DE102009045648A1 - Mixtures of molded articles and their use - Google Patents

Abstract

Mixtures of moldings, comprising (A) at least one molding of dimensions length. Width. Each in the range of 1 mm to 10 cm, prepared by treating (a) open-cell foam having a density in the range of 5 to 500 kg / m 3 and an average pore diameter in the range of 1 μm to 1 mm (b) with at least one cationic polymer (c) and a shaping step, (B) at least one shaped body with dimensions of length. Width. Each in the range of 1 mm to 3 cm, prepared by treating (a) open-cell foam having a density in the range of 5 to 500 kg / m 3 and an average pore diameter in the range of 1 μm to 1 mm (d) with at least one anionic polymer (c) and a shaping step.

Description

• (A) mindestens einen Formkörper mit Abmessungen Länge·Breite·Höhe jeweils im Bereich von 1 mm bis 10 cm, hergestellt durch Behandeln von (a) offenzelligem Schaumstoff mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm (b) mit mindestens einem kationischen Polymer (c) und einem Form gebenden Schritt,
• (B) mindestens einen Formkörper mit Abmessungen Länge·Breite·Höhe jeweils im Bereich von 1 mm bis 3 cm, hergestellt durch Behandeln von (a) offenzelligem Schaumstoff mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm (d) mit mindestens einem anionischen Polymer (c) und einem Form gebenden Schritt.

The present invention relates to mixtures of moldings comprising

• (A) at least one shaped article having dimensions length · breadth · height, each in the range of 1 mm to 10 cm, prepared by treating (a) open-cell foam having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the Range from 1 μm to 1 mm (b) with at least one cationic polymer (c) and a shaping step,
• (B) at least one shaped article having dimensions length · width · height, each in the range of 1 mm to 3 cm, prepared by treating (a) open-cell foam having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the Range of 1 micron to 1 mm (d) with at least one anionic polymer (c) and a shaping step.

Farther The present invention relates to the use of the invention Mixtures in vacuum cleaners and vacuum cleaners, including at least a mixture according to the invention. Furthermore The present invention relates to a process for the purification of Surfaces.

at Vacuum cleaners, especially in vacuum cleaners, come in many Fall dust retention systems are used, the between the air inlet of a dust collecting chamber and the suction side of a Blowers are arranged and remove the dust before entering hold back into the fan. A particularly well known Variant is a bag-shaped filter that acts on the inside is, d. h., The dust is stored inside the bag-shaped filter from. Such filters must be regular be replaced. In some vacuum cleaners, especially in micro-sucker, Multi-purpose vacuum cleaners or commercial appliances, there are external Filters surrounding the blower. An advantage of this is the larger capacity; adversely is that such filters designed only for coarse dust are and that fine dust, allergy-causing pollen and microorganisms, passes the relevant filter and back from the blower to the room to be sucked blown and even whirled up.

Next the vacuum cleaner described above, the bag or a Bag, so-called "bagless vacuum cleaners" are used, who work without dust bags. They usually contain one Cyclone for dust separation or dust pre-separation and a downstream fine dust filter. Previously known bagless vacuum cleaner have the disadvantage that when emptying the cyclone - usually this happens over a flap at the bottom of the dust collector - a cloud of dust arises, which give this system an unhygienic aspect.

WO 2008/009601 proposes to use special moldings, for example in bagless vacuum cleaners. Such moldings are said to be made of open-cell foam which is treated with aqueous formulation of at least one compound having at least one semiaminal or aminal group per molecule or at least one copolymer which contains at least one comonomer which contains at least one OH group-containing or β-dicarbonyl group-containing or epoxide group-containing comonomer ,

WO 2008/009602 proposes to use open-cell foam molded articles in bagless vacuum cleaners which are treated with cationic polymer, for example at least partially neutralized polyethylenimines or at least partially neutralized polyvinylamines.

For Some types of dirt leaves the ability the abovementioned shaped body, as a dust binder to work, but still improve.

It The task was to provide a dust binder, the especially suitable for use in vacuum cleaners is that, for example, a high dust storage capacity has, has a hygienic arrangement and that the Ability to bind fine dust. Furthermore, the Task, a method for producing inventive To provide dust binders.

Accordingly were the initially defined mixtures of moldings found.

invention Mixtures comprise at least two groups of shaped bodies, in the following as shaped body (A) and molded body (B).

moldings (A) and shaped bodies (B) each have dimensions length · width · height each in the range of 1 mm to 10 cm, preferably 2 mm to 3 cm, more preferably at least 5 mm.

moldings (A) and moldings (B) can each be any Shapes and irregular or preferably be shaped regularly. As forms come for example planar shapes in question, for example, honeycomb, square, trapezoidal, cruciform, elliptical or circular discs, where the thickness is a tenth or may be less of the other dimensions.

