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WO2001000781A1 - Emballage-portion de matiere active - Google Patents

Emballage-portion de matiere active Download PDF

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Publication number
WO2001000781A1
WO2001000781A1 PCT/EP2000/005540 EP0005540W WO0100781A1 WO 2001000781 A1 WO2001000781 A1 WO 2001000781A1 EP 0005540 W EP0005540 W EP 0005540W WO 0100781 A1 WO0100781 A1 WO 0100781A1
Authority
WO
WIPO (PCT)
Prior art keywords
washing
preparation
cleaning
water
active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2000/005540
Other languages
German (de)
English (en)
Inventor
Jens Bode
Thomas Holderbaum
Christian Nitsch
Thomas Müller-Kirschbaum
Dieter Jung
Rolf Bayersdörfer
Paul Birnbrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE1999134983 external-priority patent/DE19934983A1/de
Priority claimed from DE19961661A external-priority patent/DE19961661A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU54053/00A priority Critical patent/AU5405300A/en
Publication of WO2001000781A1 publication Critical patent/WO2001000781A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the invention relates to detergent or cleaning agent portions, in particular those in the form of packaged detergent preparations in which some of the additives are physically embedded in the packaging material.
  • the invention relates to detergent portion packs and detergent portion packs, and among these again preferably means for automatic dishwashing in new types of packaging.
  • washing or cleaning agents are usually made available to the consumer in the form of spray-dried or granulated solid products or as liquid goods.
  • products in pre-portioned form have become established on the market and are also described in the prior art.
  • detergents or cleaning agents in the form of pressed molded articles, that is to say tablets, blocks, briquettes, rings and the like, and portions of solid or liquid detergents or cleaning agents packed in bags.
  • bags made of water-soluble film have become established. These make it unnecessary for the consumer to tear open the packaging. In this way it is easy to dose a single portion by inserting the bag directly into the washing machine or dishwasher, especially in its washing-up chamber, or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand wash or Sink, possible.
  • the washing or detergent surrounding bags dissolves without residue when a certain temperature is reached or certain other predetermined conditions are set. Detergents and cleaning agents packed in bags made of water-soluble film are also described in large numbers in the prior art.
  • German Auslegeschrift 11 30 547 (Procter & Gamble) discloses packages made of water-soluble films of polyvinyl alcohol which are filled with non-liquid synthetic detergents.
  • a single dose of a detergent or bleach in a bag that has one or more seams made of water-sensitive material is described in European patent application EP 143 476 (Akzo N.V.).
  • EP 143 476 Akzo N.V.
  • a mixture of anionic and / or nonionic water-binding polymer and cationic polymer adhesive material is proposed as the water-sensitive suture material.
  • European patent application EP 158 464 (Clorox) describes low-temperature detergents which can be packaged in a bag made of water-soluble film.
  • the older patent application DE 198 31 703 discloses a portioned detergent or cleaning agent preparation in a pouch made of water-soluble film, in particular a pouch made of (optionally acetalized) Polyvinyl alcohol (PVAL), in which at least 70% by weight of the particles of the washing or cleaning agent preparation have particle sizes> 800 ⁇ m.
  • PVAL Polyvinyl alcohol
  • bitter substances it is known to add bitter substances to wash-active preparations surrounding water-soluble films, which are intended to prevent children from swallowing the preparation.
  • such bitter substances are not additives that can increase the properties of the products or the appreciation of the products by the consumer.
  • Modern detergents or cleaning agents represent a complex mixture of substances.
  • detergents or cleaning agents for high demands or those for special purposes contain additives which are themselves relatively expensive, but which develop the desired effect even at a low concentration per amount of detergent or cleaning agent used.
  • an attempt is made to use the valuable recipe components in the smallest possible amount.
  • the process-related parameters such as dosage fluctuations in the manufacturing process, the quality of the mixing process when mixing the components and / or takes into account any partial separation of individual components when filling the product.
  • detergents or cleaning agents which consist of a spray-dried basic powder
  • the components to be mixed in small quantities, provided they are thermally stable, are therefore regularly metered in via the so-called “slurry approach” and can be distributed somewhat homogeneously in the slurry.
  • This basic powder is the main constituent of the detergent or cleaning agent material to be processed in the subsequent "preparation”.
  • Perfume oils and those solid raw materials that cannot be subjected to spray drying due to their thermal instability are mixed in during the preparation. Examples of such basic substances are enzymes, bleaching agents and bleach activators. In the meantime, more and more often such raw materials are added later, ie in the "preparation stage", which withstand a spray drying process due to their thermal properties.
  • optical brighteners which are contained in universal detergents, but are undesirable in color detergents.
  • the entire system including all downstream process stages and all filter systems from which filter dust is recycled into the process, must therefore be laboriously cleaned. It is much easier - and therefore common practice - to add fine-crystalline brighteners in the preparation stage.
  • Compact detergents are usually prepared in a comparable way, with a granulate that replaces a spray-dried basic powder S
  • the inventors set themselves the task of developing a detergent or cleaning agent portion that added additives in a small amount in a reliably homogeneous distribution Contains concentrations even if these additives are only added during the preparation of the product. In particular, low values of the concentration fluctuation range should be obtained, which were previously only possible with the addition of such additives via the slurry in a spray-dried product.
  • a further object of the invention was to assign a function within the overall recipe to the flat plastic enclosure, which is usually used for active ingredient portion packs in the area of detergents or cleaning agents.
  • this plastic enclosure contains additives which are only required in small amounts in the preparations and which can be dosed evenly and with high accuracy by being incorporated into the enclosure.
