EP2978802A1 - Mousses flexibles pourvues d'une surface abrasive - Google Patents

Mousses flexibles pourvues d'une surface abrasive

Info

Publication number
EP2978802A1
EP2978802A1 EP14710578.7A EP14710578A EP2978802A1 EP 2978802 A1 EP2978802 A1 EP 2978802A1 EP 14710578 A EP14710578 A EP 14710578A EP 2978802 A1 EP2978802 A1 EP 2978802A1
Authority
EP
European Patent Office
Prior art keywords
weight
melamine
urea
formaldehyde
acrylonitrile
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.)
Withdrawn
Application number
EP14710578.7A
Other languages
German (de)
English (en)
Inventor
Matthias Schade
Rebekka Von Benten
Günter Scherr
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP14710578.7A priority Critical patent/EP2978802A1/fr
Publication of EP2978802A1 publication Critical patent/EP2978802A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
    • B24D3/28—Resins or natural or synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/18—Homopolymers or copolymers of nitriles
    • C08J2433/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2461/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2461/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the invention relates to flexible foams having a flexible, abrasive surface and to their use as abrasive foams for machine and manual floor cleaning.
  • the coating of a flexible foam with an abrasive layer has been known for a long time.
  • foams are used, for example, in cleaning and polishing sponges.
  • the foams are equipped on at least one surface with abrasive particles.
  • WO-A-99/24223 discloses flexible, abrasive foams, the surface of which has been provided with a hard, non-flexible coating containing abrasive particles, and a process for the coating thereof.
  • the known flexible, abrasive foams have the disadvantage that they scratch the surfaces to be cleaned and the poor adhesion of the abrasive particles on the foams.
  • the present invention was therefore based on the object to remedy the aforementioned disadvantages, in particular to improve the scratching of the surfaces to be cleaned.
  • new and improved flexible foams having a flexible, abrasive surface containing from 1 to 90% by weight of a mixture, based on the uncoated substrate, comprising the condensation product of from 99.985 to 20% by weight of at least one precondensate of one thermosetting resin, 0 to 10 wt .-% of a polymeric thickener selected from the group consisting of biopolymers, associative thickeners and / or fully synthetic thickeners, 0.01 to 10 wt .-% of a curing agent, 0 to 10 wt .-% surface-active substances or surfactants, 0 to 15 wt .-% dyes, pigments or mixtures thereof and 0 to 75 wt .-% water, found, which are characterized in that this mixture 10 to 70 wt .-% of one or more Binder based on the above mixture from the group of polyacrylates, polymethacrylates, polyacrylonitriles, copolymers of acrylic acid esters and
  • the flexible foams according to the invention having a flexible, abrasive surface contain from 1 to 95% by weight, preferably from 2 to 90% by weight, particularly preferably from 5 to 85% by weight, of a mi Schung containing the condensation product of at least one precondensate of a thermosetting resin, a curing agent and a binder, in particular consists thereof.
  • Possible further components of the mixture may be thickeners, surfactants, dyes, pigments or mixtures thereof.
  • Abrasive surfaces in the sense of this invention means that these surfaces exercise a rubbing or scouring action when moving over another surface.
  • Suitable flexible foams are polystyrene, polyvinyl chloride, polyurethane, polyamide, polyester, polyolefin or cellulose foams, preferably polystyrene, polyurethane, polyester or polyolefin foams, more preferably polyurethane, polyester or polyolefin Foams, in particular polyurethane foams.
  • the foam is based on polystyrene.
  • Polystyrene is used here as a generic term and includes homopolymers and copolymers of vinylaromatic monomers. Suitable monomers are styrene, ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinylstyrene, vinyltoluene, 1, 2-diphenylethylene, 1, 1-diphenylethylene or mixtures thereof. Preferred monomer is styrene.
  • blowing agent-containing, expandable polystyrene is first prepared, which is produced by the suspension process (polymerization in the presence of blowing agents), the impregnation process (impregnation of propellant-free polystyrene particles with the Propellant under pressure in a heated suspension, wherein the propellant diffuses into the softened particles, and cooling the suspension under pressure) or the extrusion process (mixing of the blowing agent in a polystyrene melt by means of an extruder, discharge of the blowing agent-containing melt under pressure, then underwater pressure granulation) can take place ,
  • the EPS particles are then foamed by pre-foaming and foaming to polystyrene foam.
  • Extrusion foams made of polystyrene are prepared by mixing the blowing agent into a polystyrene melt by means of an extruder, wherein the blowing agent-containing melt exits directly into the environment and is not discharged under pressure. Upon exiting the extruder die, the melt foams with solidification.
  • the foam is based on polyvinyl chloride.
  • Suitable polyvinyl chloride are, for example, the homopolymers hard PVC, obtainable by emulsion, suspension or bulk polymerization of vinyl chloride, as well as plasticizer-containing soft PVC, and PVC pastes.
  • vinyl chloride copolymers are those with vinyl acetate (VCVAC), with ethylene (VCE), with vinylidene chloride (VCVDC), with methyl acrylate (VCMA) or octyl acrylate, with methyl methacrylate (VCMMA), with maleic acid or maleic anhydride (VCMAH), with maleimide (VCMAI) or with acrylonitrile.
  • Chlorinated PVC C-PVC
  • Polyvinyl chloride also includes polyvinylidene chloride (PVDC), that is, copolymers of vinylidene chloride and vinyl chloride.
  • the foam is based on polyaddition products of isocyanates.
  • a preferred embodiment of the polyaddition products based on isocyanate are polyurethanes. Suitable polyurethanes may also contain other linkages, in particular isocyanurate and / or urea linkages. Suitable polymers of the foam are soft, semi-hard or hard as well as thermoplastic or crosslinked polyurethane types.
  • the preparation of the polyurethanes is described in many ways and is usually carried out by reacting isocyanates I) with isocyanate-reactive compounds II) under generally known conditions. The reaction is preferably carried out in the presence of catalysts III) and usually in the presence of auxiliaries IV). If it is foamed polyurethanes - this is preferred - they are prepared in the presence of conventional blowing agents V) or by known methods for the preparation of polyurethane foams.
  • isocyanates for example, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2, 6- Toluylene diisocyanate (TDI), 3,3'-dimethyldiphenyl diisocyanate, 1, 2-diphenylethane diisocyanate and / or p-phenylene diisocyanate (PPDI), tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2- Methyl pentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, pentamethylene-1,5 diisocyanate, butylene-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-
  • aromatic diisocyanates in particular 2,4- and / or 2,6-toluene diisocyanate (TDI), 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1 , 5-naphthylene diisocyanate (NDI) and paraphenylene diisocyanate (PPDI).
