacting 1 mol of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 Mol of a long-chain C 12 -C 26 fatty acid or its ester obtainable imidazoline compounds which are subsequently converted into the quaternary imidazolinium compounds by alkylation.
  • long-chain secondary amines such as, for example, the compounds distearyldimethylammonium chloride or ditalgalkyldimethylammonium chloride, or those by reacting 1 mol of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 Mol of a long-chain C 12 -C 26 fatty acid or its
  • the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization.
  • the alkylating agent used in the quaternization For example, chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are suitable as anions.
  • the condensation products of 1-3 moles of fatty acid or fatty acid alkyl ester or 1/3-1 mole of fatty acid triglyceride with one mole of a hydroxyalkyl polyamine for example, also come as textile plasticizers Hydroxyethylethylenediamine or hydroxyethyldiethylenetriamine.
  • a textile softener is preferably a combination of a quaternary ammonium compound of the ammonia type with two C 16 -C 20 alkyl or alkenyl groups and 2 methyl groups in the molecule, and with the chloride, bromide or methyl sulfate anion, in particular ditallow alkyl dimethyl ammonium chloride, together with the fatty acid condensation product from 1 mol of hardened tallow and 1 mol of hydroxyethylethylenediamine in a ratio of 4: 1 to 1: 4.
  • textile care active ingredients with a higher melting point which can therefore be used with advantage in the agents according to the invention, are the quaternary ammonium compounds with 2 or in particular 3 long, hydroxyl and ether group-containing long residues, such as those obtained by reacting epoxyalkanes with tertiary polyalkanolamines and subsequent quaternization. Such compounds are described in DE-OS 28 44 451.
  • the antistatic agents are generally the same or similar types of compounds as the fabric softeners.
  • the quaternary ammonium compounds with one long-chain and three short-chain aliphatic radicals are also suitable as textile antistatic agents.
  • Other suitable antistatic agents are, for example, the reaction products of one mole of an aliphatic C 6 -C 20 alcohol and more than 20 moles, preferably 35-50 moles, of ethylene oxide.
  • the suitable antimicrobial agents that is to say bactericidal or bacteriostatic or fungicidal or fungistatic compounds, are usually also quaternary ammonium compounds, in particular those which, in addition to a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals, have an aromatic, via an aliphatic carbon atom with the nitrogen atom linked, or contain an aliphatic, double bonds organic radical in the molecule.
  • Typical representatives for such antimicrobial agents are the compounds dimethylbenzyldodecylammonium chloride, or dibutyl-allyl, and ethylcyclohexyl-allyl-dodecylammonium chloride.
  • Antimicrobial agents which can also be used are the bromo-nitro alcohols, for example the compounds 2-bromo-2-nitropropane-1,3-diol, 1-bromo-1-nitro-3,3-trichloro-2-propanol, 2-bromo-2- nitrobutanul.
  • Halogenated and / or trifluoromethyl-substituted phenolic compounds in particular the halogenated salicylanilides, for example the compounds dibromo and tribromosalicyl anilide, and derivatives of p-phenoxyphenol such as the compound 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether are also suitable as antimicrobial active substances .
  • Compounds which improve the dirt-removing ability during washing are suitable as active ingredients for soil release finishing for textiles. These include compounds of the polyacrylic polyvinyl alcohol type, modified fluorocarbons and hydrophilic polymers. Polyvinyl acetates but also borax are suitable additives that make ironing the laundry easier.
  • the agents according to the invention suitable for a household washing machine generally contain 0.5 to 10, preferably 3 to 8 g of active ingredient. Depending on the size of the washing machine, the agents can also contain more or less active ingredient. It is important that about 0.1 to 0.8 g of active ingredient is contained per liter of washing liquor.
  • the active substances can be present in the agent according to the invention in pure form or as a paste.
  • the paste consists of a mixture of the active ingredients with water, where appropriate dispersants and / or water-soluble organic solvents may also be present.
  • the paste has an active ingredient content of up to about 90 percent by weight, but preferably 10 to 80 percent by weight and in particular 15 to 50 percent by weight. Because of the delayed dispersion of non-paste-like active substances in the wash liquor, active substances in this form are preferred in the context of the present invention.
  • the agent according to the invention preferably contains the active ingredients in combination with fragrances.
  • the fragrance can be used in pure form, as an alcoholic solution or as an aqueous emulsion.
  • the fragrance is preferably used as an emulsion, that is to say as a mixture of perfume oil, water and an emulsifier. Suitable as fragrances are all types of perfume which give the desired fragrance notes and which are stable under the conditions of use.
  • Suitable perfume oil emulsifiers are hydrophilic surface-active substances, such as hydrogenated castor oil with 40 moles of ethylene oxide or alkenyl succinic acid salts or their half esters.
  • the invention further relates to a method for treating textiles during washing with active ingredients which care for the use of textiles and are used only after a delay, by adding a container containing the active ingredients at the beginning of the washing process to the still cold washing liquor, which is then heated.
  • the method is characterized in that the Active ingredient and possibly fragrance-containing container for active ingredient delivery is set to a predetermined washing temperature such that the coating of water-impermeable material detaches from the water-permeable sheet material at the end of the washing process at an elevated washing liquor temperature, so that the contents of the bag are released and thereby transferred to the textiles.
  • a container or bag is made of at least partially water-permeable material, which, as described above, is coated with a water-impermeable coating which has a melting point between 30 and 100 ° C. and which detaches at the washing temperature, at the beginning the washing cycle of a household washing machine into the still cold washing liquor for the textiles to be cleaned.
  • the washing liquor is then heated to the desired washing temperature.
  • the cover detaches from the bag, the contents of the bag pass through the wall of the bag, which has become water-permeable again, and exert its textile care effect.
  • the washing liquor containing the dirt and the detergent constituents is then separated from the textiles and the textiles are dried, which have an increased utility value due to the contact with the textile care active ingredients.
  • the water-insolubilizing coating is selected for carrying out the process according to the invention in such a way that it only detaches from the bag at the washing temperature, that is to say at temperatures which are between about 30 and about 100 ° C., depending on the fabric and washing process. If you wash the textiles in a two- or multi-lye process, it is advisable to add the bag only to the last wash before the rinses.
  • the amount of the active ingredient to be reacted, in particular the fabric softener, in the bag depends on the effectiveness of the active ingredient and on the strength of the desired effect. In general, about 0.1 to 1.5 g of fabric care active ingredient are used per liter of washing liquor; Particularly good results are achieved with the use of 0.2 to 0.8 g of active ingredient, in particular textile softener per liter.
  • the coating composition consisting of hard waxes with a melting point of 82-84 ° C. or 84-88 ° C., similar softness and washing results were obtained as in the case of 60 ° C experiments carried out.

Abstract

1. A fabric-care article consisting of a sealed container containing fabric-care agents and optionally perfumes for use during the washing process, characterized in that the container consists of a sachet-like structure of two identically shaped flexible parts lying exactly on top of one another and joined to one another at their edges or of a pouch of which the entire wall in the case of the pouch or one or both parts in the case of the sachet-like structure represent(s) a water-resistant, water-permeable sheet-form structure and optionally the second part a water-resistant, non-water-permeable sheet-form structure, the outer or the inner surface of one or both water-permeable parts being provided with a waterproofing coating of a material which dissolves at a high temperature of the wash liquor and, in doing so, releases the active agents and.

Description

Die Erfindung betrifft einen Gegenstand und ein Verfahren zur Textilpflege während des Waschens in Haushaltwaschmaschinen.The invention relates to an object and a method for textile care during washing in household washing machines.

