EP1238055B1 - Detergents, agents de rin age ou nettoyants en portions a liberation du principe actif regulee par oxydoreduction - Google Patents

Detergents, agents de rin age ou nettoyants en portions a liberation du principe actif regulee par oxydoreduction Download PDF

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Publication number
EP1238055B1
EP1238055B1 EP00993413A EP00993413A EP1238055B1 EP 1238055 B1 EP1238055 B1 EP 1238055B1 EP 00993413 A EP00993413 A EP 00993413A EP 00993413 A EP00993413 A EP 00993413A EP 1238055 B1 EP1238055 B1 EP 1238055B1
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EP
European Patent Office
Prior art keywords
detergent
cleaning
active
release
washing
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EP00993413A
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German (de)
English (en)
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EP1238055A2 (fr
Inventor
Peter Schmiedel
Thomas Gassenmeier
Rolf Bayersdörfer
Christian Nitsch
Wolfgang Von Rybinski
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—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
    • C11D3/37—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
    • 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
    • C11D3/3792—Amine oxide containing polymers

Definitions

  • the present invention relates to controlled-release detergent, rinse or detergent portions. More particularly, the present invention relates to detergent, rinse or detergent portions having a system which provides controlled release of at least one active ingredient in the washing process. Rinsing process, cleaning process or aftertreatment process due to the targeted action of redox systems allowed on the portion. The invention also relates to a process for the preparation of such detergent, detergent or cleaner portions with enzyme-controlled drug release. The invention also relates to washing methods, rinsing methods or cleaning methods using said detergent, rinse or detergent portions.
  • detergents, dishwashing or cleaning agents were formulated in metered portions, all of them Contain components that are required for a wash, rinse or cleaning cycle.
  • For solid products such portions often became (sometimes containing several phases)
  • Formed moldings such as granules, beads, tablets ("tabs"), ashlars, briquettes, etc., which are dosed as a whole in the liquor.
  • Liquid products were incorporated into water-soluble coatings which dissolve on contact with the aqueous liquor and release the contents into the liquor.
  • a disadvantage of these solutions is that all components that are needed in the course of a wash cycle, rinse or cleaning cycle, get into the aqueous liquor at the same time. Not only do problems of incompatibility of certain components of a detergent, dishwashing detergent or cleaning agent with other components occur, but it also becomes impossible to meter specifically targeted components into the liquor at a defined time.
  • paraffins having a melting point above 50 ° C. have been described several times.
  • a product on the market uses a paraffin core in a dishwashing tablet as a carrier or matrix in order to release a rinse aid surfactant incorporated therein not already in the cleaning cycle, but only in the final rinse cycle of a dishwashing machine. If released too early, for example during the cleaning cycle, the rinse-aid surfactant is largely pumped off during the intermediate rinse and can then develop no or only little effectiveness in the rinse cycle.
  • the matrix material has a melting point at the temperature of the rinse cycle, it is ensured that the emulsified in the matrix or in the Ideally molecular dispersed rinse aid surfactant during the cleaning cycle, which runs at temperatures up to 55 ° C, remains trapped in the matrix and is released only in the rinse cycle, in which temperatures are reached up to about 65 ° C, after melting of the matrix material.
  • the proportion of the matrix material to the consisting of paraffin and rinse aid surfactant core of the dishwashing tablet is between 30 and 95% of the total mass of the core, regularly about 50% of the total mass.
  • the matrix material in particular in this amount, can leave residues on the items to be cleaned, for example on the dishes, and in addition also impair the activity of the rinse aid surfactant contained therein when the paraffin is melted.
  • One reason for this could be that the rinse aid surfactant remains bound at the interface between the lipophilic carrier material and the rinse liquor after melting the paraffin and thus does not exhibit the desired effect.
  • this fact can be accounted for by systems which, in contrast to a certain maximum achievable temperature, which is subject to the bandwidth described above, affect the control parameter of the Cooling react and use for targeted release of active agents or active ingredients from detergent, detergent or detergent portions.
  • the Applicant describes detergents, dishwashing detergents or cleaning compositions which contain polymers which are called LCST polymers and have the special property that they are insoluble above a certain temperature (flocculation point) and only at lower temperatures.
  • This principle can be used for all applications in which a release of certain components after falling below the flock point of the LCST polymers during the cooling phase in the washing, rinsing or cleaning process is to take place.
  • Applications which fulfill these criteria include, for example, automatic dishwashing and machine washing, as long as the washing and cleaning liquor is pumped out in intermediate rinsing and cleaning cycles and replaced by colder to cold rinsing water.
  • Another described principle is based on the fact that a cooling of an air volume heated to a certain temperature per ° Kelvin leads to a volume decrease of about 1/272.
  • a suitable administration form for example a capsule with perforation, material from the environment can be sucked into the dosage form by the negative pressure arising as a result of the air volume contraction. This step can then trigger secondary processes such as corrosion, dissolution, heating or gas formation, which allow release of the desired ingredients.
  • the object of the invention was to provide switch systems which do not have the disadvantages mentioned.
  • the object of the invention was also to provide a system for the controlled release of detergent, detergent or detergent components in the liquor from a detergent, detergent or detergent portion available, which ensures that the component as possible without or with a minimum quantity of auxiliaries necessary for the preparation reaches the fleet at a defined time or during a period of time.
  • Another object of the invention was to provide a system for separating individual components of a detergent, rinse or cleaning agent from other components of the same agent to avoid incompatibilities of the individual components in preparation, storage and / or transport, and thus to ensure that the components are free from loss of activity enter the washing, rinsing or cleaning fleet at a defined time, possibly also together with precisely defined other components.
  • Another object of the invention was to provide the possibility, in addition to naturally solid components of a detergent, detergent or cleaning agent and those components of a use - or use with those of another state of aggregation - supply, which are not in solid form, for example in liquid, gelatinous or pasty form.
  • the invention accordingly relates to a detergent, dishwashing or cleaning agent portion with two or more washing, rinsing or cleaning-active components, of which at least two are to be released at different times of a washing, rinsing or cleaning process in the fleet, the comprises at least one release-controlling (physico-) chemical switch, which is not or not exclusively subject to the temperature control, but is activated by the action of a redox system or more redox systems.
  • release-controlling phyto-
  • the invention relates in a preferred embodiment, a detergent, detergent or detergent portion of the type mentioned, in which / the Release of at least one detergent-active, rinse-active or detergent-active component-controlling (physico) -chemical switch (s) is / are substances which, on exposure to a redox system or several redox systems, are removed from the washing, Flushing or cleaning fleet learns / experienced a change in physical and / or chemical properties.
  • a detergent, detergent or detergent portion of the type mentioned in which / the Release of at least one detergent-active, rinse-active or detergent-active component-controlling (physico) -chemical switch (s) is / are substances which, on exposure to a redox system or several redox systems, are removed from the washing, Flushing or cleaning fleet learns / experienced a change in physical and / or chemical properties.
  • the invention further relates to a process for the preparation of a detergent, dishwashing or cleaning agent portion with two or more washing, rinsing or cleaning-active components, of which at least two are released into the liquor at different times of a washing, rinsing or cleaning process to be in which one is to be released later in the washing, rinsing or cleaning process in the fleet (s) washing active (n), rinse active (n) or cleaning active component (s) with a release due to the action one or more redox systems (s) controlling (physico) chemical switch and the ready-to-use (s), rinse-active or cleaning-active component (s) so prepared with one or more other detergent-active, rinse-active or detergent-active component (s) to a detergent, detergent or detergent portion processed.
  • the invention further relates to a washing method, rinsing method or cleaning method using the detergent, detergent or detergent portions described in detail below.
  • the invention primarily provides detergent portions, detergent portions or detergent portions.
  • the term “detergent portion” or “detergent portion” or “detergent portion” is understood to mean a quantity of a detergent, rinsing agent or cleaning agent which is sufficient for a washing, rinsing or cleaning process taking place in an aqueous phase , This can be, for example, a machine washing, rinsing or cleaning process, as is carried out with commercially available washing machines or dishwashers.
  • this term is also understood to mean a hand washing course (performed, for example, in a hand basin or in a bowl) or a dishwashing process carried out by hand or another process of washing, rinsing or cleaning.
  • the detergent, detergent or cleaner portions are preferably used in automatic washing, rinsing or cleaning operations.
  • detergent partial portion is understood to mean a subset of a detergent portion, detergent portion or detergent portion which is in one of other detergent, Detergent or detergent part-portions separate phase in spatial connection with other detergent portions, detergent partial portions or detergent partial portions of the same detergent portion, detergent portion or detergent portion is present and prepared by suitable measures or ready-made separated from other detergent portions, detergent partial portions or detergent partial portions of the same detergent portion, detergent portion or detergent portion added to the liquor and optionally dissolved or suspended in it.
  • a partial detergent portion, partial detergent portion or partial detergent portion may contain the same ingredients as another portion of detergent, detergent or detergent portion of the same detergent, detergent or cleaning agent portion;
  • two detergent partial portions, detergent partial portions or detergent partial portions of the same detergent, detergent or cleaner portion preferably contain different ingredients, in particular different detergent-active, rinse-active or detergent-active preparations or components.
  • the detergent, detergent or cleaner portions contain measured amounts of at least one wash-active, rinse-active or cleaning-active preparation, usually measured amounts of several washing-active, rinse-active or cleaning-active preparations. That's it possible that the portions contain only detergent-active, rinse-active or cleaning-active preparations of a particular composition. According to the invention, however, it is preferred that several, usually at least two, washing active, rinse active or cleaning active preparations of different composition in the detergent, detergent or detergent portions are included.
