WO2018138122A1 - Tensioactifs en capsules ayant un point de trouble optimisé - Google Patents

Tensioactifs en capsules ayant un point de trouble optimisé Download PDF

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Publication number
WO2018138122A1
WO2018138122A1 PCT/EP2018/051668 EP2018051668W WO2018138122A1 WO 2018138122 A1 WO2018138122 A1 WO 2018138122A1 EP 2018051668 W EP2018051668 W EP 2018051668W WO 2018138122 A1 WO2018138122 A1 WO 2018138122A1
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Prior art keywords
water
surfactant
surfactants
surfactant formulation
weight
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PCT/EP2018/051668
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German (de)
English (en)
Inventor
Inga Kerstin Vockenroth
Klaus Dorra
Thomas Weber
Alexander Schulz
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Henkel Ag & Co. Kgaa
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Publication of WO2018138122A1 publication Critical patent/WO2018138122A1/fr

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    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D17/045—Multi-compartment
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products

Definitions

  • the present invention relates to a surfactant formulation which comprises at least one liquid surfactant in a water-soluble casing, and to washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, which contain a corresponding surfactant formulation in a water-soluble casing.
  • Surfactants are used in different areas of everyday life. A prominent area is the use as detergents or cleaners and especially as dishwashing detergents. In addition to hand dishwashing detergents, this also includes those which can be used in the automatic cleaning of dishes, ie in dishwashers.
  • Solid washing or cleaning agents have the advantage that, in contrast to liquid detergents or cleaning agents, they do not require any preservatives.
  • Liquid supply forms are increasingly gaining acceptance on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients contained. This offers the consumer the opportunity to use time-shortened rinse programs and still obtain a good cleaning performance.
  • Such stains can be, for example, locally-limited stains (so-called spotting) or staining spots (so-called filming), which are caused, in particular, by insufficient rinsing performance of the washing or cleaning agent.
  • EP-A-0851024 proposes a two-layered one
  • the relevant second layer are a
  • liquid surfactants liquid at 20 ° C are particularly suitable to improve the rinsing performance of detergents or cleaners, especially dishwashing detergents, preferably automatic dishwashing detergents.
  • dishwashing detergents especially automatic dishwashing detergents.
  • the reduction of the mocking on glass and porcelain is in the foreground here.
  • liquid surfactants which are preferred for the rinsing performance are difficult to incorporate into corresponding pulverulent cleaning agents and in particular those in the form of tablets. Too high amounts of liquid surfactants sticks the powder and can not be pressed or processed in other forms in single portions.
  • Dishwashing agent can be combined in particular in portioned form.
  • the object underlying the present invention could be achieved by a
  • Surfactant formulation is above the release temperature of the enclosure.
  • the object underlying the present invention relates to a surfactant formulation having a cloud point TCP in a water-soluble casing with a release temperature TF, characterized in that
  • the surfactant formulation comprises one, two or more liquid surfactants, and the cloud point TCP of the surfactant formulation is from 5 ° C to 40 ° C above the release temperature TF of the envelope. More preferably, the at least one liquid surfactant is a nonionic surfactant.
  • a surfactant formulation according to the invention enables a particularly good rinse performance.
  • the rinse performance of liquid nonionic surfactants and surfactant formulations is highest near the cloud point.
  • the formulation according to the invention in the water-soluble coating now allows the surfactant formulation to be at least partially released from the coating before reaching the clouding temperature or the cloud point TCP.
  • a timely release of the at least one liquid surfactant in a washing or cleaning cycle is ensured.
  • the water-soluble coating enables the combination of the surfactant formulation with any detergents or cleaners whose rinse performance can be improved.
  • the present invention thus relates to a washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, which identifies a surfactant formulation according to the invention.
  • dishwashing detergent preferably automatic dishwashing detergent
  • the washing or cleaning agent in particular dishwashing detergent, preferably mechanical
  • Dishwashing detergent preferably automatic dishwashing detergent.
  • it is a
  • compacted washing or cleaning agent in particular dishwashing detergent, preferably automatic dishwashing detergent, which has two or more phases, one of the phases being a solid, in particular compressed phase and the other phase a surfactant formulation in a water-soluble coating as described herein.
  • At least one bleach catalyst means at least one type of bleach catalyst, that is, one type of bleach catalyst or a mixture of several different bleach catalysts all compounds of the specified type contained in the composition / mixture, ie
  • composition beyond the specified amount of the corresponding compounds addition no further compounds of this kind.
  • the number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent.
  • the mass average molecular weight M w can also be determined by GPC, as described for M n .
