EP2046931A1 - Agent de nettoyage ou de lavage sous forme de particules - Google Patents

Agent de nettoyage ou de lavage sous forme de particules

Info

Publication number
EP2046931A1
EP2046931A1 EP07786840A EP07786840A EP2046931A1 EP 2046931 A1 EP2046931 A1 EP 2046931A1 EP 07786840 A EP07786840 A EP 07786840A EP 07786840 A EP07786840 A EP 07786840A EP 2046931 A1 EP2046931 A1 EP 2046931A1
Authority
EP
European Patent Office
Prior art keywords
particles
type
acid
composition according
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07786840A
Other languages
German (de)
English (en)
Other versions
EP2046931B1 (fr
Inventor
Frank Meier
Matthias Sunder
Noelle Wrubbel
Dieter Nickel
Konstantin Benda
Emilie Barriau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL07786840T priority Critical patent/PL2046931T3/pl
Publication of EP2046931A1 publication Critical patent/EP2046931A1/fr
Application granted granted Critical
Publication of EP2046931B1 publication Critical patent/EP2046931B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the invention relates to a detergent or cleaning agent from at least two of a different shape having particle types.
  • Detergents are often not differentiable for the consumer. As far as they are particulate agents, they usually consist of white or more or less bright particles, which at least seem to leave behind the impression that it is a uniform-uniform product. In order to give the user, who may or may not have been sufficiently careful with the instructions for using the product, hints about which type of detergent is involved, some manufacturers have recently begun to stain portions of the particulate agent, such as one otherwise white universal detergent to add a blue or green colored particle fraction, a so-called color detergent composed of a plurality of different colored particles, or a detergent, which is to indicate particularly laundry-care properties to attach particles in muted reds or yellows. The same applies to hard surface cleaners.
  • the present invention is also based on the object of enabling an optical-aesthetic differentiation of particulate detergents or cleaning agents.
  • detergents should also include aftertreatment agents for the laundry, for example fabric softeners, as well as universal or heavy-duty detergents, mild detergents, color detergents, wool detergents, curtain detergents, modular detergents, stain salts, laundry starches and stiffeners and optionally ironing aids.
  • the invention is therefore a particulate or washing or cleaning agent comprising particulate prefabricated detergent ingredients, containing a first type of particles having a form factor of at least 0.80, and a second type of particles having a form factor of less than 0.80, preferably at least 0 , 02 is below the shape factor of the first species particle.
  • the washing or cleaning agent according to the invention thus has at least two types of particulate constituents.
  • the term "type" in the sense of this invention means that the particles do not necessarily have to differ in their composition, but that they have a different shape from each other:
  • the first kind to the unbiased viewer substantially round, that is largely spherical, and the
  • the second type differs identifiable from the spherical shape, for example, this second type may be ellipsoidal, hemispherical, or - and this is particularly preferred - be shaped quite irregularly, for example as a so-called "fracture”.
  • particles of the first and second types differ, apart from their shape, also by their ingredients.
  • the first type of particles may well comprise several different and / or composed of different ingredients particles, for example builder particles, surfactant compound particles, bleach particles, bleach activator particles, foam regulator particles or granular formulated enzymes, which are optionally different in size but are all substantially round or spherical , It is essential to the invention that at least one further particle type which is not round is present next to it.
  • the property "not round”, that is, a deviation of the shape of the particles of the ideal sphericity designated here as the second type, can be made tangible and quantified with the aid of the shape factor explained in more detail below.
  • the agent comprises particulate particles of the first type having a form factor of at least 0.83.
  • all particles of the first type are at least approximately the same size, that is, in the particles of the first type, the ratio of d50 to d90 is at least 0.60.
  • it is at least 0.65, more preferably at least 0.68, even more preferably at least 0.75, especially 0.76 to 0.99, and most preferably 0.77 to 0.95.
  • d50 represents the median value. The median value is defined as the particle size below which are 50% of the amount of particles.
  • at d90 90% of the particle quantity is below the value, ie 10% higher.
  • the composition comprises particulate particles of the first type having a shape factor of at least 0.85, preferably at least 0.90, more preferably at least 0.92, and most preferably at least 0.95.
  • the particulate particles of the first type present in the washing and / or cleaning agents according to the invention have a form factor of at least 0.84, 0.86, 0.87, 0.88, 0.89, 0.91, 0, 92, 0.93, 0.94, 0.96, 0.97, 0.98, 0.99 or 1.
  • the particulate particles of the first type present in the washing or cleaning agent are present in a narrow particle size distribution, ie the ratio of d50 to d90 is as high as possible.
  • the ratio of d50 to d90 is at least 0.78, preferably at least 0.8, more preferably at least 0.83, and most preferably at least 0.85.
  • the ratio of d50 to d90 is at least 0.76, 0.77, 0.79, 0.81, 0.82, 0.84, 0.86, 0.87 , 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98 or 0.99.