  • TDI 2,4- and / or 2,6-toluene diisocyanate
  • MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate
  • NDI 5-naphthylene diisocyanate
  • PPDI paraphenylene diisocyanate
  • isocyanates based on TDI or based on MDI are also suitable.
  • oligomeric, polynuclear aromatic isocyanates based on MDI are also suitable.
  • isocyanate-reactive compounds II for example, it is possible to use generally known compounds having a molecular weight of 60 to 10,000 and a functionality with respect to isocyanates of 1 to 8, preferably 2 to 6.
  • Suitable compounds II) are, for example, polyols, in particular those having a molecular weight of from 500 to
  • Polyetherpolyols e.g. Polyetherpolyols, polyesterpolyols, polyetherpolyesterpolyols, and / or diols, triols and / or polyols having molecular weights of less than 500.
  • catalysts III for the preparation of the polyurethanes, it is optionally possible to use compounds which are generally known which accelerate the reaction of isocyanates with the compounds which are reactive towards isocyanates, preferably a total catalyst content of 0.001 to 15% by weight, in particular 0.05 to 6 Wt .-%, based on the weight of the total isocyanate-reactive compounds II) is used, for example tertiary amines and / or metal salts, for example inorganic and / or organic compounds of iron, lead, zinc, and / or tin in conventional Oxidation levels of the metal.
  • compounds which are generally known which accelerate the reaction of isocyanates with the compounds which are reactive towards isocyanates preferably a total catalyst content of 0.001 to 15% by weight, in particular 0.05 to 6 Wt .-%, based on the weight of the total isocyanate-reactive compounds II) is used, for example tertiary amines and / or metal salts, for example inorganic and /
  • excipients IV may optionally be used conventional substances. Mention may be made, for example, of surface-active substances, fillers, dyes, pigments, flame retardants, hydrolysis protectants, fungistatic and bacteriostatic substances and also UV stabilizers and antioxidants.
  • Suitable precondensates of a thermosetting resin are melamine / formaldehyde precondensates having a molar ratio of melamine to formaldehyde of from 1: 1 to 1: 4, preferably from 1: 1 to 1: 3, more preferably from 1: 1 to 1: 2, as examples may be mentioned the Kauramin® impregnating resins from BASF SE, methanol-etherified melamine / formaldehyde precondensates with a molar ratio of melamine to formaldehyde of 1: 1 to 1: 6, preferably from 1: 1 to 1: 5.5, more preferably from 1: 1 to 1: 5, as an example may be mentioned the Luwipal® coating Netzer of BASF SE, urea / formaldehyde precondensates having a molar ratio of urea to formaldehyde of 1: 0.5 to 1: 5, preferably 1: 1 to 1: 4, particularly preferably 1: 1 to 1: 2, as examples called the Kaurit®
  • a precondensate of melamine and formaldehyde is used in which the molar ratio of formaldehyde to melamine is less than 4: 1.
  • the thermosetting resin used is preferably a precondensate of melamine and formaldehyde in which the molar ratio of formaldehyde to melamine is 1: 1 to 3: 1, more preferably 1: 1 to 2: 1.
  • Melamine / formaldehyde condensation products may contain, in addition to melamine, from 0.01 to 50% by weight, preferably from 0.1 to 20% by weight, of "other thermoset formers" (as described below) and, in addition to formaldehyde, from 0.01 to 50% by weight. %, preferably 0.1 to 20 wt .-% "other aldehydes" (as described below) in condensed form.
  • thermoset agents are, for example, alkyl- and aryl-substituted melamine, urea, urethanes, carboxamides, dicyandiamide, guanidine, sulfurylamide, sulfonic acid amides, aliphatic amines, glycols, phenol and phenol derivatives.
  • acetaldehyde, propionaldehyde, isobutyraldehyde, n-butyraldehyde, trimethylolacetaldehyde, acrolein, benzaldehyde, furfural, glyoxal, glutaraldehyde, phthalaldehyde and terephthalaldehyde can be used, for example, to partially replace the formaldehyde in the condensates.
  • the precondensates may optionally be etherified with at least one alcohol.
  • examples of these are monohydric C 1 - to C 4 alcohols, such as methanol, ethanol,
  • polyhydric alcohols such as glycol, diethylene glycol, glycerol, butanediol 1, 4, hexan
  • thermosetting resins belongs to the prior art, cf. Ullmanns Encyclopedia of Industrial Chemistry, Sixth Completely Revised Edition, Wiley-VCH Verlag GmbH Co. KGaA, Weinheim, "Amino Resins", Vol. 2, pp. 537 to 565 (2003).
  • this starts from an aqueous solution or dispersion of a precondensate, preferably of melamine and formaldehyde.
  • a precondensate preferably of melamine and formaldehyde.
  • the solids concentration is usually 5 to 95 wt .-%, preferably 10 to 70 wt .-%.
  • Suitable polymeric thickeners are biopolymers, associative thickeners, fully synthetic thickeners or mixtures thereof, preferably biopolymers, fully synthetic thickeners or mixtures thereof, particularly preferably biopolymers.
  • Suitable biopolymers are polysaccharides such as starch, guar gum, locust bean gum, agar-agar, pectins, gum arabic, xanthan, proteins such as gelatin, casein or mixtures thereof, preferably polysaccharides such as starch, guar gum, locust bean gum, agar-agar, pectins, gum arabic, Xanthan or proteins such as gelatin, casein or mixtures thereof, particularly preferably polysaccharides such as starch, guar gum, locust bean gum, agar-agar, pectins, gum arabic, xanthan gum or mixtures thereof.
  • Suitable associative thickeners are modified celluloses such as methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC) and ethylhydroxyethylcellulose (EHEC), modified starches such as hydroxyethyl starch or hydroxypropyl starch, or mixtures thereof, preferably modified ones Celluloses such as methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC), ethylhydroxyethylcellulose (EHEC) or mixtures thereof.
  • modified celluloses such as methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC), ethylhydroxyethylcellulose (EHEC) or mixtures thereof.
  • Suitable fully synthetic thickeners are, for example, polyvinyl alcohols, polyacrylamides, polyvinylpyrrolidone, polyethylene glycols or mixtures thereof.
  • Suitable hardeners are those which catalyze the further condensation of the thermosetting resins such as acids or salts thereof and aqueous solutions of these salts.
  • Suitable acids are inorganic acids such as HCl, HBr, Hl, H 2 SO 3, H 2 SO 4, phosphoric acid, polyphosphoric acid, nitric acid, sulfonic acids, for example p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, carboxylic acids such as Cr to Cs-carboxylic acids, for example formic acid, acetic acid, Propionic acid or mixtures thereof, preferably inorganic acids such as HCl, H2SO3, H2SO4, phosphoric acid, polyphosphoric acid acid, nitric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, carboxylic acids such as C to Cs-carboxylic acids, for example formic acid, acetic acid, particularly preferably inorganic acids such as H 2 SO 4, phosphoric acid,