  • Release temperature TF in the context of the present invention is the temperature at which the surfactant formulation can escape from the water-soluble coating.
  • the water-soluble coating can be deformed or already in this case, for example
  • the release temperature thus defines the temperature from the
  • the release temperature TF in water at 20 ° C (and normal pressure of 1 bar) is determined.
  • the surfactant formulation in the enclosure is placed on the device in the beaker such that the surfactant formulation is completely surrounded by the water, but does not come into direct contact with the stir bar. This can be done, for example, that inside the beaker, a device is introduced, which does not prevent the free movement of the stirring rod and the movement of the water.
  • the surfactant formulation can then be introduced into the beaker on this device on a suitable base, for example on a watch glass or a grid.
  • a suitable base for example on a watch glass or a grid.
  • surfactant formulation to avoid direct contact between stir bar and water-soluble wrapper. Nevertheless, the surfactant formulation is completely surrounded by water. Thus, the conditions prevailing in a dishwasher can be replicated. Inside the beaker there is also a thermometer, which measures the temperature of the water in the amount of the surfactant formulations according to the invention.
  • the water in the beaker is stirred at a stirring speed of 600 to 1000 rpm and heated at a heating rate of 1 to 2 ° C / min. Stirring causes a uniform heating of the water in the beaker.
  • the stirring speed is adjusted so that the water-soluble casing is not directly damaged.
  • the release temperature corresponds to the temperature at which the exit of the
  • Tenside formulation can be observed. This can be done, for example, by coloring the surfactant formulation with a dye. Suitable dyes for coloring surfactant formulations are well known to those skilled in the art. The release of the dyed dye can then be observed optically without further aids.
  • the cloud point is the temperature at which a surfactant formulation becomes cloudy.
  • the cloud point TCP of the surfactant formulation is preferably in the range from 20 ° C. to 75 ° C., in particular from 40 ° C. to 75 ° C., preferably from 50 ° C. to 70 ° C.
  • the cloud point is determined according to DIN EN 1890: 2006-9. The determination is made in cases of doubt as a 10 wt .-% solution of the surfactant in 25 wt .-% strength butyldiglycol (diethylene glycol mono-n-butyl ether) solution in water as described above DIN-specification.
  • the surfactant formulation according to the invention is preferably used in a washing or cleaning agent for mechanical cleaning of solid surfaces, in particular of dishes.
  • the usual cleaning temperature of the respective programs is usually in the range of 40 ° C to 75 ° C. At the beginning and end of a cleaning program, this temperature is often not reached, but there are lower temperatures.
  • the cloud point TCP of the surfactant formulation is now in the range of the temperatures that prevail in a purification. If the cloud point is below the stated temperature, the surfactant can not distribute evenly because it precipitates too quickly. If the cloud point is too high, the temperature is not reached or only too short, so that here too the desired effect, namely the Improvement of the rinse performance, can not or can not be achieved to the desired extent.
  • TCP - TF is in the range of 5 ° C to 40 ° C
  • the water-soluble casing can be in the form of a bag, a bag or a capsule, for example. Different geometric shapes are possible. Particularly preferred is a capsule, which is present in a round or oval shape.
  • Cleaning agent in particular dishwashing detergent, preferably a machine
  • Dishwashing detergents are combined.
  • a corresponding solid phase can be brought into a form such that a trough is formed, which essentially corresponds to the shape of the
  • a round or oval shape is also an appealing form for the consumer.
  • Corresponding beads are widely used as surfactant additives and may optionally provide an additional buying incentive through a color design.
  • the water-soluble casing comprises one or more water-soluble materials. It preferably comprises a water-soluble material.
  • water-soluble as used herein means “water-soluble” in the strict sense, but also “water-disintegrable.”
  • water-soluble in the true sense refers to the property of a substance or an object that it or it Solubility in distilled water, measured at 25 ° C, of at least 0, 1 g / l.
  • the substance and the object have a solubility of at least 0.1 to 500 g / l, measured at 25 ° C on.
  • water-disintegrable means that the substance or the object when in contact with water at temperatures between 15 and 60 ° C and
  • Suitable water-soluble materials are polymeric materials, such as polyvinyl alcohols (optionally partially alkoxylated or acetalated), polyacrylates,
  • Polyurethanes Polyethylene oxides, polyvinyl alcohol copolymers, cellulose and derivatives thereof, in particular methylcellulose or hydroxypropylmethylcellulose (HPMC).
  • HPMC hydroxypropylmethylcellulose
  • the water-soluble wrapper may also further contain additives such as dyes or brighteners to provide an attractive appearance.