In one embodiment of the present invention, moldings (A) according to the invention may be used. and shaped bodies (B) have a cuboid shape or honeycomb, cylindrical or spherical shape or the shape of square pillars. In this case, the term "honeycomb" is understood to mean that the shaped body (A) or shaped body (B) is in the form of a hexagonal disk or hexagonal column, wherein the height of the disk in the case of the hexagonal disk is preferably less than the diameter measured between two opposite one another lying corners. In the case of the hexagonal column, the height of the column is preferably greater than the diameter measured between two opposite corners.

invention Shaped body (A) or molded body (B) can also the shape of columns or slices in the form of others preferably have regular polygons, for example in the form of regular pentagons or regular octagons.

In an embodiment of the present invention Shaped body (A) and molded body (B) in each case have the same shape. Preferably have shaped bodies (A) and shaped body (B) different shape.

In an embodiment of the present invention Shaped body (A) in each case in the form of a plus sign, so cross shape.

In an embodiment of the present invention Shaped body (B) in each case the shape of a square column on.

If Moldings (A) are cruciform shaped bodies or shaped body in the form of a plus sign, so is with the length or width respectively the total length the bar meant. The thickness of the beams is preferably lower as the length.

In an embodiment of the present invention Shaped body (A) on the outer and preferably also on the inner surface at least one cationic Polymer, in the context of the present invention, also in general cationic polymer (b) called.

In an embodiment of the present invention Shaped body (B) on the outer and preferably also on the inner surface at least one anionic Polymer, in the context of the present invention, also in general called anionic polymer (d).

there the term polymer in connection with polymer (b) and Polymer (d) homopolymers and also copolymers.

• (a) offenzelligem Schaumstoff, kurz auch Schaumstoff (a) genannt, mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm, im Rahmen der vorliegenden Erfindung auch als Schaumstoff (a) bezeichnet,
• (b) mit mindestens einem kationischen Polymer
• (c) und einem Form gebendem Schritt

herstellen.Shaped bodies (A) can best be removed by treatment, preferably impregnation, of

• (a) open-cell foam, also referred to as foam (a) for short, with a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm, in the context of the present invention also as a foam (a ) designated,
• (b) with at least one cationic polymer
• (c) and a shaping step

produce.

• (a) offenzelligem Schaumstoff mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm, im Rahmen der vorliegenden Erfindung auch als Schaumstoff (a) bezeichnet,
• (d) mit mindestens einem anionischen Polymer
• (c) und einem Form gebendem Schritt

herstellen.Shaped bodies (B) can best be removed by treatment, preferably impregnation, of

• (a) open-cell foam having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm, also referred to as foam (a) in the context of the present invention,
• (d) with at least one anionic polymer
• (c) and a shaping step

produce.

there The foams used (a) each different or preferably the same.

moldings (A) and molded articles (B) each comprise at least one open-cell foam, in the context of the present invention also called foam (a). Foam (a) is preferably more synthetic organic nature.

to Production of the moldings (A) and moldings (B) used foams (a) are described in more detail below described.

Foams (a) are open-celled, that is, in them at least 50% of all lamellae are open, preferably 60 to 100% and particularly preferably 65 to 99.9%, determined according to DIN ISO 4590 ,

Foams (a) are preferably hard foams, which are for the purposes of the present invention foams which have a compressive strength of 1 kPa or more at a compression of 40%, determined by DIN 53577 ,

In one embodiment of the present invention, foams (A) have a density in the range of 3 to 500 kg / m ³ , preferably 6 to 300 kg / m ^3, and more preferably in the range of 7 to 300 kg / m ³ .

In one embodiment of the present invention, foams (a) have an average pore diameter (number average) in the range from 1 μm to 1 mm, preferably 50 to 500 μm by analysis of microscopic images on sections.

there Of course, only such moldings can (A) or molding (B) using foam (a) be made with a pore diameter of 1 mm, which itself a average diameter over 1 mm.

In one embodiment of the present invention, foams (a) A maximum of 20, preferably at most 15 and particularly preferably at most 10 pores per m ^2, which have a diameter in the range of 10 to 20 mm. The remaining pores usually have a smaller diameter.

In one embodiment of the present invention, foams (a) have a BET surface area in the range of 0.1 to 50 m ² / g, preferably 0.5 to 20 m ² / g, determined by DIN 66131 ,

Examples for foams (a) are selected from polypropylene, expanded polystyrene, in particular polystyrene, polyurethane and in particular aminoplast foams.