  • the shape factor can be precisely determined by modern particle measurement techniques with digital image processing.
  • a typical particle shape analysis as it is feasible, for example, with the Camsizer® system from Retsch Technology or with the KeSizer® from Kemira, based on the fact that the particles or the bulk material are irradiated with a light source and detects the particles as projection surfaces, digitized and processed by computer technology.
  • the underlying principle for determining the shape factor has been described, for example, by Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity" in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pages 79-81.
  • the measuring limits of this optical analysis method are 15 ⁇ m and 90 mm, respectively.
  • the numerical values for d50 and d90 are also available via the aforementioned measuring method.
  • the particulate particles of the second type contained in the washing or cleaning agents according to the invention have a form factor of at most 0.79, 0.78, 0.77, 0.76, 0.75 or 0.74.
  • the shape factor value of the second type particles is 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0 , 12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24 , 0.25 or 0.26 below the shape factor value of the first type particles.
  • the d50 values of both the first type particles and the second type particles are preferably in the range of 0.4 mm to 2 mm, more preferably 0.8 mm to 1.8 mm.
  • the d50 value for the particles of the second type is at least 0.05 mm, in particular 0.1 mm to 0.3 mm, larger than that of the particles of the first type.
  • an inventive composition is less than half, in particular from 1 wt .-% to 45 wt .-%, particularly preferably from 1 wt .-% to 10 wt .-% and for example to 1 wt .-% to 5 wt % of the second type of particles, the remainder being 100% by weight of particles of the first kind.
  • detergent ingredient particles having form factors of at least 0.80 are obtainable by various preparation methods, for example by the so-called spray agglomeration method.
  • This method has the advantage that the production of the particles and the rounding take place in one step.
  • the particles are simultaneously agglomerated and dried in a fluidized bed. Due to the onion-like application of the substances and the movement of the particles, very dense and round particles are formed.
  • Another possible Provides that initially free-flowing particulate particles, preferably by extrusion, are prepared and the particulate particles are then rounded, preferably using a Spheronizers, a rotary drum, a coating drum or a coating pan.
  • Extrusion processes suitable for this purpose are known in the prior art and are described, for example, in international patent application WO 00/23556, in international patent application WO 99/13045 or also in European patent application EP 0 665 879.
  • the production of the particles of the second type can also be carried out by the same methods known per se.
  • compact powder or particulate particles can be obtained by spraying and subsequent dry compaction, by granulation, spray agglomeration or by extrusion.
  • cylindrically shaped particles By cutting the extruded mass at the extruder head, for example, cylindrically shaped particles can be obtained.
  • the particulate particles thus obtained are rounded in a second process step.
  • the rounding of the particles of the first type takes place in such a way that they have a form factor of at least 0.80 after the rounding process.
  • the particulate particles or the extrudate are preferably rounded with the aid of a so-called spheronizer, a rotary drum, a coating drum or a coating dish.
  • care must therefore be taken that the rounding process is carried out at most for so long that these particles still have a form factor below 0.80.
  • the particles of the first type are white or not colored, and the particles of the second species are colored with a non-white color.
  • Preferred dyes are Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI 18134 ), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 11, Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5: 2 (CI 42051: 2), Food Red 7 (01 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (CI 15985), Food Yellow 4 (CI 19140), Reactive Green 12, Solvent Green 7 (CI 59040).
  • Particularly preferred dyes are water-soluble acid dyes, for example, Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Blue 80 (01 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570), Acid Green 81.
  • Food Yellow 13 Acid Yellow 3, CI 47005
  • Food Yellow 4 Acid Yellow 23, CI 19140
  • Food Red 7 Acid Red 18, CI 16255
  • Food Blue 2 Acid Blue 9, CI 42090
  • Food Blue 5 Acid Blue 3, CI 42051
  • Acid Red 249 CI 18134
  • Acid Red 52 CI 45100
  • Acid Violet 126 Acid Violet 48
  • Acid Blue 80 01 61585
  • Acid Blue 182 Acid Blue
  • water-soluble direct dyes for example Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes For example, Reactive Green 12, and the dyes Food Yellow 3 (CI 15985), Acid Yellow 184.
  • aqueous dispersions of the following pigment dyes Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Green 7 (CI 74260), Pigment Orange 5, Pigment R ed.
  • the following pigment dyes are used in the form of dispersions: Pigment Yellow 1 (CI 11680), Pigment Yellow 3 (CI 11710), Pigment Red 112 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360), Pigment Violet 23 (CI 51319), Pigment Blue 15: 1 (CI 74160), Pigment Green 7 (CI 74260), Pigment Black 7 (CI 77266).
  • water-soluble polymer dyes for example Liquitint RTM, Liquitint Blue HP. RTM., Liquitint Blue 65.
  • the particles of the first as well as the second type may in principle contain any conventional ingredients of detergents or cleaners, which here as well as otherwise make sure that due to the otherwise reduced storage stability of the agents incompatible ingredients together into a particle be incorporated.