  • the water-soluble coating particularly preferably comprises gelatin, a substance mixture of animal proteins whose main constituent is denatured or hydrolyzed collagen. Most preferably, it is a gelatin capsule. This can be obtained for example from a mixture of a gelatin granulate, glycerol and / or sorbitol and water, preferably gelatin granules, glycerol and water, which is then dried.
  • the proportion of water is preferably 20% by weight or less, in particular 15% by weight or less, preferably 5% by weight to 12% by weight or 8% by weight to 10% by weight.
  • suitable capsules can be obtained in a reasonable drying time.
  • a water-soluble coating of gelatin has been found to be particularly preferred. This can be particularly good with a solid detergent or cleaning agent, in particular
  • Dishwashing detergent preferably automatic dishwashing detergent are combined.
  • gelatin capsules can be attached without major problems.
  • a gelatin capsule is sufficiently stable to be stably stored even in a larger outer packaging in which several capsules are located, without being destroyed by the prevailing mechanical pressure.
  • water solubility or water dispersibility is high enough to allow release of the surfactant formulation contained in the capsule during conventional washing or cleaning cycles.
  • the sheath preferably has a wall thickness of 0.3 mm to 3 mm, in particular from 0.5 mm to 1, 5 mm, preferably from 0.5 mm to 1 mm.
  • a surfactant formulation in the sense of the present invention may comprise and in particular consist of a single liquid surfactant.
  • a surfactant formulation according to the present invention may also comprise or consist of two, three, four or more different surfactants.
  • the surfactant formulation consists of one or two different liquid surfactants.
  • the at least one liquid surfactant of the surfactant formulation is a nonionic surfactant. Nonionic surfactants are particularly useful for improving the rinse performance of machine-based cleaning of hard surfaces, and particularly dishes.
  • the at least one surfactant of the surfactant formulation is therefore in particular a preferably nonionic surfactant which has a cloud point TCP in the range from 20 ° C to 75 ° C, in particular from 40 ° C to 75 ° C, preferably from 50 ° C to 70 ° C.
  • Corresponding surfactants are well known to the person skilled in the art.
  • the at least one liquid surfactant of the surfactant formulation is a low foaming, in particular ethoxylated and / or propoxylated nonionic surfactant.
  • Suitable examples are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters.
  • Particularly preferred are nonionic surfactants from the group of alkoxylated alcohols.
  • Particularly preferred nonionic surfactants are alkoxylated, advantageously ethoxylated or ethoxylated and propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 mol
  • Ethylene oxide (EO) and / or propylene oxide (PO) used per mole of alcohol The alcohol radical can be linear or preferably methyl-branched in the 2-position, or linear and methyl-branched radicals can be present in the mixture as they are usually present in oxo alcohol radicals.
  • Particularly preferred are alcohol ethoxylates in which the primary alcohol has 8 to 15 C atoms and in particular 10 to 12 or 13 C atoms.
  • the corresponding alcohol is ethoxylated or ethoxylated and propoxylated.
  • the degree of alkoxylation is preferably 1 to 12 mol Alkyloxidpromol, alcohol in particular 2 to 10 mol and more preferably 6 to 12 mol. If the alcohol is only ethoxylated, this is to be understood as the amount of EO, the alcohol is ethoxylated and propoxylated, so This is the amount of EO and PO to understand.
  • Surfactant be used are linear or branched, especially branched alcohol ethoxylates, wherein the alcohol has 10 to 15 and especially 10, 1 1, 12 to 15, or 13 carbon atoms.
  • the average degree of ethoxylation is from 2 to 10 mol of ethylene oxide (EO) per mole of alcohol, in particular from 3 to 9, preferably from 3 to 8 and in particular from 3 to 6.
  • the nonionic surfactant is preferably an alcohol-ethylene oxide-propylene oxide addition product and in particular a C8- 2o-Alcoholpolyalkylenglycolether, in particular a C10-18-Alkoholpolyalkylenglycolether, preferably a C10-12 or C11-15- Alcoholpolyalkylenglycolether.
  • the present invention relates to a washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent having two or more phases, wherein a first of the phases, a solid, in particular compressed phase, and the other second phase, a surfactant formulation according to the invention in a water-soluble casing, not only the second phase in the sense of the surfactant formulation may have a surfactant.
  • the first, preferably solid and in particular compressed or compacted phase may have one, two, three or more surfactants.
  • Surfactant / corresponding surfactants is / are preferably selected from the group of anionic, nonionic and / or cationic surfactants.
  • both phases comprise at least one nonionic surfactant.