In an embodiment of the present invention chooses one foams (a) of polyurethane foams and especially preferably from aminoplast foams such as urea-formaldehyde foams and most preferably melamine foams.

• i) einem oder mehreren Polyisocyanaten, d. h. Verbindungen mit zwei oder mehr Isocyanatgruppen,
• ii) mit einer oder mehreren Verbindungen mit mindestens zwei Gruppen, die gegenüber Isocyanat reaktiv sind, in Gegenwart von
• iii) einem oder mehreren Treibmitteln,
• iv) einem oder mehreren Startern
• v) und einem oder mehreren Katalysatoren sowie
• vi) so genannten Zellöffnern.

Polyurethane foams which are particularly suitable as starting material for the preparation of mixtures of moldings according to the invention are known as such. Their preparation succeeds, for example, by implementing

• i) one or more polyisocyanates, ie compounds having two or more isocyanate groups,
• ii) with one or more compounds having at least two isocyanate-reactive groups in the presence of
• iii) one or more propellants,
• iv) one or more starters
• v) and one or more catalysts as well
• vi) so-called cell openers.

there starter iv) and propellant iii) may be identical.

Examples suitable polyisocyanates i) are known aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyvalent ones Compounds with two or more isocyanate groups.

Specific examples are:
C ₄ -C ₁₂ -alkylene diisocyanates, preferably hexamethylene-1,6-diisocyanate;
cycloaliphatic diisocyanates, such as. B. cyclohexane-1,3- and cyclohexane-1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI),
preferably aromatic di- and polyisocyanates, such as. B. 2,4- and 2,6-toluene diisocyanate and corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and corresponding isomer mixtures, mixtures of 4,4'- and 2, 4'-diphenylmethane diisocyanates, polyphenyl polymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (crude MDI) and mixtures of crude MDI with toluene diisocyanates. Polyisocyanates can be used individually or in the form of mixtures.

When Examples of ii) compounds having at least two groups, which are isocyanate-reactive, are di- and polyols, in particular polyether polyols (polyalkylene glycols), which after known methods are produced, for example by Alkali metal hydroxide catalyzed polymerization of one or a plurality of alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide are available.

All particularly preferred compounds ii) are ethylene glycol, propylene glycol, Butylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, Dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, Pentaethylene glycol, hexaethylene glycol.

When Propellants iii) are suitable: water, inert gases, in particular Carbon dioxide, and so-called physical blowing agents. For physical blowing agents is inert to the feed components Compounds that are usually liquid at room temperature and evaporate under the conditions of the urethane reaction. Preferably the boiling point of these compounds is below 110 ° C, in particular below 80 ° C. The physical blowing agents include also inert gases introduced into the insert components i) and ii) or dissolved in them, for example carbon dioxide, nitrogen or noble gases.

suitable at room temperature, liquid compounds are mostly selected from the group containing alkanes and / or cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, Acetals, fluoroalkanes of 1 to 8 carbon atoms, and tetraalkylsilanes having 1 to 3 carbon atoms in the alkyl chain, especially tetramethylsilane.

When Examples are: propane, n-butane, iso- and cyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, Methyl tert-butyl ether, formic acid methyl ester, acetone as well as fluorinated alkanes, which are degraded in the troposphere and therefore for the ozone layer are harmless, such as trifluoromethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoro-2,2,2-trichloroethane, 1,1,2-trifluoro-1,2,2-trichloroethane, difluoroethanes and heptafluoropropane. The physical blowing agents mentioned may be alone or be used in any combination with each other.

The use of perfluoroalkanes to produce fine cells is out EP-A 0 351 614 known.

When Starters iv) are suitable, for example: water, organic dicarboxylic acids, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl-substituted Diamines having 1 to 4 carbon atoms in the alkyl radical, such as. B. optionally N-mono- and N, N-dialkyl substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, aniline, phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane.

When Catalysts v) are the catalysts known in polyurethane chemistry suitable, for example, tertiary amines, such as. Triethylamine, Dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like and in particular organic metal compounds such as titanic acid esters, Iron compounds such. B. iron (III) acetylacetonate, tin compounds, z. As tin diacetate, tin dioctoate, tin dilaurate or the dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate and dibutyltin dilaurate.

• i) bis vi) werden in den in der Polyurethanchemie üblichen Mengenverhältnissen eingesetzt.

As a cell opener vi) are exemplified polar polyether polyols (polyalkylene glycols), these are those having a high content of ethylene oxide in the chain, preferably of at least 50 wt .-%. These act by segregation and influence on the surface tension during the foaming cell-opening.

• i) to vi) are used in the usual ratios in polyurethane chemistry.