  • the particle of the second kind, but not the particle of the first kind is translucent.
  • translucency is the partial translucency of a body.
  • translucent bodies In contrast to transparency, one can describe translucency as translucency and transparency as visual or visual transparency.
  • Subsurface scattering refers to the scattering of light in translucent bodies. Translucent bodies are partially translucent. In contrast to opaque bodies, they therefore do not reflect incident light directly on their surface, but only after it has penetrated into the matter. In other bodies are several partially translucent layers one above the other, z. As for organic substances such as skin and cellulose. Translucent bodies apparently break with the Refiexions must be used, because if one considers the outer surface, then the angle of incidence and angle of incidence are by no means always the same. A beam of light can enter the body at one point at an angle and exit at a completely different location at a completely different angle. This effect makes the behavior of the light practically unpredictable.
  • the degree of transmittance describes the proportion of incident radiant flux or luminous flux that completely penetrates a transparent component; So z. B. the "Durchlassgüte" of a glass.
  • the transmission of glass is for example between 80 and 100%; the particles of the second kind are preferably so translucent that they have at least 1%, in particular at least 5% and particularly preferably at least 10% more transmission than the particles of the first kind.
  • High translucency can be realized particularly easily if the particle of the second Art made from a dirtablösenFahrden polyester.
  • soil release agents are often referred to as “soil release” agents or because of their ability to render the treated surface, e.g., the fiber, soil-repellent as "soil repellents”.
  • copolyesters which contain dicarboxylic acid. units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing polyesters of the type mentioned as well as their use in detergents have been known for a long time.
  • European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • European Patent EP 185,427 discloses methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and laundry detergents containing such soil release polymer.
  • European Patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units. From the European patent EP 241 985 polyesters are known, which in addition to oxyethylene groups and terephthalic acid units 1, 2-propylene, 1,2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units and containing to C 4 alkyl groups are endemergencever publication.
  • European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 from ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to 0.95.
  • From the European patent application EP 272 033 polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units are at least partially known by Ci-4-alkyl or acyl radicals end phenomenon.
  • European Patent EP 274 907 describes sulfoethyl end-capped terephthalic acid lathy soil release polyester.
  • soil-release polyesters are prepared by sulfonation of unsaturated end groups with terephthalate, alkylene glycol and poly-C 2 - 4 glycol units.
  • the laundry detergent ingredient constituting the second type particle is a soil release polyester consisting of the structural units I to III or I to IV,
  • a, b and c independently of one another each represent a number from 1 to 200, d, e and independently of one another each represent a number from 1 to 50, g represents a number from 0 to 5,
  • Ph is a 1,4-phenylene radical
  • sPh is a 1,3-phenylene radical which is substituted in position 5 by a group -SO 3 Me
  • Tetraalkylammonium wherein the alkyl radicals of the ammonium ions to
  • R 7 is a linear or branched C 1 -C 30 -alkyl group or a linear or branched C 2 -C 30 -alkenyl group, a cycloalkyl group having 5 to 9
  • Such polyesters can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester, alkylene glycols, optionally polyalkylene glycols (at a, b and / or c> 1) and polyalkylene glycols end capped on one side (corresponding to unit III). It should be pointed out that for numbers a, b, c> 1 there is a polymeric skeleton and thus the coefficients as an average can assume any value in the given interval. This value reflects the number average molecular weight.
  • R 1 and R 2 are each H
  • polyethylene glycol-co-propylene glycol having number-average molecular weights of 100 to 2000 g / mol.
  • from 1 to 50 units (I) can be contained per polymer chain.
  • unit (II) is an ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used are the aforementioned. In the structures, for example, 1 to 50 units (II) may be present.
  • the preferred use amount of the structural unit ( III) the one to achieve the necessary below average molecular weights is necessary.
  • the use of crosslinked or branched polyester structures is also according to the invention. This is expressed by the presence of a crosslinking polyfunctional structural unit (IV) having at least three to a maximum of 6 functional groups capable of esterification reaction.
  • a crosslinking polyfunctional structural unit (IV) having at least three to a maximum of 6 functional groups capable of esterification reaction.
  • acid, alcohol, ester, anhydride or epoxy groups can be named as functional groups. Different functionalities in one molecule are also possible.
  • Citric acid malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethyl-propionic acid, may be used as examples for this purpose.
  • polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used.
  • These may also be polybasic aliphatic or aromatic carboxylic acids, such as benzene-1, 2,3-tricarboxylic acid (hemimellitic acid), benzene-1, 2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid ( Trimesithklare) act.