  • An inventively particularly preferred washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent thus comprises a first solid phase in the form of a compacted tablet, and a second phase in the form of
  • a phase is thus a self-contained spatial area of a washing or cleaning agent, in particular a dishwashing agent, preferably a machine dishwashing agent, which is visually distinguishable from another area without further aids.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. These are specified in more detail below. They are preferably contained in the at least one first and / or at least one second phase. The same or different surfactants may be included in the phases. For the inventive surfactant formulation in the second phase, the aforementioned surfactants are particularly preferred.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • Indicating oligoglycosides is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • Another class of preferred 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 1 to 4 carbon atoms in the alkyl chain.
  • 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.
  • Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • the washing or cleaning agents according to the invention in particular dishwashing detergents, preferably automatic dishwashing detergents, contain in the at least one first and / or second phase nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and
  • ethylene oxide (EO) used on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • Preferred ethoxylated alcohols include, for example Ci2-i4-alcohols with 3 EO or 4 EO, Cs-n-alcohol with 7 EO, C13 15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 2 -i8 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-alcohol with 5 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants which have been obtained from C 6-2o -monohydroxyalkanols or C 6-2o-alkylphenols or C 16-2o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol of alcohol, used.
  • a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20
  • Carbon atoms (C 16-2o-alcohol), preferably a cis-alcohol and at least 12 mol, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • C 16-2o-alcohol preferably a cis-alcohol and at least 12 mol, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow ranks ethoxylates” are particularly preferred.
  • surfactants come from the groups of 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.
  • nonionic surfactants which have proven themselves in the context of the present invention are the low-foaming nonionic surfactants which comprise alternating ethylene oxide and nonionic surfactants
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R 2 is R 3 in which R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3, -CH 2 CH 3, -CH 2 CH 2 -CH 3, -CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R -OH and ethylene or alkylene oxide.
  • the radical R in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol , are preferred. Examples of alcohols which are accessible from synthetic sources are the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • R in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or -CH (CH 3) 2 are suitable.
  • nonionic surfactants are those of the general formula R 0 (AlkO) xM (OAlk) y OR 2 , where
  • R and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
  • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
  • x and y independently represent values between 1 and 70;
  • M is an alkyl radical from the group CH 2, CHR 3, CR 3 R 4, CH 2 CHR 3 and CHR 3 CHR 4, wherein R 3 and R 4 independently represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 Carbon atoms.
  • Nonionic surfactants of the general formula are preferred here.
  • R is -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y-CH 2 CH (OH) -R 2 ,
  • R, R and R 2 independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.
  • R is -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O -CH 2 CH (OH) -R 2 ,
  • R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.
  • Preferred nonionic surfactants here are those of the general formula R-CH (OH) CH 2 O- (AO) w- (AO) x- (A "O) y - (A" O) z R 2 , in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; - A, ⁇ ', A "and A'" independently of one another from the group -CH2CH2, -
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • R-CH (OH) CH 2 O- (AO) w- (AO) x- (AO) y- (A "O) zR 2 , also referred to below as” hydroxy mixed ether " can surprisingly be markedly improved the cleaning performance of preparations according to the invention, specifically both compared to surfactant-free system and compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • end-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula
  • R which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2
  • R stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60.
  • surfactants of the formula RO [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 a linear or branched one
  • the group of these nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular also the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers , Particular preference is furthermore given to end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2
  • R and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 ,
  • R 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, n Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x are values between 1 and 30
  • k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R 3 in the above formula
  • R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2 be different.
  • R 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.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • 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 and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • the nonionic surfactants of the general formula R - CH (OH) CH 2 O - (AO) wR 2 have proved to be effective, in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26
  • A is a radical from the group CH 2 CH 2, CH 2 CH 2 CH 2, CH 2 CH (CH 3), preferably CH 2 CH 2, and
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.
  • nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • the at least one solid phase preferably comprises at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the phase is preferably 0.5% by weight to 30% by weight, preferably 5% by weight .-% to 25 wt .-% and in particular 10 wt .-% to 20% by weight.
  • nonionic surfactant of the solid phase is selected from nonionic surfactants of the general formula
  • R -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O -R 2 in which R and R 2 independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms; R 3 and R 4 independently of one another represent H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another represent values between 1 and 40.
  • R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 in which the radicals R and R 2 independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another represent values from 1 to 15 and in particular from 1 to 12 assume.
  • R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 , in which one of the radicals R and R 2 is branched.