  • Suitable salts are halides, sulfites, sulfates, hydrogen sulfates, carbonates, hydrogencarbonates, nitrites, nitrates, sulfonates, salts of carboxylic acids such as formates, acetates, propionates, preferably sulfites, carbonates, nitrates, sulfonates, salts of carboxylic acids such as formates, acetates , Propionates, particularly preferably sulfites, nitrates, sulfonates, salts of carboxylic acids such as formates, acetates, propionates, protonated, primary, secondary and tertiary aliphatic amines, alkanolamines, cyclic aromatic amines such as Cr to Cs Aminejsopropylamin, 2-ethylhexylamine, di - (2-ethylhexyl) amine, diethylamine, diprop
  • Particularly suitable salts are: ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, ammonium methanesulfonate, ammonium p-toluenesulfonate, ammonium trifluoromethanesulfonate, ammonium nonafluorobutanesulfonate, ammonium phosphate, ammonium nitrate, ammonium formate, ammonium acetate, morpholinium chloride, morpholinium bromide, morpholinium iodide, morpholinium sulfate, Morpholiniumsulfit, Morpholiniumhydrogensulfat, Morpholiniummethansulfonat, morpholinium p-toluenesulfonate, Morpholiniumtrifluormethansulfonat, Morpholiniumnonafluorbutans
  • the salts are used in the form of their aqueous solutions.
  • aqueous solutions are understood as meaning dilute, saturated, supersaturated and also partially precipitated solutions, as well as saturated solutions having a solids content of insoluble salt.
  • the curing agents according to the invention mentioned for the condensation can also be applied separately to the flat substrate.
  • the amounts used of the curing agents according to the invention are generally 0.01 to 10 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 0.5 to 10 wt .-%, based on the mixture.
  • Suitable surfactants are, for example, all surfactants.
  • nonionic surfactants are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C3-C12) and also ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: C8-C36).
  • ethoxylated mono-, di- and tri-alkylphenols degree of ethoxylation: 3 to 50, alkyl radical: C3-C12
  • ethoxylated fatty alcohols degree of ethoxylation: 3 to 80, alkyl radical: C8-C36
  • Particularly preferred are ethoxylated linear fatty alcohols of the general formula n-CxH2x + i-0 (CH 2 CH 2 O) yH, where x are integers in the range from 10 to 24, preferably in the range from 12 to 20.
  • variable y preferably stands for integers in the range from 5 to 50, more preferably 8 to 40.
  • Ethoxylated linear fatty alcohols are usually present as a mixture of different ethoxylated fatty alcohols with different degrees of ethoxylation.
  • the variable y in the context of the present invention stands for the mean value (number average).
  • Suitable nonionic surface-active substances are also copolymers, in particular block copolymers of ethylene oxide and at least one C3-Cio-alkylene oxide, for. B. triblock copolymers of the formula
  • A is a radical derived from an aliphatic, cycloaliphatic or aromatic diol, eg ethane-1, 2-diyl, propane-1,3-diyl, butane-1, 4-diyl, cyclohexyl xan-1, 4-diyl, cyclohexane-1,2-diyl or bis (cyclohexyl) methane-4,4'-diyl, B and B 'independently of one another propane-1,2-diyl, butane-1, 2- diyl or phenylethanyl independently represent a number from 2 to 100 and y2, y3 independently represent a number from 2 to 100, wherein the sum y1 + y2 + y3 +
  • A is ethane-1, 2-diyl, propane-1, 3-diyl or butane-1, 4-diyl.
  • B is preferably propane-1, 2-diyl.
  • glycols such as Zonyl ® or Capstone® (DuPont) are suitable as surface-active substances with fluorine substituted poly.
  • Suitable surface-active substances besides the nonionic surfactants are anionic and cationic surfactants. They can be used alone or as a mixture. The prerequisite for this, however, is that they are compatible with one another, ie that they produce no precipitation with each other. This requirement applies, for example, to mixtures of one compound class and to mixtures of nonionic and anionic ones Surfactants and mixtures of nonionic and cationic surfactants.
  • suitable anionic surfactants are sodium lauryl sulfate, sodium dodecylsulfate, sodium hexadecylsulfate and sodium dioctylsulfosuccinate.
  • esters of phosphoric acid or phosphorous acid and aliphatic or aromatic carboxylic acids can also be used as anionic emulsifiers.
  • cationic surfactants are quaternary alkylammonium salts, alkylbenzylammonium salts, such as dimethyl-C 2 - to cis-alkylbenzylammonium chlorides, primary, secondary and tertiary fatty amine salts, quaternary amidoamine compounds, alkylpyridinium salts, alkylimidazolinium salts and alkyloxazolinium salts.
  • the aqueous solution or dispersion may contain one or more surfactants in amounts of zero to 10 wt .-%, preferably 0.001 to 5 wt .-%, particularly preferably 0.001 to 2.5 wt .-%.
  • the flexible foams according to the invention can, in addition to the abovementioned conventional additives such as thickeners, hardeners and surfactants or dyes or pigments, preferably in an amount in the range of 0 to 15 wt .-%, preferably 0 to 10 wt. -%, particularly preferably 0 to 5 wt .-%, in particular 0.01 to 3 wt .-%, most preferably 0.01 to 1 wt .-%, contain.
  • conventional additives such as thickeners, hardeners and surfactants or dyes or pigments
  • Suitable dyes or pigments are inorganic and organic dyes or pigments, such as azo pigments and dyes, and also polycyclic pigments, especially copper phthalocyanine, indanthrene, polychloroprene copper phthalocyanine, perylenes, component f).
  • Water can be used in amounts of 0 to 75% by weight or 0 to 79.985% by weight, preferably 0 to 70% by weight, particularly preferably 0 to 65% by weight, in addition to that in the aqueous components used added water.
  • Suitable binders are polyacrylates, polymethacrylates, polyacrylonitriles, and copolymers of acrylates and acrylonitrile, styrene and acrylonitrile, acrylates and styrene and acrylonitrile, acrylonitrile and butadiene and styrene, polyurethanes, melamine-formaldehyde resins, phenol-formaldehyde resins, urea-formaldehyde Resins, melamine-urea-formaldehyde resins, melamine-urea-phenol-formaldehyde resins, urea-glyoxal resins or mixtures thereof, preferably aqueous binders
  • Polyacrylates, polymethacrylates, polyacrylonitriles, as well as copolymers of acrylates and acrylonitrile, styrene and acrylonitrile, acrylates and styrene and acrylonitrile, acrylonitrile and butadiene and styrene, can be obtained by free radical polymerization of ethylenically unsaturated compounds (monomers) according to well-known methods as they for example, Vana, P., Barner-Kowollik, C, Davis, TP and Matyjaszewski, K. 2003. Radical Polymerization Encyclopedia of Polymer Science and Technology; van Herk, A. and Heuts, H. 2009. Emulsion Polymerization.
  • Polyurethanes, melamine-formaldehyde resins, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-urea-formaldehyde resins, melamine-urea-phenol-formaldehyde resins, urea-glyoxal resins can generally be obtained by polycondensation Known processes are obtained, for example, from Ullmanns Encyclopedia of Industrial Chemistry, Sixth Completely Revised Edition, Wiley-VCH Verlag GmbH Co. KGaA, Weinheim, "Amino Resins", Vol.
  • melamine Formaldehyde resins phenol-formaldehyde resins, urea-formaldehyde resins, melamine-urea-formaldehyde resins, melamine-urea-phenol-formaldehyde resins, urea-glyoxal resins or DE-A-10161 156 for polyurethanes known are.
  • Particularly preferred binders are the Acronal®, Aerodur®, Emuldur® or Luphen® grades from BASF SE.