• vii) einem Melamin-Formaldehyd-Vorkondensat, das neben Formaldehyd weitere Carbonylverbindungen wie beispielsweise Aldehyde einkondensiert enthalten kann,
• iii) einem oder mehreren Treibmitteln,
• viii) einem oder mehreren Emulgatoren,
• ix) gegebenenfalls einem oder mehreren Härter.

Aminoplast foams and in particular melamine foams are known as such. Their preparation succeeds, for example, by foaming of

• vii) a melamine-formaldehyde precondensate which, in addition to formaldehyde, may comprise further carbonyl compounds, such as, for example, aldehydes,
• iii) one or more propellants,
• viii) one or more emulsifiers,
• ix) optionally one or more hardeners.

Melamine-formaldehyde precondensates vii) may be unmodified, but they may also be modified, for example, up to 20 mol% of the melamine by other known Duroplastbildner substituted, for example alkyl-substituted melamine, urea, Urethane, carboxylic acid amides, dicyandiamide, guanidine, sulfuryl amide, Sulfonic acid amides, aliphatic amines, phenol and phenol derivatives. As further carbonyl compounds in addition to formaldehyde can modified melamine-formaldehyde precondensates, for example acetaldehyde, trimethylolacetaldehyde, Acrolein, furfurol, glyoxal, phthalaldehyde and terephthalaldehyde included condensed.

When Propellant iii) the abovementioned propellants are suitable preferred are water, inert gases, in particular carbon dioxide, and so-called physical blowing agent. For physical blowing agents is inert to the feed components Compounds that are usually liquid at room temperature and evaporate under the conditions of the urethane reaction. Preferably the boiling point of these compounds is below 110 ° C, in particular below 80 ° C. The physical blowing agents include also inert gases, for example carbon dioxide, nitrogen or noble gases.

suitable at room temperature, liquid compounds are mostly selected from the group containing alkanes and / or cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, Acetals, fluoroalkanes of 1 to 8 carbon atoms, and tetraalkylsilanes having 1 to 3 carbon atoms in the alkyl chain, especially tetramethylsilane.

When Examples are: propane, n-butane, iso- and cyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, Methyl tert-butyl ether, formic acid methyl ester, acetone as well as fluorinated alkanes, which are degraded in the troposphere and therefore for the ozone layer are harmless, such as trifluoromethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoro-2,2,2-trichloroethane, 1,1,2-trifluoro-1,2,2-trichloroethane, difluoroethanes and heptafluoropropane. The physical blowing agents mentioned may be alone or be used in any combination with each other.

The use of perfluoroalkanes to generate open cells is out EP-A 0 351 614 known.

As emulsifiers viii) can be used conventional non-ionic, anionic, cationic or betainic surfactants, in particular C ₁₂ -C ₃₀ alkyl sulfonates, preferably C ₁₂ -C ₁₈ alkyl sulfonates and multi-ethoxylated C ₁₀ -C ₂₀ alkyl alcohols, in particular the formula R ^{1 is} -O (CH ₂ -CH ₂ -O) _y -H, wherein R ^{1 is} selected from C ₁₀ -C ₂₀ alkyl and y may be, for example, an integer in the range of 5 to 100.

When Hardener ix) are especially acidic compounds in question, such as inorganic Brønsted acids, z. As sulfuric acid or phosphoric acid, organic Brønsted acids such as acetic acid or formic acid, Lewis acids and so-called latent acids.

Examples of particularly suitable melamine foams can be found in EP-A 0017672 ,

Of course, foams used as starting material may contain additives and additives common in foam chemistry, for example, antioxidants, flame retardants, fillers, colorants such as pigments or dyes, and biocides, for example

Further examples of biocides are silver particles or monomeric or polymeric organic biocides such as phenoxyethanol, phenoxypropanol, glyoxal, thiadiazines, 2,4-dichlorobenzyl alcohols and preferably isothiazolone derivatives such as MIT (2-methyl-3 (2H) -isothiazolone), CMIT ( 5-chloro-2-methyl-3 (2H) -isothiazolone), CIT (5-chloro-3 (2H) -isothiazolone), BIT (1,2-benzisothia-zol-3 (2H) -one), further copolymers of N , N-di-C ₁ -C ₁₀ -alkyl-ω-amino-C ₂ -C ₄ -alkyl (meth) acrylate, in particular copolymers of ethylene with N, N-di-methyl-2-aminoethyl (meth) acrylate,

Examples for fillers are: activated carbon, colorants like For example, dyes or pigments, fragrances such as Perfume, and odor traps, for example cyclodextrins.

To the Incorporation of additives and / or additives can be, for example Proceed in such a way that you have at least one chemically unmodified Foam in different operations or preferably simultaneously with aqueous formulation of at least contacted an aggregate. Then you can dry.