  • Alkoxylation levels of the nonionic surfactants represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the Herste II process exist commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is suitable for both the C-chain lengths and for the
  • Degree of ethoxylation or degrees of alkoxylation may give mean values and numbers which are subsequently broken.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • said solid phase may further conventional in the art auxiliaries, such as enzymes, builders, fragrances, other solvents, bleach activators, bleach catalysts, thickeners, sequestering agents, electrolytes, corrosion inhibitors, especially silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization, UV stabilizers, pearlescing agents (INCI Opacifying Agents;
  • auxiliaries such as enzymes, builders, fragrances, other solvents, bleach activators, bleach catalysts, thickeners, sequestering agents, electrolytes, corrosion inhibitors, especially silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization, UV stabilizers, pearlescing agents (INCI Opacifying Agents;
  • glycol distearate for example Cutina ® AGS Cognis, or mixtures comprising, for example Euperlane ® Cognis
  • Preservatives for example, the technical also known as Bronopol 2-bromo-2-nitropropane-1, 3-diol (CAS 52-51-7) which is commercially available for example as Myacide ® BT or as Boots Bronopol BT from Boots
  • antimicrobial agents for example, the technical also known as Bronopol 2-bromo-2-nitropropane-1, 3-diol (CAS 52-51-7) which is commercially available for example as Myacide ® BT or as Boots Bronopol BT from Boots
  • antimicrobial agents disinfectants
  • pH adjusting agents in amounts of usually not more than 5 wt .-%.
  • Excipients may also be included in the phase with the surfactant formulation of the invention. However, this phase is preferably free of excipients and comprises exclusively surfactants.
  • a washing or cleaning agent according to the invention in particular a dishwashing detergent, preferably an automatic dishwashing detergent, has an enzyme or an enzyme preparation
  • the corresponding phase preferably has nonionic surfactants with one or more free hydroxy groups on one or both terminal alkyl radicals.
  • Hydroxy mixed ethers can improve the stability of the enzymes.
  • Suitable anionic surfactants in the washing or cleaning agents are all anionic surface-active substances. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms.
  • anionic group such as a carboxylate, sulfate, sulfonate or phosphate group
  • a lipophilic alkyl group having about 8 to 30 carbon atoms.
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions. Indicates the washing or cleaning agent, in particular
  • Dishwashing agents preferably automatic dishwashing agents, anionic surfactants, they are preferably in the first phase.
  • the second phase particularly preferably comprises only nonionic surfactant (s) as surfactant (s).
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and
  • Ethercarbon yarn having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
  • cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds.
  • builders such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.
  • the use of phosphates is largely or completely omitted.
  • the agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). Most preferably, in this embodiment, the agent is completely phosphate-free, that is, the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include in particular carbonates, citrates, phosphonates, organic
  • the proportion by weight of the total builders in the total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
  • Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, especially two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule.
  • Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • Polycarboxylic still further functional groups such as hydroxyl or
  • Amino groups carry. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, for example nitrilotriacetic acid (NTA), glutamine-N, N -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and derivatives thereof, and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and
  • polymeric polycarboxylates organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the
  • Macromolecule Polyaspartates, polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component.
  • an acidifying component In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • washing or cleaning agents according to the invention, in particular
  • Dishwashing detergents preferably automatic dishwashing detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.
  • citric acid ie citrates
  • washing or cleaning agents according to the invention, in particular
  • Dishwashing agents preferably automatic dishwasher detergents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates,
  • Amino carboxylic acids and citrates wherein the weight fraction of these builders, based on the total weight of the cleaning agent according to the invention, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has for the cleaning and rinsing performance of inventive detergents or cleaning agents, in particular
  • Dishwashing detergents preferably automatic dishwasher detergents, have proved to be advantageous.
  • one or more other builders may additionally be present.
  • Preferred washing or cleaning agents in particular dishwashing detergents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight.
  • the amount of citrate is preferably from 5 to 35% by weight, in particular from 10 to 25% by weight, very particularly preferably from 15 to 20% by weight, based in each case on the total amount of the cleaning agent, the total amount of these two being Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.
  • washing or cleaning agents according to the invention in particular dishwashing detergents, preferably automatic dishwashing detergents, can be used as further builders in particular
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance.
  • aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular Amounts of 0.5 to 8 wt .-%, most preferably from 2.5 to 7.5 wt .-%, each based on the total weight of the composition.
  • citrate particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-%
  • washing or cleaning agents in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized in that they contain, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, at least one further phosphorus-free one
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic diacetic acid
  • HEIDA Hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • a particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
  • the percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules.
