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WO2001029173A1 - Detergents ou nettoyants a base de gaz inerte en portions - Google Patents

Detergents ou nettoyants a base de gaz inerte en portions Download PDF

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Publication number
WO2001029173A1
WO2001029173A1 PCT/EP2000/009831 EP0009831W WO0129173A1 WO 2001029173 A1 WO2001029173 A1 WO 2001029173A1 EP 0009831 W EP0009831 W EP 0009831W WO 0129173 A1 WO0129173 A1 WO 0129173A1
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WO
WIPO (PCT)
Prior art keywords
detergent
water
enclosure
wash
washing
Prior art date
Application number
PCT/EP2000/009831
Other languages
German (de)
English (en)
Inventor
Wilfried Rähse
Bernd Larson
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO2001029173A1 publication Critical patent/WO2001029173A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—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

Definitions

  • the present invention relates to a detergent or cleaning agent portion containing at least one inert gas.
  • the invention relates to a detergent or cleaning agent portion with at least one detergent-active preparation and one or more enclosures completely or partially surrounding the at least one detergent-active preparation) or several water-soluble polymer materials (in which the enclosures) contain / contain at least one gas or comprise / comprise or enclose / enclose a substance which releases at least one inert gas on reaction with water
  • detergents and cleaning agents and processes for their production have long been known and are extensively described in the prior art.
  • detergents or cleaning agents are 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.
  • the older patent application DE 198 31 703 discloses a portioned washing or cleaning agent preparation in a bag made of water-soluble film, in particular a bag made of (optionally acetalized) polyvinyl alcohol (PVAL), in which at least 70% by weight of the particles of the washing or Detergent preparation have particle sizes> 800 ⁇ m.
  • PVAL polyvinyl alcohol
  • detergent or cleaning agent portions should be provided with an enclosure made of water-soluble film, the contents of which, i.e. their washing-active preparations, can be protected simply and reliably against ingress of water or moisture before the washing or cleaning cycle, so that the components of the washing-active Preparation (s) are not deactivated by reaction with water, but are actively available for the actual washing or cleaning cycle.
  • the invention relates to a detergent or cleaning agent portion with at least one wash-active preparation and one or more enclosures (s) surrounding one or more water-soluble polymer material (s) surrounding the at least one wash-active preparation, in which the enclosure (s) is / are completed and contains at least one anhydrous gas which does not react with the wash-active preparation (s). It is preferred that the enclosure (s) contain the at least one anhydrous gas in an amount such that the total pressure within the enclosed enclosure (s) is above the external pressure.
  • the enclosure (s) advantageously contain the at least one anhydrous gas in an amount such that the total pressure inside the enclosed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, even more preferably by at least 10 mbar, particularly preferably in the range from 10 to 50 mbar.
  • the invention also relates to a detergent or cleaning agent portion with at least one wash-active preparation and one or more enclosures (s) surrounding the at least one wash-active preparation made of one or more water-soluble polymer material (s), in which the enclosure (s) ) is / are completed and contain at least one substance which, when reacted with water, releases at least one gas which does not react with the wash-active preparation (s) in an amount such that the total pressure within the closed enclosure (s) increases.
  • the at least one substance advantageously releases the at least one gas in an amount such that the total pressure within the closed enclosure (s) increases by at least 1 mbar above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range of 5 up to 50 mbar.
  • the invention further relates to a method for protecting at least one wash-active preparation in a casing consisting of at least one water-soluble polymer material from decomposition as a result of contact with moisture, in which the washing-active preparation (s) with at least one casing are made of a provides water-soluble polymer material, closes it around the wash-active preparation and applies an anhydrous gas which does not react with the wash-active preparation (s) to the closed enclosure.
  • the process is advantageously carried out in such a way that the sealed enclosure is charged with the at least one water-free gas in an amount such that the total pressure within the sealed enclosure solution (s) above the external pressure, preferably that the total pressure within the closed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, even more preferably by at least 10 mbar, particularly preferably in the range of 10 up to 50 mbar
  • the invention further relates to a method for protecting at least one wash-active preparation in an enclosure consisting of at least one water-soluble polymer material from decomposition as a result of contact with moisture, in which the wash-active preparation (s) with at least one enclosure are made from one provides water-soluble polymer material, introduces at least one substance into the enclosure which, when reacted with water, can release a gas which does not react with the washing-active preparation (s) in an amount such that the total pressure within the enclosed enclosures) increases, and that Water-soluble polymer material sealed around the wash-active preparation.
  • a process is preferred in which at least one substance is introduced into the enclosure which, when reacted with water, can release at least one gas which does not react with the wash-active preparation (s) in an amount. that the total pressure within the closed scope solution (s) increases by at least 1 mbar above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range from 5 to 50 mbar
  • the invention also relates to a washing method, in particular a method for machine washing, in which a detergent portion is placed in a washing machine according to the detailed description below and by adding water and adjusting the temperature to a value at which the enclosure (s) consists of at least one Water-soluble polymer material is released, which releases the wash-active preparation (s) into the wash liquor
  • the invention also relates to a cleaning method, in particular a method for machine-washing dishes, in which a portion of the cleaning agent is placed in a dishwasher according to the detailed description below and by adding water and adjusting the temperature to a value at which the surrounding area (s) are formed at least one water-soluble polymer material is released, which releases the washing actives into the cleaning liquor
  • the term “detergent or cleaning agent portion” means an amount of a detergent or cleaning agent which is sufficient for a washing or cleaning process taking place in an aqueous phase.