  • Aqueous binder composition based on polymers obtained by radical polymerization of ethylenically unsaturated compounds (monomers), usually containing as essential binder components at least one polymer P, composed of
  • An essential constituent of the aqueous binder composition is a polymer P which is built up in copolymerized form from .alpha.1 and -i 15% by weight of at least one acid group-containing ethylenically unsaturated
  • Homopolymer has a glass transition temperature> 50 ° C (monomers F) and which differs from the monomers A to D.
  • Suitable monomers A are all ethylenically unsaturated compounds which have at least one acid group [proton donor], for example a sulfonic acid, phosphonic acid or carboxylic acid group, for example vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, 2-acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, Al - lylphosphonic acid, styrenephosphonic acid and 2-acrylamido-2-methylpropanephosphonic.
  • proton donor for example a sulfonic acid, phosphonic acid or carboxylic acid group
  • vinylsulfonic acid allylsulfonic acid, styrenesulfonic acid, 2-acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, Al - lylphosphonic
  • the monomers A to ⁇ , ⁇ -monoethylenically unsaturated, in particular C3-C6, C3 or C 4 preferably mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, allylacetic acid, crotonic acid, Vi - Nylacetic acid, fumaric acid, maleic acid, 2-methylmaleic acid.
  • the monomers A also include the anhydrides of corresponding ⁇ , ⁇ -monoethylenically unsaturated dicarboxylic acids, such as, for example, maleic anhydride or 2-methylmaleic anhydride.
  • the acid group-containing monomer A is selected from the group comprising acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid and itaconic acid, with acrylic acid, methacrylic acid and / or itaconic acid being particularly preferred.
  • the monomers A also include the fully or partially neutralized water-soluble salts, in particular the alkali metal or ammonium salts, of the abovementioned acids.
  • Suitable monomers A are all ⁇ , ⁇ -monoethylenically unsaturated C3 to C6 mono- or dicarboxylic acid amides.
  • the monomers A are the abovementioned compounds whose carboxylic acid amide group is substituted by an alkyl or a methylol group.
  • Examples of such monomers A are the amides or diamides of ⁇ , ⁇ -monoethylenically unsaturated C3 to C6, preferably C3 or C4 mono- or dicarboxylic acids such as acrylamide, methacrylamide, Ethylacrylklareamid, itaconic acid mono- or diamide, Allylacetic acid amide, crotonic acid mono- or diamide, vinylacetic acid amide, fumaric mono- or diamide, maleic acid mono- or diamide and 2-methylmaleic acid mono- or diamide.
  • Examples of ⁇ , ⁇ -monoethylenically unsaturated C3 to C6 mono- or dicarboxylic acid amides whose carboxylic acid amide group is substituted by an alkyl or a methylol group are N-alkylacrylamides and -methacrylamides such as N-tert-butylacrylamide and -methacrylamide, N-methylacrylamide and -methacrylamide and N-methylolacrylamide and N-methylolmethacrylamide.
  • Preferred amidic monomers A are acrylamide, methacrylamide, N-methylolacrylamide and / or N-methylolmethacrylamide, with methylolacrylamide and / or N-methylolmethacrylamide being particularly preferred.
  • Particularly preferred monomers A are acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, itaconic acid, acrylamide, methacrylamide, N-methylolacrylamide and / or N-methylolmethacrylamide, where acrylic acid, methacrylic acid, itaconic acid, methylolacrylamide and / or N Methylolmethacrylamid are particularly preferred.
  • the amount of polymerized in the polymer P monomers A is> 0.1 and 15% by weight, preferably> 0.5 and 10% by weight and particularly preferably> 3 and ⁇ 8.5 wt .-%.
  • Suitable monomers B are all ethylenically unsaturated compounds which have at least one nitrile group. But advantageously is in the monomers B to the nitriles, which are ⁇ -monoethylenically unsaturated ⁇ from the foregoing, especially C3 to C6, preferably C3 or C 4 derived mono- or dicarboxylic acids, such as Ac- rylnitril , Methacrylonitrile, maleic acid dinitrile and / or fumaronitrile, with acrylonitrile and / or methacrylonitrile being particularly preferred.
  • C3 to C6, preferably C3 or C 4 derived mono- or dicarboxylic acids such as Ac- rylnitril , Methacrylonitrile, maleic acid dinitrile and / or fumaronitrile, with acrylonitrile and / or methacrylonitrile being particularly preferred.
  • the amount of the monomers B copolymerized in the polymer P is> 8 and 30% by weight, preferably> 10 and> 25% by weight and particularly preferably> 10 and 20% by weight.
  • Suitable monomers C are all compounds which have at least two non-conjugated ethylenically unsaturated groups.
  • Examples include two vinyl radicals containing monomers, two vinylidene radicals having monomers and two alkenyl radicals having monomers.
  • Particularly advantageous are the diesters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and ethylene glycol dimethacrylate, 1, 2.
  • Propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, tri-esters of trihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids for example glycerol triacrylate, glycerol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and divinylbenzene, vinyl methac - Rylat, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, Methylenbisac- rylamid, cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate.
  • glycerol triacrylate glycerol trimethacrylate
  • the amount of polymerized in the polymer P monomer C is> 0 and ⁇ 5 wt .-%, preferably> 0 and ⁇ 3 wt .-% and particularly preferably> 0 and ⁇ 1, 5 wt .-%.
  • Suitable monomers D are all monoethylenically unsaturated silane-containing compounds.
  • the monomers D have a hydrolyzable silane group.
  • Hydrolyzable silane groups advantageously contain at least one alkoxy group or one halogen atom, such as, for example, chlorine.
  • Advantageously usable monomers D are disclosed in WO-A-2008/150647, page 9, lines 5 to 25.
  • 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriacetoxysilane and / or vinylethoxydimethoxysilane are used.
  • the monomers D are always preferably used when inorganic granular and / or fibrous substrates, such as in particular glass fibers or mineral fiber, for example, asbestos or rock wool to be bound.
  • the amount of the monomers D optionally polymerized in the polymer P in a preferred embodiment is> 0 and 10% by weight, preferably> 0 and 5% by weight and particularly preferably 0% by weight.
  • the amount of the monomers copolymerized in the polymer P is D> 0.1 and 10% by weight, advantageously> 0.1 and ⁇ 5 wt .-% and particularly advantageously> 0.5 and ⁇ 2.5 wt .-%.
  • Suitable monomers E are all ethylenically unsaturated monomers whose homopolymer have a glass transition temperature ⁇ 30 ° C. and which differ from the monomers A to D.
  • Suitable monomers E are, for example, conjugated aliphatic CA to Cg diene compounds, esters of vinyl alcohol and a C 1 to C 10
  • Monocarboxylic acid C 1 - to C 10 -alkyl acrylate, C 2 -to -dimethyl methacrylate, C 8- to C 10 -cycloalkyl acrylate and methacrylate, C 1 - to C 10 -dialkyl maleate and / or C 1 - to dialkylfumarate, vinyl ethers of C 3 - to Cio Alkanols, branched and unbranched C3 to C10 olefins. It is advantageous to use those monomers E whose homopolymers have Tg values ⁇ 0 ° C.