  • MGDA granules which contain as little water as possible and / or a lower hygroscopicity compared to the non-granulated powder
  • Dishwashing detergents preferably automatic dishwasher detergents, have proved to be advantageous.
  • other builders may be included.
  • organic builders polymeric polycarboxylates are also suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid,
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and particularly preferably from 1200 to 5000 g / mol, may again be preferred from this group.
  • Polycarboxylates is preferably 0.5 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 10 wt .-%.
  • Inventive washing or cleaning compositions especially dishwashing detergent, preferably automatic dishwashing detergent can be used as builder also crystalline layered silicates of general formula NaMSix02x + i ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1 , 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use 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 preferably delayed in dissolution and
  • Dishwashing agents preferably automatic dishwasher detergents, the content of silicates, based on the total weight of the washing or cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-% and in particular below 2 wt .-% limited.
  • the washing or cleaning agents according to the invention may furthermore comprise alkali metal hydroxides.
  • alkali carriers are preferably present only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below, in the washing or cleaning agents, in particular dishwashing agents, preferably automatic dishwashing agents and in particular in the at least one second phase 5 wt .-%, more preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent used.
  • Alternative washing or cleaning agents according to the invention are free of alkali metal hydroxides.
  • cleaning agents according to the invention in the at least one first and / or the at least one second phase preferably comprise enzyme (s).
  • enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Detergents according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 % by weight to 5% by weight, based on active protein.
  • the protein concentration can help with known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in detergents developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, those originally from Humicola lanuginosa
  • Lipases available, or further developed lipases, in particular those with the amino acid exchange in positions D96LT213R and / or N233R, more preferably all of the exchanges D96L, T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • mannanases xanthan lyases
  • pectin lyases pectinases
  • pectin esterases pectate lyases
  • xyloglucanases xylanases
  • pullulanases and ⁇ -glucanases.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • a protein and / or enzyme may be particularly vulnerable during storage to damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic Cleavage to be protected.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes for the at least one first and / or at least one second phase can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are as solidified Gel are included or in those of the core-shell type in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and
  • detergents which, based in each case on their total weight, are from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight, of the respective enzyme preparations contain.
  • solvent agents according to the invention preferably contain at least one alkanolamine.
  • the alkanolamine is hereby preferably selected from the group consisting of Mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
  • dishwashing detergent preferably automatic dishwashing detergent
  • the at least one second phase is free of alkanolamine and the alkanolamine is contained only in the at least one first phase.
  • Detergents or dishwashing detergents according to the invention in particular dishwashing detergents, in a preferred embodiment, in particular in the at least one first phase, contain as further constituent at least one zinc salt as glass corrosion inhibitor.
  • the zinc salt may be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is preferably present in the detergent according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of
  • Detergent Additionally or alternatively to the above-mentioned salts (especially zinc salts) may polyethyleneimines described, for example, under the name Lupasol ® (BASF) can be obtained, preferably in an amount of 0 to 5 wt .-%, particularly 0.01 to second %, are used as glass corrosion inhibitors.
  • BASF Lupasol ®
  • Polymers suitable as additives are especially maleic acid-acrylic acid copolymer Na salt (for example Sokalan ® CP 5 from the company BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na-salt (for example Sokalan ® CP 10 from BASF, Ludwigshafen
  • modified polycarboxylate-Na-salt for example Sokalan ® HP 25 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide-modified heptamethyltrisiloxane such as Silwet ® L-77 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide, modified heptamethyltrisiloxane such as Silwet ® L-7608 from BASF, Ludwigshafen (Germany)
  • polyether copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether)
  • water-soluble linear for example Sokalan ® HP 25 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide-modified heptamethyltrisiloxane such as Silwet ® L-77 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide, modified heptamethyltrisiloxane such as Silwet ® L-7608 from BASF, Ludwig
  • Polyether-terminated polyether as Tegopren® ® 5840, Tegopren® ® 5843, Tegopren® ® 5847, Tegopren® ® 5851, Tegopren® ® 5863 or Tegopren® ® 5878 from Evonik, Essen (Germany).
  • suitable builders are especially polyaspartic acid Na salt, Ethylendiamintriacetatkokosalkylacetamid (eg Rewopol® ® CHT 12 from Evonik, Essen (Germany)), methylglycine-trisodium salt and acetophosphonic.
  • Blends with surfactant or polymeric additives exhibit synergism 5863 in the case of Tegopren 5843 and Tegopren ® ®.
  • Tegopren grades 5843 and 5863 are less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to glass.
  • the additives mentioned are dispensed with.
  • a preferred washing or cleaning agent in particular dishwashing detergent, preferably automatic dishwasher detergent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst. These are, if available, contained exclusively in the at least one first phase.