  • washing or cleaning are preferred Detergent portions used in machine washing or cleaning processes
  • portion of detergent or cleaning agent is understood to mean a portion of a portion of washing or cleaning agent that is in a phase separated from other portions of washing or cleaning agent in spatial connection with other detergents or cleaning agents Partial portions of the same detergent or cleaning agent portion are present and are prepared by suitable measures so that they can be added to the liquor separately from other washing or cleaning agent partial portions of the same detergent or cleaning agent portion and, if appropriate, dissolved or suspended in them
  • a detergent or cleaning agent portion can contain the same ingredients as another detergent or cleaning agent portion portion of the same detergent or cleaning agent portion, but preferably two detergent or cleaning agent portions of the same detergent or cleaning agent portion contain different contents toffe, in particular different washing-active preparations
  • the detergent or cleaning agent portions contain measured amounts of at least one detergent-active preparation, usually measured amounts of several detergent-active preparations. It is possible that the portions only contain detergent-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least Two detergent-active preparations of different compositions are contained in the detergent or cleaning agent portions.
  • the composition can differ in terms of the concentration of the individual components of the detergent-active preparation (quantitative) and / or with regard to the type of individual components of the detergent-active preparation (qualitative). be different. It is particularly preferred that the components are adapted in terms of type and concentration to the tasks which the detergent or cleaning agent portion portions have to fulfill in the washing or cleaning process.
  • the partial portions are preferably the first, second and, if appropriate, third or even higher (fourth, fifth, etc.) measured quantities of one or more detergent-active preparation (s) which are comprised of the same or different water-soluble materials and which form a detergent. or detergent portion are combined according to the invention.
  • wash-active preparation or “rinse-active preparation” is understood to mean preparations of all conceivable substances which are relevant in connection with a washing or cleaning process Description of individual components explained in more detail, including active substances such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as, for example, peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, Bleaching catalysts, enzymes, special polymers (eg those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the term being restricted to these substance groups.
  • active substances such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as, for example, peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, Bleaching catalysts, enzymes, special polymers (eg
  • wash-active preparations or “rinse-active preparation” also includes washing aids and cleaning aids.
  • these are optical brighteners, UV protection substances, so-called soil repellents, that is to say polymers which counteract re-soiling of fibers or hard surfaces
  • Laundry treatment agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered to be detergent-active or dishwashing preparations.
  • the detergent or cleaning agent portion has at least one washing-active preparation.
  • the number of detergent-active preparations is not limited and is largely dependent on the use of the detergent or cleaning agent portion.
  • Several detergent preparations are usually contained in the detergent or cleaning agent portion according to the invention.
  • the detergent and cleaning agent portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, lead activators, enzymes, foam inhibitors, dyes and fragrances and - in the event that the detergents or cleaning agents - Portions are at least partially in the form of shaped bodies - binding and disintegration aids. These classes of substances are described below
  • the detergent and cleaning agent portions 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
  • the anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 2 .
  • alkane sulfonates obtained from C 12 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization the esters of 2-sulfofatty acids (ester sulfonates), 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 glycine nests.
  • Fatty acid glycine nests are to be understood as meaning the mono-, di- and t-esters as well as their mixtures as they are produced by esterification of a monoglycene with 1 to 3 moles of fatty acid or in the transesterification of tnglycerides with 0. 3 to 2 moles of glycene are obtained.
  • Preferred sulfonated fatty acid glycine nests are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, launic acid, palmitic acid, stearic acid or behenic acid
  • the alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half-esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, methyl, cetyl or stearyl alcohol or C 10 -C 20 -Oxo alcohols and those Half-preferred secondary alcohols of these chain lengths are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials are the C 2 -C 16 alkyl sulfates and C 12 -C 5 alkyl sulfates and C 4 -C 15 alkyl sulfates are also preferred 2,3-alkyl sulfates, which are produced for example according to US Pat. Nos. 3,234,258 or 5,075,041 and as Shell's commercial products Oil Company under the name DAN ® are suitable anionic surfactants
  • the sulfuric acid monoesters of the straight-chain or branched C 7 21 alcohols ethoxy-containing 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 18 fatty alcohols 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight
  • Suitable anionic surfactants are also the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 18 -fatty alcohol residues
  • Mixtures of these particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) yl succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof
  • anionic surfactants are, in particular, soaps.
  • Saturated fatty acid soaps such as the salts of launic acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acid, are suitable
  • the anionic surfactants, including the soaps can be present in the form of their sodium, potassium or ammonium salts and 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
  • detergent and cleaning agent portions are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight, of one or more anionic ten-s (s), included, each based on the detergent and cleaning agent portion
  • preferred washing and cleaning agent portions according to the invention have a soap content which is 0. 2% by weight, based on the total weight of the detergent and detergent portion, exceeds the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent and detergent portions being 2 to 20% by weight, preferably 2.5 to 15 % By weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), in each case based on the weight of the detergent and cleaning agent portion
  • the nonionic surfactants used are preferably alkoxy-hard, advantageously ethoxy-hard, 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 residue is branched, preferably in the 2-position, methyl may or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 14 alcohols with 3 EO or 4 EO, C 9 11 alcohol with 7 EO, C 13 15 alcohols with 3 EO, 5 EO , 7 EO or 8 EO, C 12 ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, and mixtures of C 12 1 alcohol with 3 EO and C 12 18 alcohol with 5 EO
  • the degrees of ethoxyherization shown are statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are taig 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 alkoxy, preferably ethoxy or ethoxy, and propoxy, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain , in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared 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 that can be used satisfy the general formula RO (G) 2 , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, a phatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C 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 polygiucosides 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 portions according to the invention can preferably contain alkyl polyglycosides, the contents of the detergent and cleaning agent portions of APG being greater than 0.2% by weight, based on the total shaped body, being preferred.