  • monomers E are vinyl acetate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleate, di- n-butyl fumarate, with 2-ethylhexyl acrylate, n-butyl acrylate, 1, 4-butadiene and / or ethyl acrylate being particularly preferred.
  • the amount of monomer E copolymerized in polymer P is> 20 and> 70% by weight, preferably> 25 and> 65% by weight and particularly preferably> 30 and> 60% by weight.
  • Suitable monomers F are all ethylenically unsaturated monomers whose homopolymerized polymers have a glass transition temperature> 50.degree. C. and which differ from monomers A to D.
  • Suitable monomers F are, for example, vinylaromatic monomers and Cr to C4-alkyl methacrylates.
  • vinyl aromatic monomers is meant in particular derivatives of styrene or of ⁇ -methylstyrene in which the phenyl nuclei are optionally substituted by 1, 2 or 3 C 1 to C 4 alkyl groups, halogen, in particular bromine or chlorine and / or methoxy groups. Preference is given to those monomers whose homopolymers have a glass transition temperature> 80 ° C.
  • Particularly preferred monomers are styrene, ⁇ -methylstyrene, o- or p-vinyltoluene, p-acetoxystyrene, p-bromostyrene, p-tert-butylstyrene, o-, m- or p-chlorostyrene, methyl methacrylate, tert-butyl acrylate, tert-butylstyrene.
  • the amount of the monomers F copolymerized in the polymer P is> 25 and 71, 9 wt .-%, preferably> 25 and ⁇ 64.5 wt .-% and particularly preferably> 25 and ⁇ 57% by weight.
  • An aqueous binder composition comprising a polyurethane composed of
  • the aqueous dispersions comprise polyurethanes which, among other monomers, are derived from diisocyanates 1 a), preference being given to using those diisocyanates 1 a) which are customarily used in polyurethane chemistry.
  • Diisocyanates X (NCO) 2 where X is an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical with 6 to 15 Kohlenstotiatomen or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl ) -propane, trimethylhexane diisocyanate, 1, 4-
  • HMDI bis (4-isocyanatocyclohexyl) methane
  • Such diisocyanates are available commercially.
  • the mixture of 80 mol% of 2,4-diisocyanatotoluene and 20 mol% of 2,6-diisocyanatotoluene is suitable.
  • the mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates being 4: 1 to 0.25 : 1 is.
  • polyurethanes can be used as compounds except the aforementioned also isocyanates, in addition to the free isocyanate groups further capped isocyanate groups, z. B. wear uretdione groups.
  • diols (1 bi) predominantly higher molecular weight diols (bi) into consideration, which have a molecular weight of 500 to 5000 g / mol, preferably from 1000 to 3000 g / mol.
  • the diols (1 bi) are in particular polyester polyols, the z. B. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, page 62 to 65th
  • polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids.
  • the free polycarboxylic acids may also be the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof used to prepare the polyester polyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally, for. B. by halogen atoms, substituted and / or unsaturated.
  • Examples which may be mentioned are: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimers Fatty acids.
  • dicarboxylic acids of the general formula HOOC- (CH 2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • Suitable polyhydric alcohols are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1, 4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1, 3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol , Dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration.
  • Alcohols of the general formula HO- (CH 2) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • examples of these are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.
  • polycarbonate diols as they come z.
  • polycarbonate diols by reacting phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones to suitable difunctional starter molecules.
  • Preferred lactones are those which are derived from compounds
  • polyether diols are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF3 or by addition of these compounds, optionally in admixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, for example water , Ethylene glycol, propane-1,2-diol, propane-1,3-diol, 1,2-bis (4-hydroxydiphenyl) propane or aniline.
  • reactive hydrogen atoms such as alcohols or amines
  • polytetrahydrofuran having a molecular weight of 240 to 5000, and especially 500 to 4500.
  • mixtures of polyester diols and polyether diols can be used as monomers (1 bi).
  • polyhydroxyolefins preferably those having 2 terminal hydroxyl groups, for. B. ⁇ - ⁇ -Dihydroxypolybutadien, ⁇ - ⁇ -Dihydroxypolymethacrylester or ⁇ - ⁇ - Dihydroxypolyacrylester as monomers (1 ci).
  • Such compounds are known, for example, from EP-A-622378.
  • Further suitable polyols are polyacetals, polysiloxanes and alkyd resins.
  • the polyols can also be used as mixtures in a ratio of 0.1: 1 to 9: 1.
  • the monomers (1 b2) used are in particular the synthesis components of the short-chain alkanediols mentioned for the preparation of polyester polyols, diols having 2 to 12 carbon atoms, unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms. Atoms and pentane-1, 5-diol and neopentyl glycol are preferred.
  • the ratio of the diols (1 bi) to the monomers (1 b2) is 0.1: 1 to 5: 1, particularly preferably 0.2: 1 to 2: 1.
  • the polyurethanes in addition to the components (1 a), (1 b) and optionally (1 d) from the components (1 a), (1 b) and (1 d) different monomers ( 1 c) which carry at least one isocyanate group or at least one isocyanate-reactive group and moreover at least one hydrophilic group or a group which can be converted into a hydrophilic group.
  • the term "hydrophilic groups or potentially hydrophilic groups” is abbreviated to "(potentially) hydrophilic groups”. The (potentially) hydrophilic groups react much more slowly with isocyanates than the functional groups of the monomers which serve to build up the polymer main chain.
  • the proportion of components with (potentially) hydrophilic groups in the total amount of components (1 a), (1 b), (1 c), (1 d) and (1 e) is generally such that the molar amount of ( potentially) hydrophilic groups, based on the amount by weight of all monomers (1 a) to (1 e), 30 to 1000 mmol / kg, preferably 50 to 500 mmol / kg and particularly preferably 80 to 300 mmol / kg.
  • (Potentially) ionic monomers (1 c) are z. As described in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, page 31 1 to 313 and for example in DE-A-14 95 745 in detail.
  • monomers having tertiary amino groups are of particular practical importance, for example: tris- (hydroxyalkyl) -amines, N, N'-bis (hydroxyalkyl) -alkylamines, N-hydroxyalkyl-1 - dialkylamines, tris (aminoalkyl) amines, N, N'Bis (aminoalkyl) alkylamines, N-aminoalkyl-dialkylamines, wherein the alkyl radicals and Alkanediyl units of these tertiary amines independently of one another consist of 1 to 6 carbon atoms.
  • tertiary nitrogen atoms containing polyether having preferably two terminal hydroxyl groups such as, for example, by alkoxylation of two amino nitrogen-bonded hydrogen atoms containing amines, such as methylamine, aniline or ⁇ , ⁇ '-dimethylhydrazine, in per se conventional manner, into consideration .