  • high-molecular substances such as the polymers used for the production of plastic films, generally dissolve more slowly than low-molecular substances.
  • the invention therefore relates to an active ingredient portion pack comprising at least one washing, cleaning or rinsing active preparation and at least one an at least one washing, cleaning or rinsing active preparation completely or partially enclosing enclosure, wherein the enclosure is soluble under washing, cleaning or rinsing conditions and contains bound at least one individual component of the washing, cleaning or rinsing active preparation.
  • the invention relates in particular to an active ingredient portion pack which contains a detergent preparation and a flat plastic part which completely or at least predominantly surrounds it, and which is characterized in that individual components which control the effectiveness of the detergent preparation or increase its consumer acceptance (“additives”) fully or predominantly physically bound in the flat plastic part.
  • the invention further relates to a method for producing active ingredient portion packs from at least one washing, cleaning or rinsing active preparation and at least one completely or partially enclosing at least one washing, cleaning or rinsing active preparation, in which one or more enclosing materials ( ien) brings it into a liquid form, a finely dispersible preparation of at least one individual component of the washing, cleaning or rinsing active preparation is added to the liquid surrounding material (s), the mixture is processed into a flat structure and the washing, cleaning or completely or partially encloses active washing with the flat structure.
  • one or more enclosing materials ( ien) brings it into a liquid form
  • a finely dispersible preparation of at least one individual component of the washing, cleaning or rinsing active preparation is added to the liquid surrounding material (s)
  • the mixture is processed into a flat structure and the washing, cleaning or completely or partially encloses active washing with the flat structure.
  • the invention relates to a washing process in which an active ingredient portion package is placed in a washing machine in accordance with the detailed description below and the additives contained in the casing are released by adding water and heating the washing liquor above the solution point of the casing, and a process for mechanical Dishwashing, in which an active ingredient portion pack according to the following detailed description is placed in the metering chamber of a machine dishwasher and by adding water and releasing the active ingredient portion pack from the Dosing chamber releases the additives while loosening the casing, and a method for automatic dishwashing using an active ingredient portion pack according to the invention, in which one selects a casing that only becomes water-soluble above room temperature, places the active detergent preparation in the interior of the dishwasher and by adding water and heating the Rinsing liquor over the solution point of the enclosure releases the additives contained in the enclosure while loosening the enclosure.
  • the term “active ingredient portion pack” is understood to mean a sufficient amount of a detergent or cleaning agent or dishwashing detergent for a washing or cleaning process taking place in an aqueous phase.
  • This can be, for example, a machine washing or cleaning process, as is the case with commercially available washing machines
  • this term also includes a hand wash cycle (for example carried out in a hand wash basin or in a bowl) or a dishwashing cycle carried out by hand or another washing or cleaning process.
  • the active ingredient portion packs in machine washing machines are preferred. or cleaning operations or machine dishwashing operations.
  • the active ingredient portion packs contain measured amounts of at least one wash-active, cleaning-active or rinse-active preparation, usually measured amounts of several wash-, cleaning- or rinse-active preparations. It is possible for the active ingredient portion packs to contain only washing, cleaning or rinsing active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, washing, cleaning or rinsing active preparations of different compositions are contained in the active ingredient portion packs.
  • the composition can be in terms of the concentration of each Components of the washing-cleaning or rinsing-active preparation (quantitative) and / or with regard to the type of the individual components of the washing-, cleaning- or rinsing-active preparation (qualitatively) are different.
  • the components are adapted in terms of type and concentration to the tasks which the active ingredient portion packs have to fulfill in the washing or cleaning or rinsing process.
  • the partial portions are preferably the first, second and optionally third or even higher (fourth, fifth, etc.) measured amounts of one or more washing, cleaning or rinsing active preparation (s) comprised of the same or different water-soluble materials. which are combined to form an active ingredient portion pack according to the invention.
  • the active ingredient portion packs comprise at least one washing, cleaning or rinsing active preparation.
  • wash-active preparation or “cleaning-active preparation” or “rinse-active preparation” - these terms are used interchangeably in the present description - in the context of the present invention, preparations of all conceivable, in connection with washing or cleaning, are used Substances relevant to the washing or rinsing process. These are primarily the actual detergents or cleaning agents or rinsing agents with their individual components, which are explained in more detail in the further course of the description.
  • active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances ( inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances substances (perfumes) without the term being restricted to these substance groups.
  • active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances ( inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances substances (perfumes) without the term being restricted to these substance groups.
  • active substances such as surfactants (anionic, non-ionic,
  • washing-active or cleaning-active or rinsing-active preparations also includes washing aids and cleaning aids and / 0
  • Rinse aid understood. Examples of these are optical brighteners, UV protection substances, so-called soil repelients, that is to say polymers which counteract re-soiling of fibers or hard surfaces, and silver protection agents. Laundry treatment agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered according to the invention as wash-active or cleaning-active or rinse-active preparations.
  • the active ingredient portion pack in addition to the washing, cleaning or rinsing active preparation, also comprises at least one completely or partially enclosing at least one washing, cleaning or rinsing active preparation.
  • This must be soluble under washing, cleaning or rinsing conditions in the system under consideration, for example in a washing liquor, cleaning liquor or rinsing liquor, and must contain at least one individual component of the washing, cleaning or rinsing active preparation.
  • the enclosure comprises a water-soluble polymer material.
  • the enclosure is even more preferably a flat plastic part, even more preferably a plastic packaging.
  • Plastic capsules or bottles and in particular packaging in the form of a water-soluble polymer film are preferred here.