In an embodiment of the present invention such aqueous formulation one or more Aggregate (s) in proportions of 0 to a total of 50 wt .-%, based on foam, preferably 0.001 to 30 wt .-%, particularly preferably 0.01 to 25 wt .-%, most preferably 0.1 to 20 wt .-%.

moldings (A) Prepare foam (a) with at least one cationic polymer (b) and a shaping step (c) performs.

Under cationic polymers (b) are within the scope of the present invention to understand organic (co) polymers containing at least one (co) monomer in copolymerized form with a cationic charge and the have a positively charged polymer backbone. The positive Charge can be permanent, d. H. pH-independent, or not permanently, d. H. pH dependent. To compensate for positive charge of the polymer backbone can be cationic Have polymeric organic or preferably inorganic counterions, which are preferably non-polymeric in nature. Particularly suitable are halide ions, for example chloride, furthermore acetate, phthalate, Terephthalate, formate, sulphate, hydrogen sulphate, monomethylsulphate, Phosphate, nitrate or hydrogen phosphate.

If cationic polymers (b) are copolymers, the cationic polymers (b) in question may contain, in copolymerized form, at least one comonomer with cationic charge and moreover further comonomers which have no electrical charge, in particular olefins such as α- Olefins, (meth) acrylonitrile and (meth) acrylic acid C ₁ -C ₂₀ -alkyl esters, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

In An embodiment of the present invention may be cationic Polymer (b) be a copolymer that in addition to at least one of above-mentioned monomers with cationic charge and optionally non-ionic monomers also at least one comonomer with negative electrical Contains polymerized charge that permanently or preferably can not be permanent, especially (meth) acrylic acid. However, it should be noted that the number of comonomers per polymer molecule with a positive charge that of the monomers with negative charge is chosen so that the positive Cargo predominates.

In one embodiment of the present one chooses cationic polymer (b) of polymers containing at least one primary or secondary or tertiary or preferably having quaternized amino group per molecule.

Preferred examples of cationic poly mers (b) are homopolymers or copolymers of (co) monomers which have at least one nitrogen atom quaternized permanently or at acidic pH per molecule of (co) monomer, in particular polyacrylamide, polyvinylamine and polyethyleneimine. Further examples are resins based on urea and cyclic urea derivatives, in particular resins based on DMDHEU (1,3-dimethylol-4,5-dihydroxyethyleneurea), which may be mono- or polyetherified with C ₁ -C ₄ -alkanol or with ethylene glycol can.

In one embodiment of the present invention, cationic polymer (b) has an average molecular weight M _w in the range of 150 to 750,000 g / mol, in particular in the range of 10,000 to 50,000 g / mol, molecular weights M _w in the range of 150 to 600 g / mol are preferred for resins based on urea and cyclic urea derivatives.

In One embodiment of the present invention is foam (a) modified with a total of 1 to 30% by weight of cationic polymer (b), preferably with 10 to 20 wt .-%.

moldings (B) is prepared by adding foam (a) with at least one anionic polymer (d) treated and a shaping step (c) performs.

Under anionic polymers (d) are within the scope of the present invention to understand organic (co) polymers containing at least one (co) monomer in copolymerized form with an anionic charge and the have a negatively charged polymer backbone. The negative Charge can be permanent, d. H. pH-independent, or not permanently, d. H. pH dependent. To compensate for positive charge of the polymer backbone can be anionic Have polymeric organic or preferably inorganic counterions, which are preferably non-polymeric in nature. Particularly suitable are ammonium ions that can carry organic substituents, furthermore alkaline earth metals and in particular alkali metals, whole particularly preferred are potassium and sodium.

If anionic polymers (d) are copolymers, the anionic polymers (d) in question may contain, in copolymerized form, at least one comonomer with anionic charge and, in addition, further comonomers which have no electrical charge, in particular olefins such as α- Olefins, (meth) acrylonitrile and (meth) acrylic acid C ₁ -C ₂₀ -alkyl esters, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

In An embodiment of the present invention may be anionic Polymer (d) be a copolymer that in addition to at least one of above-mentioned monomers having a negative charge and optionally nonionic monomers also at least one comonomer with positive contains polymerized polymerized charge that is permanent or preferably can not be permanent. It is, however, on it to pay attention to the number of comonomers per polymer molecule with negative charge that of the monomers with positive charge so it is chosen that the negative charge predominates.

In an embodiment of the present invention chooses one anionic polymer (d) of polymers containing at least one sulfonic acid group or at least one carboxylic acid group per molecule exhibit.

preferred Examples of anionic polymers are homo- or copolymers of (meth) acrylic acid, in particular of acrylic acid, furthermore (co) polymers of maleic acid, maleic anhydride, Itaconic acid and itaconic anhydride.