In vielen Fällen ist es wünschenswert, verschmutzten Textilien außer durch Waschen durch zusätzliche pflegende Maßnahmen vorteilhaftere Gebrauchseigenschaften, zum Beispiel einen weicheren Griff, angenehmen Geruch, antistatische Eigenschaften, leichte Bügelbarkeit, antimikrobiellen Schutz zu verleihen. Hierzu werden im Anschluß an den Waschprozeß häufig dem letzten Spülbad flüssige Mittel zugesetzt. Um für diese Nachbehandlungsmethode geeignet zu sein, müssen sich diese Mittel, die hauptsächlich textilweich- und antistatischmachende Wirkstoffe und Duftstoffe enthalten, nicht nur in der kalten Spülflotte gleichmäßig verteilen, sondern sie müssen auch in kurzer Zeit aus der kalten Flotte auf die Textilien aufziehen.In many cases, it is desirable to give soiled textiles more advantageous usage properties, for example a softer feel, pleasant smell, antistatic properties, easy ironing, antimicrobial protection, in addition to washing by additional care measures. For this purpose, liquid agents are often added to the last rinsing bath after the washing process. In order to be suitable for this aftertreatment method, these agents, which mainly contain fabric softening and antistatic agents and fragrances, not only have to be evenly distributed in the cold washing liquor, but also have to be absorbed from the cold liquor onto the textiles in a short time.

Mit dem Einsatz von Geräten zum Wäschetrocknen, die in gewerblichen Wäschereien und in Privathaushalten ständig zunehmen, ergeben sich Möglichkeiten, den Prozeß der Wäschepflege in den Wäschetrockner zu verlegen und gleichzeitig mit dem Trocknen der Wäsche vorzunehmen. Man verwendet zu diesem Zweck mit textilpflegenden Wirkstoffen gefüllte Behältnisse bzw Behälter oder mit Wirkstoffen imprägnierte, mehr oder weniger saugfähige starre oder flexible Trägermaterialien, die zusammen mit den gewaschenen Textilien im Wäschetrockner während des Trocknungsvorgangs umgewälzt werden und dabei Wirkstoffe auf die Textilien übertragen. Nachteilig ist hierbei, daß die Übertragung oft ungleichmäßig erfolgt und stets ein manchmal nicht unerheblicher Teil der Wirkstoffe in dem Behälter oder auf dem Trägermaterial verbleibt.With the use of devices for drying clothes, which are constantly increasing in commercial laundries and in private households, there are possibilities for moving the laundry care process into the tumble dryer and simultaneously carrying out the drying of the laundry. For this purpose, containers or containers filled with textile care active ingredients or more or less absorbent rigid or flexible carrier materials impregnated with active ingredients are used, which are circulated together with the washed textiles in the tumble dryer during the drying process and thereby transfer active ingredients to the textiles. The disadvantage here is that the transfer is often uneven and a sometimes not insignificant part of the active ingredients remains in the container or on the carrier material.

Man hat daher auch schon vorgeschlagen, die textilpflegenden Wirkstoffe während des Waschganges von automatischen Haushaltswaschmaschinen mit den Textilien in Kontakt zu bringen. Dabei besteht aber die Schwierigkeit, daß die Waschmittel-Tenside und die textilpflegenden Wirkstoffe sich in ihrer Wirkung gegenseitig beeinträchtigen. Zur Beseitigung dieses Nachteils werden in der DE-OS 27 02 162 teilchenförmige Textilkonditionierungsmittel aus einem quartären Ammoniumsalz und hydriertem Rizinusöl beschrieben, die in tensidhaltigen Waschflotten auf die Textilien "aufgeschmiert" und später im Wäschetrockner gleichmäßig verteilt und fixiert werden. In der DE-OS 27 49 555 ist ein Gegenstand beschrieben, der aus zwei ineinander angeordneten Behältern besteht, einem äußeren Behälter aus einem in Wasser löslichen oder dispergierbaren Material und einem inneren Behälter, der wenigstens zum Teil aus einem in Wasser löslichen oder dispergierbaren Material besteht. Der innere Behälter enthält eine wirksame Menge eines Textilkonditioniermittels und befindet sich zusammen mit einem Elektrolyten und/oder einem Mittel zur Regulierung des pH-Wertes, die den inneren Behälter in der Waschflotte unlöslich beziehungsweise undispergierbar machen, in dem äußeren Behälter. Dieser kompliziert aufgebaute Gegenstand wird zusammen mit den Textilien in die Waschmaschine gegeben und . nach dem Waschen und Spülen beziehungsweise erst nach dem Trocknen entfernt. Die FR-A- 1 328 999 betrifft mit Einweich- bzw. mit Waschmittelwirkstoffen gefüllte Beutel, die aus einem bei bestimmten Temperaturen sich in Wasser auflösendem Material bestehen, wodurch die Wirkstoffe in das Wasser abgegeben werden. Für Wirkstoffe, die bei unterschiedlichen Temperaturen abgegeben werden sollen, wählt man nach der Lehre der französischen Patentschrift mehrere Beutel aus verschiedenen beutelmaterialien, die sich bei den entsprechenden Temperaturen auflösen. Die bisher bekannten Lösungen sind alle unbefriedigend, weil entweder die Wirkstoffe nur zum Teil ausgenutzt werden oder weil die Auswahl der Wirkstoffe durch das Erfordernis der Löslichkeit beziehungsweise Dispergierbarkeit in kaltem Wasser und Aufziehvermögen auf die Textilien aus kaltem Spülwasser beschränkt ist, oder weil der Aufbau und die Herstellung der beschriebenen Gegenstände aufwendig und kompliziert ist, oder weil das Waschergebnis durch die Anwesenheit textilpflegender Wirkstoffe in der Waschflotte verschlechtert wird.It has therefore already been proposed to bring the textile care active ingredients into contact with the textiles during the washing cycle of automatic household washing machines. However, there is the difficulty that the detergent surfactants and the textile care active ingredients affect each other in their effect. To eliminate this disadvantage, DE-OS 27 02 162 describes particulate textile conditioning agents made from a quaternary ammonium salt and hydrogenated castor oil, which are "smeared" onto the textiles in detergent-containing washing liquors and later evenly distributed and fixed in the tumble dryer. DE-OS 27 49 555 describes an object which consists of two containers arranged one inside the other, an outer container made of a water-soluble or dispersible material and an inner container which consists at least in part of a water-soluble or dispersible material . The inner container contains an effective amount of a textile conditioning agent and is located in the outer container together with an electrolyte and / or a pH regulator which render the inner container insoluble or undispersible in the wash liquor. This complicated structure is put into the washing machine together with the textiles. removed after washing and rinsing or only after drying. FR-A-1 328 999 relates to bags filled with soaking or detergent active substances, which consist of a material that dissolves in water at certain temperatures, as a result of which the active substances are released into the water. For active substances that are to be released at different temperatures, several bags made of different bag materials are selected according to the teaching of the French patent specification, which dissolve at the corresponding temperatures. The previously known solutions are all unsatisfactory either because the active ingredients are only partially used or because the selection of the active ingredients is limited to the textiles from cold rinsing water due to the requirement of solubility or dispersibility in cold water and absorbency, or because the structure and the Manufacture of the items described is complex and complicated, or because the washing result is deteriorated by the presence of fabric care ingredients in the wash liquor.

Der Erfindung liegt daher die Aufgabe zugrunde, die geschilderten Nachteile der bekannten Wäschepflegemittel zu verringern oder zu beseitigen.The invention is therefore based on the object of reducing or eliminating the disadvantages of the known laundry care products.