  • glued and / or sealed plastic film packaging is preferred among the plastic film packaging. It is particularly advantageous for the enclosure to be a water-soluble polymer film glued with a water-soluble adhesive.
  • Such films are known in principle from the prior art and come, for example, from the group (optionally acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polyacrylates, water-soluble polyurethanes, polyethylene oxide, gelatin, cellulose and mixtures thereof.
  • Polyvinyl alcohols are polymers of the general structure //
  • polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups. The latter are sometimes referred to as "acetalized" PVAL.
  • PVAL eg Mowiol ® types from Hoechst
  • PVAL polyvinyl acetates with a residual acetyl group content of approximately 1 to 2 or 11 to 13 mol%.
  • PVAL water solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
  • PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL foils examples include the PVAL foils available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be determined to the degree / 2, and there are films in this product range available which are soluble in the aqueous phase in all temperature ranges relevant to the application.
  • PVP Polyvinylpyrrolidones
  • PVP are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range of approx. 2500-750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • Amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.
  • gelatin In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
  • portioned detergent and cleaning agent compositions the pouch of which consists of water-soluble film made from at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: from approx. 20-30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000), besides that contain small amounts of lipids, phosphoric acid and cations.
  • starch derivatives are also obtainable from starch by polymer-analogous reactions.
  • Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ oO 5 ) ⁇ and formally represents a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and amino celluloses.
  • Preferred enclosures made of water-soluble film consist of a polymer with a molecular weight between 5,000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons.
  • the water-soluble film which forms the enclosure preferably has a thickness of 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, particularly preferably 5 to 75 ⁇ m and in particular 10 to 50 ⁇ m.
  • these water-soluble films can be produced by various manufacturing processes.
  • blowing, calendering and casting processes should be mentioned here.
  • the films are blown from a melt with air through a blow mandrel to form a tube.
  • the additives are plasticized by suitable additives / r
  • Raw materials for forming the films are atomized. Here it may be necessary to connect drying to the atomization.
  • an aqueous polymer preparation is placed on a heatable drying roller; after the water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.
  • individual methods described here can be particularly preferred for specially functionalized films.
  • the flat plastic parts of the active ingredient portion pack contain individual components (additives) of the wash-active preparation.
  • the individual component (s) are / are particularly preferred those components which control the effectiveness of the washing, cleaning or rinsing active preparation (s) or increase their consumer acceptance.
  • Such components are frequently referred to in the present description and in the patent claims as "additives”.
  • additives it is preferred to incorporate those additives which are only required in small amounts in the washing, cleaning or rinsing active preparations and consequently
  • additives which, together with the material of the plastic film have a positive effect on the detergency or cleaning power.
  • fragrances can also be incorporated.
  • fragrances when incorporating fragrances, it is important to use suitable ones To take measures to prevent the premature volatilization of the fragrance cavity, for example encapsulation of the fragrances or embedding of the fragrances in a matrix.
  • polymers that are related to or even identical to the film materials can used to protect the fragrances.
  • the fragrances serve to give the packaged product a pleasant smell.
  • a preferred group of additives to be added according to the invention are optical brighteners.
  • the optical brighteners customary in detergents, as detailed below, can be used here. These are added as an aqueous solution or as a solution in an organic solvent to the polymer solution, which is converted into the film.
  • a further preferred group of additives to be added according to the invention are color transfer inhibitors. These are special polymers that usually contain nitrogen-containing monomers. Numerous different compounds which can be used in detergents are known to the person skilled in the art in this field.
  • UV protection substances are substances which are released in the washing liquor during the washing process or during the subsequent fabric softening process and which accumulate on the fiber in order to then achieve a UV protection effect.
  • Products from Ciba Specialty Chemicals that are commercially available under the name Tinosorb are suitable, for example.
  • additives which are preferred in special embodiments are surfactants which can in particular influence the solubility of the film, but also can control its wettability and the foam formation when dissolved, and foam inhibitors, but also bitter substances, which inadvertently swallow such packaging or parts of such packaging Can prevent children.
  • additives preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes are preferred here, as are usually used to improve the visual appearance of products in washing and cleaning agents and dishwashing detergents. IT
  • polymers Another class of additives that can be added to plastic parts according to the invention are polymers.
  • polymers which show cobuilder properties during washing or cleaning or rinsing, for example polyacrylic acids, also modified polyacrylic acids or corresponding copolymers.
  • Another group of polymers are polyvinyl pyrrolidone and other graying inhibitors such as copolymers of polyvinyl pyrrolidone, cellulose ether and the like.
  • so-called soil repellents are also suitable as polymers.
  • bleaching catalysts in particular bleaching catalysts for automatic dishwashing detergents or detergents.
  • Complexes of manganese and cobalt are used here, especially with nitrogen-containing ligands.
  • Another preferred group of additives in the sense of the invention are silver protection agents. These are a large number of mostly cyclic organic compounds which are also familiar to the person skilled in the art addressed here.
  • enzymes are in particular enzymes, as are explained in detail below and are mentioned by way of example. Enzymes are incompatible with a number of washing, cleaning and rinsing active components or only under special conditions, so that ways have already been sought to separate them from the rest of the formulation of a washing, cleaning or rinsing agent. Furthermore, it has long been a goal to use enzymes at specific, precisely definable points in time iS
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP),
  • Diethylene triamine pentamethylene phosphonate (DTPMP) as well as their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.
  • HEDP is preferably used as the cobuilder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Usable organic cobuilders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these , 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. 13
  • Suitable organic cobuilders are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which German Patent Application P 195 40 086.0 discloses that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Suitable polymeric polycarboxylates are, for example, 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.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber 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 polymers Carboxylic acids, glue, gelatin, salts of 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, for example degraded starch, aldehyde starches, etc.