  • the proportion by weight of crosslinking monomers, based on the total weight of the polyester, can be, for example, up to 10% by weight, in particular up to 5% by weight and more preferably up to 3% by weight.
  • the polyesters containing the structural units (I), (II) and (III) and optionally (IV) generally have number average molecular weights in the range from 700 to 50,000 g / mol, wherein the number average molecular weight can be determined by size exclusion chromatography in aqueous solution using a calibration using narrowly distributed polyacrylic acid Na salt standards.
  • the number-average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular from 1,000 to 15,000 g / mol, particularly preferably from 1,200 to 12,000 g / mol.
  • solid polyesters which have softening points above 40 ° C. are preferably used as part of the particle of the second type; they preferably have a softening point between 50 and 200 ° C., more preferably between 80 ° C. and 150 ° C., and most preferably between 100 ° C. and 120 ° C.
  • the synthesis of the polyesters can be carried out by known processes, for example by adding the abovementioned Components are first heated under normal pressure with addition of a catalyst and then builds up the necessary molecular weights in vacuo by distilling off superstoichiometric amounts of the glycols used.
  • the known transesterification and condensation catalysts such as For example, titanium tetraisopropylate, dibutyltin oxide, alkali or alkaline earth metal alkoxides or antimony trioxide / calcium acetate.
  • Preferred polyesters are of solid consistency and can easily be ground into powder or compacted or agglomerated into granules of defined particle sizes.
  • the granulation can be carried out by solidifying the copolymers obtained as melt in the synthesis by cooling in a cool gas stream, for example air or nitrogen, or by application to a flaking roll or to a treadmill to form flakes or flakes.
  • This coarse material can optionally be further ground, for example, in the roll mill or in the screen mill, which can be followed by a sieving and a rounding as described above.
  • the granulation can also be carried out in such a way that the polyesters are ground to powder after solidification and then reacted by compaction or agglomeration and the above-described rounding into granules with defined particle sizes.
  • Such soil-release polymers can be incorporated into particles of the first and / or second type; they are preferably incorporated into particles of the second type, and in a particular embodiment of the invention, the particles of the second type consist of such soil-release polymer.
  • an agent according to the invention contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof , in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
  • Another embodiment of such agents comprises the presence of synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid esters and / or sulfofatty acid disalts, in particular an amount in the range of 2% to 25% by weight.
  • the anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.
  • Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
  • alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters such as may be prepared according to the process disclosed in International Patent Application WO 90/13533, and fatty acid polyhydroxyamides, as prepared according to the processes of US Pat. Nos.
  • alkyl polyglycosides are compounds of the general formula (G) n -OR, in which R is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • R is an alkyl or alkenyl radical having 8 to 22 carbon atoms
  • G is a glycose unit
  • n is a number between 1 and 10 mean.
  • the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, Galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • Preferred monomer building block is glucose because of its good availability.
  • Nonionic surfactant is preferably present in agents according to the invention in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight.
  • Such agents may instead or additionally, other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, respectively to total means, included.
  • Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation.
  • alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a customary sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • Such alkyl and / or alkenyl sulfates are contained in the compositions which contain a polymer according to the invention, preferably in amounts of 0.1 wt .-% to 20 wt .-%, in particular from 0.5 wt .-% to 18 wt .-%.
  • the sulfate-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.
  • soaps suitable being saturated soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight.
  • an agent according to the invention contains water-soluble and / or water-insoluble builders, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% by weight to 60% by weight. It preferably contains from 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • water-soluble and / or water-insoluble builders in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% by weight to 60% by weight. It preferably contains from 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, preferably a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives derives, is substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers can be prepared in particular by processes which are described in German Patent DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10000 on. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight.
  • crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials.