  • the composition may be (qualitatively) different with regard to the concentration of the individual components of the washing-active, rinsing-active or cleaning-active preparation (quantitatively) and / or with regard to the nature of the individual components of the washing-active, rinsing-active or cleaning-active preparation. It is particularly preferred that the components are adapted in terms of nature and concentration to the tasks that have to meet the detergent, detergent or detergent partial portions in the washing, rinsing or cleaning process.
  • the term "detergent-active preparation / component”, “detergent-active preparation / component” or “detergent-active preparation / component” is understood to mean preparations or components of all conceivable substances which are relevant in connection with a washing, rinsing or cleaning process Understood. These are primarily the actual detergents, dishwashing detergents or cleaning agents with their individual components explained in the further course of the description.
  • active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers (for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.
  • active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers (for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.
  • detergent-active preparations / component is also understood to mean washing auxiliaries, rinse aids and cleaning auxiliaries.
  • these are optical brighteners, UV protective substances, so-called soil repellents, ie polymers which counteract re-soiling of fibers or hard surfaces, and silver protectants.
  • Laundry-treating agents such as fabric softeners or dishwashing detergent additives, such as rinse aids, are also considered as washing-active, rinse-active or cleaning-active preparations or components according to the invention.
  • the detergent portions, detergent portions or detergent portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, dyes and fragrances and - in the event that the detergents , Detergent or detergent portions at least partially present as a shaped body - binding and disintegration aid.
  • surfactants surfactant compounds
  • builders bleaching agents
  • bleach activators enzymes
  • foam inhibitors dyes and fragrances and - in the event that the detergents , Detergent or detergent portions at least partially present as a shaped body - binding and disintegration aid.
  • the detergent, detergent and cleaner portions according to the invention may contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants being clearly preferred for economic reasons and because of their power spectrum.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Suitable surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as, for example, from C 12-18 -monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of 2-sulfo fatty acids such as the 2-sulfonated Methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • 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) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 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.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. They are used in detergents, dishwashing detergents or cleaners only in relatively small amounts, for example in amounts of 1 to 5 wt .-%, due to their high foaming behavior.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic 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.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be 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 present 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, detergent and cleaner portions are preferred which contain from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 15 to 25% by weight, of one or more anionic Surfactant (s), in each case based on the detergent, detergent and cleaning agent portion.
  • anionic Surfactant s
  • anionic surfactants which are used in the detergent, detergent or cleaner portions according to the invention, there are no restrictions to be kept in the way of formulation freedom.
  • preferred detergent, detergent or cleaning agent portions according to the invention have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent, detergent or cleaning agent portion.
  • Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent, detergent and cleaner portions containing 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (E), in each case based on the weight of the detergent, detergent or cleaning agent portion
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, and mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • Fatty alcohols with more than 12 EO can be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example, in Japanese Patent Application JP 58/217598, or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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 that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the detergent, detergent or cleaner portions according to the invention may preferably contain alkylpolyglycosides, with contents of the detergent portions of APG being above 0.2% by weight, based on the total molding, being preferred.
  • Particularly preferred detergent, detergent and cleaner portions contain APG in amounts of from 0.2 to 10% by weight, preferably in amounts of from 0.2 to 5% by weight and in particular in amounts of from 0.5 to 3% by weight .-%.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms is a linear, where C are preferred 1-4 alkyl or phenyl
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [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 be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • anionic and nonionic surfactants it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably carried out as Wasch maybesbooster, with only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably present in the compositions in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 3.0% by weight.
  • the detergent, detergent or cleaner portions according to the invention are detergents
  • they usually comprise one or more surfactants in total amounts of from 5 to 50% by weight, preferably in amounts of 10 to 35 wt .-%, wherein in partial portions of the detergent portions of the invention surfactants may be contained in greater or smaller amount.
  • the amount of surfactant is not the same in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.
  • the detergent, detergent or cleaner portions according to the invention are detergents, in particular dishwashing agents, more preferably dishwashing compositions
  • these usually contain one or more surfactants in total amounts of from 0.1 to 10 wt .-%, preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the detergent or detergent portions of the invention surfactants may be contained in greater or smaller amount.
  • the amount of surfactant is not the same for cleaning or dishwashing detergents in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.
  • builders are the most important ingredients of detergents, dishwashing detergents and cleaning agents.
  • builders usually used in detergents, dishwashing detergents and cleaners can be present, in particular 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 x O 2x + 1 .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 layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, and ⁇ -sodium disilicate can be obtained, for example, by the method described in International Patent Application WO-A-91/08171.
  • amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 delay-delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous" is also understood to mean "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.
  • Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • a fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P.
  • Zeolite MAP eg, commercial product: Doucil A24 from Crosfield
  • zeolite X eg, commercial product: Doucil A24 from Crosfield
  • zeolite X and mixtures of the zeolites A, X and / or P are also suitable, however, are zeolite X and mixtures of the zeolites A, X and / or P.
  • Commercially available and preferably usable in the context of the present invention is, for example, also a cocrystal of zeolite X and zeolite A (about 80% by weight).
  • zeolite X which is marketed by CONDEA Augusta SpA under the trade name AX VEGOBOND ® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular from 20 to 22% by weight, of bound water.
  • phosphates as builders possible, unless such use should not be avoided for environmental reasons.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided 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 thereof.
  • the acids themselves can also be used.
  • the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of washing and cleaning agent portions according to the invention.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned in this context.
  • polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.
  • the molecular weights stated 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. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses 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 which have molecular weights of from 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol, may 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 from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 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 detergent, detergent or cleaning agent portions of (co) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids, such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • allylsulfonic acids such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • Biodegradable polymers from more than two different monomer units for example those which according to DE-A 43 00 772 as monomers are salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C 42 21 381, are particularly preferred as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and 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 as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives of which German Patent Application DE-A 195 40 086 discloses that they also have a bleach-stabilizing effect in addition to co-builder properties.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids having 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 prepared from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Acid such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which are obtained by partial hydrolysis of Strengths can be obtained.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 owns.
  • 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 described in particular in 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 in 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 the German patent application DE-A 196 00 018.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are also other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) whose synthesis is described, for example, in the document US-A 3,158,615, preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this connection, as described, for example, in US Pat. Nos. US Pat. No. 4,524,009 and US Pat. No. 4,639,325, in European Patent Application EP-A 0 150 930 and in Japanese Patent Application JP-A 93 / 339,896.
  • Suitable amounts are in zeolithumblen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic co-builders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present 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 are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the Aminoalkanphosphonate also have a pronounced heavy metal binding capacity. Accordingly, it may be preferred, especially when the detergent, detergent or cleaner portions according to the invention also contain bleach, to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.
  • the detergents, dishwashing or cleaning agent portions according to the invention may contain further ingredients customary in detergents, dishwashing detergents or cleaning compositions from the group of bleaches, bleach activators, enzymes, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • 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, ⁇ -phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxya
  • Chlorine or bromine releasing substances can also be used as bleaching agents in machine dishwashing compositions.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • bleach activators may be incorporated into the detergent, rinse and detergent portions according to the invention.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic 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 stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.
  • TAED tetraacety
  • bleach catalysts can also be incorporated into the detergent, detergent, and detergent portions.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived 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 in particular cellulase-containing mixtures are of particular interest. Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Enzymes are added according to the prior art primarily to a detergent composition, in particular a dishwashing agent, which is intended for the main rinse. Disadvantage was that the optimum effect of enzymes used limited the choice of temperature and also encountered problems in the stability of the enzymes in a strongly alkaline medium. With the detergent, detergent or cleaner portions according to the invention, it is possible to use enzymes in the pre-wash and thus to use the pre-rinse cycle in addition to the main rinse for an enzyme action on contaminants of the dishes.
  • enzymes to the rinse-active preparation or cleaning-active preparation or partial portion of a detergent portion and to further comprise such a preparation with a material that is already water-soluble at low temperature, for example the enzyme-containing material Preparation to protect against loss of effect due to environmental conditions.
  • the enzymes are more preferably optimized for use under the conditions of the pre-wash cycle, that is, for example, in cold water.
  • the detergent or cleaner portions according to the invention can then be when the enzyme preparations are liquid, as they are sometimes available commercially, because then a rapid effect can be expected, already in (relatively short and carried out in cold water) pre-wash entry.
  • the enzymes are used in solid form and they are provided with an enclosure of a water-soluble material that is already soluble in cold water, the enzymes can unfold their effect even before the main wash or main cleaning.
  • an enclosure of water-soluble material, in particular of cold water-soluble material is that the enzyme / enzymes in cold water after dissolution of the enclosure comes to effect quickly / come. Thus, their duration of action can be extended, which benefits the washing or rinsing results.
  • the detergent, detergent or cleaner portions according to the invention also contain further additives known from the state of the art as additives for detergents, dishwashing detergent preparations or detergent compositions. These can be added either to one or more, if necessary, all partial portions (washing active or, active washing or cleaning active preparations) detergent, detergent or detergent portions of the invention or - as in the copending patent application no. 199 29 098.9 entitled "Active Ingredient Portion Packing" - in water-soluble, the detergent-containing preparations, ie, for example, be incorporated into water-soluble enclosing films, but also in the capsules or coatings according to the invention.
  • optical brighteners are used in the invention.
  • Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B.
  • salts of 4, 4'-bis (2-anilino-4-morpholino1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the type of substituted Diphenylstyryle in the partial portions (washing active or rinse active or cleaning active preparations) of the detergent according to the invention, detergent or cleaner portions may be included, for.
  • alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) 4 '- (2 -sulfostyryl-) biphenyl can be used.
  • UV protection substances are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb Ciba Specialty Chemicals.
  • additives which are preferred in specific embodiments are surfactants which in particular influence the solubility of the water-soluble film but can also control their wettability and foaming upon dissolution, as well as foam inhibitors, but also bitter substances, which can prevent inadvertent ingestion of such packages or parts of such children's packaging.
  • dyes in particular water-soluble or water-dispersible dyes.
  • dyes Preference is given here to dyes, as they are usually used to improve the appearance of the optical product in detergents, detergents and cleaning agents.
  • the selection of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the detergent-active, rinse-active or cleaning-active preparations and to light and no pronounced substantivity to textile fibers in order not to dye them.
  • the dyes according to the invention in the detergent, detergent or detergent portions in amounts of less than 0.01 wt .-% present.
  • polymers which show washing or cleaning or rinsing Cobuilder properties, so for example polyacrylic acids, and modified polyacrylic acids or corresponding copolymers.
  • Another group of polymers are polyvinylpyrrolidone and other grayness inhibitors, such as copolymers of polyvinylpyrrolidone, cellulose ethers, and the like.
  • so-called soil repellents are also suitable as polymers, as are known to the detergent, dishwashing or cleaning agent specialist and will be described in detail below.
  • bleach catalysts in particular bleach catalysts for automatic dishwashing detergents or detergents.
  • used here are complexes of manganese and cobalt, especially with nitrogen-containing ligands.
  • silver protectants are a variety of mostly cyclic organic compounds, which are also familiar to the person skilled in the art and contribute to prevent the tarnishing of silver-containing objects in the cleaning process. Specific examples may be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.
  • the detergent, detergent or cleaning agent portions may also contain so-called.
  • Soil repellents ie polymers which are based on fibers or hard surfaces (for example on porcelain and glass), positively influence the oil and Fettauswaschles from textiles and thus specifically counteract re-soiling. This effect becomes particularly evident when a textile or a hard object (porcelain, glass) is contaminated which has been washed, rinsed or cleaned several times in advance with a detergent, dishwashing or cleaning agent according to the invention containing this oil and fat-dissolving component has been.
  • nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content 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 known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these compounds are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • All of these additives are added to the inventive detergent, detergent or cleaner portions in amounts of at most 30 wt .-%, preferably 2 to 20 wt .-%.
  • the addition can also be made to a material of a water-soluble enclosure comprising the or one of the wash-active, rinse-active or cleaning-active preparation (s).
  • the skilled person it is therefore possible for the skilled person to increase the plastic material for the enclosure either in its weight so as to achieve the depot effect of the invention is achieved exploit, or in addition at least partially in additives the remaining detergent-active, rinse-active or cleaning active preparation to keep. However, this is less preferred.
  • Fragrances are added to the detergent, detergent or cleaner portions according to the invention in order to improve the aesthetic overall impression of the products and to provide the consumer in addition to the technical performance (fabric softening result, rinse aid result) a sensory typical and distinctive product.
  • perfume oils or perfumes individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether.
  • the aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, purple and bourgeonal.
  • the ketones include the ionone, ⁇ -isomethylionone, and methyl cedryl ketone.
  • the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • mixtures are different Used fragrances that are coordinated so that they produce an appealing scent together.
  • perfume oils may also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the content of fragrances in the range up to 2 wt .-% of the total detergent or cleaning agent portion.
  • the fragrances can be incorporated directly into the detergent preparations; but it may also be advantageous to apply the fragrances on carriers that enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven.
  • the cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.
  • the perfumes and fragrances can in principle be contained in each of the partial portions (wash-active, rinse-active or cleansing-active preparations) of the detergent, dishwashing or cleaning agent portions according to the invention. However, it is particularly preferred that they in a detergent in a provided for Nachwaschgang or rinse cycle or rinse cycle or rinse cycle part-detergent portion, partial detergent portion or partial detergent portion or in a detergent, especially in a dishwashing detergent, in a part-detergent portion or partial-detergent portion provided for the final rinse or rinse cycle.
  • the detergent, detergent or cleaner portions according to the invention may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate.
  • antimicrobial action and antimicrobial active ingredient have the usual meaning within the scope of the teaching of the invention, which is described, for example, by KH Wallophusser in "Praxis der Sterilisation, Desinfetechnisch - Konservierung: Keimidentification - Racegiene” (5th Edition - Stuttgart, New York: Thieme, 1995 ), wherein all the substances described there can be used with antimicrobial activity.
  • Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butylcarbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above compounds or connection groups.
  • the antimicrobial active ingredient may be selected from the group of the compounds mentioned below, it being possible to use one or more of the compounds mentioned: ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, Glycerol, undecylenic acid, benzoic acid, Salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholineacetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2 '-hydroxydiphenyl ether (dichlosan), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N' (1,10-decanedi
  • halogenated xylene and cresol derivatives such as p-chloro-meta-cresol or p-chloro-meta-xylene, and natural antimicrobial agents of vegetable origin (eg from spices or herbs), animal and microbial origin.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - or Arsonium distr, peroxo compounds and chlorine compounds are used. Also substances of microbial origin, so-called bacteriocins, can be used.
  • the quaternary ammonium compounds (QAV) suitable as antimicrobial agents have the general formula (R 1 ) (R 2 ) (R 3 ) (R 4 ) N + X - , in which R 1 to R 4 are identical or different C 1 - to C 22 -alkyl radicals, C 7 - to C 28 -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic incorporation as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound and X - halide ions, sulfate ions, hydroxide ions or similar anions are.
  • at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethyl enoxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethyl enoxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethyl enoxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethyl enoxide produced.
  • alkylating agents e.g. Meth
  • Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B ( m, p- dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6). , Benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No.
  • benzetonium chloride N, N-dimethyl N- [2- [2- [p - (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0
  • dialkyl dimethyl such as di- n - decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazolinium iodide (CAS No.
  • QACs are the benzalkonium chlorides having C 8 - to C 18 -alkyl radicals, in particular C 12 - to C 14 -alkylbenzyldimethylammonium chloride.
  • Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® by Lonza, Marquat® ® from Mason, Variquat ® from Witco / Sherex and Hyamine ® company Lonza, and Bardac ® from Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® from Dow, benzethonium chloride such as Hyamine ® 1622, the company Rohm & Haas, methylbenzethonium as Hyamine ® 10X from Rohm & Haas and cetylpyridinium as Cepacol the company Merrell Labs.