  • 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 are preferably used.
  • Detergents or cleaning agents or dishwashing detergents, but also washing aids, such as, in particular, builder or bleaching compositions, can be used as wash-active preparations.
  • Laundry treatment agents or dishwashing detergent additives, such as rinse aid are also considered to be detergent-active preparations according to the invention.
  • the water-soluble polymer materials or plastic parts can also contain components which have a positive influence on the washability of oil and fat from textiles, so-called soil repelients. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and
  • All of these additives are added to the flat plastic parts according to the invention in amounts of up to 60% by weight, preferably in amounts of up to at most 30% by weight, with further advantage in amounts of 2 to 20% by weight.
  • a further aspect of the invention are methods for producing the active ingredient portion packs.
  • liquid forms such as melts or solutions of the surrounding material or materials are used, preferably solutions in a suitable solvent.
  • this solvent is water.
  • a finely dispersible preparation of at least one individual component or at least one additive of a washing, cleaning or rinsing active preparation is added to the liquid encasing material (s).
  • the mixture is then processed into a flat structure according to methods which are known per se and which are familiar to the person skilled in the art in this field.
  • the sheet-like structure obtained in this way is used to completely or partially enclose one or more washing, cleaning or rinsing active preparations and thus largely to shield them from external influences.
  • a finely dispersible preparation of an additive / several additives is added to the melt or a solution of the encasing material / the encasing materials obtained in the conventional way, the solution being particularly preferably an aqueous solution.
  • Particularly preferred 2 Z is the additive (s) in finely divided form if a melt of the surrounding material is used.
  • the additive (s) are added as solutions or as a dispersion in the solvent used, particularly preferably in water. For example, one can start from aqueous solutions of one or more polyvinyl alcohols and add aqueous solutions or dispersions of the additives to these solutions.
  • the active ingredient portion packs according to the invention comprise one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, colorants and fragrances as well as binding and disintegration aids. These classes of substances are described below.
  • the portioned detergent and cleaning agent compositions according to the invention can contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their performance spectrum.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 9 . ⁇ 3 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example from 18 C ⁇ 2- monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates from C- ⁇ -i 2 8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization won become.
  • the esters of 2-sulfofatty acids for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monogiycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • 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.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid semiesters of the C 2 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio-C ⁇ o-oxo alcohol and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C ⁇ 2 -C 16 alkyl sulfates and alkyl sulfates From the washing the C ⁇ 2 -C 16 alkyl sulfates and alkyl sulfates, and C ⁇ -C ⁇ 2 -Ci5 4 -C ⁇ preferably 5 alkyl sulfates.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 2 ⁇ alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9 n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 -i 8 -Fatty alcohols with 1 to 4 EO are suitable. They are used in detergents because of their 2 V high foaming behavior is used only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -i 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • surfactants are used in the form of their magnesium salts.
  • portioned detergent and cleaning agent compositions are preferred which are 5 to 50% by weight, preferably 7.5 to 40 wt .-% and in particular 15 to 25 wt .-% anionic surfactant (s), each based on the detergent and cleaning composition.
  • portioned detergent and cleaning agent compositions When selecting the anionic surfactants that are used in the portioned detergent and cleaning agent compositions according to the invention, there are no restrictions to be observed in terms of freedom of formulation. However, preferred portioned detergent and cleaning agent compositions have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent and cleaning agent composition.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred washing and
  • Detergent compositions contain 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 5 to 10 wt .-% fatty alcohol sulfate (s), each based on the weight of the detergent and cleaning composition
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C ⁇ ⁇ 2- 4 alcohols containing 3 EO or 4 EO, C 9 . ⁇ t alcohol containing 7 EO, C ⁇ ⁇ 3- 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , C 12 . t8 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ⁇ 2 . ⁇ 4 alcohol with 3 EO and C ⁇ 2 -i 8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, too Fatty alcohols with more than 12 EO can be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides which 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 Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the detergent and cleaning agent compositions according to the invention can preferably contain alkyl polyglycosides, APG contents of the detergent and cleaning agent compositions of more than 0.2% by weight, based on the entire molded body, being preferred.
  • Particularly preferred detergent and cleaning agent compositions contain APG in amounts of 0.2 to 10 2 *
  • % By weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R-CO-N- [Z] (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, d-4-alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this rest.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • cationic surfactants in addition to anionic and nonionic surfactants. They are preferably used as washing performance boosters, whereby only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably contained in the agents in amounts of 0.01 to 10% by weight, in particular 0.1 to 3.0% by weight.
  • the active ingredient portion packs or detergent and cleaning agent portions according to the invention are detergents
  • these usually contain one or more surfactant (s) in total amounts of 5 to 50% by weight, preferably in amounts of 10 up to 35% by weight, with partial portions of the detergent portions according to the invention containing surfactants in larger or smaller amounts.
  • the amount of surfactant is not the same in all portions; rather can Partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided.
  • the active ingredient portion packs or detergent and cleaning agent portions according to the invention are cleaning agents, in particular dishwashing detergents
  • these usually contain one or more surfactant (s) in a total amount of 0.1 to 10% by weight. , preferably in amounts of 0.5 to 5% by weight, with partial or large portions of the detergent portions according to the invention containing surfactants.
  • the amount of surfactant is not the same in all portions, even with detergents or dishwashing detergents; rather, partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided.
  • washing and cleaning agent compositions according to the invention can contain all builders normally used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi ⁇ 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 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3.