  • Particularly preferred detergent and cleaning agent portions contain APG in amounts of 0.2 to 10% by weight, preferably in amounts of 0.2 to 5% by weight and in particular in amounts
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-d ⁇ hydroxyethylam ⁇ nox ⁇ d, and the fatty Acid alkanolamides may be suitable.
  • the amount of these nonionic surfactants is preferably no more than that of the ethoxy-modified fatty alcohols, in particular not more than half of them
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cychly alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cychschen alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, d ⁇ -alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups, or alkoxy radicals, preferably ethoxy radicals or propoxy radicals 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.
  • Alkoxy- or N-aryloxy-substituted compounds can then be converted, for example according to the teaching of international application WO-A-95/07331, into the desired polyhydroxyfatty acid amides by reaction with fatty acid thyme diesters 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, only small amounts of cationic surfactants being required. If cationic surfactants are used, they are preferably in amounts of 0 in the compositions , 01 to 10% by weight, in particular 0.1 to 3.0% by weight
  • the detergent and cleaning agent portions according to the invention are detergents
  • surfactants can be present in larger or smaller amounts.
  • the amount of surfactant is not the same in all partial portions, rather partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided
  • the detergent and cleaning agent portions according to the invention are cleaning agents, in particular dishwashing agents, they usually contain one or more surfactants in total amounts of 0.1 to 10% by weight, preferably in amounts from 0.5 to 5% by weight, with partial portions of the cleaning agent portions according to the invention containing surfactants in larger or smaller amounts. In other words, the amount of surfactant is not the same in all partial portions even with detergents or dishwashing agents, rather partial portions can with relatively larger and partial portions with a relatively smaller surfactant content.
  • builders are the most important ingredients of detergents and cleaning agents.
  • the detergent and cleaning agent portions according to the invention may contain builders usually used in detergents and cleaning agents, in particular zeolites, sihcates . Carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also phosphates Suitable crystalline, layered sodium silicates have the general formula NaM
  • Amorphous sodium silicates with a Na 2 O SiO 2 module of from 1 2 to 1 3.3, preferably from 1 2 to 1 2.8 and in particular from 1 2 to 1 2.6, which are loosely delayed and have secondary washing properties, can also be used Loose delay compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”.
  • the silicates do not provide sharp X-ray reflections in X-ray diffraction experiments, 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 bullder properties if the Sihcat particles contribute Elektronenbeugungsexpe ⁇ ment provide washed-out or even sharp diffraction maxima. This is to be interpreted as meaning that the products have microcrystalline regions of the size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm being preferred.
  • Such so-called X-ray amorphous silicates which are also having a loose delay compared to conventional water glasses are described, for example, in German patent application DE-A-44 00 024. Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred
  • An optionally used finely crystalline, synthetic and bound water-containing zeo th is preferably Zeohth A and / or P.
  • Zeohth MAP eg commercial product Doucil A24 from Crosfield
  • Zeohth X and mixtures of A, X and / or P are also commercially available and can preferably be used in the context of the present invention, for example a co-crystallate of Zeohth X and Zeohth A (about 80% by weight Zeohth X), which is from is sold by CONDEA Augusta S p A under the brand name VEGOBOND AX ® and through the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, Coulter Counter measurement method) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water
  • the sodium salts of the orthophosphates, the pyrophosphates and in particular the polyphosphates are particularly suitable
  • Usable organic scent substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures of these, including the acids themselves can be used
  • the acids typically also have the property of an acid component and thus also serve to set a lower and milder pH value for detergent and cleaning agent portions, in particular according to the invention
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned
  • 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 basically determined by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external poly acrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight data for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene acid are generally significantly higher than those in the context of the present invention specified molecular weights
  • Suitable polymers are in particular polyacrylates, which preferably have a molar mass of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, the molar masses of 2,000 to 10,000 g / mol, particularly preferably of, can be preferred 3,000 to 5,000 g / mol
  • 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 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 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 allyl sulfonic acids, such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methyl sulfonic acid as a monomer
  • allyl sulfonic acids such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methyl sulfonic acid
  • biodegradable polymers of more than two different monomer units are preferred, for example those which, according to DE-A 43 00 772, as monomers, salts of acrylic acid and maleic acid, and vinyl alcohol or vinyl alcohol derivatives, or according to DE-C 42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives
  • copolymers are those which are 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
  • preferred builder substances are 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 they are used in addition to co-builders - Properties 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, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid
  • dextrins for example ohgomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes.
  • the products are hydrolysis products with average molecular weights in the range from 400 up to 500,000 g / mol
  • DE dextrose equivalent
  • a preferred dextrin is described in British patent application 94 19 091
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide to the carboxylic acid function.
  • oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide 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 as well as 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 known
  • an oxidized Ohgosaccha d according to German patent application DE-A 196 00 018.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous
  • Ethylenediamine-N, N'-disuccinate (EDDS) the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferred in the form of its sodium - or magnesium salts are furthermore preferred in this connection, too.
  • Glycene disuccinates and glycine nesuccinates, as described, for example, in US Pat. Nos. 4,524,009 and 4,639,325, in European patent application EP-A 0 150 930 and in Japanese patent application JP- A 93 / 339,896 are described. Suitable amounts are 3 to 15% by weight in formulations containing zeolites and / or silicates.
  • organic co-builders are, for example, acetyheric hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups.
  • Such co-builders are described, for example, in international patent application WO 95 / 20029
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroalkane phosphonates 1-hydroxyethane-1,1-phosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-phosphonate
  • Aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues.
  • EDTMP hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, in particular if the detergent or cleaning agent portions according to the invention also contain bleach, it may be preferred to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the washing or 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, graying inhibitors, which are common in washing or 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-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecotacic acid. If cleaning or bleaching preparations 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) 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 peroxy acids, such as Peroxylaunnsaure, Peroxysteannsaure, ⁇ -Phthahmidoperoxy-capronsaure [Phthaloiminoperoxyhexansureure (PAP)], o-Carboxybenzamido-peroxycapronsaure, N-Nonenylamido-peradipinsaure and N-Nonenylamidopersuccinate, and (a) carboxamate and, (a) carbonic acid 12-peroxydonate, and (a) carboxamate and, (a) carbonic acid 12-peroxy
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in compositions for machine dishwashing.
  • suitable chlorine or bromine-releasing materials are, for example, heterocyclic N-bromine and N-chloramides, for example tnchloroisocyanuric acid, trichloroisocyanuric acid
  • Dibromo isocyanuric acid and / or dichlonsocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are also suitable.
  • Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin, are also suitable.
  • bleach activators can be incorporated into the detergent and cleaning agent portions.
  • Bleach activators can be compounds which contain periphocarboxylic acids with preferably 1 to 10 carbon atoms under perhydrolysis conditions, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used. Substances which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups are preferred.
  • acy erte alkylenediamines especially tetraacetylethylenediamine (TAED), acyherte triazindenvate, especially 1, 5-d ⁇ acetyl-2,4-d ⁇ oxohexahydro-1, 3,5-tr ⁇ az ⁇ n (DADHT), acyherte glycolunle, especially tetraacetylglycol), N-TAGU Acyhmide, especially N-Nonanoylsuccinimid (NOSI), acyherte Phenolsulfonate, in particular n-Nonanoyl- or Isononanoyloxybenzo Isulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acyherte polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-d ⁇ hydrofuran
  • TAED te
  • bleach catalysts can also be incorporated into the detergent and cleaning agent portions.
  • These substances are bleach-strengthening transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene complexes or carbonyl complexes.
  • Amine complexes can be used as bleaching catalysts
  • Enzymes from the class of proteases, lipases, amylases, cellulases or their mixtures are particularly suitable.
  • Bacterial strains or fungi such as Bacillus subti s, Bacillus hcheniformis and Streptomyces griseus, are particularly suitable.
  • Proteases of the subtihsin type and are preferred in particular proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase -containing mixtures of particular interest Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carrier substances and / or embedded in shell substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the invention Appropriate compositions can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight
  • enzymes are primarily added to a detergent preparation, in particular to a dishwashing detergent 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 also problems with the stability of the enzymes in the strongly alkaline Milieu occurred
  • the detergent or cleaning agent portions according to the invention it is possible to use enzymes also in the pre-wash cycle and thus to use the pre-wash cycle in addition to the main wash cycle for enzyme action on soiling of the ware
  • the washing-active preparation or partial portion of a detergent portion it is therefore particularly preferred to add enzymes to the washing-active preparation or partial portion of a detergent portion and then - more preferably - to include such a preparation with a material that is already water-soluble at low temperature, for example in order to prevent the enzyme-containing preparation from losing its effectiveness
  • the enzymes are furthermore preferably optimized for use under the conditions of the fast-moving 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 are partially available commercially, because then a quick effect can be expected that already occurs in the (relatively short and cold water) pre-wash cycle even if - as usual - the enzymes are used in solid form and they are provided with a cover made of a water-soluble material that is already soluble in cold water, the enzymes can develop their effect before the main wash or main wash cycle.
  • 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.
  • additives for washing or cleaning agent preparations can be either one or more, if necessary, all of them - Portions (detergent-active preparations) of the detergent or cleaning agent portions according to the invention are added or - as described in the copending patent application No. 199 29 098 9 entitled "Active ingredient portion pack" - into the water-soluble materials comprising the detergent preparations, ie for example, can be incorporated into the water-soluble films, but also into the capsules or coatings according to the invention
  • 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 partial portion (detergent active Preparation) of a washing or cleaning agent added in solid or liquid form.
  • optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • suitable salts are 4,4'-B ⁇ s (2-an ⁇ hno-4-morphol ⁇ no1, 3.5 -t ⁇ az ⁇ nyl-6-am ⁇ no) st ⁇ lben-2,2'-disulfonic acid or compounds of the same structure which carry a diethanol-amino group, a methylamino group, an anhno group or a 2-methoxyethylamino group instead of the morphohno group
  • brighteners of the type of the substituted diphenylstyryl can be in the partial portions (Washing-active preparations) of the detergent or cleaning agent portions according to the invention may be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls Mixtures of the
  • UV protection substances are substances which are released in the washing liquor during the washing process or during the subsequent soft rinsing process and which accumulate on the fiber, in order then to have a UV protection effect
  • Ciba Speciahty Chemicals which are commercially available under the name Tinosorb, are suitable
  • surfactants which in particular can influence the solubility of the water-soluble film, but can also control its wettability and the foaming when dissolved, as well as inhibitors of foam, but also bitter substances, which inadvertently swallow such packaging or parts can prevent such packaging from children
  • Another preferred group of additives 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 detergents and cleaning agents. The selection of such dyes is not difficult for the person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the wash-active preparations and to light and have no pronounced substantivity to textile fibers so as not to dye them.
  • the dyes according to the invention are in the detergent or cleaning agent portions in amounts of less than 0.01 % By weight
  • polymers which can be added to the detergent or cleaning agent portions according to the invention are polymers.
  • polymers which, on washing or cleaning or rinsing, have cobuilder properties, for example polyacrylic acids, also modified Polyacrylic acids or corresponding copolymers
  • polyacrylic acids also modified Polyacrylic acids or corresponding copolymers
  • polyvinyl pyrrod and other graying inhibitors such as copolymers of polyvinyl pyrrodon, Cellulose ethers and the like
  • so-called soil repellents are also suitable as polymers, as are known to those skilled in the detergent and cleaning agent and are described in detail below
  • bleaching catalysts in particular bleaching catalysts for machine dishwashing detergents or detergents.
  • Complexes of manganese and cobalt are used here, in particular with ligands containing nitrogen
  • silver protection agents are a large number of mostly cych organic compounds which are also familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process T ⁇ azoles, Benzotnazole 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, that is to say polymers which build up on fibers or hard surfaces (for example on porcelain and glass) which have a positive effect on the oil and fat washability from textiles and thus one Counteracting re-soiling in a targeted manner
  • soil repellents that is to say polymers which build up on fibers or hard surfaces (for example on porcelain and glass) which have a positive effect on the oil and fat washability from textiles and thus one Counteracting re-soiling in a targeted manner
  • the preferred oil- and fat-free components are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic cellulose ethers, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or
  • the sulfonated derivatives of phthalic 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.
  • the addition can also be made to a material of a water-soluble enclosure, the one or the other
  • the washing action (s) comprises (s)
  • 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 softening result), to provide the consumer with a sensorially typical and distinctive product.
  • Individual perfume compounds can be used as perfumes or fragrances are, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon fragrance compounds of the ester type are, for example, benzyl acetate, phenoxy thyrobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, phthal nylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl sahyl cylate
  • the ketones include the lonones, ⁇ -isomethyhonone, and methyl cedryl ketone.
  • the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons are mainly terpenes such as limonene and pmen. Mixtures of different fragrances are preferably used are coordinated with one another in such a way that they together produce an appealing fragrance.
  • Such perfumes can also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang.
  • the fragrance content usually lies in the range up to 2% by weight of the total detergent or cleaning agent portion
  • the fragrances can be incorporated directly into the wash-active preparations, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the wash and ensure a long-lasting fragrance for the textiles due to a slower release of the fragrance Cyclodextrins preserved
  • the cyclodextine-perfume complexes can additionally be coated with other auxiliaries
  • the perfumes and fragrances can be contained in each of the partial portions (washing-active preparations) of the detergent or cleaning agent portions according to the invention.
  • they are contained in a detergent in a partial detergent provided for the post-wash cycle or fabric softener cycle.
  • this is for example with a bag consisting of several chambers s foils of different water solubility possible
  • the at least one (or more) wash-active preparation (s) is completely or partially surrounded by one or more enclosures.
  • an enclosure can be present that completely or at least one wash-active preparation partially includes, or there may be several enclosures that completely or partially comprise the same or different detergent-active preparations. It is possible for the detergent or cleaning agent portion to contain one enclosure or one or more water-soluble ones -
  • Polymer material ( ⁇ en) contains or that several enclosures are included.
  • the presence of an enclosure is preferred, which has advantages in the choice of materials and also in view of the requirement that the water-soluble polymer material be residue-free in the washing or
  • the enclosure (s) can be made from a single water-soluble polymer material or can be made from several different polymer materials. In view of the present task, the use of several different polymer materials can be particularly preferred according to the invention, whereupon will be discussed in more detail below
  • the water-soluble polymer material that partially or completely surrounds the at least one washing-active preparation is a water-soluble packaging.
  • a water-soluble packaging This is understood to mean a flat-shaped part that partially or completely surrounds at least one washing-active preparation.
  • the exact form of such packaging is not critical and can be largely adapted to the conditions of use There are, for example, various shapes (such as tubes, cushions, cylinders, bottles, disks or the like) processed plastic foils or plates, capsules and other conceivable shapes in question.
  • foils are particularly preferred, for example can be glued and / or sealed to packaging such as hoses, pillows or the like after they have been provided with partial portions of the detergent or cleaning agent portions according to the invention or with the detergent or cleaning agent portfolio according to the invention themselves have been filled
  • plastic foal packaging made of water-soluble polymer materials is further preferred according to the invention due to the properties which can be adapted to the desired physical conditions
  • all polymer materials can be considered as water-soluble polymer materials which, under the given conditions (temperature, pH value, concentration of detergent components), can be completely dissolved in the aqueous phase.