  • the antimicrobial agents are in detergent, detergent or detergent portions according to the invention in amounts of 0.0001 wt .-% to 1 wt .-%, preferably from 0.001 wt .-% to 0.8 wt .-%, particularly preferably from 0.005 wt .-% to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.
  • the detergent portions, detergent portions or detergent portions comprise at least two, but optionally also more than two, wash-active, rinse-active or cleaning-active components or preparations, for example those according to the above detailed description, which release into the liquor at different times should be.
  • these may be washing-active preparations or components for the pre-wash of a washing process on the one hand and for the main wash of a washing process on the other hand or washing-active components or preparations for the main wash of a washing process on the one hand and for the post-wash cycle of a washing process on the other hand.
  • the respective gears are aisles of a washing process in a washing machine.
  • the at least two components can be rinse-active components or preparations for the pre-rinse and main rinse or for the main rinse and rinsing a rinse, preferably in a dishwasher.
  • the detergents, dishwashing or cleaning agent portions according to the invention with two or more washing, rinsing or cleaning-active components, of which at least two are to be released into the liquor at different times of a washing, rinsing or cleaning process comprise at least one of the Release controlling (physico) chemical Switch, which is not or not exclusively subject to the temperature control, but is activated by the action of one or more redox systems.
  • the Release controlling (physico) chemical Switch which is not or not exclusively subject to the temperature control, but is activated by the action of one or more redox systems.
  • the term "(physico-) chemical switch” means that the detergent, detergent or cleaning agent portion is blocked by means of suitable components comprised by it, due to one or more changes.
  • the washing, rinsing or cleaning program of a machine can be controlled accordingly, can be brought to to release at least two washing-active, rinse-active or cleaning-active components contained in it at different times or during different periods of the washing, rinsing or cleaning process into the respective liquor.
  • such components may be, for example, structural components.
  • structural configuration of the detergent portion, detergent portion or detergent portion is designed so that release of one or more detergent, rinse active or detergent active component (s) of the respective portion is independent of one or more others detergent-active, rinse-active or cleaning-active component (s) of the respective portion in the wash liquor, wash liquor or cleaning liquor can be done.
  • this structural design may be a layered or sliced construction, in which - just to name one of many conceivable and practically usable examples, without limiting the invention thereto -
  • One or more washing active, rinsing active or cleaning active component (s) of a detergent, detergent or detergent portion to be released later into the liquor (s) in one or more layers of a in shape of a shaped body present portion is / are exposed to the entry of an aqueous liquor later / as one or more other washing active, rinse active or cleaning active component (s) a detergent, detergent or detergent portion that already to a earlier time of the washing, rinsing or cleaning process is to be released into the fleet (s).
  • a structure can be counted in the particles of individual (or more) washing active, flushing or cleaning active components or aggregates of such particles that are released at a late time of a washing, rinsing or cleaning process in the fleet , are surrounded by one or more layers of one or more wash-active, rinse-active or cleaning-active components which can be released into the liquor at an early stage.
  • the (physic) chemical switch (s) controlling the release of at least one detergent active, rinse active or detergent active component (s) is one or more structural or substantial component (s) of the detergent, or rinse or detergent Cleaner portion.
  • the detergent portion, detergent portion or detergent portion contains as component at least one substance which, in response to changes in the environment of the detergent, detergent or cleaning agent portion, for example, changes in certain properties of the wash liquor, Rinsing liquor or cleaning liquor - this may include, for example, the electrolyte concentration or the H + ion concentration (ie the pH) or the concentration of one or more other components such as the concentration of enzymes or the concentration of components of a redox system, prevents or delays the release of one or more washing-active, rinsing-active or cleaning-active component (s) into the wash liquor, washing liquor or cleaning liquor while one or more other component (s) of the respective washing agent, detergent or cleaning agent portion or part release into the fleet was released.
  • the electrolyte concentration or the H + ion concentration ie the pH
  • concentration of one or more other components such as the concentration of enzymes or the concentration of components of a redox system
  • the substantive component (s) preventing or delaying release may themselves be non-detergent, non-rinse or non-detergent active substances; however, it is in accordance with a preferred embodiment of the detergent, rinse or detergent portion of the invention that one or more of such substantive component (s) preventing or delaying release is itself a wash-active, rinse-active or cleaning-active component (s) are.
  • the (physic) chemical switch (s) controlling the release of at least one detergent-active, rinse-active or detergent-active component may comprise one or more structural component (s) or one or more substantive component (s) or even a combination one or more structural component (s) with one or more substantial component (s) of the detergent, rinse or detergent portion.
  • redox system is understood as meaning one or more components of a combination of components which in the context of a chemical reaction in the sense of the action of one or more oxidants on an oxidation-sensitive substance or on several oxidation-sensitive substances or in the sense of the action of one or more reducing agent (s) on a reduction-sensitive substance or more reduction-sensitive substances.
  • the oxidizing agent is reduced while the oxidation-sensitive substance is oxidized
  • the reducing agent is oxidized while the reduction-sensitive substance is reduced.
  • oxidation and “reduction” are understood in this context in their broadest sense.
  • the invention is described below using the example of the action of an oxidizing agent on an oxidation-sensitive substance; however, this is only illustrative of the invention and not limitation thereof.
  • the action of several oxidizing agents on one or more oxidation-sensitive substance (s) and the action of one or more reducing agents on one or more reduction-sensitive substance (s) for release of one or more washing-active, rinsing active or cleaning active component (s) of a detergent Detergent or detergent portion of the invention comprises.
  • oxidation-sensitive or reduction-sensitive organic and inorganic substances and polymers are suitable as redox-sensitive materials.
  • An example of an oxidation-sensitive redox-sensitive material is polyvinylpyridine.
  • the oxidizing agent can be used, for example, a percarbonate, the latter in particular in combination with a bleach activator such. TAED.
  • detergent portions, detergent portions or detergent portions in which the (or) (physic) -chemical switch (s) controlling the release of at least one wash-active, rinse-active or detergent-active component are also preferred ) is / are experiencing a change in the physical and / or chemical properties on exposure to a redox system or more redox systems from the washing, rinsing or cleaning fleet.
  • a (physico-) chemical switch which brings about a redox-system-controlled release of active substance.
  • the difference in the content of the liquor, for example, of the cleaning cycle and the final rinse cycle on a component of a redox system, for example the content of an oxidizing agent, can be utilized.
  • the (s) oxidizing agent (s) mentioned by way of example may be one or more component (s) contained per se in the detergent, detergent or cleaning agent portion, which develop / develop a washing-active, rinsing-active or cleaning-active action there, or the oxidizing agent (s) may be one or more component (s) added to the detergent, rinse or detergent portion or the particular application liquor at a time which will permit targeted release of the agent at a desired time
  • Component (s) permits, for example, at a point in time which is so far before the desired time of release of the component (s) to be subsequently released, that the action of the oxidizing agent can cause the release at the desired time.
  • the activity of the oxidizing agent (s) acting on the detergent, dishwashing or cleaning agent (partial) portion as well as its optimum exposure temperature, the suitable pH, the optimum electrolyte concentration in the fleet, etc.
  • one or more redox-sensitive material (s), ie material (s) degradable by the action of one or more oxidants will be either as Carrier or as material (s) for coating particles of, moldings or capsules for ingredients of detergent, rinse or detergent portions used in a washing, rinsing or cleaning process at a time or during a period of time are to be released to the or during the other components are already in the fleet or have already been used in a previous course of the washing process, rinsing process or cleaning process and / or have already been deducted after use with the application fleet.
  • the detergent portions, detergent portions or detergent portions thus comprise those (physico-) chemical switches which, when exposed to one or more components of one (or more) redox systems (s) from the application fleet undergo a change in physicochemical properties.
  • such substances be used as (physico-) chemical switches that undergo a change in solubility due to exposure to one or more component (s) of one or more redox systems (s) occurring in the application liquor preferably have an increased solubility in water.
  • switch substances are preferred which in the case of an action of a redox system From the application fleet, a change, in particular a decrease, the diffusion density experienced and / or a change, more preferably an acceleration, experience the kinetics of the solution and / or experience a change, more preferably a decrease, the mechanical stability.
  • redox-sensitive switches according to the invention and used according to the invention can be used for all applications, in particular in the washing, rinsing or cleaning agent sector, in which an active ingredient is released in the presence of one or more components of one (or more) redox systems (s) shall be. This may be the case both in the washing machine washing and in the automatic dishwashing.
  • detergent portions are included in which components of a dishwashing detergent formulation for machine dishwashing (eg surfactants, perfume, soil repellant, acid, complexing agents, builders, etc., or preparations containing these active ingredients) with the polymer according to the invention be formulated so that these components in the main rinse in the absence of suitable redox systems or their components (eg., Oxidizing agent or reducing agent) are not released into the wash liquor, but in the subsequent rinse in the presence (and after sufficiently long exposure) one or several component (s) of one (or more) redox systems (s), in the presence of which the polymer becomes water-soluble.
  • suitable redox systems or their components eg., Oxidizing agent or reducing agent
  • the polymer soluble in the action of one or more redox systems may be used both as coating material and as matrix material, binder or disintegrant for the component (s) to be released at a later time or over a later period of time. It is not necessary that the polymer completely dissolves at the conditions inherent in the polymer (type of redox system / redox systems, pH, temperature, electrolyte concentration) to release the drug. Rather, it is sufficient if, for example, the permeability of a polymer film changes and, for example, allows the penetration of water into the active ingredient formulation and a removal of the dissolved components through the holes or pores formed becomes.