In one embodiment of the present invention, anionic polymer (d) has an average molecular weight M _w in the range from 1000 to 100,000 g / mol, preferably up to 70,000 g / mol and particularly preferably up to 15,000 g / mol.

The Treating foam (a) with cationic polymer (b) or For example, anionic polymer (d) can be so that foam (a) with at least one formulation of cationic Polymer (b) or anionic polymer (d) contacted, so that cationic Polymer (b) or anionic polymer (d) on foam (a) deposited and chemically or physically bound. For formulations of cationic polymer (b) or anionic polymer (d) may be to melts or solutions or preferably aqueous Formulations such as aqueous solutions, Emulsions or dispersions act. Particularly preferred are aqueous Emulsions and solutions. Used watery Emulsions or dispersions may have a content of anionic or cationic polymer in the range of 1 to 45 wt .-%, preferably up to 5% by weight.

The Treatment can be done by methods known per se, for example, spraying, sprinkling, impregnating, Dipping, soaking or printing, with impregnation is preferred. After the actual treatment you can still harden, for example thermally or photochemically, especially thermally. So it is possible after the actual Treat at temperatures in the range of 50 to 150 ° C to harden (temperature of the environment).

you can be allowed to act in the range of 1 second to 10 hours, preferably are 5 seconds to 5 minutes.

In An embodiment of the present invention can be rinse after contacting, for example with one or more solvents and preferably with Water.

In An embodiment of the present invention can be after contacting and, if necessary, rinsing dry, for example mechanically by z. B. wringing or calendering, in particular by squeezing through two rollers, or thermally, For example, in microwave ovens, hot air blowers or in drying cabinets, in particular vacuum ovens, wherein drying ovens, for example, at temperatures in the Range of 30 to 150 ° C can operate. Under vacuum can one in connection with vacuum drying a pressure for example, in the range of 0.1 to 850 mbar.

The Time that one can carry out if desired By drying steps, by definition does not belong for exposure in the context of the present invention.

In An embodiment of the present invention can be perform thermal drying by heating Temperatures in the range of 20 ° C to 150 ° C, for example over a period of 10 seconds to 20 hours.

shaping Steps (c) may be, for example: tearing, especially tearing, punching and cutting. punch is preferred.

invention Mixtures are then obtained by combining, merging or mixing at least one shaped body (A) and at least a shaped body (B).

In an embodiment of the present invention it is in moldings (A) and / or moldings (B) to colored moldings. Preferably Shaped body (A) and molded body (B) each in different colors inked. The coloring can be done according to known Procedures happen, and preferably before the shaping Step.

In An embodiment of the present invention are molded articles (A) and shaped body (B) each in color, and the same color or preferably different colors.

In an embodiment of the present invention Shaped body (A) has a red color.

In an embodiment of the present invention Shaped body (B) has a blue or black color.

When Coloring agent for coloring of shaped bodies (A) or Shaped bodies (B) are suitable pigments and dyes.

In an embodiment of the present invention chooses as Red Colorant Pigment Red 3.

In an embodiment of the present invention chooses as a blue colorant Pigment Blue 15: 3.

In an embodiment of the present invention chooses as a black colorant carbon black.

invention Mixtures can be used, for example, as dust binders in vacuum cleaners, and preferably so that they are not fixed in the relevant Vacuum cleaners are installed, but when operating the vacuum cleaner in the vacuum cleaner in question within certain limits. One Another object of the present invention is the use of mixtures according to the invention in vacuum cleaners.

invention Mixtures can be used as dust binders, especially in so-called bagless vacuum cleaners deploy.

dustproofer For the purposes of the present invention grobstaub assets and preferably also the fine dust sucked into the vacuum cleaner to bind, partially or preferably for the most part Proportion, for example more than 50 wt .-%.

For example, the use of mixtures according to the invention as dust binders can be carried out as follows:
It provides a vacuum cleaner, in particular a bagless vacuum cleaner having a dust collector, which is located in the air flow. The dust collecting vessel may be formed, for example, as a cyclone.

In one embodiment of the present invention, a mixture according to the invention is metered directly into the dust collecting vessel. For metering, use is made of one or more addition devices which can be integrated within the vacuum cleaner or in a suction attachment or can be designed as an external apparatus with a receiving device for the dust collection vessel. So you need no more active elements in the vacuum cleaner. The adding device or the adding devices can, for example, as flap, piston, Be formed screw or nozzle. The addition of moldings can be done directly or via a lock.