  • the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Suitable substitutes or partial substitutes for said aluminosilicate are crystalline alkali metal silicates which may be present alone or in admixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • Those with a molar ratio Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 can be prepared by the process of European Patent Application EP 0 425 427. They are preferably added in the course of the production as a solid and not in the form of a solution.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + I y H 2 O used in the x, the so-called module is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both .beta.- and d-sodium are preferred, with beta-sodium disilicate being obtainable, for example, by the method described in International Patent Application WO 91/08171.
  • the sodium silicates having a modulus between 1.9 and 3.2 can be prepared according to Japanese Patent Application JP 04/238809 or JP 04/260610.
  • Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are disclosed in US Pat Another preferred embodiment of detergents or cleaning agents containing a polymer according to the invention used.
  • Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance.
  • alkali metal aluminosilicate in particular zeolite
  • the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • water-soluble or water-insoluble inorganic substances may be used in the compositions. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight, but is preferably absent entirely.
  • the agents may contain other ingredients customary in detergents and cleaners.
  • These optional ingredients include, in particular, enzymes, enzyme stabilizers, bleaches, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, grayness inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyrdine N-oxide, foam inhibitors, for example organopolysiloxanes or Paraffins, and optical brighteners, for example stilbene disulphonic acid derivatives.
  • enzymes enzyme stabilizers
  • bleaches bleach activators
  • complexing agents for heavy metals for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids
  • grayness inhibitors for example cellulose ethers
  • color transfer inhibitors for example polyvinylpyrrolidone
  • optical brightener in particular one or more compounds from the class of substituted 4,4'-bis ( 2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulphonic acids, up to 5% by weight, in particular from 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, up to 3% by weight, in particular from 0.5% by weight to 2% by weight, of and contain up to 2% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, the weight proportions in each case referring to the total agent.
  • optical brightener in particular one or more compounds from the class of substituted 4,4'-bis ( 2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulphonic acids, up to 5% by weight, in particular from 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and
  • present enzymes are preferably selected from the group comprising protease, amylase, pullulanase, mannanase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof.
  • proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms, for example, in the German patents DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738, European Patent Application EP 006 638 and international patent application WO 91/02792.
  • Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
  • the lipase which can be used can be prepared from Humicola lanuginosa, as described for example in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384 717 , from Pseudomonas species, as for example in the European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international Patent application WO 90/10695, from Fusarium species, as described for example in European patent application EP 130 064, from Rhizopus species, as described
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl® and Termamyl®.
  • the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
  • Such cellulases are known, for example, from German disclosure DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or the European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339,550 known.
  • Suitable foam inhibitors include long-chain soaps, in particular heel soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as for example in German Offenlegungsschrift DE 34 36 194, European Patent Applications EP 262 588, EP 301 414, EP 309 931 or European Patent EP 150 386 described.
  • an agent containing a polymer of the present invention may contain graying inhibitors.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, for example partially hydrolyzed starch. Na-carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and mixtures thereof are preferably used.
  • a further embodiment of an agent according to the invention contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts ranging from 2% by weight to 10% by weight.
  • These bleaches which are suitable are the solid peroxygen compounds which are generally used in detergents, such as perborate, which may be in the form of tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts.
  • Such bleaching agents are in Detergents preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on the total agent present.
  • the optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylgly
  • the bleach activators may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, as for example according to in European Patent EP 37,026 can be prepared, and / or granular l, 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described by the method described in German Patent DD 255,884 can be prepared, is particularly preferred.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • percarboxylic acids such as peroxydodecanedioic acid (DPDA), peroxysuccinic nonylamide (NAPSA), nonylamide of peroxyadipic acid nonylamide (NAPAA) decyldiperoxysuccinic acid (DDPSA) or phthalimidoperoxycaproic acid (PAP) become.