  • Other useful bleaching agents are, for example
  • Peroxypyrophosphates citrate perhydrates and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred. A particularly preferred oxygen bleach is sodium percarbonate.
  • 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.
  • Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • the bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe-Cu and Ru ammine complexes are also known Bleach catalysts usable.
  • complexes of manganese in the oxidation state II, III, IV or IV are used, preferably one or more
  • ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1 -1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • bleach catalyst s
  • the washing or cleaning agent according to the invention in particular dishwashing detergent, preferably automatic dishwashing detergent, can be tightly enveloped by a water-soluble film or contained in a water-soluble bag.
  • the water-soluble film or the water-soluble bag preferably comprises a water-soluble polymer.
  • Some preferred water-soluble polymers which are preferably used as water-soluble packaging are polyvinyl alcohols, acetalized
  • Polyvinyl alcohols polyvinylpyrrolidones, polyethylene oxides, celluloses and gelatin, wherein polyvinyl alcohols and acetalated polyvinyl alcohols are particularly preferably used.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure
  • Polymerization degrees in the range of about 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 87-99 mol%, so still contain a residual content of acetyl groups.
  • the water-soluble packaging at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mole%.
  • the water-soluble packaging consists of at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol, the Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%, is.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the
  • Packaging material comprises a polyvinyl alcohol whose molecular weight in the range of 5,000 g-mol to 100,000 g-mol, preferably from 10,000 g-mol to 90,000 g-mol "1 , more preferably from 12,000 g-mol " to 80,000 g-mol " and in particular from 15,000 g-mol " to 70,000 g-mol “ 1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • the water solubility of polyvinyl alcohol can be improved by post-treatment with aldehydes
  • the water-soluble bag preferably has a thickness of from 10 ⁇ m to 500 ⁇ m, in particular from 20 ⁇ m to 400 ⁇ m, particularly preferably from 30 ⁇ m to 300 ⁇ m, in particular from 40 ⁇ m to 200 ⁇ m, in particular from 50 ⁇ m to .mu.m 150 ⁇ .
  • a particularly preferred polyvinyl alcohol is available, for example, under the trade name M8630 (Monosol).
  • the water-soluble film which is preferably used in the narrow enclosure), particularly preferably comprises polyvinyl alcohol, as described above, wherein as starting thickness preferably a thickness of 10 ⁇ to 100 ⁇ , in particular from 12 ⁇ to 60 ⁇ , particularly preferably from 15 ⁇ to 50 ⁇ , especially from 20 ⁇ to 40 ⁇ , in particular from 22 ⁇ to 35 ⁇ is used.
  • a disposable portion of the washing or cleaning agent in particular dishwashing detergent, preferably automatic dishwashing detergent, is enclosed.
  • dishwashing detergent preferably automatic dishwashing detergent
  • the envelope is even under tension, which is not absolutely necessary. This dense covering of the envelope is conducive to disintegration: upon first contact with water, the envelope will pass a small amount of water at some point, and at first it does not need to dissolve at all. At this point begins that contained in the tablet
  • the mechanism described here does not work as the tablet can swell without bursting the cladding thereby.
  • the use of a swellable disintegrating agent is superior to a gas-developing system, since its explosive effect in each case leads to a rupture of the casing.
  • the explosive effect may "fizzle out" of the enclosure by leakage of the gas from a leak.
  • Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 ⁇ , preferably 0.5 to 500 ⁇ , particularly preferably 1 to 250 ⁇ and in particular 2.5 to 100 ⁇ , is.
  • the film wrapping is first laid loosely around a washing or cleaning agent portion and welded and then shrunk onto it, so that a close contact between the film package and the detergent concentrate is given.
  • washing or cleaning agents according to the invention are single portions characterized in that the envelope is a shrunk on this film packaging.
  • this wrapping can be done by placing a water-soluble lower film on a conveyor chain or a mold (s) tool, then one or more detergent or cleaning agent portion (s) are placed on the lower film; Subsequently, a water-soluble upper film placed on the washing or cleaning agent portion (s) on the lower film and then fixed on the lower film including the washing or cleaning agent portion (s), Alternatively, this step can also be done by a single-strand film, which then as Hose is placed around the disposable portions. This is followed by sealing and optional cutting of the films. Subsequently, then the shrinking of the film by the use of hot air or infrared radiation, optionally with pressing done.
  • inventive surfactant formulation and detergents or cleaners according to the invention in particular dishwashing agents, preferably automatic dishwashing detergents, are described in a nonlimiting manner.