  • ß-Natriumdisiiicat can be obtained for example by the method / described in the international patent application WO-A-91 08,171th
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • amorphous is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • Zeolite MAP eg commercial product Doucil A24 from Crosfield
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Zeolite A approximately 80% by weight Zeolite X
  • VEGOBOND AX ® the formula
  • 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.
  • phosphates As builders, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, 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, nitrilotriacetic acid (NTA), as long as their 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 adjust a lower and milder pH value of detergent and cleaning agent portions according to the invention.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should 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 molar masses given for polymeric polycarboxylates are weight-average molar masses 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 to 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 acids are generally significantly higher than the molecular weights specified in the context of the present invention.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 2,000 to 10,000 g / mol, particularly preferably 3,000 to 5,000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid or 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 molar mass, 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.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the detergent or cleaning agent portions according to the invention is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, in EP-B 0 727 448, allyloxybenzoisulfonic acid and methallylsulfonic acid as a monomer.
  • allylsulfonic acids such as, for example, in EP-B 0 727 448, allyloxybenzoisulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units are preferred, for example those which, according to DE-A 43 00 772, are monomers as salts of acrylic acid and maleic acid and also vinyl alcohol or vinyl alcohol derivatives or according to DE-C 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those described in German patent applications DE-A 43 03 320 and DE-A 44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A 195 40 086 that, in addition to co-builder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A 0 280 223.
  • Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, 3V
  • Terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights 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.
  • oxidizing agents 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 in particular 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 from international patent applications WO 92/18542 , WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • An oxidized oligosaccharide according to German patent application DE-A 196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • organic co-builders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are described, for example, in international patent application WO 95/20029.
  • phosphonates Another class of substances with co-builder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates, which have already been described above.
  • washing and cleaning agents according to the invention can contain further ingredients from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, and graying inhibitors, which are common in detergents and cleaning agents , Color transfer inhibitors and corrosion inhibitors included.
  • 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. If cleaning or bleaching agent compositions for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxyhexanoic acid ( ⁇ -phthalimidoperoxyhexanoic acid) )], o-
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in compositions for machine dishwashing.
  • Suitable materials which 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 cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. 3 " ?
  • bleach activators can be incorporated into the detergent and cleaning agent composition.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • bleach catalysts can also be incorporated into the detergent and cleaning agent composition.
  • 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 can also be used as bleaching catalysts.
  • Enzymes from the class of proteases, lipases, amyiases, cellulases or mixtures thereof are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases derived from Bacillus are preferred lentus are used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, approximately 0.1 to 5% by weight, preferably 0.1 to approximately 2% by weight.
  • enzymes are primarily added to a cleaning agent preparation, in particular a dishwashing agent which is intended for the main wash cycle.
  • the disadvantage here was that the optimum effect of the enzymes used restricted the choice of temperature and problems also occurred with the stability of the enzymes in a strongly alkaline environment.
  • the detergent or cleaning agent portions according to the invention it is possible to use enzymes also in the pre-rinse cycle and thus to use the pre-rinse cycle in addition to the main rinse cycle for enzyme action on soiling of the wash ware.
  • enzymes to the wash-active preparation or partial portion of a detergent portion intended for the pre-rinse cycle, and then - more preferably - to include such a preparation with a material that is already water-soluble at low temperature, in order, for example, to prevent the enzyme-containing preparation from losing its effectiveness To protect environmental conditions.
  • the enzymes are furthermore preferably optimized for use under the conditions of the pre-rinse cycle, for example in cold water.
  • the detergent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as some are commercially available, because then a quick effect can be expected that already occurs in the (relatively short and cold water) pre-rinse cycle. Even if - as usual - the enzymes are used in solid form and these are provided with a covering made of a water-soluble material that is already soluble in cold water, the enzymes can be used before
  • a casing made of water-soluble material in particular of a material soluble in cold water, is that the enzyme (s) quickly comes into effect in cold water after the casing has been dissolved. This can extend their effectiveness, which benefits the washing or rinsing result.
  • the detergent or cleaning agent portions according to the invention also contain further additives as are known from the prior art as additives for washing or cleaning agent preparations. These can either be added to one or more portions of the detergent or cleaning agent portions according to the invention, if necessary also to all partial portions (detergent-active preparations), or according to the invention in the water-soluble materials comprising the detergent-active preparations, for example in the water-soluble films, but also in Capsules or coatings can be incorporated, which can serve as enclosures.
  • optical brighteners customary in detergents can be used here. These are added as an aqueous solution or as a solution in an organic solvent to the polymer solution which is converted into the film, or are added to a portion (detergent-active preparation) of a detergent or cleaning agent in solid or liquid form.
  • optical brighteners are derivatives of diaminostilbenedisulfonic acid Ho or their alkali metal salts. Are suitable for. B.
  • Preparations) of the detergent or cleaning agent portions according to the invention may be included, for. B. the alkali salts of 4,4'-bis (2-sulfostyryl-) diphenyl, 4,4'-
  • a further group of additives preferred according to the invention were UV protection substances, surfactants, which in particular can influence the solubility of the water-soluble film, but can also control its wettability and the foam formation when dissolved, as well as foam inhibitors and bitter substances, which inadvertently swallow such packaging or Can prevent parts of such packaging from children, and also polymers and bleaching catalysts mentioned above.
  • dyes in particular water-soluble or water-dispersible dyes.
  • Dyes are preferred here, as are usually used to improve the visual appearance of products in detergents and cleaning agents.
  • the selection of such dyes does not pose any difficulties for the person skilled in the art, in particular since such customary dyes have a high storage stability and insensitivity to the other ingredients of the detergent preparations and to light, and have no pronounced substantivity towards textile fibers in order not to dye them.
