Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
  • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other

Definitions

• the invention relates to a foam composite which contains at least one layer of an open-cell aminoplast resin MF and a polyurethane foam PU and in which at least one of the layers contains a formaldehyde scavenger.
• EP-A 1 428 847 describes a process for reducing emissions of polyurethane foams by adding polymers containing amino groups, such as polyvinylamine.
• WO 02/126872 describes the treatment of an open-cell, elastic melamine / formaldehyde resin foam with a polymer containing primary and / or secondary amino groups for lowering the emission of formaldehyde and its use for hygiene articles.
• the object of the present invention was to find a foam composite with reduced formaldehyde emission.
• the foam composite preferably consists of a core of an open-cell aminoplastic foam MF, in particular of an open-cell melamine-formaldehyde resin foam and an all-round jacket of a polyurethane foam PU.
• the jacket of polyurethane foam PU contains the formaldehyde scavenger.
• both the layers of the open-cell aminoplast resin MF and the layers of the polyurethane foam PU may contain the formaldehyde scavenger.
• open-cell foams are preferably elastic foams based on a melamine / formaldehyde condensation product having a specific gravity of 5 to 100 g / l, in particular from 8 to 20 g / l used.
• the cell count is usually in the range of 50 to 300 cells / 25 mm.
• the tensile strength is preferably in the range of 100 to 150 kPa and the elongation at break in the range of 8 to 20%.
• a highly concentrated propellant-containing solution or dispersion of a melamine-formaldehyde precondensate can be foamed and cured with hot air, water vapor or by microwave irradiation.
• Such foams are commercially available under the name Basotect® from BASF Aktiengesellschaft.
• the molar ratio of melamine / formaldehyde is generally in the range of 1: 1 to 1: 5.
• the molar ratio in the range of 1: 1, 3 to 1: 1, 8 is selected and a sulfite group-free precondensate used, such as. B described in WO 01/94436.
• the foams can then be tempered and pressed.
• the foams can be cut to the desired shape and thickness and laminated on one or both sides with cover layers.
• cover layers For example, a polymer or metal foil can be applied as a cover layer.
• the thickness of the layer of open-cell melamine-formaldehyde resin foam MF depends on the intended use.
• the open-cell foam z. B used for seat cushion in a thickness in the range of 5 to 500 mm, preferably in the range of 10 to 100 mm.
• the polyurethane foams PU are generally obtainable by reacting polyisocyanates with compounds containing isocyanate-reactive hydrogen atoms, if appropriate in the presence of catalysts, blowing agents and / or additives.
• the polyurethane foam can be applied as a layer to one or more surfaces of the aminoplast resin foam, for example by gluing.
• the polyurethane resin foam components are foamed in-situ around the aminoplast resin foam as the core, thereby obtaining an all-round encapsulation.
• the thickness of the layers or sheath polyurethane foam PU depends on the intended use In general, the open-cell foam z. B used for seat cushion in a thickness in the range of 5 to 500 mm, preferably in the range of 10 to 100 mm.
• the formaldehyde scavenger used can be an amino-containing polymer having a molecular weight of at least 500 g / mol and an amino functionality of at least 3.
• the formaldehyde scavenger can be added, preferably in small amounts, the addition being effected before, during or after the preparation of the polymer. Urethane or Aminoplastschaumstoffs can be done.
• the formaldehyde scavenger can be used both in the layer of the open-cell aminoplastic foam MF or in the layer of polyurethane foam PU or in both layers.
• amino-containing polymers having a molecular weight of at least 500 and an amino functionality of at least 3, wherein the ratio of molecular weight to amino functionality of 40 to 500, in an amount of 10 " 4 to less than 0.1 wt .-%, In preferred embodiments, it was possible to lower the formaldehyde emissions of foam composites below the detection limit of the measuring method used.
• polymers comprising amino groups are understood as meaning all polymeric substances which have primary and / or secondary amino groups. It is preferred here that the primary or secondary amino groups are arranged as a side group in the polymer.
• the amino-containing polymers have a number-average molecular weight of at least 500 g / mol, preferably of at least 1000 g / mol, more preferably of at least 1500 g / mol, particularly preferably of at least 2000 g / mol, in particular of at least 2,500 g / mol.
• the upper limit of the number average molecular weight is generally not limited, preferably it should not be more than 1,000,000 g / mol, more preferably not more than 750,000 g / mol.
• the polymers having amino groups generally have an amino functionality per polymer molecule of at least 3, preferably of at least 5, more preferably of at least 10, particularly preferably of at least 20 and in particular of at least 50.
• the upper limit of the amino functionality is generally not limited, preferably it should not be more than 20,000, more preferably not more than 15,000, in particular not more than 10,000.
• the amino-containing polymers have a ratio of molecular weight to amino functionality of from 40 to 500, more preferably from 50 to 300, particularly preferably from 60 to 250, in particular from 70 to 200.
• the polymers containing amino groups are preferably selected from polymers comprising vinylamine units, crosslinked polyamidoamines, crosslinked polyamidoamines grafted with ethyleneimine, polyethyleneimines, alkoxylated polyethyleneimines, crosslinked polyethyleneimines, amidated polyethyleneimines, alkylated polyamino ethyleneimines, polyamines, amine-epichlorohydrin polycondensates, water-soluble polyaddition products of multifunctional epoxides and multifunctional amines, alkoxylated polyamines, polyallylamines, and condensates of lysine, ornithine or arginine, or mixtures thereof.