  • the polymer materials can particularly preferably be removed from the groups ) Belong to polyvinyl alcohol, polyvinylpyrrohdon, polyethylene oxide, gelatin, cellulose and their derivatives and mixtures of the materials mentioned
  • Polyvinyl alcohols (PVAL for short) are polymers of the general structure
  • polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, technically in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. These technical processes also make PVAL accessible which contain a predetermined residual proportion of acetate groups.
  • PVAL eg Mowiol ® types from Hoechst
  • PVAL eg Mowiol ® types from Hoechst
  • degrees of polymerization in the range from approximately 500 to 2500 (corresponding to molar masses from approximately 20,000 to 100,000 g / mol) and have different degrees of hydrolysis from 75 to 99 mol% or from 85 to 92 mol% or from 87 to 89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1 to 25 mol% or 8 to 15 mol% or 11 to 13 mol%.
  • PVAL foils are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVP films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the degree, and films of this product series are available, which are soluble in the aqueous phase in all temperature ranges relevant to the application.
  • Polyvinylpyrrohones abbreviated as PVP, can be described by the following general formula
  • PVP are produced by radical polymerization of 1-vinyl pyrrolidon
  • Commercial PVP have molar masses in the range from about 2500 to 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 obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the 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 Hullmatenal is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules.
  • Gelatin is found in the form of foils because of their compared to the above mentioned polymers high price only little use
  • detergent and cleaning agent portions whose packaging is made of water-soluble film from at least one polymer the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof
  • Starch is a homoglycan, whereby the glucose units are linked ⁇ -glycosidically.
  • Starch is made up of two components of different molecular weights from approx. 20 to 30% straight-chain amylose (MW approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin ( MG approx. 300,000 to 2,000,000)
  • MW approx. 50,000 to 150,000 straight-chain amylose
  • MG approx. 300,000 to 2,000,000 branched-chain amylopectin
  • small amounts of lipids, phosphoric acid and cations are contained.
  • amylose forms long, helical, intertwined chains with about 300 to 1200 glucose molecules due to the binding in the 1,4 position, branches the chain in the case of amylopectin after an average of 25 glucose units by means of a 1,6-bond to form an astahnhchen structure with about 1,500 to 12,000 molecules of glucose.
  • Starch derivatives obtainable from starch by polymer-analogous reactions include such chemically modified starches Products from esterifications or etherifications, for example, in which hydroxyl hydrogen atoms have been substituted, but also starches, in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom, can be used as starch derivatives in the group the starch derivatives include, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starters and amino starches
  • CMS carboxymethyl starch
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5000 glucose - Units and therefore 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 But 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, alkahcelluloses, Carboxymethylcellulo se (CMC), cellulose esters and ethers as well as amino celluloses
  • Preferred enclosures made of water-soluble film consist of a polymer with a molecular weight of between 5000 and 500,000 Daltons, preferably between 7500 and 250,000 Daltons and in particular between 10,000 and 100,000 Daltons.
  • the water-soluble film which forms the casing preferably has a thickness of 1 to 150 ⁇ m, preferably from 2 to 100 ⁇ m, particularly preferably from 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m
  • These water-soluble films can be produced by various manufacturing processes. Blowing, calendering and casting processes are to be mentioned here in principle. In a preferred process, the films are blown from a melt with air through a blowing mandrel to form a tube. In the calendering process, this also One of the preferred manufacturing processes used is that the raw materials plasticized by suitable additives are used to form the films. In this case, it may be necessary, in particular, to connect drying to the evaporations. In the casting process, which is also one of the preferred manufacturing processes, an aqueous polymer preparation is applied to a heatable drying roller, after the evaporation of the water is optionally cooled and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal
  • the one or more enclosures is / are completed.
  • the detergent or cleaning agent portions to protect the contents of the enclosure (s) from moisture contain at least one gas.
  • the enclosure (s) is / are closed and contains / contain at least one water-free gas which does not react with the wash-active preparation (s), more preferably in an amount that the Total pressure within the closed enclosure (s) is above the external pressure, even more preferably at least 1 mbar above the external pressure.
  • Particularly preferred embodiments of the detergent or cleaning agent Portions according to the invention contain at least one anhydrous gas which does not react with the wash-active preparations in such an amount that the total pressure within the closed enclosure (s) is at least 5 mbar, more preferably at least 10 mbar, very particularly preferably in Range from 10 mbar to 50 mbar.
  • exital pressure is understood to mean the pressure that prevails on the surrounding side of the enclosure (s) and acts on the exterior of the enclosure (s), specifically at the time of filling the (if necessary, the washing act (s) or spulakt ⁇ ve (n ) Preparations) already containing) with the respective least ens a water-free gas
  • the enclosure (s) can either contain an anhydrous gas or can contain several anhydrous gases.
  • a gas it is preferred to apply a gas to the enclosure (s) due to the associated lower costs
  • the present invention understood that the gas (s) are carefully dried before use in the detergent or cleaning agent portions according to the invention and therefore contain no or almost no water when used, a water content approaching zero being preferred.
  • washing or Re Detergent portions comprise as gas (s) at least one anhydrous gas which is selected from the group N 2 , noble gas (s), C0 2 , N 2 0, O 2 , H 2 , air, gaseous hydrocarbons, entirely especially N 2 , which is available cheaply everywhere and can be completely “dried” by methods known per se.