  • the dyes are present in the detergent or cleaning agent portions in amounts of less than 0.01% by weight. V /
  • silver protection agents are a large number of mostly cyclic organic compounds which are likewise familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process.
  • Specific examples can be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.
  • the detergent or cleaning agent portions can also contain so-called soil repellents, i.e. polymers which build up on fibers or hard surfaces (for example on porcelain and glass), have a positive influence on the oil and fat washability from textiles and thus on re-soiling counteract specifically. This effect is particularly evident when a textile or a hard object (porcelain, glass) is soiled that has already been washed several times beforehand with a washing or cleaning agent according to the invention which contains this oil and fat-dissolving component.
  • soil repellents i.e. polymers which build up on fibers or hard surfaces (for example on porcelain and glass)
  • 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 methoxy groups from 15 to 30% by weight and of hydroxypropoxy groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • All of these additives are added to the detergent or cleaning agent portions according to the invention in amounts of up to at most 30% by weight, preferably 2 to 20% by weight. According to the invention, the addition can be made to a material of a water-soluble enclosure, which comprises one or more of the wash-active V
  • Preparation (s) includes.
  • Fragrances are added to the detergent and cleaning agent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softener result), to provide the consumer with a sensorially typical and distinctive product.
  • Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carboxyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropionate
  • the ethers include, for example, benzyl ethyl ether.
  • the aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.
  • the ketones include the ionones, ⁇ -isomethyl ionone and methyl cedryl ketone.
  • Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different fragrances are preferably used which are coordinated with one another in such a way that together they produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, HZ
  • Lemon balm oil mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrance content is usually in the range up to 2% by weight of the total detergent or cleaning agent portion.
  • These are therefore typical additives which, owing to their small amount in conventional formulations, are difficult to distribute homogeneously, but which, according to the present invention, can ideally be added to the material of the enclosure (s) and are therefore present in a uniform distribution in the active ingredient packs according to the invention.
  • the fragrances can be incorporated directly into the wash-active preparations; However, it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven themselves as such carrier materials.
  • the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • the perfumes and fragrances can in principle be contained in each of the partial portions (detergent preparations) of the detergent or cleaning agent portions according to the invention. However, it is particularly preferred that they are in a detergent portion in a partial detergent portion intended for the post-wash or softener stage or in a detergent, especially in a dishwashing detergent, in a portion of the detergent portion intended for the final rinse or rinse stage, special portion of detergent portion are included. According to the invention, therefore, they must be of a material which is water-soluble only under the conditions (in particular at the temperature) of the post-wash or rinse cycle, and under the conditions (in particular at the temperature) of the preceding wash cycles or rinse cycles, in particular of W a corresponding film or capsule may be included. According to the invention, this can be done, for example, with a pouch consisting of a plurality of compartments made of foils of different water solubility.
  • the invention also relates to a washing process, in which an active ingredient portion package is placed in a washing machine according to the above detailed description and the additives contained in the enclosure are released by adding water and heating the washing liquor above the solution point of the enclosure while loosening the enclosure. Furthermore, the present invention also relates to a method for machine dishwashing, in which an active ingredient portion pack according to the detailed description above is added to the metering chamber of an automatic dishwasher and the additives are released by adding water and releasing the active ingredient portion pack from the metering chamber while loosening the enclosure.
  • the invention also relates to a method for automatic dishwashing using an active ingredient portion pack according to the detailed description above, in which a cover is selected which only becomes water-soluble above room temperature, the active detergent preparation is placed in the interior of the dishwasher and by adding water and heating the washing liquor via the solution point of the enclosure releases the additives contained in the enclosure while loosening the enclosure.
  • Aerosil R972 from Degussa-Huls; silica
  • Sokalan HP 53 BASF; polyvinylpyrrolidone Vr Tinopal CBS-X; Ciba, 4,4'-bis (2-sulfostyrene) biphenyl; Disodium salt
  • sorbitol 60 parts by weight of sorbitol are stirred into an approximately 40 percent aqueous solution.
  • a film with a thickness of 10 to 50 ⁇ m is produced from this solution by thermal calendering.
  • the film is used to pack machine dishwashing detergents in TabForm or a detergent tablet by breaking these tabs and sealing the edges of the film.
  • the dissolution point of the film can be varied between 0 and 80 ° C. In the present case, a solution was obtained at 20 ° C
  • Example 1 5% by weight of an optical brightener
  • Example 2 5% by weight of a UV protection substance
  • Example 3 5% by weight of a blue detergent dye
  • Example 4 10% by weight of a detergent perfume mixture
  • Example 5 20% by weight of a soil repellent polymer based on ethylene glycol and terephthalic acid;
  • Example 6 3% by weight of a cobaltamine complex; or
  • Example 7 10% by weight of benzotriazole added.
  • the substances mentioned can be easily incorporated into the polymer films using mechanical energy. Incorporation takes place - where possible - in an aqueous solution, otherwise in an aqueous dispersion. The resulting films are even and dissolve completely during rinsing attempts, so that the additives are released.
  • a film was produced which ( ⁇ ) 13.5% by weight Optiblanc 2MG (9% active content); (ß) 2.2% by weight of Tinopal CBS-X (2% active content); and ( ⁇ ) contained 84.3% by weight of PVAL and auxiliaries. The amount of brightener which was intended for the megaperls was thus present in 1.5 g of film. The film was transparent with an opalescent sheen, but was not colored in a disturbing way.