In In another embodiment, one gives an inventive Mix directly into the dust collector and set the dust collector together with the moldings in the vacuum cleaner.

In another embodiment of the present invention one metered mixture according to the invention automatically in the dust collector. This will be continuous certain proportions of moldings described above (A) and (B) are dosed and continuously replenished appropriate amounts. Such automatic replenishment can be additionally perform dust-dependent.

Dust collectors can have any shape and any size depending on the type of vacuum cleaner. Thus dust collecting vessels in the sense of the present invention may be cube-shaped, cylindrical, conical or irregularly shaped. Examples of suitable volumes are 0.1 dm ³ to 2 dm ³ , but also larger volumes up to 10 dm ³ are conceivable.

The Dust collecting container, for example, as a bag or bag, as a box or as a cyclone (Centrifugal separator). The level of the dust collector can be monitored electronically or mechanically be, for example with sensors.

In another embodiment, especially in bagless vacuum cleaners, which do not contain a bag, the dust collector as Box or be designed as a cyclone.

In an embodiment of the present invention the dust collector a device for mixing, For example, a mechanical device such as a Stirrer, or a motor moving the dust collector in motion offset, for example in vibrations or rotations. In a another embodiment of the present invention the dust collector no device for mixing.

In an embodiment of the present invention fills with the dust collecting vessel to 10 to 60 vol .-% with inventive mixture, preferably 25 to 50% by volume.

In another embodiment of the present invention you fill at least two, for example two to twenty and in particular to six of the above-described moldings (A) and (B) in a dust collecting vessel, namely such that at least one shaped body (A) and at least one shaped body (B) are in the dust collector.

In an embodiment of the present invention Mixture according to the invention up to 3000 wt .-% dust to bind, based on their own weight, for example 500 bis 3000% by weight. The dust-binding capacity can be, for example determine gravimetrically.

One Another object of the present invention are vacuum cleaners, in particular bagless vacuum cleaner, comprising at least one inventive Mixture.

Prefers are bagless vacuum cleaners, comprising at least one inventive Mixture, hereinafter also referred to as bagless vacuum cleaner according to the invention designated. When operating the inventive Bagless vacuum cleaner is fiction, contemporary mixture swirled in the cyclone together with the dust. The inventive Mixture works practically in this embodiment Dust binders (dust collectors), in particular for u. U. allergieauslösenden fine dust. Through the common Verwirbeln of dust and inventive mixture adhere the dust particles to the molding (A) or (B) and are therefore no longer free to move, d. H. you can When emptying the cyclone, do not whirl up more than a cloud of dust. Instead, they coincide with inventive Mixture as a whole or with moldings (A) or moldings (B) to the ground. In this application are mainly the surface properties (Adsorption) of the shaped bodies (A) and (B) used. Your advantageous filter properties are rather secondary in this case.

additionally it is possible, according to the invention Mixture also in or as a fine dust filter to use to its Extend service life; The same applies to dust bags.

One Another object of the present invention is a method for cleaning surfaces, in particular floors, using vacuum cleaners according to the invention, hereinafter also called cleaning process according to the invention. For carrying out the cleaning method according to the invention you can proceed as known. By the use of one or more vacuum cleaners according to the invention is very pure exhaust air produced and only a few fine dust swirled.

Shaped bodies (A) and (B) prove in combination to be particularly good dust-binding agents, especially in so-called bagless vacuum cleaners. You have an excellent ability To bind dust, so that the exhaust air of the vacuum cleaner is particularly pure. In addition, the emptying of the vacuum cleaner is particularly hygienic, because the dust adheres to and / or in the moldings according to the invention particularly well.

The Invention will be explained by working examples. In the Working examples were each using mineral test dust "slate" with Grain diameter band <200 μm and the 50% value <30 μm tested. But you can also use other dust, for example House dust, garden dust, sand, flour (kitchen dust), Pollen and soot.

I.1 Preparation of unmodified foam (a.1)

In an open vessel became a spray dried one Melamine / formaldehyde precondensate (molar ratio 1: 3, molecular weight about 500 g / mol) to an aqueous solution 3 wt .-% formic acid and 1.5% of the sodium salt of a Mixture of alkyl sulfonates having 12 to 18 carbon atoms in the alkyl radical (Emulsifier K 30 of the Fa.