  • the enclosure (s) is / are closed and contain at least one substance which, when reacted with water, contains a gas which does not react with the washing-active preparation (s) in one Quantity releases that the total pressure within the closed enclosure (s) increases.
  • Those detergent or cleaning agent portions in which the at least one substance contained in the enclosure (s) is at least one gas in reaction with water are particularly advantageous releases a quantity such that the total pressure within the closed enclosure (s) increases by at least 1 mbar above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range from 5 to 50 mbar.
  • This embodiment is of particular advantage in that their manufacture compared to the embodiment in which the gas in the closed enclosure g is contained, is greatly simplified, since only the at least one substance that generates at least one gas when in contact with moisture / water in the closed enclosure must be added.
  • any moisture that has penetrated into the enclosure is immediately capable of reacting with water Substance absorbed and converted and is therefore no longer available for a deterioration in the quality of the components of the detergent preparation.
  • Mixed forms of detergent or detergent preparation are also conceivable, in which both (at least) one anhydrous gas is in the sealed enclosure from the start as well as a substance capable of reacting with water is contained.
  • the substance which releases a gas with water is a constituent part of the wash-active preparation and is - even more preferably - a hygroscopic substance which is contracted with the components of the wash-active preparations).
  • Moisture or water when this access to the inside of the enclosure, is immediately absorbed with the formation of a gas which increases the internal pressure inside the enclosure to a value above atmospheric pressure and thus surprisingly the access of further moisture or further water difficult or impossible
  • Examples of such substances are, without being understood as limiting, substances which are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, hydrides and carbides, more preferably a substance, which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M A M B H 4 , where M A is an alkali metal (particularly preferably Li or Na) (for example L ⁇ AIH 4 , NaBH
  • detergent or cleaning agent portions are preferred in which the water-free gas contained in the enclosure (s), with which the enclosure (s) are directly applied, is selected from the group N 2 , noble gas (s), CO 2 , HO, O 2 , H 2 , air, gaseous hydrocarbons or mixtures thereof.
  • Preferred gas - or at least one of the preferred gases used - is N 2 , because of the fact that nitrogen is available cheaply everywhere and works well with conventional ones Agents can be dried or stored dry
  • Also preferred according to the invention are those detergent or cleaning agent portions in which the at least one gas formed within the enclosure by the substance reactive with water or moisture is selected from the group CO 2 , N 2 , H 2 , 0 2 , gaseous Hydrocarbons such as, in particular, methane, ethane, propane or a mixture of several of the gases mentioned.
  • gaseous Hydrocarbons such as, in particular, methane, ethane, propane or a mixture of several of the gases mentioned.
  • the gases mentioned are advantageously inert to the components of the detergent-active preparation and are therefore sometimes referred to as “inert gases” in the context of the present invention
  • the invention also relates to a method for protecting at least one washing-active preparation in an enclosure consisting of at least one water-soluble polymer material from decomposition as a result of contact with moisture or undesired access to water.
  • This can be moisture, for example, as is the case when storing or storing laundry - or cleaning agent portions occur, e.g. in the washroom or laundry room, in the kitchen or during transport or storage between manufacturer and consumer
  • the invention proposes two variants of the method.
  • the wash-active (s) or spulact-active (s) preparation (s) are provided with at least one enclosure made of a water-soluble polymer.
  • Material in both cases, in the last step, this is also sealed around the at least one wash-active or spool-active preparation, for example by sealing, gluing, fusing, clamping or a combination of the said steps of sealing or by any person skilled in the art in the field of washing detergents. or detergent portions known procedure
  • Particularly preferred are methods of sealing, fusing or gluing, water-soluble adhesives being particularly preferably used in the case of the latter procedure.
  • the two embodiments of the method according to the invention now differ in that in one case the enclosure (s) filled with the wash-active preparation (s) and then closed are made of water-soluble polymer material with at least one with the wash-active preparation (s) ) non-reacting water-free gas can be applied.
  • One gas or several gases can be used. pressure or overpressure occur.
  • the at least one anhydrous gas is particularly preferably applied to the enclosure (s) in an amount of the at least one anhydrous gas which is so large that the total pressure within the enclosed enclosure (s) increases.
  • the total pressure within the closed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, particularly preferably by at least 10 mbar and most preferably at a pressure in the range from 10 mbar to 50 mbar above that External pressure is present, that is to say above the pressure which acts from the outside on the enclosure (s) made of the at least one waterless polymer material which surrounds / surrounds the detergent or cleaning agent portion according to the invention.
  • This embodiment allows access of moisture or water in the interior of the enclosure and thus contact of moisture or water with the wascha Make effective preparation (s) effectively difficult or even prevent
  • the gas is particularly preferably selected from the group N 2 , one or more noble gases, CO 2 , N 2 0, 0 2 , H 2 , air, gaseous hydrocarbons and mixtures of the gases mentioned.
  • N 2 is used with particular advantage
  • At least one substance is introduced into the enclosure which, when reacted with moisture or water, can release at least one gas which does not react with the wash-active substance (s).