  • a secondary effect for example the activation of an effervescent system or the swelling of a water-swellable disintegrant, which are known in particular from pharmacy, for the complete release of the / wash-active, rinse-active or active cleaning agents (s) provide.
  • the invention provides that the detergent, detergent or cleaning agent portion according to the invention contains at least two switches, of which at most one is subject to temperature control.
  • switches By using two or more switches, it is possible for at least two differently acting switches to improve or even refine the controlled release of a washing-active, rinsing-active or cleaning-active active ingredient or a combination of such active ingredients.
  • two differently acting switches cause the controlled release of two or more different different washing active, rinse active or cleaning active ingredients or combinations of different active ingredients at different times or in different periods of the washing, rinsing or cleaning process.
  • At least two switches which are not or not solely subject to temperature control, are contained in the detergent portion, detergent portion or detergent portion, for example in the case of a shaped body having a cavity or trough are contained as cavity or trough filling. It may well be advantageous if several (physico-) chemical switch, of which at least one is not or not alone subject to the temperature control, are included in the cavity or well filling.
  • one of the abovementioned (physico-) chemical switches for example a redox-sensitive switch, is combined with a switch which controls the temperature subject.
  • so-called inverse temperature switches which can be realized by so-called LCST substances, are preferred.
  • LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as low critical solubility temperature or low low turbidity or flocculation point substances.
  • the lower critical demixing temperature should be between room temperature and the temperature of the heat treatment in the respective washing, rinsing or cleaning process, for example between 20 ° C and 120 ° C, preferably between 30 ° C and 100 ° C, in particular between 30 ° C and 50 ° C.
  • the LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and mixtures of one or more of these substances.
  • alkylated and / or hydroxyalkylated polysaccharides are hydroxypropylmethylcellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), Hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydroxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC) and Propyl cellulose (PC).
  • HPMC hydroxypropylmethylcellulose
  • EHEC hydroxyethyl cellulose
  • LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the above-mentioned (co-) polymers.
  • polyethylene oxide or copolymers thereof such as ethylene oxide-propylene oxide copolymers, graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit of the natural protein elastin, and certain alginates.
  • LCST lower critical separation temperature
  • a redox-sensitive switch is combined with an LCST substance.
  • a detergent portion, detergent portion or detergent portion according to the present invention may also contain other switches.
  • switches which can control a controlled by the electrolyte concentration, particularly preferably controlled by the pH in the application fleet release washing-active, flushing or cleaning active ingredients at least two different times or during at least two different periods.
  • Such switches for an electrolyte-controlled or pH-controlled in the application fleet drug release are described in the co-pending patent application entitled "Detergent, detergent or detergent portion controlled release drug".
  • Such electrolyte or pH shift controlled switches can be used in combination with the redox sensitive switches of the detergent, rinse or detergent portions of the present invention.
  • pH-shift boosters are used used in addition to the abovementioned pH-shift-sensitive switches. This can be prevented, at least to a large extent, that after the rinse cycle residues, which in particular consist of the pH-dependent soluble polymer substance itself, are found in the application liquor.
  • suitable pH-shift boosters are all substances and formulations which are capable of controlling the extent of the shift in the pH (of the pH shift) either locally, i. in the immediate vicinity of the respectively used, for a shift of the pH-sensitive substance, or generalized, i. in the entire rinsing, to enlarge.
  • These include - to name a group of substances which are particularly suitable according to the invention as pH-shift boosters - all organic and / or inorganic water-soluble acids or acidic salts, in particular at least one substance from the group of alkylbenzenesulfonic acids, alkylsulfuric acids, citric acid, oxalic acid and / or alkali metal hydrogen sulfates.
  • the above-mentioned substances may be used alone or in a combination of two or more of them.
  • the optionally additionally usable pH-shift booster can be incorporated into the washing, rinsing or cleaning agent.
  • a pH-shift-sensitive switch preferably in combination with a pH-shift booster, is combined with a redox-sensitive switch.
  • both a pH-shift-sensitive switch preferably in combination with a pH-shift booster, as well as a redox-sensitive switch and an LCST substance can be used.
  • switches besides electrolyte-sensitive or pH-shift-sensitive switches also enzyme-controlled switch in question, ie such switches, with their help the release of washing active, rinse active or cleaning active ingredients at least two different times or during at least two different periods in the context of an action of one or more enzymes can be effected.
  • enzyme-sensitive switches are described in the co-pending patent application entitled "Detergent, Detergent or Detergent Portion with Enzyme-Controlled Drug Release".
  • Proteases, amylases, cellulases and / or lipases may be considered as enzymes for the (physicochemical) chemical switches in particularly preferred embodiments, but without restricting the invention thereto.
  • Such enzymes are commercially available as individual substances or substance mixtures and are used with particular advantage in the detergent, detergent or detergent portions according to the invention as additional (physico-) chemical switch.
  • Suitable enzyme-sensitive substances are celluloses and their derivatives, starches and their derivatives, partially oxidized starch derivatives, glycerides, proteins and mixtures thereof and are used with advantage.
  • a redox-sensitive switch is used together with an LCST substance and / or an enzyme-sensitive switch and / or a pH-shift-sensitive switch, preferably in combination with a pH-shift booster , Furthermore, it is preferable to use all three switches, that is to say a redox-sensitive switch, an enzyme-sensitive and / or pH-shift-sensitive switch and a switch subject to a temperature control, for example an LCST substance, in particular in combination with a pH shift. Booster, use.
  • a further preferred embodiment of the invention provides for combining a redox-sensitive switch with an enzyme-sensitive switch.
  • this combination may again comprise an LCST substance and / or a pH-shift-sensitive switch, in particular in combination with a pH shift booster.
  • the detergent, dishwashing or cleaning agent portion according to the invention contains a redox-sensitive switch and one or more of the aforementioned pH-shift-sensitive switches, optionally in combination with a pH-shift booster Electrolyte-sensitive switch, an enzyme-sensitive switch and an LCST substance.
  • the detergent, dishwashing or cleaning agent portions according to the invention are present in solid form, for example as powder, granulate, agglomerate, pellet, roll compact and / or extrudate.
  • a detergent, detergent or detergent portion representing shaped body, wherein one or more moldings can be used per application in a washing, rinsing or cleaning process / can.
  • the embodiment is particularly advantageous as a tablet or as a capsule. It is possible that one or more tablet (s) and / or one or more capsule (s), optionally together with powder, granules, agglomerates, pellets, Walzenkompaktaten and / or extrudates, are used.
  • two or more moldings or the mentioned mixtures of different embodiments are offered in a wrapper such as a pouch or in a foil which is either opened prior to use so that the detergent, rinse or detergent portion in the dosing chamber of the washing machine or the dishwasher can be introduced or which is / are water-soluble, so that he / she can be introduced into the machine together with the washing active, rinse-active or cleaning-active preparation, without rinsing or cleaning process residues remain of it.
  • a dosage on the dosing is possible as well as the washing, rinsing or cleaning agent chamber of each machine.
  • a particularly preferred embodiment is a tablet with a round, oval or rectangular to cuboid base surface, which may have rounded corners and edges.
  • These may be single-layered white or colored tablets which preferably have differently colored speckles, but may also be multi-layered, at least two-layered tablets which in particular contain at least two colors, one of which may be white.
  • the single-layered or multi-layered shaped bodies and in particular tablets have at least one cavity.
  • This cavity can be designed so that it extends from the upper surface to the lower base surface and thus the shaped body forms a ring around a cavity.
  • the cavity is designed so that it does not extend from the upper surface to the lower base, but merely forms a trough, which may be formed either only over a layer or over several layers of the tablet.
  • such wells have a round, oval or rectangular to cuboid base.
  • the cavity, and preferably the well contains part of the total composition of the composition.
  • this part of the overall composition can fill a part of the cavity or the trough or the entire cavity or trough.
  • one or more elevated-temperature mixture (s) which may comprise washing-active, rinse-active or cleaning-active components in addition to carriers and excipients, for example in the form of a melt, placed in the cavity or trough. The melt solidifies on cooling.
  • the Kavticians- or depression filling separately and then insert into the cavity or trough.
  • the cavity or trough filling can then be solid, for example by gluing, or loose in the cavity or trough, for example in the form of a plug connection.
  • the separately produced cavity or trough filling can be produced in various ways. Preferred methods include the production of a non-pressed molding, in particular a solidified melt body, or a compressed body.
  • the separately produced packing can assume a different form than by the cavity or trough predetermined form.
  • the trough it is possible for the trough to be a semicircular opening in a tablet and the filling to be in spherical form, but the latter possibly having a smaller diameter than the semicircular trough.
  • the trough has an oval base, but the filling has a spherical shape.
  • the shaped body including the cavity or trough filling has a plane or nearly planar surface.
  • a further embodiment of the invention provides that the cavity is internal and their filling is not visible from the outside.
  • the actual molded body and in particular the actual tablet thus represent a jacket which completely encloses the particular filled cavity.
  • the cavity filling can in turn be prepared in the manner already described either separately as a fused body or compact and then potted or pressed to the final molded body, or the cavity filling is brought in the form of a melt in a pre-compressed molded body, and this is then pressed to the final molded body.
  • the invention provides that the cavity or well filling contains at least one switch for the controlled release of active ingredient, which is not or not alone subject to Temperatursteue- tion.
  • the shaped body is present as a capsule. If only parts of the total composition are encapsulated, then it is possible that said switch systems are incorporated into the capsule shell. For bags is analogous.
  • surfactants preferably an active chlorine, acids, preferably citric acid, sulfamic acid or bisulfate, phosphonates, complexing agents, surfactants with complexing properties, builders and co-builders.