  • a film was produced which contained ( ⁇ ) 25% by weight of polyvinylpyrrolidone (active content from aqueous Sokolan HP53 solution) and ( ⁇ ) 75% by weight of PVAL and auxiliaries.
  • the amount of graying inhibitor (PVP) that was intended for Megaperls Color was thus present in 1.5 g of film.
  • the film was colorlessly transparent.
  • PVA films for detergent enclosures were made, which contained various detergent ingredients or plasticizers. Films 1 and 2 were blown films, films 3 to 9 were pressed films. The mixtures given below were processed in a Brabender twin-screw kneader (DSK) 42/7. The DSK worked with counter-rotating screws, which ensured extremely good mixing. The temperatures for processing the mixtures were 140 ° C in the three zones along the screw and 147 ° C in the outlet nozzle.
  • Mixtures 1 and 2 were processed at 50 rpm and granulated.
  • the granules obtained were processed in a film blowing system (single-screw kneader / Brabender).
  • the temperature profile from the feed zone to the nozzle was set as follows: Heating zones 1 to 6: 180, 175, 160, 150, 120, 120 ° C.
  • the screw was operated at 50 rpm, which resulted in a torque of 80 Nm.
  • a film removal speed of 1.3 was set.
  • Mixtures 3 to 9 were extruded at 50 rpm and through a ribbon die.
  • the dimensions of the nozzle are 50 x 0.5 mm, so that a tape 45 mm wide and 0.5 mm thick was obtained.
  • the tape obtained was pressed into films using a heatable press (from Webre). 120 to 180 ° C were chosen as pressing temperatures; the contact pressure was 50 to 60 bar.
  • the films obtained contained the respective additive (s) in uniform concentration, i.e. H. the additive (s) was / were evenly distributed in the respective film material.
  • the films showed excellent properties in the manufacture of active ingredient packs and could be easily processed on the existing machines.
  • the films of the active ingredient portion packs obtained dissolved as well and completely in the aqueous phase as the corresponding films containing no additive (s).
  • the effect of the additives in the films led to the same result as that of the additives in the detergent preparation; in contrast to the former, however, a greater concentration of the additives in the preparations of the prior art was required in order to compensate for the concentration fluctuations due to the inhomogeneous distribution.

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Abstract

L'invention concerne des enveloppes plates en polymère soluble dans l'eau habituellement utilisées dans le cas d'emballages-portions de matières actives. Selon l'invention, ces enveloppes sont dotées d'une fonction dans le cadre de leur formulation générale. De tels emballages-portions de matières actives contiennent une préparation détersive et un élément plastique plat. L'élément plastique entoure complètement ou au moins partiellement la préparation. L'élément plastique plat contient des composants individuels liés complètement ou essentiellement, ces composants individuels commandant la puissance de la préparation détersive ou augmentant leur acceptation par les consommateurs ("additifs").
PCT/EP2000/005540 1999-06-25 2000-06-16 Emballage-portion de matiere active Ceased WO2001000781A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54053/00A AU5405300A (en) 1999-06-25 2000-06-16 Packaging for a portion of an active substance

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE19929098 1999-06-25
DE19929098.9 1999-06-25
DE19934983.5 1999-07-26
DE1999134983 DE19934983A1 (de) 1999-07-26 1999-07-26 Verwendung von Polyvinylalkoholen als schmutzablösevermögende Waschmittelzusätze
DE19961661A DE19961661A1 (de) 1999-06-25 1999-12-21 Wirkstoffportionspackung
DE19961661.2 1999-12-21

Publications (1)

Publication Number Publication Date
WO2001000781A1 true WO2001000781A1 (fr) 2001-01-04

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AU (1) AU5405300A (fr)
CA (1) CA2312157A1 (fr)
WO (1) WO2001000781A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1149897A1 (fr) * 2000-04-27 2001-10-31 The Procter & Gamble Company Emballage pour détergent sous forme de dose unitaire et son procédé d'utilisation
WO2002006431A3 (fr) * 2000-07-14 2002-05-30 Henkel Kgaa Corps creux a compartiment
WO2002048309A1 (fr) * 2000-12-16 2002-06-20 Henkel Kommanditgesellschaft Auf Aktien Portions de produit de lavage, de rinçage ou de nettoyage a enveloppe transparente
WO2002053695A3 (fr) * 2001-01-05 2002-11-07 Henkel Kgaa Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage contenant des tensioactifs
WO2003016444A3 (fr) * 2001-08-17 2003-11-06 Henkel Kgaa Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre
EP1375637A1 (fr) * 2002-06-17 2004-01-02 Unilever N.V. Compositions détergentes
US7022659B2 (en) 2000-04-27 2006-04-04 The Procter & Gamble Company Packaged unit dose of detergent and method of treating fabrics
US7192911B2 (en) 2001-07-07 2007-03-20 Henkel Kgaa Nonaqueous 3 in 1 dishwasher products
CN102302430A (zh) * 2011-05-19 2012-01-04 大连九羊食品有限公司 一种含有羊乳脂的洗手液及其制备方法
WO2014040865A1 (fr) * 2012-09-14 2014-03-20 Henkel Ag & Co. Kgaa Détergent liquide structuré à faible teneur en eau contenant des particules
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