Diese Aufgabe wird erfindungsgemäß durch ein en Textilien pflegenden bestehend aus einem geschlossenen, Textilienpflegende Wirkstoffe und gegebenenfalls Duftstoffe enthaltenden Behältnis zur Anwendung während des Waschvorgangs gelöst. Der Gegenstand ist dadurch gekennzeichnet, daß das Behältnis aus einem kissenförmigen Gebilde aus zwei gleichgeformten, deckungsgleich aufeinanderliegenden und an den Rändern miteinander verbundenen flexiblen Teilen oder aus einem Säckchen besteht, wovon im Fall des Säckchens die ganze Säckchenwand oder im Fall des kissenförmigen Gebildes ein Teil oder beide Teile ein wasserfestes, wasserdurchlässiges Flächengebilde und gegebenenfalls der zweite Teil ein wasserfestes, wasserundurchlässiges Flächengebilde darstellen und wobei die äußere oder die innere Oberfläche der einen oder der beiden wasserdurchlässigen Teile mit einem wasserundurchlässigmachendem Überzug aus einem sich bei erhöhter Temperatur der Waschflotte ablösenden und dadurch die im Behältnis vorhandenen Wirk- und gegebenenfalls Duftstoffe zur Übertragung auf die Textilien freigebenden Material beschichtet sind.According to the invention, this object is achieved by a container which maintains textiles and consists of a closed container which contains textile-care agents and optionally fragrances for use during the washing process. The object is characterized in that the container consists of a pillow-shaped structure made of two identical shaped, congruent superimposed and connected at the edges interconnected flexible parts or a sachet, of which in the case of the sachet the whole wall of the sachet or in the case of the pillow-shaped structure a part or both parts represent a waterproof, water-permeable sheet and optionally the second part a waterproof, water-impermeable sheet and the outer or the inner surface of one or the two water-permeable parts with a water-impermeable coating from a detachable at elevated temperature of the wash liquor and thereby the im Containing active ingredients and possibly fragrances are coated for transfer to the textiles-releasing material.

Das Behältnis gibt seinen Inhalt nicht bereits in der noch kalten Waschflotte ab, sondern erst gegen Ende des Waschvorgangs, wenn die Temperatur der Waschflotte ihren höchsten Wert erreicht hat. Die textilpflegenden Wirkstoffe treffen zu diesem Zeitpunkt auf bereits vom Schmutz weitgehend befreite Textilien und können sich auf diese ohne nennenswerte Beeinträchtigung durch die Tenside ablagern, wobei andererseits keine Verschlechterung des Waschergebnisses durch die Anwesenheit von textilpflegenden Wirkstoffen in der Waschflotte beobachtet wird. Durch diese Verfahrensweise ist es außerdem möglich, textilpflegende Wirkstoffe einzusetzen, deren Anwendüng in kalten Spülflotten oder im Wäschetrockner nicht möglich oder nicht wirtschaftlich ist.The container does not already contain its contents the still cold washing liquor, but only towards the end of the washing process when the temperature of the washing liquor has reached its highest value. At this point in time, the textile care agents meet textiles that have already been largely freed of dirt and can deposit on them without any noticeable impairment by the surfactants, while on the other hand no deterioration in the washing result is observed due to the presence of textile care agents in the wash liquor. This procedure also makes it possible to use active ingredients which care for textiles, the use of which in cold washing liquors or in the tumble dryer is not possible or is not economical.

Der erfindungsgemäße Gegenstand besteht ganz oder teilweise aus einem wasserfesten, wasserdurchlässigen Behältnis, in das die Wirk-und gegebenenfalls Duftstoffe eingeschlossen sind. Zur Vermeidung einer vorzeitigen Freisetzung des Inhalts ist mindestens der wasserdurchlässige Teil des beutelartigen Behältnisses, eventuell auch das ganze Behältnis auf der Innenseite und/oder der Außenseite, vorzugsweise aber nur auf der Außenseite mit einem Überzug versehen, der das wasserdurchlässige Behältnismaterial in der kalten Waschflotte wasserundurchlässig macht. Erst bei Erreichen einer erhöhten WaschflottenTemperatur gegen Ende des Waschvorgangs löst sich der Überzug von dem an sich wasserdurchlässigen Behältnismaterial allmählich ab und gibt den Inhalt frei, so daß er in Kontakt mit den von Schmutz bereits weitgehend oder ganz befreiten Textilien treten kann. Die Temperatur, bei der sich der Überzug ablöst, hängt von der Art des Überzugsmaterials ab und kann auf die gewünschte Waschflottentemperatur, die zwischen etwa 30 bis maximal etwa 100 °C liegt, durch Auswahl des Schmelzpunktes des Überzugsmaterials eingestellt werden.The object according to the invention consists entirely or partially of a waterproof, water-permeable container in which the active ingredients and optionally fragrances are included. To prevent premature release of the contents, at least the water-permeable part of the bag-like container, possibly also the entire container on the inside and / or the outside, but preferably only on the outside, is provided with a coating which makes the water-permeable container material in the cold wash liquor impermeable makes. Only when an elevated washing liquor temperature is reached towards the end of the washing process does the coating gradually detach from the container material, which is water-permeable per se, and releases the contents, so that it can come into contact with the textiles which have already been largely or completely freed from dirt. The temperature at which the coating peels depends on the type of coating material and can be adjusted to the desired wash liquor temperature, which is between about 30 to a maximum of about 100 ° C., by selecting the melting point of the coating material.

Die Bestandteile des erfindungsgemäßen Mittels und dessen Merkmale werden im folgenden näher beschrieben:The components of the agent according to the invention and its features are described in more detail below:

Das wasserdurchlässige BehältermaterialThe water-permeable container material

Es kann ein textiles gewobenes oder nichtverwobenes Material sein, also beispielsweise Gewebe oder Gewirke aus natürlichen und/oder synthetischen Fasern, beispielsweise aus Cellulose, Wolle, Seide, Leinen, Jute, Sisal, Polyamid, Polyester, Polyacrylnitril, Polyvinylderivate, polyolefine, Rayon. Ebenfalls geeignet sind Schaumstoffe oder Schwämme aus Viskose oder synthetischen Polymeren, insbesondere Polyurethan. Geeignet sind ferner Vliesstoffe aus den genannten Fasern, die mit Bindemitteln und/oder thermoplastischen Fasern gebunden sind und entweder aus gerichteten Fasern oder willkürlich angeordneten Fasern bestehen können. Vliesstoffe werden durch bekannte Ablagerungsverfahren in Wasser oder Luft hergestellt; sie können regelmäßig oder unregelmäßig angeordnete und geformte Öffnungen aufweisen. Auch wasserfeste, wasserdurchlässige Papiere sind geeignet.It can be a textile woven or non-woven material, for example woven or knitted fabrics made of natural and / or synthetic fibers, e.g. made of cellulose, wool, silk, linen, jute, sisal, polyamide, polyester, polyacrylonitrile, polyvinyl derivatives, polyolefins, rayon. Foams or sponges made of viscose or synthetic polymers, in particular polyurethane, are also suitable. Also suitable are nonwovens made from the fibers mentioned, which are bound with binders and / or thermoplastic fibers and which can either consist of oriented fibers or randomly arranged fibers. Nonwovens are made by known deposition processes in water or air; they can have regularly or irregularly arranged and shaped openings. Waterproof, water-permeable papers are also suitable.

Weiterhin geeignet sind ferner-an sich wasserundurchlässige flexible FoTien, die durch Schlitze oder Löcher wasserdurchlässig gemacht wurden. Geeignete Folienmaterialien sind beispielsweise Polyolefin, Polyvinylderivate, Polyester, Polyamid, Celluloseester.Also suitable are further inherently water-impermeable flexible films which have been made water-permeable by slots or holes. Suitable film materials are, for example, polyolefin, polyvinyl derivatives, polyester, polyamide, cellulose esters.

Bevorzugt verwendet werden offenzellige Schaumstoffe der Stärke 0,5 mm bis 3 mm. Die Dichte geeigneter Schäume liegt vorzugsweise im Bereich 0,01 bis 0,04 g pro cm3. Besonders bevorzugt sind 0,05 mm bis 2 mm dicke Vliesstoffe insbesondere aus polyester und/oder Cellulose, wobei die Vliesstoffe ein Flächengewicht zwischen 10 und 100 g pro m2 aufweisen.Open-cell foams with a thickness of 0.5 mm to 3 mm are preferably used. The density of suitable foams is preferably in the range from 0.01 to 0.04 g per cm 3. Particularly preferred are 0.05 mm to 2 mm thick nonwovens, in particular made of polyester and / or cellulose, the nonwovens having a basis weight between 10 and 100 g per m 2 .