  • acids preferably citric acid, sulfamic acid or bisulfate, phosphonates, complexing agents, surfactants with complexing properties, builders and co-builders.
  • Particularly preferred active ingredients are nonionic surfactants which have a clear rinsing effect and a melting point above room temperature, ie above 20 ° C., more preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C.
  • nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants ("nonionic surfactants”) which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant which consists of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 C atoms, preferably at least 12 mol, more preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" are particularly preferred.
  • C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols having more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol of alcohol.
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred processes are characterized in that the core tablet contains ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule are up to 25 wt .-%, preferably make up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • nonionic surfactants of the following formula are preferred R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ] where R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x is values between 0.5 and 1.5 and y represents a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in the R 1 and R 2 for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl radical, ethyl radical, n-propyl radical, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
  • x is values between 1 and
  • k and j are values between 1 and 12, preferably between 1 and 5.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • the alkylene oxide unit can be varied in the square bracket.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • end-capped poly (oxyalkylated) nonionic surfactants are of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • cavity or well fillings which comprise a nonionic surfactant or surfactant mixture having a clear rinse effect in amounts of from 20 to 50% by weight, one or more (physicochemical) chemical switches, optionally in combination with a temperature-sensitive switch in amounts of 40 to 70 wt .-% and optionally a pH-shift booster in amounts of 2 to 15 wt .-%, in particular in amounts to 10 wt .-%, containing the wt .-% - refer to the fillings.
  • a nonionic surfactant or surfactant mixture having a clear rinse effect in amounts of from 20 to 50% by weight
  • one or more (physicochemical) chemical switches optionally in combination with a temperature-sensitive switch in amounts of 40 to 70 wt .-% and optionally a pH-shift booster in amounts of 2 to 15 wt .-%, in particular in amounts to 10 wt .-%, containing the wt .-% - refer to the fillings.
  • the particular solid detergent, detergent or detergent portions may contain conventional ingredients in conventional amounts.
  • inventive detergent, detergent or cleaner portions with a conventional Effervescent system for example, from carbonate and citric acid, equip, it may be particularly preferred that the cavity or trough filling additionally having such a shower system.
  • This effervescent system can be activated by changing the water permeability of the coating with the material of the (physico-) chemical switch as a result of the change of the respectively relevant parameter during the washing, rinsing or cleaning cycle.
  • a disintegrating agent known, for example, from pharmacy or from detergent technology.
  • Conditioning components enzymes, alkalis, acids, fragrances, dyes, fluorescers, optical brighteners, anti-shrinkage agents, anti-wrinkling agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing auxiliaries, repellents and impregnating agents, UV absorbers and any mixtures of the abovementioned detergent components.
  • the present invention can be used with solid automatic dishwashing agents to transport active ingredients throughout the main rinse cycle into the rinse cycle.
  • a formulation which contains, for example, rinse aid surfactant or also other of the active ingredients listed above, with one or more redox-sensitive material (s) and / or one or more other than (physico) chemical (s) suitable switch, above in individual described material (s) coated or in a matrix of one or more redox-sensitive material (s) and / or from one or more other than (physico) chemical (s) suitable switch, in detail described above material (ien ) incorporated.
  • This formulation is then formulated together with the customary rinse-active component (s), for example, added to a powder cleaner or combined with a molding.
  • the redox-sensitive switch it is not essential that the redox-sensitive material completely dissolves under the appropriate conditions in the rinse cycle to release the flushing active ingredient. Rather, it is sufficient if the permeability of the redox-sensitive film or the corresponding matrix changes and, for example, the penetration of water into the active ingredient formulation is made possible. This can provide a secondary effect, eg the activation of a effervescent system for the complete release of the active ingredient.
  • detergent, dishwashing detergent or detergent preparations having a plurality of wash-active, rinse-active or detergent-active components are provided, in which components to be liberated in the respective liquor, for example rinse aid surfactants, acids in a later stage of the washing process, rinsing process or cleaning process (such as citric acid), fragrances, soil repellents, enzymes, catalysts, bleach, etc. in automatic dishwashing compositions - in bulk or in a capsule - coated with a redox-sensitive coating, using a redox-sensitive coating Binder be formulated into a wash-active, rinse-active or cleaning active preparation or formulated using a redox-sensitive matrix material to a washing active, rinse active or cleaning active preparation.
  • the coated or preformed product thus obtained also contains other customary detergent-active, rinse-active or detergent-active components of detergent, detergent or cleaner portions, as described in detail above.
  • the said materials can be used not only as a coating for detergent-active, rinse-active or cleaning-active preparations in capsules or in the form of moldings (granules, tablets, etc.), but also for fixing in recesses of moldings (for example Muldentabs , Ring tabs etc.) or in bags of water-soluble polymers together with other components of washing active, dishwashing or cleaning active preparations.
  • the invention also relates to a process for the preparation of the detergent, detergent or cleaning agent portions described above in detail, preferably those with two or more washing, rinsing or cleaning-active components, of which at least two at different times or in two different periods a washing, rinsing or cleaning process to be released into the fleet.
  • the washing-active, rinse-active or cleaning-active component (s) to be liberated into the liquor at a later point in time of the washing, rinsing or cleaning process are packaged with a release due to the action of or multiple (redox) system (s) controlling (physico) chemical switch, and processing the thus prepared wash active, rinse active or cleaning active component (s) with one or more others wash-active, rinse-active or cleaning-active component (s) to a detergent, detergent or cleaning agent portion.
  • the release of at least one detergent-active, rinse-active or detergent-active component is selected on the basis of the action of one or more redox systems (s) controlling (physico) chemical switch (s) a plurality of structural or substantial component (s) of a detergent, rinse or detergent portion. Suitable structural or substantial components of the detergent, rinse or detergent portion are described in detail above.
  • one or more substances from the group of oxidation-sensitive or reduction-sensitive organic and inorganic substances and polymers are used as the (physico-) chemical switch.
  • An example of an oxidation-sensitive redox-sensitive material is polyvinylpyridine.
  • the oxidizing agent can be used, for example, a percarbonate, the latter in particular in combination with a bleach activator such. TAED.
  • the invention also relates to a washing method, in particular washing method in a washing machine, in which brings a detergent portion according to the above detailed description with laundry in contact, in particular in the dispensing compartment of a commercial washing machine and rinsed with water of the first wash cycle in the wash liquor, the early ones Carrying out steps of the washing process in a conventional manner and then sets conditions under which / the liberation controlling (physic) chemical (s) switch (s) which are not or not exclusively subject to temperature control, but by the action of a or several redox systems (s) is activated / released, the later release into the wash liquor (s) component (s) in the wash liquor / release.
  • a washing method in particular washing method in a washing machine, in which brings a detergent portion according to the above detailed description with laundry in contact, in particular in the dispensing compartment of a commercial washing machine and rinsed with water of the first wash cycle in the wash liquor, the early ones Carrying out steps of the washing process in a conventional manner and then sets conditions under which / the liber
  • the invention further relates to a rinsing method, in particular rinsing method in a dishwasher, wherein bringing a detergent portion according to the above detailed description with items in contact, in particular in the dispensing compartment of a commercial dishwasher inserts and rinsed with water of the first rinse in the rinse, the Performs early steps of the rinsing process in the usual way and then sets conditions under which / the release controlling (physio) chemical (s) switch (s) are not or not exclusively subject to the temperature control, but by action one or more redox systems (s) is / are activated, the later release into the wash liquor releasing (s) component (s) in the wash liquor / release.
  • a rinsing method in particular rinsing method in a dishwasher, wherein bringing a detergent portion according to the above detailed description with items in contact, in particular in the dispensing compartment of a commercial dishwasher inserts and rinsed with water of the first rinse in the rinse, the Performs early steps of the rinsing process in the
  • the invention relates to a cleaning method in which a detergent portion according to the above detailed description is brought into contact with items to be cleaned, which performs the early steps of the cleaning operation in a conventional manner and then sets conditions under which the release controlling (s) ( physico-) chemical switch (s) which is not or not exclusively subject to temperature control, but is activated by the action of one or more redox systems (s) which will later release into the cleaning liquor (s) ( n) in the cleaning liquor releases / release.
  • release controlling physico-
  • chemical switch s
  • Example 1 were coated moldings or capsules prepared which (500 mg Poly Tergent SLF 18B45 ®) an effective amount of rinse surfactant contained. Subsequently, these products were coated by film coating with the same aminoalkyl methacrylate copolymer as used in Example 1, except that polyvinyl pyridine was mixed in an amount of 10% by weight with the coating material, based on the whole coating material (Example 2).
  • the tablets or capsules so prepared were subjected together with a commercial tableted automatic dishwashing detergent (Somat Professional ®, Henkel KGaA) a 65 ° C-cleaning program, wherein the shaped bodies have been introduced with the capsules over the dosing chamber.
  • Somat Professional ® Henkel KGaA
  • Example 1 After the cleaning cycle, the coated and rinsing agent-containing tablets or capsules of Example 1 were almost undissolved. After rinsing, the tablets or capsules were mostly dissolved, with the detectable residues predominantly consisting of coating material. A clear rinsing effect on dishes could be detected.
  • Example 2 After the cleaning cycle, the coated tablets or capsules of Example 2 were undissolved. At the sites where polyvinylpyridine-containing domains were present in the coating material, small holes were seen.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (13)