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Abstract

L'invention concerne le problème pour le consommateur de la non-disponibilité de détergents suffisamment différentiables. Ce problème est sensiblement résolu par des agents de lavage ou de nettoyage constitués de matériaux de nettoyage ou de lavage sous forme de particules ou fabriqués sous forme de particules, contenant un premier type de particules, présentant un facteur de forme supérieur ou égal à 0,80, et un second type de particules, présentant un facteur de forme inférieur à 0,80.
EP07786840.4A 2006-08-04 2007-06-26 Agent de nettoyage ou de lavage sous forme de particules Active EP2046931B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07786840T PL2046931T3 (pl) 2006-08-04 2007-06-26 Środek piorący lub czyszczący w postaci cząstek

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006036895A DE102006036895A1 (de) 2006-08-04 2006-08-04 Teilchenförmiges Wasch- oder Reinigunsmittel
PCT/EP2007/056340 WO2008015055A1 (fr) 2006-08-04 2007-06-26 Agent de nettoyage ou de lavage sous forme de particules

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EP2046931A1 true EP2046931A1 (fr) 2009-04-15
EP2046931B1 EP2046931B1 (fr) 2013-08-21

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DE (1) DE102006036895A1 (fr)
ES (1) ES2429409T3 (fr)
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ES2602989T3 (es) 2007-07-20 2017-02-23 Boston Scientific Neuromodulation Corporation Sistema de estimulación para controlar el orden de reclutamiento neuronal y el efecto clínico

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US4970017A (en) * 1985-04-25 1990-11-13 Lion Corporation Process for production of granular detergent composition having high bulk density
GB8907100D0 (en) * 1989-03-29 1989-05-10 Unilever Plc Particulate detergent additive product,preparation and use thereof in detergent compositions
US5795856A (en) * 1994-03-28 1998-08-18 Kao Corporation Method for producing detergent particles having high bulk density
JP2001515955A (ja) * 1997-09-11 2001-09-25 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 粒状洗剤の製法
DE19848024A1 (de) * 1998-10-17 2000-04-20 Henkel Kgaa Verfahren zur Herstellung extrudierter Formkörper
DE19855381A1 (de) 1998-12-01 2000-06-08 Henkel Kgaa Tensidmischung in fester Form zum Einsatz als Wasch- und Reinigungsmittel
DE19918457A1 (de) * 1999-04-23 2000-10-26 Henkel Kgaa Leistungsgesteigerte teilchenförmige Reinigungsmittel für das maschinelle Geschirrspülen
DE19954959A1 (de) * 1999-11-16 2001-05-17 Henkel Kgaa Umhüllte teilchenförmige Peroxoverbindungen
DE10129467A1 (de) * 2001-06-19 2003-03-20 Henkel Kgaa Lagerstabiles, zeolitharmes Wasch- und/oder Reinigungsmittel
DE102004053385A1 (de) * 2004-11-02 2006-05-11 Henkel Kgaa Kugelförmige Agglomerate
EP2007866A1 (fr) * 2006-04-20 2008-12-31 The Procter and Gamble Company Composition de détergent à lessive particulaire solide comprenant des particules de parfum

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Title
See references of WO2008015055A1 *

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EP2046931B1 (fr) 2013-08-21
DE102006036895A1 (de) 2008-02-07
PL2046931T3 (pl) 2014-01-31
ES2429409T3 (es) 2013-11-14
WO2008015055A1 (fr) 2008-02-07

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