  • Such polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are reacted either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids, or by reaction with suitable quaternizing agents such as C 1 to C 6 alkyl halides or benzyl halides, e.g. Bromides or chlorides, in
  • Suitable monomers with (potentially) anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least one alcoholic hydroxyl group or at least one primary or secondary amino group. Preference is given to dihydroxyalkylcarboxylic acids, in particular having 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054. Otherwise suitable are dihydroxyl compounds having a molecular weight above 500 to 10,000 g / mol with at least 2 carboxylate groups, which are known from DE-A-39 11 827.
  • dihydroxyl compounds are obtainable by reacting dihydroxyl compounds with tetracarboxylic dianhydrides such as pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride in a molar ratio of 2: 1 to 1:05 in a polyaddition reaction.
  • tetracarboxylic dianhydrides such as pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride in a molar ratio of 2: 1 to 1:05 in a polyaddition reaction.
  • Suitable dihydroxyl compounds are, in particular, the monomers (1 b2) listed as chain extenders and the diols (1 bi).
  • Suitable monomers (1c) with isocyanate-reactive amino groups are aminocarboxylic acids such as lysine, ⁇ -alanine or the adducts of aliphatic diprimary diamines mentioned in DE-A-20 34 479 to ⁇ , ⁇ -unsaturated carboxylic or sulfonic acids ,
  • the adducts of the above-mentioned aliphatic diprimary diamines with 2-acrylamido-2-methylpropanesulfonic acid e.g. in DE Patent 19 54 090 are described.
  • the polyurethanes preferably contain 1 to 30, particularly preferably 4 to 25, mol%, based on the total amount of components (1 b) and (1 d) of a polyamine having at least 2 isocyanate-reactive amino groups as monomers (1 d).
  • Monomers (1 e), which are optionally used, are monoisocyanates, monoalcohols and monoprimers and -secondary amines. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers.
  • These monofunctional compounds usually carry further functional groups such as olefinic groups or carbonyl groups and serve to introduce functional groups into the polyurethane which make it possible to disperse or crosslink or further polymer-analogous conversion of the polyurethane.
  • Suitable for this purpose are monomers such as isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate (TMI) and esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • TMI isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate
  • esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • the components (1 a) to (1 e) and their respective molar amounts are chosen such that the ratio A: B is 0.5: 1 to 2: 1, preferably 0.8: 1 to 1, 5: 1, more preferably 0.9: 1 to 1, 2: 1. Most preferably, the ratio A: B is as close as possible to 1: 1, in the
  • the monomers used (1 a) to (1 e) carry on average usually 1, 5 to 2.5, preferably 1, 9 to 2.1, more preferably 2 isocyanate groups or functional groups which can react with isocyanates in an addition reaction ,
  • the polyaddition of the monomers 1 a), 1 b), 1 c) and optionally 1 d) and 1 e) for the preparation of the PUR dispersion takes place in the presence of a suitable catalyst.
  • Suitable catalysts are tin compounds, for example dibutyltin dilaurate, tertiary amines, iron, zinc, zirconium, copper, bismuth, titanium, molybdenum and cesium compounds.
  • Preferred cesium compounds are cesium salts in which the following anions are used: F, Cr, CIO " , CI0 3 , CI0 4 , Br, J, J0 3 -, CN-, OCN-, N0 2 -, N0 3 -, HC0 3 - C0 3 2 " , S 2" , SH-, HSO 3 -, S0 3 2 -, HSO 4 -, S2O 2 2 -, S 2 0 4 2 -, S 2 0 5 2 -, S 2 0 6 2 - , S2O7 2 -, S 2 0 8 2 -, H 2 P0 2 -, H 2 P0 4 -, HPCv, P0 4 3 " , P 2 0 7 4" , (OC n H 2n + i) -, (C n H 2n -iO 2 ) -, (C n + iH 2n - 2 0 4 ) 2 -, where
  • cesium carboxylates in which the anion satisfies the formulas (C n H 2n -i0 2 ) "and (C n + iH 2n - 2 0 4 ) 2" with n being 1 to 20.
  • Very particularly preferred cesium salts have monocarboxylates of the general formula (C n H 2n -iO 2 ) -, where n for the numbers 1 to 20 stands. Particular mention should be made here of formate, acetate, propionate, hexanoate and 2-ethylhexanoate.
  • the cesium salts are used in amounts of 0.01 to 10 mmol cesium salt per kg solvent-free approach. They are preferred in amounts of 0.05 to
  • the dispersions generally have a solids content of 10 to 75, preferably from 20 to 65 wt .-% and a viscosity of 10 to 500 m Pas (measured at a temperature of 20 ° C and a shear rate of 250 s -1 ).
  • aqueous polyurethane dispersions are described, for example, in DE-A-101 61 156.
  • the aqueous solution or dispersion of a precondensate of a thermosetting resin and a binder may optionally contain a surfactant.
  • Nonionic, anionic and cationic surfactants and mixtures of at least one nonionic and at least one anionic surfactant, mixtures of at least one nonionic and at least one cationic surfactant, mixtures of several nonionic or of several cationic or of several anionic surfactants are suitable, for example.
  • the flexible foams according to the invention can be prepared as follows:
  • the foams can first be treated with an aqueous solution or dispersion of a precondensate of at least one thermosetting resin and a binder.
  • the solution or dispersion of the precondensate and the binder may contain a hardener, but may also be used without hardener.
  • a process for producing flexible foams having an abrasive surface may be carried out by subjecting an aqueous solution or dispersion of at least one precondensate of a thermosetting resin and the binder to the top and / or bottom of a flexible foam in an amount in the range of 0.1 to 90% by weight, based on the uncoated, dry foam, then the precondensate is crosslinked and the treated foam is dried.
  • dyes or pigments are added to the final aqueous solution or dispersion of the precondensate before it is applied to the foam.
  • the dyes or pigments are added in the preparation of the aqueous solution or dispersion of the precondensate and this is then applied to the foam.
  • dyes or pigments are added in the preparation of the precondensate. This mixture is then transferred shortly before application in an aqueous solution or dispersion and then applied to the foam.
  • aqueous solution or dispersion of the precondensate and binder should be fluid enough to spread easily on the substrate, but not so fluid that it will quickly penetrate or be drawn into the deeper layers of the substrate upon spreading.
  • aqueous solution or dispersion of the precondensate and of the binder on the corresponding resin application devices, for example pressure rollers, doctor blades or screens, in order to uniformly transfer the aqueous solution or dispersion of the precondensate to ensure the foam.
  • a suitable viscosity of the aqueous solution or dispersion of the precondensate and the binder so that when applying the aqueous solution or dispersion of the precondensate and the binder with the spray method, the drop size of the precondensate is minimized, the drops do not clog the spray nozzle and distribute evenly on the foam.
  • the aqueous solution or dispersion of the precondensate and the binder therefore contains a polymeric thickener in the range from 0 to 10% by weight, preferably in the range from 0 to 5% by weight, based on the aqueous solution or dispersion of the precondensate.