  1. Portion d'agent de lavage, de rinçage ou de nettoyage comprenant deux composants actifs en lavage, rinçage ou nettoyage ou plus, dont au moins deux composants sont libérés dans le bain à des moments différents d'un processus de lavage, de rinçage ou de nettoyage, comprenant au moins un commutateur (physico-)chimique contrôlant la libération, qui n'est pas soumis au contrôle par la température ou pas exclusivement, mais est activé par l'effet d'un ou de plusieurs systèmes redox.
  2. Portion d'agent de lavage, de rinçage ou de nettoyage selon la revendication 1, dans laquelle le/les commutateur(s) (physico-)chimique(s) contrôlant la libération d'au moins un composant actif en lavage, en rinçage ou en nettoyage est/sont un ou plusieurs composant(s) structurel(s) ou substantiel(s) de la portion d'agent de lavage, de rinçage ou de nettoyage.
  3. Portion d'agent de lavage, de rinçage ou de nettoyage selon la revendication 1 ou la revendication 2, contenant comme commutateur(s) (physico-)chimique(s) une ou plusieurs substance(s) qui, sous l'effet d'un ou de plusieurs système(s) redox du bain de lavage, de rinçage ou de nettoyage,
    (a) subit/subissent une modification de la solubilité dans l'eau ; et/ou
    (b) subit/subissent une modification de la densité de diffusion ; et/ou
    (c) subit/subissent une modification de la cinétique de solubilisation ; et/ou
    (d) subit/subissent une modification de la stabilité mécanique ;
    de préférence
    (a) subit/subissent une augmentation de la solubilité dans l'eau ; et/ou
    (b) subit/subissent une diminution de la densité de diffusion ; et/ou
    (c) subit/subissent une accélération de la cinétique de solubilisation ; et/ou
    (d) subit/subissent une diminution de la stabilité mécanique.
  4. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une ou plusieurs des revendications 1 à 3, contenant comme commutateur(s) (physico-)chimique(s) une ou plusieurs substance(s) du groupe formé par les substances et les polymères organiques et inorganiques sensibles à l'oxydation, de préférence la polyvinylpyridine, en combinaison avec un oxydant du groupe des percarbonates, en particulier ensemble avec un activateur de blanchiment, tel que le TAED.
  5. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une ou plusieurs des revendications 1 à 4, contenant au moins deux commutateurs, dont de préférence au maximum un est soumis à un contrôle par la température.
  6. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une ou plusieurs des revendications 1 à 5, contenant un commutateur sensible à un système redox en combinaison avec un commutateur soumis à un contrôle par la température ou un commutateur sensible à un système redox et un commutateur sensible à un déplacement de pH en combinaison avec un commutateur soumis à un contrôle par la température ou un commutateur sensible à un système redox et un commutateur sensible à une/des enzyme(s) en combinaison avec un commutateur soumis à un contrôle par la température.
  7. Procédé pour la préparation d'une portion d'agent de lavage, de rinçage ou de nettoyage comprenant deux composants actifs en lavage, rinçage ou nettoyage ou plus, dont au moins deux composants sont libérés dans le bain à des moments différents d'un processus de lavage, de rinçage ou de nettoyage, dans lequel on confectionne le ou les composant(s) actif(s) en lavage, rinçage ou nettoyage à libérer dans le bain à un moment ultérieur du processus de lavage, de rinçage ou de nettoyage avec un commutateur (physico-)chimique contrôlant la libération sous l'effet d'un ou de plusieurs système(s) redox et on transforme le ou les composant(s) actif(s) en lavage, en rinçage ou en nettoyage ainsi confectionné(s) avec un ou plusieurs autres composant(s) actif(s) en lavage, rinçage ou nettoyage en une portion d'agent de lavage, de rinçage ou de nettoyage.
  8. Procédé selon la revendication 7, dans lequel on choisit comme commutateur(s) (physico-)chimique(s) contrôlant la libération d'au moins un composant actif en lavage, en rinçage ou en nettoyage, un ou plusieurs composant(s) structurel(s) ou substantiel(s) d'une portion d'agent de lavage, de rinçage ou de nettoyage.
  9. Procédé selon la revendication 7 ou la revendication 8, dans lequel on choisit, comme commutateur(s) (physico-)chimique(s), une ou plusieurs substance(s) qui, sous l'effet d'un ou de plusieurs système(s) redox dans le bain de lavage, de rinçage ou de nettoyage,
    (a) subit/subissent une modification de la solubilité dans l'eau ; et/ou
    (b) subit/subissent une modification de la densité de diffusion ; et/ou
    (c) subit/subissent une modification de la cinétique de solubilisation ; et/ou
    (d) subit/subissent une modification de la stabilité mécanique ;
    de préférence
    (a) subit/subissent une augmentation de la solubilité dans l'eau ; et/ou
    (b) subit/subissent une diminution de la densité de diffusion ; et/ou
    (c) subit/subissent une accélération de la cinétique de solubilisation ; et/ou
    (d) subit/subissent une diminution de la stabilité mécanique.
  10. Procédé selon l'une quelconque des revendications 7 à 9, dans lequel on utilise comme commutateur(s) (physico-)chimique(s) une ou plusieurs substances du groupe formé par les substances et les polymères organiques ou inorganiques sensibles à l'oxydation, de préférence la polyvinylpyridine, en combinaison avec un oxydant du groupe des percarbonates, en particulier ensemble avec un activateur de blanchiment, tel que le TAED.
  11. Procédé de lavage, en particulier procédé de lavage dans un lave-linge, dans lequel on met en contact une portion d'agent de lavage selon l'une quelconque des revendications 1 à 6 avec du linge, on la place en particulier dans le compartiment à détergent d'un lave-linge usuel du commerce et on l'introduit avec l'eau du premier processus de lavage dans le bain de lavage, on réalise les premières étapes du processus de lavage de manière usuelle, puis on règle des conditions dans lesquelles le/les commutateur(s) (physico-)chimique(s) contrôlant la libération, qui n'est/ne sont pas exclusivement soumis à un contrôle par la température, mais qui est/sont activé(s) sous l'effet d'un ou de plusieurs système(s) redox, libère(nt) le ou les composant(s) à libérer ultérieurement dans le bain de lavage.
  12. Procédé de rinçage, en particulier procédé de rinçage dans un lave-vaisselle, dans lequel on met en contact une portion d'agent de rinçage selon l'une quelconque des revendications 1 à 6 avec la vaisselle, on la place en particulier dans le compartiment à détergent d'un lave-vaisselle usuel du commerce et on l'introduit avec l'eau du premier processus de rinçage dans le bain de rinçage, on réalise les premières étapes du processus de rinçage de manière usuelle, puis on règle des conditions dans lesquelles le/les commutateur(s) (physico-)chimique(s) contrôlant la libération, qui n'est/ne sont pas exclusivement soumis à un contrôle par la température, mais qui est/sont activé(s) sous l'effet d'un ou de plusieurs système(s) redox, libère(nt) le ou les composant(s) à libérer ultérieurement dans le bain de rinçage.
  13. Procédé de nettoyage, dans lequel on met en contact une portion d'agent de nettoyage selon l'une quelconque des revendications 1 à 6 avec le produit à nettoyer, on réalise les premières étapes du processus de nettoyage de manière usuelle, puis on règle des conditions dans lesquelles le/les commutateur(s) (physico-)chimique(s) contrôlant la libération, qui n'est/ne sont pas exclusivement soumis à un contrôle par la température, mais qui est/sont activé(s) sous l'effet d'un ou de plusieurs système(s) redox, libère(nt) le ou les composant(s) à libérer ultérieurement dans le bain de nettoyage.
EP00993413A 1999-12-13 2000-12-02 Detergents, agents de rin age ou nettoyants en portions a liberation du principe actif regulee par oxydoreduction Expired - Lifetime EP1238055B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19960072 1999-12-13
DE19960072 1999-12-13
PCT/EP2000/012129 WO2001044421A2 (fr) 1999-12-13 2000-12-02 Detergents, agents de rinçage ou nettoyants en portions a liberation du principe actif regulee par oxydoreduction