  • the reaction should preferably be used
  • the amount of gas released must be so great that the pressure within the (later) closed enclosure rises, particularly preferably so far that it rises by at least 1 mbar, even more preferably by at least 5 mbar and most preferably by 5 to 50 mbar above the external pressure. Then the water-soluble polymer material is sealed around the wash-active preparation
  • the substance (s) reacting with moisture or water can either be incorporated into the washing agent (s) or spulacting agent (s), that is to say carefully in the mixture (s) ( en) the components of the detergent preparations are distributed, which can be done in the usual ways of mixing and according to the invention in particular which is preferred, or the substance (s) reacting with moisture or water can be introduced into the enclosure (s) in addition to the components of the wash-active or rinse-active preparations. Both alternatives of this process step lead to a reliable absorption of moisture or water that has penetrated into the interior of the enclosure and therefore contribute to effectively preventing an interaction of the moisture or water with the component (s) of the detergent preparation.
  • a hygroscopic substance into the washing-active preparation (s) or to add a hygroscopic substance to the preparations.
  • at least one substance (or also a plurality of substances) which is / are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, hydrides and carbides, more preferably a substance , which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M A M B H 4 , where M A is an alkali metal (particularly preferably Li or Na) and M B is B or Al , for example LiAIH 4 , NaBH 4 or NaAIH, or M ' 2 C 2 or M "C 2 , in which M 1 is a monovalent metal and M" is a divalent metal, for example CaC 2 , but this should not be
  • those substances which are introduced into the enclosure (s) and which can release at least one gas which is selected from the group CO 2 , N when reacted with water or moisture are used with further advantage 2 , H 2 , O 2 , gaseous hydrocarbons such as methane, ethane, propane and mixtures of the gases mentioned. If one or more of these gases is present, it can surprisingly be prevented that further moisture or water penetrates into the enclosure (s) and this leads to a deterioration in the quality of one or more components of the wash-active or rinse-active preparation (s) of the invention Serving detergent or cleaning agent portions.
  • the invention also relates to a washing method, in particular a method for machine washing, in which a detergent portion according to the detailed description above is placed in a washing machine and by adding water and adjusting the temperature to a value at which the enclosure (s) detaches from at least one water-soluble polymer material and releases the wash-active preparation (s) into the wash liquor.
  • the invention also relates to a cleaning method, in particular a method for machine washing dishes, in which a portion of the cleaning agent according to the detailed description above is placed in a dishwasher and by adding water and adjusting the temperature to a value at which the dimensions) dissolves at least one water-soluble polymer material, which releases the washing-active preparation (s) into the cleaning liquor.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne des détergents ou des nettoyants en portions, qui contiennent au moins une préparation détergente et une ou plusieurs enveloppes en matériau(x) polymère(s) qui entourent au moins une préparation détergente. L'enveloppe ou les enveloppes est/sont fermée(s) et contien(nen)t au moins un gaz exempt d'eau ne réagissant pas avec la(les) préparation(s) détergente(s) ou au moins une substance libérant un gaz ne réagissant pas, en cas de réaction avec de l'eau ou de l'humidité, avec la(les) préparation(s) détergente(s), de manière que la pression globale régnant à l'intérieur de l'enveloppe /des enveloppes fermée(s) soit supérieure à la pression extérieure. L'invention concerne également un procédé correspondant visant à protéger au moins une préparation détergente dans des détergents ou de nettoyants en portions de la désagrégation par suite d'un contact avec de l'eau ou de l'humidité.
PCT/EP2000/009831 1999-10-16 2000-10-07 Detergents ou nettoyants a base de gaz inerte en portions WO2001029173A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19949980.2 1999-10-16
DE1999149980 DE19949980A1 (de) 1999-10-16 1999-10-16 Inertgas enthaltende Wasch- oder Reinigungsmittel-Portion

Publications (1)

Publication Number Publication Date
WO2001029173A1 true WO2001029173A1 (fr) 2001-04-26

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PCT/EP2000/009831 WO2001029173A1 (fr) 1999-10-16 2000-10-07 Detergents ou nettoyants a base de gaz inerte en portions

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WO (1) WO2001029173A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1354939A1 (fr) * 2002-04-19 2003-10-22 The Procter & Gamble Company Compositions detergentes en sachet
DE10244802B4 (de) * 2002-09-26 2011-12-22 Henkel Ag & Co. Kgaa Pralle Waschmittelformkörper
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US20140308162A1 (en) 2013-04-15 2014-10-16 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US9023784B2 (en) 2012-09-13 2015-05-05 Ecolab Usa Inc. Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3695989A (en) * 1970-08-12 1972-10-03 Robert E Albert Cold water soluble foam plastic package
US4973416A (en) * 1988-10-14 1990-11-27 The Procter & Gamble Company Liquid laundry detergent in water-soluble package
US5534178A (en) * 1994-12-12 1996-07-09 Ecolab Inc. Perforated, stable, water soluble film container for detersive compositions
DE19831703A1 (de) * 1998-07-15 2000-01-20 Henkel Kgaa Portionierte Wasch- und Reinigungsmittelzusammensetzung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3695989A (en) * 1970-08-12 1972-10-03 Robert E Albert Cold water soluble foam plastic package
US4973416A (en) * 1988-10-14 1990-11-27 The Procter & Gamble Company Liquid laundry detergent in water-soluble package
US5534178A (en) * 1994-12-12 1996-07-09 Ecolab Inc. Perforated, stable, water soluble film container for detersive compositions
DE19831703A1 (de) * 1998-07-15 2000-01-20 Henkel Kgaa Portionierte Wasch- und Reinigungsmittelzusammensetzung

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Publication number Publication date
DE19949980A1 (de) 2001-04-19

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