  • the solution or dispersion of the precondensate (hereinafter also referred to as "preparation solution”) can be applied either over the entire surface or in the form of a pattern to the foam.
  • the viscosity of the preparation solution ie the aqueous solution or dispersion of the precondensate and of the binder with or without hardener, is usually adjusted by adding the thickeners according to the invention and then applied to the substrate and only then cured.
  • the preparation solution according to the invention is preferably by spraying, knife coating, rolling, printing, inter alia by screen printing, or by means of suitable other technical devices which are known in the art, such.
  • a size press As a size press, a film press, an air brush, a curtain coating unit, are applied to the foam.
  • non-contact methods or methods are applied to the sheet substrate with the least possible pressure, such as spraying, to reduce the impact of the resin in the substrate.
  • the job can be done on one side or on both sides, either simultaneously or one after the other.
  • the amount of curable resin which is applied to the flat substrate with the aid of the preparation solution is, for example, 1 to
  • thermosetting resin and the binder and drying are carried out with an overlay of a precondensate of a thermosetting resin and the binder
  • An advantageous embodiment consists in crosslinking the thermosetting resin and the binder in a moist atmosphere and then drying the product.
  • the thermal curing of the resins and the drying of the products can take place, for example, in the temperature range from 20 to 250.degree. C., preferably from 20 to 200.degree. C., particularly preferably from 20 to 150.degree.
  • the drying step can also be carried out, for example, in gas dryers or in IR tumblers. The higher the particular temperature applied, the shorter the residence time of the material to be dried in the drying device.
  • the product of the invention can be tempered after drying at temperatures up to 300 ° C. Even temperatures above 300 ° C can be used for curing the resin, but then the required residence times are very short.
  • Glues and resins which are respectively sold as an aqueous binder or powders based on condensates of urea, melamine and formaldehyde as Kauramin ® and Kaurit ® from BASF SE, is used in the furniture and building industry for the production of plate-shaped wood materials such as Chipboard, plywood and shuttering panels, cf. Technical Information Kaurit ® .
  • Impregnated impregnated papers have a hard surface. Such products are found, for example, in surfaces of laminate flooring or in the decoration of furniture, cf. Technical Information Kauramin ® . This gives flexible, abrasive foams that are used for cleaning surfaces in the home and in the industry. They are particularly suitable as abrasive foams, which are used for mechanical and manual floor cleaning.
  • the foams according to the invention unfold when wiping surfaces of glass, metal or plastic a scouring effect, which is desired for the cleaning of these surfaces.
  • the scouring effect is much lower than that provided by abrasive particles cleaning foams, so that the substrates according to the invention for all those Applications come into consideration in which only a small abrasive effect is desired for the removal of dirt, so that the surface of the wiped with the foams of the invention materials is virtually not damaged or scratched.
  • the percentages in the examples are by weight unless otherwise indicated in the context.
  • An aqueous polyurethane dispersion (Emuldur® 360 A, BASF SE) is treated with 1 1, 4 g of completely demineralized water and 2.6 g of a methanol-etherified precondensate of melamine and formaldehyde (Saduren® 163, BASF SE). mixed.
  • Preparation Solution 4 45 g of an aqueous dispersion of a copolymer of acrylic acid esters and acrylonitrile
  • Example 1 coating of flexible foams by spraying, 2 spraying runs
  • Example 3 coating of flexible foams by spraying, 1 spray
  • Preparation solution 3 is mixed with 20 g of preparation solution 2 and 0.6 g of concentrated formic acid and the resulting solution is sprayed onto a 15 x 22 cm piece of flexible polyester-polyurethane foam with the aid of a spray gun. The specimen is then dried for 15 min at 80 ° C in a drying oven. Thereafter, the foam body was dry and crosslinked. The total application to the foam after drying was 135 g / m 2 .
  • Example 2 coating of flexible foams by spraying, 2 sprays
  • a portion of the preparation solution 4 was first sprayed using a spray gun and then dried for 5 min at 1 10 ° C. Subsequently, 30 g of the preparation solution 2 were mixed with 0.9 g of concentrated formic acid and the resulting solution was sprayed onto the previously produced layer with the aid of a spray gun. The specimen is then dried for 15 min at 150 ° C in a drying oven. Thereafter, the foam body was dry and crosslinked.
  • the coated papers obtained according to the Examples were tested for their suitability as wipes and compared to commercial, uncoated papers.
  • the test sample was fixed in each case on one side of a quatratician stamp with a side length of 25 mm and a weight of 460 g with the aid of an adhesive.
  • a glass plate was attached on a shaking machine (Crock meter) a glass plate was attached.
  • Several strips were then drawn on the glass plate with a permanent marker (Permanent Marker Edding 3000).
  • the square punch was placed on this surface, with the side of the stamp, which was stuck to the sample to be tested, each resting on glass plate.
  • the area of the plate to be cleaned was moistened with 0.5 ml of completely demineralized water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des mousses flexibles à surface abrasive flexible, qui contiennent 1 à 90 % en poids d'un mélange, rapporté au substrat non revêtu, lequel contient le produit de condensation composé de 99,985 à 20 % en poids d'au moins un précondensat d'une résine thermodurcissable, 0 à 10 % en poids d'un épaississant polymère choisi dans le groupe constitué par les biopolymères, les épaississants associatifs et/ou les épaississants entièrement synthétiques, 0,01 à 10 % en poids d'un durcisseur, 0 à 10 % en poids de tensioactifs, 0 à 15 % en poids de colorants, de pigments ou de leurs mélanges et 0 à 75 % en poids d'eau, ledit mélange contenant 10 à 70 % en poids d'un ou de plusieurs liants, rapporté au mélange susmentionné, lesquels sont choisis dans le groupe constitué par les polyacrylates, les polyméthacrylates, les polyacrylonitriles, les copolymères esters d'acide acrylique-acrylonitrile, les copolymères styrène-acrylonitrile, les copolymères ester d'acide acrylique-styrène-acrylonitrile, les copolymères acrylonitrile-butadiène-styrène, les polyuréthanes, les résines mélamine-formaldéhyde, les résines phénol-formaldéhyde, les résines urée-formaldéhyde, les résines mélamine-urée-formaldéhyde, les résines mélamine-urée-phénol-formaldéhyde, les résines urée-glyoxal.
EP14710578.7A 2013-03-28 2014-03-18 Mousses flexibles pourvues d'une surface abrasive Withdrawn EP2978802A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14710578.7A EP2978802A1 (fr) 2013-03-28 2014-03-18 Mousses flexibles pourvues d'une surface abrasive