Publications (2)

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EP1238055A2 EP1238055A2 (fr) 2002-09-11
EP1238055B1 true EP1238055B1 (fr) 2007-02-21

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EP00993413A Expired - Lifetime EP1238055B1 (fr) 1999-12-13 2000-12-02 Detergents, agents de rin age ou nettoyants en portions a liberation du principe actif regulee par oxydoreduction
EP00989940A Expired - Lifetime EP1238054B2 (fr) 1999-12-13 2000-12-02 Fraction de produit de lavage, de produit de rinçage ou de produit de nettoyage a liberation du principe actif regulee par des enzymes

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EP00989940A Expired - Lifetime EP1238054B2 (fr) 1999-12-13 2000-12-02 Fraction de produit de lavage, de produit de rinçage ou de produit de nettoyage a liberation du principe actif regulee par des enzymes

Country Status (7)

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EP (2) EP1238055B1 (fr)
AT (2) ATE354633T1 (fr)
AU (3) AU1706901A (fr)
CA (1) CA2328326A1 (fr)
DE (3) DE10035781A1 (fr)
ES (2) ES2281378T3 (fr)
WO (3) WO2001044421A2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003200070B2 (en) 2002-01-25 2008-01-24 Rohm And Haas Company Triggered response compositions
KR20040012487A (ko) * 2002-07-31 2004-02-11 롬 앤드 하스 캄파니 트리거드 반응 조성물
DE102004016821B4 (de) * 2004-04-01 2011-01-13 Rational Ag Verfahren zum Reinigen des Innenraums von Gargeräten und Gargerät zum Durchführen dieses Verfahrens
DE102004055075A1 (de) * 2004-10-22 2006-07-06 Henkel Kgaa Wasch- oder Reinigungsmitteldosiereinheit
DE102006029837A1 (de) * 2006-06-27 2008-01-03 Henkel Kgaa Wasch- oder Behandlungsmittelportion II
EP2262885B1 (fr) 2008-03-28 2013-05-15 Novozymes A/S Particules comportant un système de libération déclenché par une enzyme
DE102014205869A1 (de) * 2014-03-28 2015-10-01 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel
DE102018208651A1 (de) * 2018-05-30 2019-12-05 Henkel Ag & Co. Kgaa Verfahren zur zeitversetzten Dosierung von Reinigungszusammensetzungen in automatischen Geschirrspülmaschinen
DE102019126683A1 (de) * 2019-10-02 2021-04-08 Henkel Ag & Co. Kgaa Copolymere zur Verbesserung der Lagerstabilität von Enzymen in Wasch- und Reinigungsmitteln
CN115404137A (zh) * 2022-09-23 2022-11-29 深圳市减化生物科技有限公司 洗衣凝珠及其制备方法

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GB1390503A (en) * 1971-03-30 1975-04-16 Unilever Ltd Liquid detergent compositions
JPS521924B2 (fr) * 1973-11-12 1977-01-19
US4082678A (en) * 1976-11-10 1978-04-04 The Procter & Gamble Company Fabric conditioning articles and process
US5453216A (en) * 1994-04-28 1995-09-26 Creative Products Resource, Inc. Delayed-release encapsulated warewashing composition and process of use
US6800598B1 (en) * 1998-07-29 2004-10-05 Reckitt Benckiser N.V. Composition for use in a dishwashing machine
DE10003429A1 (de) * 1999-03-03 2000-09-07 Henkel Kgaa Wasch- oder Reinigungsmittelportion mit kontrollierter Wirkstofffreisetzung

Also Published As

Publication number Publication date
ATE354633T1 (de) 2007-03-15
EP1238055A2 (fr) 2002-09-11
ES2281378T3 (es) 2007-10-01
WO2001044421A2 (fr) 2001-06-21
AU1706901A (en) 2001-06-25
EP1238054B2 (fr) 2012-06-20
DE10035781A1 (de) 2001-07-12
WO2001044421A3 (fr) 2001-11-01
DE50013790D1 (de) 2007-01-04
ES2277865T5 (es) 2012-11-02
ES2277865T3 (es) 2007-08-01
WO2001044435A1 (fr) 2001-06-21
EP1238054A1 (fr) 2002-09-11
DE50014097D1 (de) 2007-04-05
AU2839701A (en) 2001-06-25
EP1238054B1 (fr) 2006-11-22
AU2671301A (en) 2001-06-25
WO2001044434A1 (fr) 2001-06-21
ATE346134T1 (de) 2006-12-15
CA2328326A1 (fr) 2001-06-13

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