Das wasserundurchlässige MaterialThe waterproof material

Geeignete wasserundurchlässige wasserfeste Materialien sind flexible Folien aus beispielsweise Polyolefin, Polyvinylderivaten, Polyester, Polyamid, Celluloseester oder ähnlichen Polymeren. Sie haben eine Dicke von 0,03 mm bis 0,15 mm, vorzugsweise 0,05 bis 0,08 mm.Suitable water-impermeable, waterproof materials are flexible films made of, for example, polyolefin, polyvinyl derivatives, polyester, polyamide, cellulose esters or similar polymers. They have a thickness of 0.03 mm to 0.15 mm, preferably 0.05 to 0.08 mm.

Es können aber auch flexible Metallfolien und Verbundfolien beispielsweise aus Metall und organischen Polymeren eingesetzt werden.However, flexible metal foils and composite foils, for example made of metal and organic polymers, can also be used.

Besonders bevorzugt als wasserundurchlässiges Folienmaterial sind Polyolefinfolien.Polyolefin films are particularly preferred as the water-impermeable film material.

Das BehältnisThe container

Das Behältnis bzw der Behälter weist im allgemeinen die Form eines Kissens auf; er kann jedoch auch die Form eines kleinen Säckchens haben. Im letzteren Fall ist das Wandmaterial zweckmäßigerweise vollständig wasserdurchlassig.The container or the container generally has the shape of a pillow; however, it can also have the shape of a small bag. In the latter case, the wall material is expediently completely permeable to water.

In der bevorzugten Kissenform besteht das Behältnis aus zwei aufeinanderliegenden Flächengebilden, von denen eins oder beide aus einem wasserdurchlässigen Material bestehen. Sie haben eine Größe von vorzugsweise etwa 30 cm2 bis 400 cm2. Sie sind an den Rändern stoffschlüssig miteinander verbunden. Geeignete Verbindungstechniken sind alle diejenigen, die zu einer wasserfesten Verbindung führen und sich durch die Einwirkung der mechanischen Kräfte beim Waschvorgang nicht lösen. Beispiele für geeignete Verbindungstechniken sind Kleben, Prägen, Schweißen, Nähen, wovon Schweißen und Nähen bevorzugt sind. Weist der Behälter die Form eines Säckchens auf, sind auch Zunähen, Zuklemmen mit Klammern oder Zuschnüren mit Bindfäden mögliche Verschlußarten.In the preferred pillow form, the container consists of two superimposed flat structures, one or both of which consist of a water-permeable material. They have a size of preferably about 30 cm 2 to 400 cm 2 . They are bonded together at the edges. Suitable connection techniques are all those that lead to a waterproof connection and do not come loose due to the action of mechanical forces during the washing process. Examples of suitable joining techniques are gluing, embossing, welding, sewing, of which welding and sewing are preferred. If the container has the shape of a bag, sewing, pinching with clips or tying are also included Twine possible types of closures.

Der Behälter ist mit den Wirkstoffen und gegebenenfalls Duftstoffen gefüllt, wobei die Duftstoffe an ein saugfähiges Trägermaterial gebunden sein können, das nach dem Tränken oder sonstigen Imprägnieren mit dem Duftstoff in den Behälter eingeführt wird. Geeignete Trägermaterialien sind saugfähige Vliese, Papier, Schaumstoffe, Schwämme oder textile Stoffe in passender Größe.The container is filled with the active ingredients and, if appropriate, fragrances, it being possible for the fragrances to be bound to an absorbent carrier material which is introduced into the container after impregnation or other impregnation with the fragrance. Suitable backing materials are absorbent nonwovens, paper, foams, sponges or textiles of the appropriate size.

Die Herstellung des Behältnisses in der bevorzugten Kissenform erfolgt zweckmäßigerweise, indem man das wasserdurchlässige Material zunächst zum Beispiel durch Aufrakeln, Tauchen oder Besprühen mit dem durch Aufschmelzen oder Auflösen verflüssigten Überzugsmaterial wasserundurchlässig macht, trocknet oder erstarren läßt, das Material gegebenenfalls zusammen mit dem wasserundurchlässigen Material in passende Stücke schneidet oder stanzt und nach Auf- beziehungsweise Einbringen der Wirk- und gegebenenfalls Duftstoffe allseitig verschließt, so daß das Kissen entweder aus einer oder aus zwei wasserundurchlässig gemachten wasserdurchlässigen Schichten besteht. Eine andere Art der Herstellung des erfindungsgemäßen Mittels besteht darin, daß man zunächst den Behälter aus nicht überzogenem Material anfertigt und ihn nach dem Füllen und Verschließen mit dem Überzug beispielsweise durch Tauchen überzieht. In diesem Fall befindet sich der Überzug nur oder vorwiegend auf der Außenseite. Grundsätzlich schadet es nicht, den Überzug aufzubringen, indem man das Material durch und durch mit der Überzugsmasse tränkt. Bringt man den Überzug vor dem Verschließen an, kann man den Überzug auch auf die Innenseite des Behältermaterials auftragen. Es ist ratsam, nicht mehr Überzugsmaterial zu verwenden, als für das Wasserundurchlässigmachen des Beutels erforderlich ist. Ist der Auftrag an Überzugsmaterial zu groß, kann dies zu einer verzögerten oder unvollständigen Freisetzung der Wirkstoffe führen. Die günstigste Auftragsmenge hängt auch von der Art des Uberzugsmaterials, des Behältermaterials und der Auftragstechnik ab. Eine geeignete Auftragsmenge ist leicht durch Versuche zu ermitteln.The container in the preferred pillow form is expediently made by first making the water-permeable material water-impermeable, drying or solidifying, for example by knife coating, dipping or spraying with the coating material liquefied by melting or dissolving, the material optionally together with the water-impermeable material in cuts or punches suitable pieces and closes them on all sides after application or introduction of the active ingredients and, if appropriate, fragrances, so that the pillow consists either of one or of two water-impermeable, water-permeable layers. Another way of producing the agent according to the invention is that the container is first made from uncoated material and, after filling and sealing, is coated with the coating, for example by dipping. In this case the cover is only or predominantly on the outside. Basically, there is no harm in applying the coating by thoroughly soaking the material with the coating compound. If you apply the cover before closing, you can also apply the cover to the inside of the container material. It is advisable not to use more coating material than is necessary to make the pouch impervious. If the application of coating material is too large, this can lead to a delayed or incomplete release of the active ingredients. The cheapest order quantity also depends on the type of coating material, the container material and the application technique. A suitable order quantity can easily be determined by tests.

Das ÜberzugsmaterialThe covering material

Die Art des wasserundurchlässigmachenden Uberzugsmaterials richtet sich nach der Waschflottentemperatur, bei welcher sich das Überzugsmaterial von-der wasserdurchlässigen Behälterwand ablösen soll. Der Schmelzpunkt des Überzugsmaterials muß ähnlich liegen wie die Waschflottentemperatur, bei der die Wirk-und Duftstoff-Freigabe erfolgen soll. Geeignet sind daher kaltwasserunlösliche Materialien mit einem Schmelzpunkt im Bereich der Waschtemperaturen also etwa 30 °C bis etwa 100 °C. Bewährt haben sich Paraffinkohlenwasserstoffe, gesättigte und ungesättigte Fettalkohole und Fettsäuren, a-o-Alkandiole, Fettsäureester, Amide von ungesättigten Fettsäuren sowie die Mischungen der genannten Stoffe untereinander. Besonders geeignet und daher bevorzugt sind Paraffinkohlenwasserstoffe, Fettalkohole, Fettsäureamide und deren Gemische mit einem Schmelzpunkt zwischen etwa 30 °C und 100 ° C.The type of water-impermeable coating material depends on the wash liquor temperature at which the coating material is to separate from the water-permeable container wall. The melting point of the coating material must be similar to the wash liquor temperature at which the active ingredient and fragrance are to be released. Materials which are insoluble in cold water and therefore have a melting point in the range of the washing temperatures, ie about 30 ° C. to about 100 ° C., are suitable. Paraffinic hydrocarbons, saturated and unsaturated fatty alcohols and fatty acids, a-o-alkanediols, fatty acid esters, amides of unsaturated fatty acids and the mixtures of the substances mentioned have proven themselves. Paraffin hydrocarbons, fatty alcohols, fatty acid amides and mixtures thereof with a melting point between about 30 ° C. and 100 ° C. are particularly suitable and therefore preferred.