  • the cloud point measurement was carried out as a 10% by weight solution in 25% by weight of butyl diglycol in water. The results are shown below.
  • Surfactant formulation was 50 ° C to 70 ° C.
  • the gelatin capsules were placed on a watch glass (diameter: 8 cm) and carefully placed on the watch glass on the metal device in the beaker. The capsules were completely surrounded by water. Inside the beaker, there was also a rod thermometer, which measured the temperature of the water in the amount of the surfactant formulations according to the invention.
  • the water in the beaker was stirred at a stirring speed of 800 rpm and heated at a heating rate of about 1.5 ° C / min.
  • solubility was additionally determined in the machine.
  • capsules were described as in Example 2a) in the metering box of the Bosch dishwasher (Bosch
  • SMS68M62 (without ware) placed (small basket in which the tablet when opening the
  • Rinse creases based on the visual appearance of the dry ware were assigned as parameters.
  • a phosphate-free, MGDA-free commercial dishwashing detergent in the form of a tablet with core (V1) was used. Then, the core was replaced by a surfactant-filled capsule according to the invention, in this case various surfactants S1 -S3, which are described in Example 1, used (E1, E2, E3). As a comparison, the tablet without core was used (V2).
  • this deficit can be partially reversed (E1, E2, E3).
  • a surfactant with lower TCP is poorer in metal (E1), whereas a surfactant with high TCP (E2, E3) can compensate for all deficiencies. Only a surfactant with medium TCP (E2) can even gain an advantage in porcelain.
  • a surfactant formulation according to the invention S2, S3, S4 was added to a phosphate-free, commercially available MGDA-containing formula. The procedure was as described above.
  • the deposit inhibition was determined in Miele GSL dishwashers in the 65 ° program after 30 cycles incl. Dirt loading at a water hardness of 21 ° dH.
  • topping marks on the basis of the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts and stainless steel). Shown in the
  • Result table are the arithmetic mean values of the scores of all pieces of the respective substrates.
  • Potato starch 0.41% benzoic acid, 7, 1 1% margarine and 3.05% butterfat) to simulate a normally soiled load.
  • the crockery items in the black box were visually scored.
  • streaks, coatings and films are rated on a scale of 1 to 10. 10 means no coatings / films, 1 means strong coating / film formation.
  • Example 2 The two best surfactants from Example 2 (S2, S3) were used, each with 1 g / job and 0.5 g / job dosage.
  • a commercial phosphate-free dishwashing detergent was used as in V1.
  • the surfactant formulation according to the invention thus significantly reduces the amount of fat deposited in the filter.

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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

La présente invention concerne une formulation de tensioactifs qui comprend au moins un tensioactif liquide dans une enveloppe hydrosoluble, ainsi que des détergents, en particulier des détergents à vaisselle, de préférence des détergents pour lave-vaisselle qui contiennent une formulation de tensioactifs correspondante dans une enveloppe hydrosoluble.
PCT/EP2018/051668 2017-01-24 2018-01-24 Tensioactifs en capsules ayant un point de trouble optimisé WO2018138122A1 (fr)

Applications Claiming Priority (2)

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DE102017201095.9 2017-01-24
DE102017201095.9A DE102017201095A1 (de) 2017-01-24 2017-01-24 Tenside in Kapseln mit optimiertem Trübungspunkt

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WO2018138122A1 true WO2018138122A1 (fr) 2018-08-02

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EP0851024A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Comprimés détergents pour le lavage de vaisselle en machine avec un effet de rinçage bénéfique
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DE19854267A1 (de) * 1998-11-25 2000-05-31 Henkel Kgaa Verkapseltes Reinigungsmittel
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EP1194523A1 (fr) * 1999-07-09 2002-04-10 Henkel Kommanditgesellschaft auf Aktien Portion de detergent ou nettoyant
WO2003099985A2 (fr) 2002-05-24 2003-12-04 Henkel Kommanditgesellschaft Auf Aktien Tablettes a dosage dans le compartiment a detergent
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US4259315A (en) * 1980-06-13 1981-03-31 A. H. Robins Company, Inc. Controlled release potassium dosage form
EP0851024A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Comprimés détergents pour le lavage de vaisselle en machine avec un effet de rinçage bénéfique
DE19834180A1 (de) * 1998-07-29 2000-02-03 Benckiser Nv Zusammensetzung zur Verwendung in einer Geschirrspülmaschine
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WO2003099985A2 (fr) 2002-05-24 2003-12-04 Henkel Kommanditgesellschaft Auf Aktien Tablettes a dosage dans le compartiment a detergent
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