WO2017158002A1 (fr) 2016-03-16 2017-09-21 Basf Se Films polymères à action détergente et nettoyante, procédé pour les produire et leur utilisation
WO2018109201A1 (fr) 2016-12-16 2018-06-21 Basf Se Films multicouche à action détergente et nettoyante, procédé de production desdits films et utilisation correspondante
WO2018109200A1 (fr) 2016-12-16 2018-06-21 Basf Se Feuilles multicouches, leur procédé de fabrication et leur utilisation
WO2018108687A1 (fr) 2016-12-16 2018-06-21 Basf Se Procédé pour la fabrication de feuilles fonctionnelles solubles dans l'eau

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1808482A1 (fr) 2006-01-14 2007-07-18 Dalli-Werke GmbH & Co. KG Compositions detergentes et procede de fabrication

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Publication number Priority date Publication date Assignee Title
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4692494A (en) * 1980-12-15 1987-09-08 Colgate-Palmolive Company Water soluble films of polyvinyl alcohol and polyacrylic acid and packages comprising same
EP0291198A2 (fr) * 1987-05-14 1988-11-17 The Clorox Company Films en PVA modifié par des comonomères anioniques non hydrolysables contenant des additifs
DE4115286A1 (de) * 1991-05-10 1992-11-12 Henkel Kgaa Waschmittelerzeugnis
DE4416481A1 (de) * 1994-05-10 1995-11-16 Stefan Dr Rer Nat Geyer Wasch- und Reinigungsmittel einschließlich Verpackung
EP0700989A1 (fr) * 1994-09-12 1996-03-13 The Procter & Gamble Company Détergent emballé par dose

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4692494A (en) * 1980-12-15 1987-09-08 Colgate-Palmolive Company Water soluble films of polyvinyl alcohol and polyacrylic acid and packages comprising same
EP0291198A2 (fr) * 1987-05-14 1988-11-17 The Clorox Company Films en PVA modifié par des comonomères anioniques non hydrolysables contenant des additifs
DE4115286A1 (de) * 1991-05-10 1992-11-12 Henkel Kgaa Waschmittelerzeugnis
DE4416481A1 (de) * 1994-05-10 1995-11-16 Stefan Dr Rer Nat Geyer Wasch- und Reinigungsmittel einschließlich Verpackung
EP0700989A1 (fr) * 1994-09-12 1996-03-13 The Procter & Gamble Company Détergent emballé par dose

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1149897A1 (fr) * 2000-04-27 2001-10-31 The Procter & Gamble Company Emballage pour détergent sous forme de dose unitaire et son procédé d'utilisation
WO2001081530A1 (fr) * 2000-04-27 2001-11-01 The Procter & Gamble Company Sachet pour dose unitaire de detergent et son procede d'utilisation
US7022659B2 (en) 2000-04-27 2006-04-04 The Procter & Gamble Company Packaged unit dose of detergent and method of treating fabrics
WO2002006431A3 (fr) * 2000-07-14 2002-05-30 Henkel Kgaa Corps creux a compartiment
US7417019B2 (en) 2000-07-14 2008-08-26 Henkel Kommanditgesellschaft Auf Aktien Hollow body with a compartment, containing a portion of a washing, cleaning or rinsing agent
US7601679B2 (en) 2000-07-14 2009-10-13 Henkel Ag & Co. Kgaa Process for producing a hollow body with a compartment, containing a portion of a washing, cleaning or rinsing agent
WO2002048309A1 (fr) * 2000-12-16 2002-06-20 Henkel Kommanditgesellschaft Auf Aktien Portions de produit de lavage, de rinçage ou de nettoyage a enveloppe transparente
WO2002053695A3 (fr) * 2001-01-05 2002-11-07 Henkel Kgaa Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage contenant des tensioactifs
US7192911B2 (en) 2001-07-07 2007-03-20 Henkel Kgaa Nonaqueous 3 in 1 dishwasher products
WO2003016444A3 (fr) * 2001-08-17 2003-11-06 Henkel Kgaa Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre
US7153816B2 (en) 2001-08-17 2006-12-26 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Dishwasher detergent with improved protection against glass corrosion
EP1375637A1 (fr) * 2002-06-17 2004-01-02 Unilever N.V. Compositions détergentes
CN102302430A (zh) * 2011-05-19 2012-01-04 大连九羊食品有限公司 一种含有羊乳脂的洗手液及其制备方法
WO2014040865A1 (fr) * 2012-09-14 2014-03-20 Henkel Ag & Co. Kgaa Détergent liquide structuré à faible teneur en eau contenant des particules
US10364409B2 (en) 2013-10-09 2019-07-30 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9840683B2 (en) 2013-10-09 2017-12-12 Basf Se Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
WO2017158002A1 (fr) 2016-03-16 2017-09-21 Basf Se Films polymères à action détergente et nettoyante, procédé pour les produire et leur utilisation
CN108779212A (zh) * 2016-03-16 2018-11-09 巴斯夫欧洲公司 洗涤和清洁活性聚合物膜，其制备方法及其用途
US10822443B2 (en) 2016-03-16 2020-11-03 Basf Se Washing- and cleaning-active polymer films, process for the production thereof and use thereof
WO2018109200A1 (fr) 2016-12-16 2018-06-21 Basf Se Feuilles multicouches, leur procédé de fabrication et leur utilisation
WO2018108687A1 (fr) 2016-12-16 2018-06-21 Basf Se Procédé pour la fabrication de feuilles fonctionnelles solubles dans l'eau
WO2018109201A1 (fr) 2016-12-16 2018-06-21 Basf Se Films multicouche à action détergente et nettoyante, procédé de production desdits films et utilisation correspondante
CN110291119A (zh) * 2016-12-16 2019-09-27 巴斯夫欧洲公司 洗涤和清洁多层膜、其生产方法和用途
CN110291120A (zh) * 2016-12-16 2019-09-27 巴斯夫欧洲公司 多层膜、其生产方法和用途

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AU5405300A (en) 2001-01-31
CA2312157A1 (fr) 2000-12-25

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