Die WirkstoffeThe active ingredients

Als Wirkstoffe kommen vor allem Textilweichmacher und Textilantistatika in Frage. Daneben sind Soil-release-Substanzen, Textilsteifen, Bügelhilfen, Antimikrobika sowie in untergeordnetem Maße Imprägniermittel, Flammschutz- und Mottenschutzmittel geeignete Wirkstoffe. Sie werden einzeln oder im Gemisch verwendet.The main active substances are textile softeners and textile antistatic agents. In addition, soil release substances, textile stiffeners, ironing aids, antimicrobials and to a lesser extent impregnating agents, flame retardants and moth protection agents are suitable active ingredients. They are used individually or in a mixture.

Als textilweichmachende Wirkstoffe eignen sich die quartären Ammoniumverbindungen mit vorzugsweise zwei langkettigen, vorzugsweise gesättigten aliphatischen Resten mit je 14 - 26, vorzugsweise 16 - 20 Kohlenstoffatomen und wenigstens einem quartären Stickstoffatom im Molekül. Die langkettigen aliphatischen Reste können geradkettig oder verzweigt sein und dementsprechend von Fettsäuren, beziehungsweise von Fettaminen, Guerbetaminen, oder aus den durch Reduktion von Nitroparaffinen erhältlichen Alkylaminen abstammen. Bei diesen quartären Ammoniumverbindungen handelt es sich insbesondere um Derivate des Ammoniaks, das heißt um die durch Alkylierung von langkettigen sekundären Aminen erhältlichen quartären Salze, wie zum Beispiel die Verbindungen Distearyldimethylammoniumchlorid beziehungsweise Ditalgalkyldimethylammoniumchlorid, oder um die durch Umsetzung von 1 Mol eines Aminoalkylethylendiamins oder Hydroxyalkylethylendiamins mit 2 Mol einer langkettigen C12-C26-Fettsäure oder deren Ester erhältlichen Imidazolinverbindungen, die anschließend durch Alkylierung in die quartären Imidazoliniumverbindungen übergeführt werden. In diesen quartären Ammoniumverbindungen besteht das Anion im allgemeinen aus dem Säurerest, der aus dem bei der Quaternierung verwendeten Alkylierungsmittel entstanden ist. Beispielsweise kommt als Anion daher Chlorid, Bromid, Methylsulfat, Ethylsulfat, Methan-, Ethan-oder Toluolsulfonat in Betracht. Neben diesen quartären Ammoniumverbindungen kommen als Textilweichmacher auch die Kondensationsprodukte aus 1 - 3 Mol Fettsäure oder Fettsäurealkylester oder 1/3 - 1 Mol Fettsäuretriglycerid mit einem Mol eines Hydroxyalkylpolyamins, beispielsweise Hydroxyethylethylendiamin oder Hydroxyethyldiethylentriamin, in Betracht. Besonders geeignet ist das durch Umsetzung von 1 Mol eines Fettsäuretriglycerids, insbesondere gehärtetem Talg, mit 1 Mol Hydroxyethylethylendiamin bei 50 - 150 °C erhältliche Produkt. Vorzugsweise wird als Textilweichmacher eine Kombination aus einer quartären Ammoniumverbindung des Ammoniaktyps mit zwei C16-C20-Alkyl- oder Alkenylgruppen und 2 Methylgruppen im Molekül, und mit dem Chlorid-, Bromid- oder Methylsulfat-Anion, insbesondere Ditalgalkyldimethylammoniumchlorid, zusammen mit dem Fettsäurekondensationsprodukt aus 1 Mol gehärtetem Talg und 1 Mol Hydroxyethylethylendiamin im Verhältnis 4: 1 bis 1: 4 eingesetzt. Diese Kombinationen führen bei den behandelten Textilien zu einer gleichmäßigen markanten Griffverbesserung ohne Fleckenbildung. Beispiele für textilpflegende Wirkstoffe mit höherem Schmelzpunkt, die aufgrund dessen mit Vorteil in den erfindungsgemäßen Mitteln eingesetzt werden können, sind die quartären Ammoniumverbindungen mit 2 oder insbesondere 3 langen, Hydroxyl- und Ethergruppen enthaltenden langen Resten, wie man sie durch Umsetzung von Epoxyalkanen mit tertiären Polyalkanolaminen und anschließende Quaternierung erhält. Derartige Verbindungen sind in der DE-OS 28 44 451 beschrieben.The quaternary ammonium compounds with preferably two long-chain, preferably saturated aliphatic radicals each having 14-26, preferably 16-20, carbon atoms and at least one quaternary nitrogen atom in the molecule are suitable as fabric softening agents. The long-chain aliphatic radicals can be straight-chain or branched and can accordingly be derived from fatty acids, or from fatty amines, Guerbetamines, or from the alkylamines obtainable by reduction of nitroparaffins. These quaternary ammonium compounds are, in particular, derivatives of ammonia, that is to say the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for example, the compounds distearyldimethylammonium chloride or ditalgalkyldimethylammonium chloride, or those by reacting 1 mol of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 Mol of a long-chain C 12 -C 26 fatty acid or its ester obtainable imidazoline compounds which are subsequently converted into the quaternary imidazolinium compounds by alkylation. In these quaternary ammonium compounds, the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization. For example, chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are suitable as anions. In addition to these quaternary ammonium compounds, the condensation products of 1-3 moles of fatty acid or fatty acid alkyl ester or 1/3-1 mole of fatty acid triglyceride with one mole of a hydroxyalkyl polyamine, for example, also come as textile plasticizers Hydroxyethylethylenediamine or hydroxyethyldiethylenetriamine. The product obtainable by reacting 1 mol of a fatty acid triglyceride, in particular hardened tallow, with 1 mol of hydroxyethylethylenediamine at 50-150 ° C. is particularly suitable. A textile softener is preferably a combination of a quaternary ammonium compound of the ammonia type with two C 16 -C 20 alkyl or alkenyl groups and 2 methyl groups in the molecule, and with the chloride, bromide or methyl sulfate anion, in particular ditallow alkyl dimethyl ammonium chloride, together with the fatty acid condensation product from 1 mol of hardened tallow and 1 mol of hydroxyethylethylenediamine in a ratio of 4: 1 to 1: 4. These combinations lead to a uniform, striking improvement in the treated textiles without staining. Examples of textile care active ingredients with a higher melting point, which can therefore be used with advantage in the agents according to the invention, are the quaternary ammonium compounds with 2 or in particular 3 long, hydroxyl and ether group-containing long residues, such as those obtained by reacting epoxyalkanes with tertiary polyalkanolamines and subsequent quaternization. Such compounds are described in DE-OS 28 44 451.

Bei den antistatischmachenden Wirkstoffen handelt es sich im allgemeinen um gleiche oder ähnliche Verbindungstypen wie bei den Textilweichmachern. Außer den oben beschriebenen quartären Ammoniumverbindungen und Fettsäurekondensationsprodukten eignen sich auch die quartären Ammoniumverbindungen mit einem langkettigen und drei kurzkettigen aliphatischen Resten als Textilantistatika. Weitere geeignete Antistatika sind beispielsweise die Umsetzungsprodukte aus einem Mol eines aliphatischen C6-C20-Alkohols und mehr als 20 Mol, vorzugsweise 35 - 50 Mol Ethylenoxid.The antistatic agents are generally the same or similar types of compounds as the fabric softeners. In addition to the quaternary ammonium compounds and fatty acid condensation products described above, the quaternary ammonium compounds with one long-chain and three short-chain aliphatic radicals are also suitable as textile antistatic agents. Other suitable antistatic agents are, for example, the reaction products of one mole of an aliphatic C 6 -C 20 alcohol and more than 20 moles, preferably 35-50 moles, of ethylene oxide.