Bavarian AG), wherein the percentages on the melamine / formaldehyde precondensate are given. The concentration of melamine / formaldehyde precondensate, based on the total mixture of melamine / formaldehyde precondensate and Water, was 74 wt .-%. The mixture thus obtained was stirred vigorously, then 20 wt .-% of n-pentane added. It was stirred (about 3 minutes), until a homogeneous-looking dispersion was formed. This was on a Teflonized glass fabric as a carrier material and in a drying cabinet in which an air temperature of 150 ° C prevailed, foamed and hardened. It presented As the melt temperature in the foam, the boiling point of the n-pentane, which under these conditions at 37.0 ° C. lies. After 7 to 8 minutes, the maximum height of rise of the Foam achieved. The foam was still another 10 min leave at 150 ° C in a drying oven; subsequently it was annealed at 180 ° C for 30 minutes. One received unmodified Foam (a.1).

• 99,6% offenzellig nach DIN ISO 4590 ,
• Stauchhärte (40%) 1,3 kPa bestimmt nach DIN 53577 ,
• Dichte 7,6 kg/m³ bestimmt nach EN ISO 845 , mittlerer Porendurchmesser 210 μm, bestimmt durch Auswertung mikroskopischer Aufnahmen an Schnitten,
• BET-Oberfläche von 6,4 m²/g, bestimmt nach DIN 66131 ,
• Schallabsorption von 93%, bestimmt nach DIN 52215 ,
• Schallabsorption von mehr als 0,9, bestimmt nach DIN 52212 .

The following properties were determined on the unmodified foam (a.1) from example 1.1:

• 99.6% open-celled DIN ISO 4590 .
• Compression hardness (40%) 1.3 kPa determined by DIN 53577 .
• Density 7.6 kg / m ³ determined after EN ISO 845 , mean pore diameter 210 μm, determined by analysis of microscopic images on sections,
• BET surface area of 6.4 m ² / g, determined by DIN 66131 .
• Sound absorption of 93%, determined by DIN 52215 .
• Sound absorption of more than 0.9, determined by DIN 52212 ,

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - WO 2008/009601 [0005]
• - WO 2008/009602 [0006]
• EP 0351614 A [0045, 0054]
• EP 0017672A [0057]

Cited non-patent literature

• - DIN ISO 4590 [0027]
• - DIN 53577 [0028]
• - DIN 66131 [0033]
• - DIN ISO 4590 [0117]
• - DIN 53577 [0117]
• - EN ISO 845 [0117]
• - DIN 66131 [0117]
• - DIN 52215 [0117]
• - DIN 52212 [0117]

Claims (17)

Mixtures of molded articles comprising (A) at least one shaped article having dimensions of length x width x height, each in the range of 1 mm to 10 cm, prepared by treating (a) open-cell foam having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range from 1 μm to 1 mm (b) with at least one cationic polymer (c) and a shaping step, (B) at least one shaped body with dimensions length × width × height, in each case in the range from 1 mm to 3 cm, prepared by treating (a) open-cell foam having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm (d) with at least one anionic polymer (c) and a mold giving step. Mixtures according to Claim 1, characterized that open-cell foams (a) polyurethane foams or are aminoplast foams. Mixtures according to Claim 1 or 2, characterized the open-cell foams (a) are the same in each case. Mixtures according to one of claims 1 to 3, characterized in that the forming step (c) respectively is chosen from cutting, tearing and punching. Mixtures according to one of claims 1 to 4, characterized in that it is in the treatment with anionic or cationic polymer in each case is impregnation. Mixtures according to one of claims 1 to 5, characterized in that one selects cationic polymer (b) of polymers containing at least one primary or secondary or tertiary or quaternized amino group per molecule exhibit. Mixtures according to one of claims 1 to 6, characterized in that one selects anionic polymer (d) from polymers containing at least one sulphonic acid group or at least one carboxylic acid group per molecule exhibit. Mixtures according to one of claims 1 to 7, characterized in that one selects cationic polymer (b) polyvinylamines, polyamides, polyvinylimidazoles, polyvinylpyrolidine, Polyethyleneimines, resins based on urea and cyclic Urea derivatives. Mixtures according to one of claims 1 to 8, characterized in that anionic organic polymers selects from poly (meth) acrylates and (co) polymers of maleic acid, Maleic anhydride, itaconic acid and itaconic anhydride. Mixtures according to one of claims 1 to 9, characterized in that molded body (A) and molded body (B) are each colored. Mixtures according to one of claims 1 to 10, characterized in that molded body (A) has the shape of a Have plus sign. Mixtures according to one of claims 1 to 11, characterized in that molded body (B) takes the form of a have square column. Mixtures according to one of claims 1 to 12, characterized in that molded body (A) has a red color exhibit. Mixtures according to one of claims 1 to 13, characterized in that shaped body (B) has a blue one or black color. Use of mixtures according to one of the claims 1 to 14 in vacuum cleaners. Vacuum cleaner, comprising at least one mixture according to one of claims 1 to 14. Method for cleaning surfaces using a vacuum cleaner according to claim 15.