• R 1 and R 2 may be the same or different and are hydrogen and C 1 to C 6 alkyl.
• the stated monomers can be polymerized either alone, in admixture with one another or together with other monoethylenically unsaturated monomers.
• Polymers containing vinylamine units are known, for example, from US Pat. No. 4,421,602, US Pat. No. 5,334,287, EP-A-0 216 387 and EP-A-0 251 182. They are obtained by hydrolysis of polymers which contain the monomers of the formula I copolymerized with acids, bases or enzymes.
• Suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are all compounds which can be copolymerized therewith.
• vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate
• vinyl ethers such as C 1 to C 6 alkyl vinyl ethers, e.g. Methyl or ethyl vinyl ether.
• Suitable comonomers are ethylenically unsaturated C3- to C6-carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinylacetic acid and their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate, Ethyl acrylate and ethyl methacrylate.
• C3- to C6-carboxylic acids for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinylacetic acid and their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate, Ethyl acrylate and ethyl methacrylate.
• carboxylic acid esters are derived from glycols or polyalkylene glycols, in each case only one OH group esterified, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and acrylic acid monoesters of polyalkylene glycols having a molecular weight of 500 to 10,000.
• Esters of ethylenically unsaturated carboxylic acids with aminoalcohols such as, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate.
• aminoalcohols such as, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate.
• the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form.
• Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
• Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids having alkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylamides, such.
• N-vinylpyrrolidone N-vinylcaprolactam
• acrylonitrile methacrylonitrile
• N-vinylimidazole substituted N-vinylimidazoles, such as e.g. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines
• N-vinylimidazoline N-vinyl-2-methylimidazoline and N- vinyl-2-ethylimidazoline.
• N-vinylimidazoles and N-vinylimidazolines are used, except in the form of the free bases, also in neutralized or quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.
• diallyldialkylammonium halides such as, for example, Diallyldimethylammonium.
• alkenes such as e.g. Ethene, propene, butene, isobutene, hexene and butadiene.
• sulfo-containing monomers such as, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate, the content of anionic units exceeding the cationic units amphoteric copolymer content so that the polymers have a total cationic charge.
• the copolymers contain, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate, the content of anionic units exceeding the cationic units amphoteric copolymer content so that the polymers have a total cationic charge.
• the copolymers contain, for example
• R 2 has the meaning given in formula I, polymers, the vinylamine units of the formula
• the homopolymers of the N-vinylcarboxamides of the formula I and their copolymers can be hydrolyzed to from 0.1 to 100, preferably from 70 to 100, mol%. In most cases, the degree of hydrolysis of the homopolymers and copolymers is 5 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the content of the polymers of vinylamine units. In the case of copolymers which contain copolymerized vinyl esters, in addition to the hydrolysis of the N-vinylformamide units, hydrolysis of the ester groups to form vinyl alcohol units may occur.
• the homopolymers and copolymers containing vinylamine units may optionally contain up to 20 mol% of amidine units which are formed, for example, by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with an adjacent amide group, for example of polymerized N-vinylformamide.
• the molar masses of polymers containing vinylamine units are, for example, 500 to 10 million, preferably 1000 to 5 million (determined by light scattering).
• This molecular weight corresponds to, for example, K values of from 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 0 C and a polymer concentration of 0.5 wt .-%.
• the polymers containing vinylamine units are preferably used in salt-free form.
• Salt-free aqueous solutions of polymers comprising vinylamine units can be prepared, for example, from the above-described salt-containing polymer solutions by means of ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons.
• the aqueous solutions of other polymers containing amino and / or ammonium groups described below can also be obtained by means of ultrafiltration in salt-free form.
• Polyethyleneimines are prepared, for example, by polymerization of ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids as catalyst.
• Polyethyleneimines have, for example, molecular weights of up to 2 million, preferably from 200 to 1,000,000. Particular preference is given to using polyethyleneimines having molecular weights of from 500 to 750,000.
• water-soluble crosslinked polyethyleneimines which are obtainable by reaction of polyethyleneimines with crosslinkers such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units and still have free primary and / or secondary amino groups.
• amidic polyethyleneimines which are obtainable, for example, by amidation of polyethyleneimines with C 1 to C 22 monocarboxylic acids.
• cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimides. mine. In the alkoxylation used, for example, per NH unit in polyethyleneimine 1 to 5 ethylene oxide or propylene oxide.
• Suitable primary and / or secondary amino and / or ammonium groups containing polymers are also polyamidoamines, which are obtainable for example by condensing dicarboxylic acids with polyamines.
• Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids having 4 to 10 carbon atoms with polyalkylenepolyamines which contain 3 to 10 basic nitrogen atoms in the molecule.
• suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid.
• polyamidoamines In the preparation of the polyamidoamines it is also possible to use mixtures of dicarboxylic acids, as well as mixtures of several polyalkylenepolyamines.
• Suitable polyalkylenepolyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
• the dicarboxylic acids and polyalkylenepolyamines are heated to higher temperatures, for example to temperatures in the range of 120 to 220, preferably 130 to 18O 0 C, to produce the polyamidoamines.
• the water formed during the condensation is removed from the system.
• lactones or lactams of carboxylic acids having 4 to 8 C atoms in the condensation.
• 0.8 to 1.4 moles of a polyalkylenepolyamine are used per mole of a dicarboxylic acid.
• polymers containing amino groups are polyamidoamines grafted with ethyleneimine. They are obtainable from the polyamidoamines described above by reaction with ethyleneimine in the presence of acids or Lewis acids such as sulfuric acid or boron trifluoride etherates at temperatures of, for example, 80 to 100 ° C. Compounds of this type are described for example in DE-B-24 34 816.
• the optionally crosslinked polyamidoamines which may additionally be additionally grafted before crosslinking with ethyleneimine, are suitable as cationic polymers.
• the crosslinked polyethyleneamines grafted with ethyleneimine are water-soluble and have e.g. an average molecular weight of 3000 to 2 million daltons.
• Typical crosslinkers are e.g. Epichlorohydrin or bischlorohydrin ethers of alkylene glycols and polyalkylene glycols.
• polyallylamines are also suitable as polymers which have primary and / or secondary amino and / or ammonium groups.
• Polymers of this type are obtained by homopolymerization of allylamine, preferably in acid neutralized form, or by copolymerizing allylamine with other monoethylenically unsaturated monomers described above as comonomers for N-vinylcarboxamides.
• the polymer having amino groups is polyvinylamine.
• the polyvinylamine used has a number average molecular weight of 500 to 1,000,000 g / mol and a ratio of number average molecular weight to amino functionality of 40 to 500.
• the polymers containing amino groups are added in an amount to the polyurethane or Aminoplastharzschaumstoff which is sufficient to reduce the formaldehyde emission by the desired level. In general, a small amount of amino-containing polymer is necessary.
• the polymer containing amino groups is present in an amount of from 10 " 4 to 5 wt%, preferably from 10" 4 to 1 wt%, more preferably from 0.001 to less than 0.1 wt%, in particular from 0.005 to 0.05, based on the total weight of the polyurethane or Aminoplastharzschaumstoffs, added to the polyurethane or Aminoplastharzschaumstoff.
• amino-containing polymers to the polyurethane or aminoplast resin foam can be accomplished by various approaches.
• the addition of the amino-containing polymer can take place before and / or during the production of the polyurethane or aminoplast resin foam.
• either the isocyanate component or the polyol component, preferably the polyol component, the polymer having amino groups is added and then reacted with the other component.
• the addition can be done both before the mixing of polyol component and isocyanate component as well as directly during mixing of the components themselves.
• the addition is carried out in the amounts described above.
• the polymer containing amino groups can be added in pure form or it is previously taken up in a solvent and then added to the isocyanate component or the polyol component.
• a preferred solvent for the amino-containing polymer is water.
• Another possibility is the addition of the amino-containing polymer to the finished polyurethane or Aminoplastharzschaumstoffs.
• This addition is generally carried out by applying a solution or dispersion containing the polymer.
• the application can be effected, for example, by immersing a polyurethane or aminoplast resin foam in a liquid which contains a primary and / or secondary amino-containing polymer in dissolved or dispersed form.
• the liquid with the dissolved or dispersed polymeric treatment agent can also be sprayed onto the foam topcoat. be applied surface. Thereafter, the solvent is removed from the thus treated foam body, for example by drying the foam.
• the addition of the amino group-containing polymer preferably takes place after the production of the foam, if appropriate during the annealing.
• the Aminoplastharzschaumstoff to remove all volatile constituents with hot annealing air which contains the amino-containing polymer z. B. was added in the form of an aerosol, are flowed through.
• the formaldehyde emission of the foams can be lowered and, if appropriate, a hydrophilization can be achieved without having to subse- quently subject the foams to further treatment.
• the foam composite according to the invention can be used for various applications in which low formaldehyde emissions are desired.
• the foam composite according to the invention is preferably used for a seat upholstery, for example in rail vehicles or aircraft.

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• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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• Detergent Compositions (AREA)

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• 2007
  • 2007-08-01 KR KR1020097004846A patent/KR20090040373A/ko not_active Application Discontinuation
  • 2007-08-01 EP EP07802450A patent/EP2051855A1/de not_active Withdrawn
  • 2007-08-01 CN CNA2007800297196A patent/CN101500806A/zh active Pending
  • 2007-08-01 US US12/376,808 patent/US20100179238A1/en not_active Abandoned
  • 2007-08-01 BR BRPI0715380-5A patent/BRPI0715380A2/pt not_active IP Right Cessation
  • 2007-08-01 WO PCT/EP2007/057927 patent/WO2008017627A1/de active Application Filing
  • 2007-08-01 JP JP2009523247A patent/JP2010500188A/ja not_active Withdrawn

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