Bei den geeigneten antimikrobiellen Wirkstoffen, das heißt bakterizid oder bakteriostatisch beziehungsweise fungizid oder fungistatisch wirkenden Verbindungen, handelt es sich meist ebenfalls um quartäre Ammoniumverbindungen, insbesondere solche, die neben einem langkettigen aliphatischen und zwei kurzkettigen aliphatischen Kohlenwasserstoffresten einen aromatischen, über ein aliphatisches Kohlenstoffatom mit dem Stickstoffatom verknüpften, oder einen aliphatischen, Doppelbindungen aufweisenden organischen Rest im Molekül enthalten. Typische Vertreter für derartige antimikrobielle Wirkstoffe sind die Verbindungen Dimethylbenzyldodecylammoniumchlorid, oder Dibutyl-allyl-, und Ethylcyclohexyl-allyl-dodecylammoniumchlorid. Brauchbare antimikrobielle Wirkstoffe sind auch die Bromnitroalkohole wie zum Beispiel die Verbindungen 2-Brom-2-nitropropan-1,3-diol, 1-Brom-1-nitro-3,3-trichlor-2-propanol, 2-Brom-2-nitrobutanul. Als antimikrobielle Wirkstoffe eignen sich auch halogenierte und/oder trifluormethylsubstituierte phenolische Verbindungen, insbesondere die halogenierten Salicylanilide, zum 4Beispiel die Verbindungen Dibromund Tribromsalicylanilid, sowie Derivate des p-Phenoxyphenols wie zum Beispiel die Verbindung 2-Hydroxy-2',4,4'-trichlordiphenylether.The suitable antimicrobial agents, that is to say bactericidal or bacteriostatic or fungicidal or fungistatic compounds, are usually also quaternary ammonium compounds, in particular those which, in addition to a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals, have an aromatic, via an aliphatic carbon atom with the nitrogen atom linked, or contain an aliphatic, double bonds organic radical in the molecule. Typical representatives for such antimicrobial agents are the compounds dimethylbenzyldodecylammonium chloride, or dibutyl-allyl, and ethylcyclohexyl-allyl-dodecylammonium chloride. Antimicrobial agents which can also be used are the bromo-nitro alcohols, for example the compounds 2-bromo-2-nitropropane-1,3-diol, 1-bromo-1-nitro-3,3-trichloro-2-propanol, 2-bromo-2- nitrobutanul. Halogenated and / or trifluoromethyl-substituted phenolic compounds, in particular the halogenated salicylanilides, for example the compounds dibromo and tribromosalicyl anilide, and derivatives of p-phenoxyphenol such as the compound 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether are also suitable as antimicrobial active substances .

Als Wirkstoffe zur Soil-release-Ausrüstung für Textilien eignen sich Verbindungen, die das Schmutzablösevermögen während der Wäsche verbessern. Dazu gehören Verbindungen vom Typ der Polyacrylpolyvinylalkohole, der modifizierten Fluorkohlenwasserstoffe und hydrophile Polymere. Polyvinylacetate aber auch Borax eignen sich als Zusätze, die das Bügeln der Wäsche erleichtern.Compounds which improve the dirt-removing ability during washing are suitable as active ingredients for soil release finishing for textiles. These include compounds of the polyacrylic polyvinyl alcohol type, modified fluorocarbons and hydrophilic polymers. Polyvinyl acetates but also borax are suitable additives that make ironing the laundry easier.

Die für eine Haushaltswaschmaschine geeigneten erfindungsgemäßen Mittel enthalten im allgemeinen 0,5 bis 10, vorzugsweise 3 bis 8 g Wirkstoff. Je nach der Größe der Waschmaschine können die Mittel auch mehr oder weniger Wirkstoff enthalten. Wichtig ist, daß je Liter Waschflotte etwa 0,1 bis 0,8 g Wirkstoff enthalten sind.The agents according to the invention suitable for a household washing machine generally contain 0.5 to 10, preferably 3 to 8 g of active ingredient. Depending on the size of the washing machine, the agents can also contain more or less active ingredient. It is important that about 0.1 to 0.8 g of active ingredient is contained per liter of washing liquor.

Die Wirkstoffe können in dem erfindungsgemäßen Mittel in reiner Form oder als eine Paste vorliegen. Die Paste besteht aus einem Gemisch der Wirkstoffe mit Wasser, wobei gegebenenfalls Dispergiermittel und/oder wasserlösliche organische Lösungsmittel ebenfalls enthalten sein können. Die Paste weist einen Wirkstoffgehalt bis zu etwa 90 Gewichtsprozent vorzugsweise aber 10 bis 80 Gewichtsprozent und insbesondere 15 bis 50 Gewichtsprozent auf. Wegen der verzögerten Dispergierung nichtpastenförmiger Wirkstoffe in der Waschflotte sind Wirkstoffe in dieser Form im Rahmen der vorliegenden Erfindung bevorzugt.The active substances can be present in the agent according to the invention in pure form or as a paste. The paste consists of a mixture of the active ingredients with water, where appropriate dispersants and / or water-soluble organic solvents may also be present. The paste has an active ingredient content of up to about 90 percent by weight, but preferably 10 to 80 percent by weight and in particular 15 to 50 percent by weight. Because of the delayed dispersion of non-paste-like active substances in the wash liquor, active substances in this form are preferred in the context of the present invention.

Das erfindungsgemäße Mittel enthält die Wirkstoffe vorzugsweise in Kombination mit Duftstoffen. Der Duftstoff kann in reiner Form, als alkoholische Lösung oder als wäßrige Emulsion eingesetzt werden. Bevorzugt wird der Duftstoff als Emulsion, das heißt als Gemisch aus Parfümöl, Wasser und einem Emulgator eingesetzt. Als Duftstoffe geeignet sind alle Parfümarten, die die gewünschten Duftnoten geben und die unter den Anwendungsbedingungen stabil sind.The agent according to the invention preferably contains the active ingredients in combination with fragrances. The fragrance can be used in pure form, as an alcoholic solution or as an aqueous emulsion. The fragrance is preferably used as an emulsion, that is to say as a mixture of perfume oil, water and an emulsifier. Suitable as fragrances are all types of perfume which give the desired fragrance notes and which are stable under the conditions of use.

Als Parfümölemulgatoren sind hydrophile oberflächenaktive Substanzen geeignet, wie zum Beispiel hydriertes Ricinusöl mit 40 Mol Ethylenoxid oder Alkenylbernsteinsäuresalze oder deren Halbester.Suitable perfume oil emulsifiers are hydrophilic surface-active substances, such as hydrogenated castor oil with 40 moles of ethylene oxide or alkenyl succinic acid salts or their half esters.