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13161530 2013-03-28
PCT/EP2014/055368 WO2014154524A1 (fr) 2013-03-28 2014-03-18 Mousses flexibles pourvues d'une surface abrasive
EP14710578.7A EP2978802A1 (fr) 2013-03-28 2014-03-18 Mousses flexibles pourvues d'une surface abrasive

Publications (1)

Publication Number Publication Date
EP2978802A1 true EP2978802A1 (fr) 2016-02-03

Family

ID=47997222

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14710578.7A Withdrawn EP2978802A1 (fr) 2013-03-28 2014-03-18 Mousses flexibles pourvues d'une surface abrasive

Country Status (3)

Country Link
US (1) US20160046780A1 (fr)
EP (1) EP2978802A1 (fr)
WO (1) WO2014154524A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016091797A1 (fr) 2014-12-09 2016-06-16 Basf Se Procédé de production de matériaux lignocellulosiques multicouches comportant une âme présentant des propriétés spéciales et au moins une couche de recouvrement supérieure et inférieure
CN109400945A (zh) * 2018-11-02 2019-03-01 郑州峰泰纳米材料有限公司 一种超低甲醛三聚氰胺泡绵的生产工艺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5849051A (en) * 1997-11-12 1998-12-15 Minnesota Mining And Manufacturing Company Abrasive foam article and method of making same
US6239049B1 (en) * 1998-12-22 2001-05-29 3M Innovative Properties Company Aminoplast resin/thermoplastic polyamide presize coatings for abrasive article backings
US6328773B1 (en) * 1999-10-20 2001-12-11 3M Innovative Properties Company Flexible abrasive article
WO2007147730A1 (fr) * 2006-06-20 2007-12-27 Basf Se Matériau poreux pourvu d'une couche de revêtement nanoporeuse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014154524A1 *

Also Published As

Publication number Publication date
US20160046780A1 (en) 2016-02-18
WO2014154524A1 (fr) 2014-10-02

Similar Documents

Publication Publication Date Title
WO2014154527A1 (fr) Substrats flexibles plans pourvus d'une surface abrasive
EP2346682B1 (fr) Corps moulés multicouches contenant de la lignocellulose, à faible émission de formaldéhyde
EP2035112B1 (fr) Matériau poreux pourvu d'une couche de revêtement nanoporeuse
DE69935266T2 (de) In einer Presse durchgeführter Prozess zur Beschichtung von Verbundwerkstoff-Substraten
EP3515990B1 (fr) Procédé de fabrication de matériaux en lignocellulose
WO2015104349A2 (fr) Procédé servant à fabriquer des matériaux à base de lignocellulose
DE1620777B2 (de) Verfahren zur Herstellung von Kork- und gegebenenfalls Schaumstorrteiicnen enthaltenden Massen
WO1999006459A1 (fr) Dispersions aqueuses contenant des polyurethanes avec des groupes carbodiimide
EP3274143B1 (fr) Procédé destiné à la fabrication de matières dérivées du bois
DE2135072B2 (de) Verfahren zur erzeugung hochglaenzender oberflaechen auf dekorpapieren
DE2009338A1 (fr)
WO2008090136A2 (fr) Substrats plats flexibles présentant une surface abrasive
DE2221087A1 (de) Produkte mit Plueschoberflaeche und Verfahren zu deren Herstellung
DE102015119546A1 (de) Holzwerkstoffplatte aus einem Holz-Kunststoff-Verbundwerkstoff und Isocyanat, und ein Verfahren zu deren Herstellung
WO2012130711A2 (fr) Dispersion de polyuréthane réactif latent à réticulation activable
WO2014154524A1 (fr) Mousses flexibles pourvues d'une surface abrasive
JP2019537646A (ja) コーティングの製造方法
WO2006069703A1 (fr) Procede de contrecollage au moyen d'agents reticulants speciaux comportant des groupes carbodiimide
EP3274144A1 (fr) Procédé de production de matières lignocellulosiques monocouches ou multicouches à l'aide de trialkylphosphate
WO2020030330A1 (fr) Procédé de fabrication d'un composite polymère/fibre thermoformable
WO1997011103A1 (fr) Dispersions contenant des polyurethanes ayant des groupes carbonyle en fonction ceto
DE69929333T2 (de) Gebundener schaum und herstellungsverfahren dafür
EP0664355B1 (fr) Revêtement de sol ou muraux et son procédé de fabrication
DE19816528A1 (de) Wässrige Dispersionen enthaltend Polyurethane mit Carbodiimidgruppen
KR101556865B1 (ko) 각종 가구용 및 생활용품에 적용되는 폴리우레탄수지 코팅액을 이용한 친환경 합성피혁의 제조방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20151028

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20160518