Die Erfindung betrifft ferner ein Verfahren zur Behandlung von Textilien während des Waschens mit Textilien pflegenden erst verzögert zum Einsatz gelangenden Wirkstoffen durch Zusatz eines die Wirkstoffe enthaltenden Behältnisses zu Beginn des Waschvorganges zur noch kalten Waschflotte, die dann aufgeheizt wird. Das Verfahren ist asdurch gekennzeichnet, daß das Wirkstoffe und gegebenenfalls Duftstoffe enthaltende Behältnis zur Wirkstoffabgabe auf eine vorbestimmte Waschtemperatur eingestellt ist derart, daß sich der Überzug aus wasserundurchlässigem Material gegen Ende des Waschvorganges bei erhöhter Waschflottentemperatur vom wasserdurchlässigen Flächengebilde loslöst, so daß der Beutelinhalt freigesetzt und dadurch auf die Textilien übertragen wird. Zur Durchführung des erfindungsgemäßen Verfahrens gibt man ein Behältnis bzw. Beutel einen aus mindestens teilweise wasserdurchlässigem Material, welches, wie zuvor beschrieben, mit einem bei der Waschtemperatur sich ablösenden, wasserundurchlassig machenden Überzug mit einem Schmelzpunkt zwischen 30 und 100 °C überzogen ist, am Beginn des Waschcyclus einer Haushaltswaschmaschine in die noch kalte Waschflotte zu den zu reinigenden Textilien. Man heizt dann die Waschflotte auf die gewünschte Waschtemperatur auf. Bei dieser Temperatur löst sich der Überzug von dem Beutel ab, der Beutelinhalt tritt durch die wieder wasserdurchlässig gewordene Beutelwand und übt seine textilpflegende Wirkung aus. Man trennt dann die den Schmutz und die Waschmittelbestandteile enthaltende Waschflotte von den Textilien ab und trocknet die Textilien, die durch den Kontakt mit den textilpflegenden Wirkstoffen einen erhöhten Gebrauchswert aufweisen. Den wasserunlöslichmachenden Überzug wählt man für die Durchführung des erfindungsgemäßen Verfahrens so aus, daß er sich erst bei der Waschtemperatur, das heißt bei Temperaturen, die je nach Textilgut und Waschverfahren zwischen etwa 30 und etwa 100 °C liegen, von dem Beutel ablöst. Wäscht man die Textilien in einem zwei- oder Mehrlaugenverfahren, fügt man zweckmäßigerweise den Beutel erst dem letzten Waschgang vor den Spülgängen zu.The invention further relates to a method for treating textiles during washing with active ingredients which care for the use of textiles and are used only after a delay, by adding a container containing the active ingredients at the beginning of the washing process to the still cold washing liquor, which is then heated. The method is characterized in that the Active ingredient and possibly fragrance-containing container for active ingredient delivery is set to a predetermined washing temperature such that the coating of water-impermeable material detaches from the water-permeable sheet material at the end of the washing process at an elevated washing liquor temperature, so that the contents of the bag are released and thereby transferred to the textiles. To carry out the method according to the invention, a container or bag is made of at least partially water-permeable material, which, as described above, is coated with a water-impermeable coating which has a melting point between 30 and 100 ° C. and which detaches at the washing temperature, at the beginning the washing cycle of a household washing machine into the still cold washing liquor for the textiles to be cleaned. The washing liquor is then heated to the desired washing temperature. At this temperature, the cover detaches from the bag, the contents of the bag pass through the wall of the bag, which has become water-permeable again, and exert its textile care effect. The washing liquor containing the dirt and the detergent constituents is then separated from the textiles and the textiles are dried, which have an increased utility value due to the contact with the textile care active ingredients. The water-insolubilizing coating is selected for carrying out the process according to the invention in such a way that it only detaches from the bag at the washing temperature, that is to say at temperatures which are between about 30 and about 100 ° C., depending on the fabric and washing process. If you wash the textiles in a two- or multi-lye process, it is advisable to add the bag only to the last wash before the rinses.

Die Menge des umzusetzenden Wirkstoffs, insbesondere des Textilweichmachers im Beutel richtet sich nach der Wirksamkeit des Wirkstoffs und nach der Stärke des gewünschten Effektes. Im allgemeinen verwendet man etwa 0,1 bis 1,5 g textilpflegenden Wirkstoff pro Liter Waschflotte; besonders gute Resultate erzielt man, mit einem Einsatz von 0,2 bis 0,8 g Wirkstoff, insbesondere Textilweichmacher pro Liter.The amount of the active ingredient to be reacted, in particular the fabric softener, in the bag depends on the effectiveness of the active ingredient and on the strength of the desired effect. In general, about 0.1 to 1.5 g of fabric care active ingredient are used per liter of washing liquor; Particularly good results are achieved with the use of 0.2 to 0.8 g of active ingredient, in particular textile softener per liter.

BeispieleExamples

Ein ca. 0,13 mm dicker bindemittelgebundener Vliesstoff aus 70 % Cellulosefasern und 30 % thermoplastischen Schmelzfasern, Flächengewicht des Vliesstoffes ca. 34 g pro m2 wurde mit unterschiedlichen Überzugsmaterialien beschichtet, in 8 cm x 7,5 cm große Stücke geschnitten, auf die 6 g des Textilweichmachers Dimethyldistearylammoniumchlorid gegeben wurden und mit einem gleichgroßen Stück eines ebenfalls beschichteten gleichartigen Vliesstoffs bedeckt. Die bündig aufeinander liegenden Stücke wurden an den Kanten vernäht. Sodann wurden Baumwoll-Frottierlappen, die durch 3- maliges Waschen mit einem handelsüblichen Vollwaschmittel bei 95 °C und anschließendes 96- stündiges Behandeln mit einer Flotte bei 95 °C, die 4 g Natriumtripolyphosphat pro Liter enthielt, Spülen und hängendem Trocknen gehärtet waren, zusammen mit 3 kg Füllwäsche in einer vollautomatischen HaushaltswasGhmaschine bei einer Waschtemperatur von 60 °C mit einem handelsüblichen 60 oe-Waschmittel, das mit 7,5 g pro Liter Waschflotte bei einer Wasserhärte von 16 °d dosiert wurde, im 1-Laugenverfahren gewaschen. Zu Beginn der Wäsche wurden zusammen mit den Textilien die Beutel mit dem Textilweichmacher, der einer Menge von 0,3 g pro Liter Waschflotte entsprach, in die Waschmaschine gegeben. Die Überzugsmasse der Beutel bestand aus Paraffin, Fp. 57 - 60 °C, Paraffin, Fp. 68 -72 °C, ein 1: 1-Gemisch aus den beiden vorgenannten Stoffen, Sorbitanester, Fp. 60 °C, Glycerinmonostearat, Fp. 54 -60 °C. Als Vergleich wurde ein vollständiger Verfahrensablauf ohne Zusatz eines Beutels gewählt. Nach dem Waschen, Spülen und Trocknen wurde der Verfahrensablauf und an den Frottierlappen die Weichheit durch 6 erfahrene Personen beurteilt. Die mit den erfindungsgemäßen Beuteln behandelten Textilien wiesen überraschenderweise eine markant bessere Weichheit auf, als die nicht erfindungsgemäß behandelten Textilien, so daß sich eine separate weichmachende Nachbehandlung erübrigte. Die Weichheit wurde als weitgehend dem einer separaten Nachbehandlung entsprechend beurteilt; der Verfahrensablauf wurde insgesamt akzeptiert, da das oft lästige und ungenaue Dosieren eines flüssigen Nachbehandlungsmittels entfiel. Bemerkenswert ist, daß das Waschergebnis durch den Einsatz der erfindungsgemäßen Mittel in keiner Weise beeinträchtigt werde.An approx. 0.13 mm thick binder-bound nonwoven made of 70% cellulose fibers and 30% thermoplastic melt fibers, basis weight of the nonwoven approx. 34 g per m 2 , was coated with different coating materials, cut into 8 cm x 7.5 cm pieces, onto which 6 g of the fabric softener Dimethyldistearylammoniumchlorid were given and covered with a piece of the same size of a similarly coated nonwoven fabric. The pieces lying flush on top of each other were sewn at the edges. Then cotton terry cloths, which had been hardened by washing three times with a commercial heavy-duty detergent at 95 ° C. and then treating with a float at 95 ° C. containing 4 g of sodium tripolyphosphate per liter for 96 hours, rinsing and hanging drying were combined with 3 kg of ballast washing in a fully automatic Haushaltswas g sewing machine at a washing temperature of 60 ° C with a commercially available 60 o e-detergent which g with 7.5 per liter of wash liquor was dosed at a water hardness of 16 ° d, washed in 1-liquor process . At the beginning of the wash, the bags with the fabric softener, which corresponded to a quantity of 0.3 g per liter of wash liquor, were placed in the washing machine together with the textiles. The coating mass of the bags consisted of paraffin, mp. 57-60 ° C, paraffin, mp. 68-72 ° C, a 1: 1 mixture of the two aforementioned substances, sorbitan ester, mp. 60 ° C, glycerol monostearate, mp. 54 -60 ° C. A complete process sequence without the addition of a bag was chosen for comparison. After washing, rinsing and drying, the procedure and the softness of the terry towels were assessed by 6 experienced people. The textiles treated with the bags according to the invention surprisingly had a markedly better softness than the textiles not treated according to the invention, so that a separate softening aftertreatment was unnecessary. The softness was largely judged to correspond to that of a separate aftertreatment; the overall procedure was accepted because the often annoying and inaccurate dosing of a liquid aftertreatment agent was eliminated. It is remarkable that the washing result is in no way impaired by the use of the agents according to the invention.

Wiederholte man die Beispiele mit einer Menge an Textilweichmacher im Beutel, die 0,4 beziehungsweise 0,5 g pro Liter Waschflotte entsprach, erhielt man noch bessere Weichheitsergebnisse.If the examples were repeated with an amount of fabric softener in the bag which corresponded to 0.4 or 0.5 g per liter of washing liquor, even better softness results were obtained.

Wiederholte man die Versuche der zuvor beschriebenen Beispiele bei einer Waschtemperatur von 90 ° C, wobei die Uberzugsmasse aus Hartwachsen mit einem Schmelzpunkt von 82 - 84 °C beziehungsweise 84 - 88 °C bestand, erhielt man ähnliche Weichheits-und Waschergebnisse wie bei den bei 60 °C durchgeführten Versuchen.If the tests of the examples described above were repeated at a washing temperature of 90 ° C., the coating composition consisting of hard waxes with a melting point of 82-84 ° C. or 84-88 ° C., similar softness and washing results were obtained as in the case of 60 ° C experiments carried out.

Wiederholte man die zuvor beschriebenen Versuche mit Beuteln, deren Material nach dem Füllen und Verschließen mit dem Überzug versehen wurde, erhielt man praktisch identische Weichheitsergebnisse.If the experiments described above were repeated with bags, the material of which was provided with the covering after filling and sealing, the results obtained were practically identical.

Claims (15)

1. A fabric-care article consisting of a sealed container containing fabric-care agents and optionally perfumes for use during the washing process, characterized in that the container consists of a sachet-like structure of two identically shaped flexible parts lying exactly on top of one another and joined to one another at their edges or of a pouch of which the entire wall in the case of the pouch or one or both parts in the case of the sachet-like structure represent(s) a water-resistant, water-permeable sheet-form structure and optionally the second part a water-resistant, non-water-permeable sheet-form structure, the outer or the inner surface of one or both water-permeable parts being provided with a waterproofing coating of a material which dissolves at a high temperature of the wash liquor and, in doing so, releases the active agents and, optionally, perfumes present in the container for transfer to the fabrics.
2. An article as claimed in Claim 1, characterized in that the water-permeable sheet-form structure consists of open-cell foams or sponge materials and, more especially, nonwovens.
3. An article as claimed in Claims 1 and 2, characterized in that the water-permeable sheet-form structure is a nonwoven, preferably of polyester and/or cellulose, with a thickness of from 0.05 to 2 mm.
4. An article as claimed in Claim 3, characterized in that the nonwoven has a weight per unit area of from 10 to 100 g/m2.
5. An article as claimed in Claims 1 to 4, characterized in that the non-water-permeable sheet form structure consists of metal, synthetic or natural polymers, composites or more especially polyolefin.
6. An article as claimed in Claim 5, characterized in that the thickness of the non-water-permeable sheet-form structure is from 0.03 to 0.15 mm.
7. An article as claimed in Claims 1 to 6, characterized in that the flexible sheet-form structure has a size of from 30 to 400 cm2
8. An article as claimed in Claims 1 to 7, characterized in that the sheet-form structures are joined to one another at their edges, preferably to form a sachet-like container, by bonding, stamping or more especially by welding or stitching.
9. An article as claimed in Claims 1 to 8, characterized in that the coating has a melting point of from 30 to 100° C.
10. An article as claimed in Claim 9, characterized in that the coating material is selected from the group comprising paraffin hydrocarbons, saturated and unsaturated fatty alcohols and fatty acids, ceo-alkanediols, fatty acid esters, amides of unsaturated fatty acids and mixtures thereof.
11. An article as claimed in Claims 9 and 10, characterized in that the coating material is a paraffin hydrocarbon, a fatty alcohol, a fatty acid amide or a mixture thereof.
12. An article as claimed in Claims 1 to 11, characterized in that it contains soil-release agents, fabric stages, ironing aids, antimicrobial agents and, in particular, fabric softeners and antistatic agents as the active fabric-care agents.
13. An article as claimed in Claims 1 to 12, characterized in that it contains the active agents in combination with perfumes.
14. A method for treating fabrics during washing with active fabric-care agents which are only used with delay by addition of a container containing the active agents at the beginning of washing to the still cold wash liquor which is then heated, characterized in that the container containing active agents and optionally perfumes as defined in at least one of Claims 1 to 13 is designed to release the active agents at a predetermined washing temperature in such a way that the coating of non-water-permeable material detaches itself from the water-permeable sheet-form material towards the end of the washing process at an elevated wash- liquor temperature so that the contents of the container are released and thus transferred to the fabrics. -
15. A method as claimed in Claim 14, characterized in that from 0.1 to 1.5 g and preferably from 0.2 to 0.8 g of active fabric-care agent, particularly fabric softener, is introduced into the container per liter of wash liquor.
EP83102772A 1982-03-29 1983-03-21 Agent for the care of textiles Expired EP0090311B1 (en)

Priority Applications (1)

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AT83102772T ATE20363T1 (en) 1982-03-29 1983-03-21 MEANS FOR CARE OF TEXTILES.

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DE3211470 1982-03-29
DE19823211470 DE3211470A1 (en) 1982-03-29 1982-03-29 AGENTS FOR CARE OF TEXTILES

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Publication number Priority date Publication date Assignee Title
GB8605734D0 (en) * 1986-03-07 1986-04-16 Unilever Plc Dispensing treatment agents
GB8607832D0 (en) * 1986-03-27 1986-04-30 Caligen Foam Ltd Fabric treatment products
GB8618428D0 (en) * 1986-07-29 1986-09-03 Unilever Plc Conditioning fabrics
DE3834699A1 (en) * 1988-01-27 1989-08-10 Henkel Kgaa Fibre web
DE3834698A1 (en) * 1988-01-27 1989-08-10 Henkel Kgaa DEVICE FOR RECEIVING AND DELIVERING A TREATMENT AGENT
DE3844621C2 (en) * 1988-01-27 1994-04-28 Henkel Kgaa Nonwoven washing dirt trap
EP1072716A1 (en) * 1999-07-19 2001-01-31 The Procter & Gamble Company A dispensing device for a detergent tablet
GB0712991D0 (en) * 2007-07-05 2007-08-15 Reckitt Benckiser Nv Improvement in or relating to compositions
DE102013004367B4 (en) * 2013-03-12 2018-12-27 Comtag Ag Disposable container with additive for water for the treatment of objects

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FR1328999A (en) * 1962-04-25 1963-06-07 Thomson Houston Comp Francaise Improvements to the use of dosed sachets in washing machines or appliances
US4082678A (en) * 1976-11-10 1978-04-04 The Procter & Gamble Company Fabric conditioning articles and process
DE2658989A1 (en) * 1976-12-27 1978-07-06 Henkel Kgaa AGENT FOR AFTER-TREATING THE LAUNDRY IN THE DRYER
DE8201126U1 (en) * 1982-01-20 1982-04-22 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Dosing device for solids

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DE3211470A1 (en) 1983-10-06

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